WorldWideScience

Sample records for atom transfer radical

  1. prepared via atom transfer radical polymerization, reverse atom

    Indian Academy of Sciences (India)

    Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse atom transfer radical polymerization and ... Zydex Industries, 25-A Gandhi Oil Mill Compound, Gorwa, Vadodara 390 016, India; Rubber Technology Centre, Indian Institute of Technology Kharagpur, ...

  2. Palladium-Catalyzed Atom-Transfer Radical Cyclization at Remote Unactivated C(sp3 )-H Sites: Hydrogen-Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates.

    Science.gov (United States)

    Ratushnyy, Maxim; Parasram, Marvin; Wang, Yang; Gevorgyan, Vladimir

    2018-03-01

    A novel mild, visible-light-induced palladium-catalyzed hydrogen atom translocation/atom-transfer radical cyclization (HAT/ATRC) cascade has been developed. This protocol involves a 1,5-HAT process of previously unknown hybrid vinyl palladium radical intermediates, thus leading to iodomethyl carbo- and heterocyclic structures. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Monomode microwave-assisted atom transfer radical polymerization

    NARCIS (Netherlands)

    Zhang, H.; Schubert, U.S.

    2004-01-01

    The first monomode microwave-assisted atom transfer radical polymerization (ATRP) is reported. The ATRP of methyl methacrylate was successfully performed with microwave heating, which was well controlled and provided almost the same results as experiments with conventional heating, demonstrating the

  4. Atom transfer radical polymerization of styrene under pulsed microwave irradiation

    International Nuclear Information System (INIS)

    Cheng Zhenping; Zhu Xiulin; Zhou Nianchen; Zhu Jian; Zhang Zhengbiao

    2005-01-01

    A homogeneous solution atom transfer radical polymerization (ATRP) and reverse atom transfer radical polymerization (RATRP) of styrene (St) in N,N-dimethylformamide (DMF) were successfully carried out under pulsed microwave irradiation (PMI), using 1-bromo-1-phenylethane (1-PEBr)/CuCl/N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) as an initiating system at 85 deg. C and 2,2'-azo-bis-isobutyrontrile (AIBN)/CuCl 2 /PMDETA as an initiating system at 95 deg. C, respectively. The polymerization rates under PMI were greatly increased in comparison with those under identical conventional heating (CH)

  5. 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......(bpy) as initiating system. A linear (M) over bar(n), versus monomer conversion plot was found in good accordance with the theoretical line, indicating 100% initiating efficiency. The polymerization is first order in respect to monomer up to about 70% monomer conversion. Deviations from linearity at higher conversion...

  6. Atom transfer radical polymerization of n-butyl acrylate catalyzed by atom transfer radical polymerization of n-butyl acrylate catalyzed by

    NARCIS (Netherlands)

    Zhang, H.; Linde, van der R.

    2002-01-01

    The homogeneous atom transfer radical polymerization (ATRP) of n-butyl acrylate with CuBr/N-(n-hexyl)-2-pyridylmethanimine as a catalyst and ethyl 2-bromoisobutyrate as an initiator was investigated. The kinetic plots of ln([M]0/[M]) versus the reaction time for the ATRP systems in different

  7. TRANSITION METAL CATALYSIS IN CONTROLLED RADICAL POLYMERIZATION: ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    Science.gov (United States)

    Novel and diversified macromolecular structures, which include polymers with designed topologies (top), compostions (middle), and functionalities (bottom), can be prepared by atom transfer radical polymerization processes. These polymers can be synthesized from a large variety of...

  8. Atom transfer radical copolymerization of styrene and butyl acrylate

    NARCIS (Netherlands)

    Chambard, G.; Klumperman, B.; Matyjaszewski, K.

    2000-01-01

    Atom transfer radical polymerization of styrene and butyl acrylate has been investigated from a kinetic point of view. Attention is focused on the activation of the dormant species as well as on the termination that plays a role in these reactions. It has been shown that the activation of a styrene

  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. 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-...

  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. Functionalized polymer film surfaces via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Hu, Y.; Li, J.S.; Yang, W.T.; Xu, F.J.

    2013-01-01

    The ability to manipulate and control the surface properties of polymer films, without altering the substrate properties, is crucial to their wide-spread applications. In this work, a simple one-step method for the direct immobilization of benzyl chloride groups (as the effective atom transfer radical polymerization (ATRP) initiators) on the polymer films was developed via benzophenone-induced coupling of 4-vinylbenzyl chloride (VBC). Polyethylene (PE) and nylon films were selected as examples of polymer films to illustrate the functionalization of film surfaces via surface-initiated ATRP. Functional polymer brushes of (2-dimethylamino)ethyl methacrylate, sodium 4-styrenesulfonate, 2-hydroxyethyl methacrylate and glycidyl methacrylate, as well as their block copolymer brushes, have been prepared via surface-initiated ATRP from the VBC-coupled PE or nylon film surfaces. With the development of a simple approach to the covalent immobilization of ATRP initiators on polymer film surfaces and the inherent versatility of surface-initiated ATRP, the surface functionality of polymer films can be precisely tailored. - Highlights: ► Atom transfer radical polymerization initiators were simply immobilized. ► Different functional polymer brushes were readily prepared. ► Their block copolymer brushes were also readily prepared

  13. 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.

  14. Reactivity of hydropersulfides toward the hydroxyl radical unraveled: disulfide bond cleavage, hydrogen atom transfer, and proton-coupled electron transfer.

    Science.gov (United States)

    Anglada, Josep M; Crehuet, Ramon; Adhikari, Sarju; Francisco, Joseph S; Xia, Yu

    2018-02-14

    Hydropersulfides (RSSH) are highly reactive as nucleophiles and hydrogen atom transfer reagents. These chemical properties are believed to be key for them to act as antioxidants in cells. The reaction involving the radical species and the disulfide bond (S-S) in RSSH, a known redox-active group, however, has been scarcely studied, resulting in an incomplete understanding of the chemical nature of RSSH. We have performed a high-level theoretical investigation on the reactions of the hydroxyl radical (˙OH) toward a set of RSSH (R = -H, -CH 3 , -NH 2 , -C(O)OH, -CN, and -NO 2 ). The results show that S-S cleavage and H-atom abstraction are the two competing channels. The electron inductive effect of R induces selective ˙OH substitution at one sulfur atom upon S-S cleavage, forming RSOH and ˙SH for the electron donating groups (EDGs), whereas producing HSOH and ˙SR for the electron withdrawing groups (EWGs). The H-Atom abstraction by ˙OH follows a classical hydrogen atom transfer (hat) mechanism, producing RSS˙ and H 2 O. Surprisingly, a proton-coupled electron transfer (pcet) process also occurs for R being an EDG. Although for RSSH having EWGs hat is the leading channel, S-S cleavage can be competitive or even dominant for the EDGs. The overall reactivity of RSSH toward ˙OH attack is greatly enhanced with the presence of an EDG, with CH 3 SSH being the most reactive species found in this study (overall rate constant: 4.55 × 10 12 M -1 s -1 ). Our results highlight the complexity in RSSH reaction chemistry, the extent of which is closely modulated by the inductive effect of the substituents in the case of the oxidation by hydroxyl radicals.

  15. The effect of reducing monosaccharides on the atom transfer radical polymerization of butyl methacrylate

    NARCIS (Netherlands)

    Vries, de Andrew; Klumperman, B.; Wet-Roos, de D.; Sanderson, R.D.

    2001-01-01

    The effect of various reducing monosaccharides on the rate of atom transfer radical polymerization (ATRP) of butyl methacrylate is reported in this study. The addition of reducing sugars affects the rate of ATRP positively with a 100% increase in the rate of polymerization in some cases. In

  16. Atom-transfer radical polymerization of methyl methacrylate (MMA) using CuSCN as the catalyst

    NARCIS (Netherlands)

    Singha, N.K.; Klumperman, B.

    2000-01-01

    The effect of CuSCN as a catalyst in atom-transfer radical polymerization (ATRP) was investigated. CuSCN can successfully be used for the ATRP of MMA. Substituted bipyridines as well as imines can be used to stabilize the copper complex in solution. CuSCN induces faster polymerization compared to

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

    DEFF Research Database (Denmark)

    Iruthayaraj, Joseph; Chernyy, Sergey; Lillethorup, Mie

    2011-01-01

    This work features the controllability of surface-initiated atom transfer radical polymerization (SI-ATRP) of methyl methacrylate, initiated by a multilayered 2-bromoisobutyryl moiety formed via diazonium chemistry. The thickness as a function of polymerization time has been studied by varying di...

  18. 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...

  19. 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...

  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...

  1. On the mechanism of activation of copper-catalyzed atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Isse, Abdirisak Ahmed; Bortolamei, Nicola; De Paoli, Patrizia; Gennaro, Armando

    2013-01-01

    The mechanism of activation of atom transfer radical polymerization (ATRP) has been analyzed by investigating the kinetics of dissociative electron transfer (ET) to alkyl halides (RX) in acetonitrile. Using a series of alkyl halides, including both bromides and chlorides, the rate constants of ET (k ET ) to RX by electrogenerated aromatic radical anions (A· − ) acting as outer-sphere donors have been measured and analyzed according to the current theories of dissociative ET. This has shown that the kinetic data fit very well the “sticky” dissociative ET model with the formation of a weak adduct held together by electrostatic interactions. The rate constants of activation, k act , of some alkyl halides, namely chloroacetonitrile, methyl 2-bromopropionate and ethyl chloroacetate, by [Cu I L] + (L = tris(2-dimethylaminoethyl)amine, tris(2-pyridylmethyl)amine, 1,1,4,7,7-pentamethyldiethylenetriamine) have also been measured in the same experimental conditions. Comparisons of the measured k act values with those predicted assuming an outer-sphere ET for the complexes have shown that activation by Cu(I) is 7–10 orders of magnitude faster than required by outer-sphere ET. Therefore, the mechanism of RX activation by Cu(I) complexes used as catalysts in ATRP occurs by an inner-sphere ET or more appropriately by a halogen atom abstraction

  2. Functionalization of lanthanum hydroxide nanowires by atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zhou Mi; Yuan Jinying; Yuan Weizhong; Yin Yingwu; Hong Xiaoyin

    2007-01-01

    Atom transfer radical polymerization (ATRP) has been used to prepare a core-shell hybrid nanostructure successfully: a hard core of single-crystalline lanthanum hydroxide nanowires and a soft shell of polystyrene (PS) brushes. Transmission electron microscopy (TEM) images indicated that the resulting products presented special structures and different thicknesses of polymer layers. The chemical components and grafted PS quantities of the samples were measured by Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). The polymers showed narrow polydispersity, which proved that the lanthanum hydroxide nanowires initiated the 'living'/controlled polymerization of styrene. With the modifiability of lanthanum hydroxide nanowires, the solubility increased, which affords a new way to functionalize nanowires

  3. Effect of Inhibitors on Atom Transfer Radical Polymerization of MMA

    Institute of Scientific and Technical Information of China (English)

    张鸿; 徐冬梅; 张可达

    2005-01-01

    Effect of a series of inhibitors as additives on atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) with FeCl2/PPh3 as catalyst system was studied, including 2,4,6-trinitrophenol (TNP), 4-methoxyphenol (4-MP), hydroquinone (HQ) and nitrobenzene (NB). It was found that TNP was the only. efficient additive for ATRP among these inhibitors. In the presence of small amounts of TNP, the polymerization proceeded rapidly after induction period to yield the polymers with controlled molecular weights and narrow molecular weight distributions (MWD). The initiating efficiency of the modified catalyst system with TNP was increased. The mechanism was proposed and confirmed by the end group analysis of the polymer.

  4. ATOM TRANSFER RADICAL POLYMERIZATION OF N-BUTYL METHACRYLATE IN AQUEOUS DISPERSED SYSTEMS: A MINIEMULSION APPROACH. (R826735)

    Science.gov (United States)

    Ultrasonication was applied in combination with a hydrophobe for the copper-mediated atom transfer radical polymerization of n-butyl methacrylate in an aqueous dispersed system. A controlled polymerization was successfully achieved, as demonstrated by a linear correlation between...

  5. N-Chlorosuccinimide (NCS): A Novel Initiator for Atom Transfer Radical Polymerization of Methyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    WANG,Xia-Yan; CHANG,Li-Qun; ZHOU,Hong; ZHANG,Ke-Da

    2006-01-01

    Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was achieved, using N-chlorosuccinimide (NCS) as an initiator together with catalytic system CuCl/PMDETA (N,N,N',N',N"-pentamethyldiethyl-enetriamine), CuCl/MA5-DETA (N,N,N',N',N"-penta(methylacrylate)diethylenetriamine), and CuCl/bipy (bipy=2,2'-bipyridyl) respectively. The results indicated that the polymerization possessed typical controlled/living radical polymerization characteristics. The analysis for terminal group of obtained polymer by 1H NMR proved that NCS is an initiator for ATRP. In comparison with NBS, the polymerization rate was slower and the resulted polymer had narrower molecular weight distribution (MWD) when NCS was employed as the initiator.

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

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2014-01-01

    The versatility of the atom transfer radical polymerization (ATRP) of pentafluorostyrene (FS) is comprehensively evaluated. The ATRP of a wide range of monomers derived from FS is likewise discussed with emphasis on the potential polymer applications. A large number of block and star copolymers...... centred around polypentafluorostyrene (PFS) and prepared primarily using the bromomacroinitiator concept is surveyed. Here the main emphasis is on the feasibility of the polymer design, but also the very many different applications are highlighted. The potential grafting onto PFS and PFS block copolymers...... 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...

  7. Synthesis of triblock and random copolymers of 4- acetoxystyrene and styrene by living atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela

    1997-01-01

    Triblock copolymers containing polystyrene (PSt) and poly(4-acetoxystyrene) (PAcOSt) segments have been prepared by atom transfer radical polymerization (ATRP). In the first step one of the two monomers was polymerized in bulk using the initiating system alpha,alpha'-dibromo-p-xylene/CuBr/2,2'-bi...

  8. 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...

  9. Peptide block copolymers by N-carboxyanhydride ring-opening polymerization and atom transfer radical polymerization: The effect of amide macroinitiators

    NARCIS (Netherlands)

    Habraken, G.J.M.; Koning, C.E.; Heise, A.

    2009-01-01

    The synthesis of polypeptide-containing block copolymers combining N-carboxyanhydride (NCA) ring-opening polymerization and atom transfer radical polymerization (ATRP) was investigated. An amide initiator comprising an amine function for the NCA polymerization and an activated bromide for ATRP was

  10. Studies on atom transfer radical polymerization of acrylates and styrenes with controlled polymeric block structures

    OpenAIRE

    Ibrahim, Khalid

    2006-01-01

    Atom transfer radical polymerization (ATRP) was applied to homo and block copolymerization of vinyl monomers methacrylates, acrylates, and styrene with iron (FeCl2.4H2O) as the transition metal in most cases. As complexing ligand either a commercially available ligand (triphenyl phosphine) (PPh3) or synthetic aliphatic amines were used. As initiators, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate, α,α-dichloroacetophenone, and poly(ethylene oxide) macroinitiator were employed. Block ...

  11. Iron halide mediated atom transfer radical polymerization of methyl methacrylate with N-Alkyl-2-pyridylmethanimine as the ligand

    NARCIS (Netherlands)

    Zhang, H.; Schubert, U.S.

    2004-01-01

    The controlled atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) catalyzed by iron halide/N-(n-hexyl)-2-pyridylmethanimine (NHPMI) is described. The ethyl 2-bromoisobutyrate (EBIB)-initiated ATRP with [MMA]0/[EBIB]0/[iron halide]0/[NHPMI]0 = 150/1/1/2 was better controlled in

  12. Fabrication of Robust and Antifouling Superhydrophobic Surfaces via Surface-Initiated Atom Transfer Radical Polymerization.

    Science.gov (United States)

    Xue, Chao-Hua; Guo, Xiao-Jing; Ma, Jian-Zhong; Jia, Shun-Tian

    2015-04-22

    Superhydrophobic surfaces were fabricated via surface-initiated atom transfer radical polymerization of fluorinated methacrylates on poly(ethylene terephthalate) (PET) fabrics. The hydrophobicity of the PET fabric was systematically tunable by controlling the polymerization time. The obtained superhydrophobic fabrics showed excellent chemical robustness even after exposure to different chemicals, such as acid, base, salt, acetone, and toluene. Importantly, the fabrics maintained superhydrophobicity after 2500 abrasion cycles, 100 laundering cycles, and long time exposure to UV irradiation. Also, the surface of the superhydrophobic fabrics showed excellent antifouling properties.

  13. In situ AFM investigation of electrochemically induced surface-initiated atom-transfer radical polymerization.

    Science.gov (United States)

    Li, Bin; Yu, Bo; Zhou, Feng

    2013-02-12

    Electrochemically induced surface-initiated atom-transfer radical polymerization is traced by in situ AFM technology for the first time, which allows visualization of the polymer growth process. It affords a fundamental insight into the surface morphology and growth mechanism simultaneously. Using this technique, the polymerization kinetics of two model monomers were studied, namely the anionic 3-sulfopropyl methacrylate potassium salt (SPMA) and the cationic 2-(metharyloyloxy)ethyltrimethylammonium chloride (METAC). The growth of METAC is significantly improved by screening the ammonium cations by the addition of ionic liquid electrolyte in aqueous solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. The role of the achiral template in enantioselective transformations. Radical conjugate additions to alpha-methacrylates followed by hydrogen atom transfer.

    Science.gov (United States)

    Sibi, Mukund P; Sausker, Justin B

    2002-02-13

    We have evaluated various achiral templates (1a-g, 10, and 16) in conjunction with chiral Lewis acids in the conjugate addition of nucleophilic radicals to alpha-methacrylates followed by enantioselective H-atom transfer. Of these, a novel naphthosultam template (10) gave high enantioselectivity in the H-atom-transfer reactions with ee's up to 90%. A chiral Lewis acid derived from MgBr(2) and bisoxazoline (2) gave the highest selectivity in the enantioselective hydrogen-atom-transfer reactions. Non-C(2) symmetric oxazolines (20-25) have also been examined as ligands, and of these, compound 25 gave optimal results (87% yield and 80% ee). Insights into rotamer control in alpha-substituted acrylates and the critical role of the tetrahedral sulfone moiety in realizing high selectivity are discussed.

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

    DEFF Research Database (Denmark)

    Nielsen, Mads Møller

    The cornerstone in this dissertation is made up by three individual assessments of the diversity in the macromolecular landscape that can be obtained by applying relatively few efficient chemical tools. The intention is to gain deeper knowledge on the chemical tuning of proton exchange membranes...... 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...... of control by ATRP and click chemistry enables a wide selection of polymer structures with the handles: degree of substitution (DS), polymerization and sulfonation, and blending....

  16. 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...... angle measurements and XPS. Moreover, ATR FTIR has been used to confirm the formation of initiating groups. Grafting of PEGMA from PEEK was performed in aqueous solution. The presence of the PPEGMA grafts on PEEK was revealed by the thermograms from TGA whereas investigations with AFM rejected changes...

  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 (H 2 S) and disulfides (RSSR) and/or sulfenic acids (RSOH). RSSH have been investigated for their ability to store H 2 S 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 (α 2 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 ) in

  18. 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-C α 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

  19. Structure and Reactivity of the Glutathione Radical Cation: Radical Rearrangement from the Cysteine Sulfur to the Glutamic Acid alpha-Carbon Atom

    NARCIS (Netherlands)

    Osburn, S.; Berden, G.; Oomens, J.; Gulyuz, K.; Polfer, N.C.; O'Hair, R.A.J.; Ryzhov, V.

    2013-01-01

    A gas-phase radical rearrangement through intramolecular hydrogen-atom transfer (HAT) was studied in the glutathione radical cation, [-ECG](+.), which was generated by a homolytic cleavage of the protonated S-nitrosoglutathione. Ion-molecule reactions suggested that the radical migrates from the

  20. Poly(vinyl acetate-Based Block Copolymer/Clay Nanocomposites Prepared by In Situ Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    M.A. Semsarzadeh

    2009-12-01

    Full Text Available Atom transfer radical polymerization of styrene (St and methyl methacrylate (MMA was performed at 90oC in the absence and presence of nanoclay (Cloisite 30B. Trichloromethyl-terminated poly(vinyl acetate telomerand CuCl/ PMDETA were used as a macroinitiator and catalyst system, respectively. The experimental results showed that the atom transfer radical polymerization of St and MMA in the absence or presence of nanoclay proceeds via a controlled/living mode. It was observed that nanoclay significantly enhances the homopolymerization rate of MMA, which was attributed to the activated conjugated C=C bond of MMA monomer via interaction between the carbonyl group of MMA monomer and the hydroxyl moiety (Al-O-H of nanoclay as well as the effect of nanoclay on the dynamic equilibrium between the active (macro radicals and dormant species.Homopolymerization rate of St (a non-coordinative monomer with nanoclay decreased slightly in the presence of nanoclay. This could be explained by insertion of a portion of macroinitiator into the clay galleries, where no sufficient St monomer exists due to the low compatibility or interaction of St monomer with nanoclay to react with the macroinitiator. The results obtained from XRD, TEM and TGA analyses were fully in agreement with the kinetic data. Structure of the poly(vinyl acetate-bpolystyrene nanocomposite was found to be a combination of stacking layers and exfoliated structures while poly(vinyl acetate-b-poly(methyl methacryale nanocomposite had an exfoliated structure. This difference in the structure of nanocomposites was attributed to the different capability of the monomers (styrene and methyl methacrylate to react with the hydroxyl moiety (Al-O-H of nanoclay.

  1. 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

  2. Synthesis of Environmentally Responsive Polymers by Atom Transfer Radical Polymerization: Generation of Reversible Hydrophilic and Hydrophobic Surfaces

    Directory of Open Access Journals (Sweden)

    Vikas Mittal

    2010-05-01

    Full Text Available Environmentally responsive poly(N-isopropylacrylamide brushes were grafted from the surface of polymer particles or flat surfaces in order to generate reversible hydrophilic and hydrophobic surfaces. The use of atom transfer radical polymerization was demonstrated for the grafting of polymer brushes as it allows efficient control on the amount of grafted polymer. The polymer particles were generated with or without surfactant in the emulsion polymerization and their surface could be modified with the atom transfer radical polymerization (ATRP initiator. The uniform functionalization of the surface with ATRP initiator was responsible for the uniform grafting of polymer brushes. The grafted brushes responded reversibly with changes in temperature indicating that the reversible responsive behavior could be translated to the particle surfaces. The particles were observed to adsorb and desorb protein and virus molecules by changing the temperatures below or higher than 32 °C. The initiator functionalized particles could also be adsorbed on the flat surfaces. The adsorption process also required optimization of the heat treatment conditions to form a uniform layer of the particles on the substrate. The grafted polymer brushes also responded to the changes in temperatures similar to the spherical particles studied through water droplets placed on the flat substrates.

  3. Atom Transfer Radical Polymerization of Styrene in Presence of Mesoporous Silica Nanoparticles: Application of Reverse, Simultaneous Reverse and Normal Initiation Techniques

    Directory of Open Access Journals (Sweden)

    Khezrollah Khezri

    2014-04-01

    Full Text Available Atom transfer radical polymerization (ATRP of styrene in presence of mesoporous silica nanoparticles was carried out at 110 °C. Reverse atom transfer radical polymerization (RATRP and simultaneous reverse and normal initiation for atom transfer radical polymerization (SR&NI ATRP techniques were used as two appropriate introduced techniques for circumventing oxidation problems. Usage of metal catalyst in its higher oxidation state was the main feature of these initiation techniques in which deficiencies of normal ATRP were circumvented. Structure, surface area and pore diameter of synthesized mesoporous silica nanoparticles were evaluated using X–ray diffraction and nitrogen adsorption/desorption isotherm analysis. Average particle size was estimated around 600 nm by electron microscopy images. In addition, according to these images, nanoparticles revealed an appropriate size distribution. Particles size and their distribution were examined using scanning. Final monomer conversion was determined by using gas chromatography. The number and weight average molecular weights (Mn and Mw and polydispersity indexes (PDI were also evaluated by gel permeation chromatography. According to the results obtained, addition of mesoporous silica nanoparticles in both RATRP and SR&NI ATRP systems revealed similar effects: decrement of conversion and Mn and also increment of PDI values observed by increasing of mesoporous silica nanoparticles content. Improvement in thermal stability of the nanocomposites in comparison with neat polystyrene was demonstrated by thermogravimetric analysis (TGA. Moreover, in case of nanocomposites, thermal stability was obtained by higher loading of nanoparticles. A decrease in glass transition temperature by higher content of mesoporous silica nanoparticles has been demonstrated by differential scanning calorimetry analysis.

  4. PREPARATION AND PROPERTIES OF MMA/1-PROPYLMETHACRYLATE-POSS COPOLYMER WITH ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    He-xin Zhang; Ho-young Lee; Young-jun Shin; Dong-ho Lee; Seok Kyun Noh

    2008-01-01

    The methyl methacrylate(MMA)/1-propylmethacrylate-polyhedral oligomeric silsesquioxane(PM-POSS) copolymers were synthesized via atom transfer radical polymerization with CuBr as catalyst.The unreacted PM-POSS monomer could be removed completely by washing the copolymerization product with n-hexane.The copolymers were characterized with 1H-NMR,X-ray diffraction,difierential scanning calorimetry,thermogravimetric analysis and gel permeatlon chromatography.With increasing PM-POSS feed ratio.the total conversion increased while the glass transition temperatures of copolymer decreased.The thermogravimetric analysis demonstrated that the thermal stability of copolymer improved slightly with PM-POSS addition.The molecular weight of copolymers increased with incorporation of PM-POSS.

  5. When hydroquinone meets methoxy radical: Hydrogen abstraction reaction from the viewpoint of interacting quantum atoms.

    Science.gov (United States)

    Petković, Milena; Nakarada, Đura; Etinski, Mihajlo

    2018-05-25

    Interacting Quantum Atoms methodology is used for a detailed analysis of hydrogen abstraction reaction from hydroquinone by methoxy radical. Two pathways are analyzed, which differ in the orientation of the reactants at the corresponding transition states. Although the discrepancy between the two barriers amounts to only 2 kJ/mol, which implies that the two pathways are of comparable probability, the extent of intra-atomic and inter-atomic energy changes differs considerably. We thus demonstrated that Interacting Quantum Atoms procedure can be applied to unravel distinct energy transfer routes in seemingly similar mechanisms. Identification of energy components with the greatest contribution to the variation of the overall energy (intra-atomic and inter-atomic terms that involve hydroquinone's oxygen and the carbon atom covalently bound to it, the transferring hydrogen and methoxy radical's oxygen), is performed using the Relative energy gradient method. Additionally, the Interacting Quantum Fragments approach shed light on the nature of dominant interactions among selected fragments: both Coulomb and exchange-correlation contributions are of comparable importance when considering interactions of the transferring hydrogen atom with all other atoms, whereas the exchange-correlation term dominates interaction between methoxy radical's methyl group and hydroquinone's aromatic ring. This study represents one of the first applications of Interacting Quantum Fragments approach on first order saddle points. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

  6. The potential of Cu(I)Cl/2,2'-bipyridine catalysis in a triblock copolymer preparation by atom transfer radical polymerization

    Czech Academy of Sciences Publication Activity Database

    Masař, Bohumil; Vlček, Petr; Kříž, Jaroslav

    2001-01-01

    Roč. 81, č. 14 (2001), s. 3514-3522 ISSN 0021-8995 R&D Projects: GA MŠk OC P1.10; GA AV ČR KSK2050602 Institutional research plan: CEZ:AV0Z4050913 Keywords : atom transfer radical polymerization * triblock copolymers * sequential synthesis Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.992, year: 2001

  7. 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.

  8. PREPARATION OF BLOCK COPOLYMERS OF POLY(STYRENE) AND POLY(T-BUTYL ACRYLATE) OF VARIOUS MOLECULAR WEIGHTS AND ARCHITECTURES BY ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    Science.gov (United States)

    Block copolymers of polystyrene and poly(t-butyl acrylate) were prepared using atom transfer radical polymerization techniques. These polymers were synthesized with a CuBr/N,N,N,NA 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...

  9. 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.

  10. Three Arm Star Homo- And Co-Polymers Via Atom Transfer Radical Polymerization

    International Nuclear Information System (INIS)

    Amin, A.; Sobh, R.A.; Ayoub, M.M.H.

    2005-01-01

    Star homo and co-polymers of some vinyl monomers such as methylmethacrylate, butylmethacrylate and styrene (MMA, BMA, St.) were prepared using N, N, N', N' tetramethylethylenediamine ligand/ CuBr catalytic system via atom transfer radical polymerization (ATRP). Three armed benzene based core was successfully used as initiator. Low polydispersities and regular molecular weight values were obtained in most cases especially at low conversions. MMA and BuMA showed comparable behavior where controlled and true ATRP was observed even at the high conversions. However, styrene monomer recorded irregular high polydispersities at high conversions in spite of the relatively low molecular weight values. 1HNMR confirmed the structures of the resulting polymers. Transmission Electron microscope (TEM) proved the nano-structure of the star polymers. The thermal behavior of the MMA star homo and copolymers was studied. The effect of the star shape on the thermal behavior was very clear with respect to the linear ones

  11. Kinetics of elementary atom and radical reactions: Progress report

    International Nuclear Information System (INIS)

    Gordon, R.J.

    1986-01-01

    Our research program is concerned with the kinetics of elementary gas phase reactions and energy transfer involving polyatomic molecules. We report here on three ongoing projects: The reaction of oxygen atoms with hydrogen molecules, the electronic relaxation of NH radicals, and the vibrational relaxation of highly excited SF 6 molecules. 10 refs., 5 figs

  12. Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

    OpenAIRE

    Shahabuddin, Syed; Hamime Ismail, Fatem; Mohamad, Sharifah; Muhamad Sarih, Norazilawati

    2015-01-01

    Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydro...

  13. 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.

  14. Surface modification of thermoplastic poly(vinyl alcohol)/saponite nanocomposites via surface-initiated atom transfer radical polymerization enhanced by air dielectric discharges barrier plasma treatment

    International Nuclear Information System (INIS)

    Zhen Weijun; Lu Canhui

    2012-01-01

    To improve the water resistance of thermoplastic poly(vinyl alcohol)/saponite nanocomposites (TPVA), a simple two-step method was developed for the covalent immobilization of atom transfer radical polymerization (ATRP) initiators on the TPVA surfaces enhanced by air dielectric barrier discharges (DBD) plasma treatment, and hydrophobic poly(methyl methacrylate) (PMMA) brushes were then grafted onto the surface of TPVA via surface-initiated atom transfer radical polymerization (SI-ATRP). The chemical composition, morphology and hydrophobicity of the modified TPVA surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), respectively. The water resistance of the surface-functionalized PMMA was evaluated by the contact angle and water adsorption method. It was shown that air DBD plasma treatment activated the TPVA surface and accelerated the immobilization of ATRP initiator on the TPVA surface. Compared with TPVA control, TPVA modified by SI-ATRP can be grafted well-defined and covalently tethered network PMMA brushes onto the surface and the hydrophobicity of TPVA were significantly enhanced.

  15. 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.

  16. 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.

  17. Free radical transfer in polymers

    International Nuclear Information System (INIS)

    Sonntag, C. von; Bothe, E.; Ulanski, P.

    1998-01-01

    For the present study of free-radical transfer in polymers pulse radiolysis and product studies have been carried out in aqueous solutions using thus far only the water-soluble polymers polyacrylic acid, polymethacrylic acid and polyvinyl alcohol. When OH radicals, generated in the radiolysis of N 2 O-saturated aqueous solutions, react with polymers the lifetime of the polymer radical thus created very much depends on the number of radicals per polymer chain. When there are a large number of radicals per chain their bimolecular decay may be faster than the corresponding (diffusion controlled) decay of monomeric radicals, but when the macromolecule contains only few or even just one radical their lifetime is considerably prolonged. Highly charged polymers such as polyacrylic acid at high pH attain a rod-like conformation which again favors a long lifetime of the radicals. Under such conditions, radical transfer reactions can occur. For example, in polyacrylic acid OH radicals generate two kinds of radicals side by side. The radical in β-position to the carboxylate group converts into the thermodynamically more stable α-radicals by an H-transfer reaction as can be followed by spectrophotometry. Besides radical transfer reactions β-fragmentation reactions occur causing chain scission. Such reactions can be followed in a pulse radiolysis experiment by conductometry, because counter ions are released upon chain scission. Such a process is especially effective in the case of polymethacrylic acid, where it results in a chain depolymerization. An intramolecular H-abstraction is also observed in the γ-radiolysis of polyacrylic acid with the corresponding peroxyl radicals. This causes a chain reaction to occur. The resulting hydroperoxides are unstable and decarboxylate given rise to acetylacetone-like products. In polyvinyl alcohol the peroxyl radicals in α-position to the alcohol function undergo HO 2 -elimination. This prevents a scission of the polymer chain in the

  18. Synthesis of poly(2-ethyl-2-oxazoline)-b-poly(styrene) copolymers via a dual initiator route combining cationic ring-opening polymerization and atom transfer radical polymerization

    NARCIS (Netherlands)

    Becer, C.R.; Paulus, R.M.; ppener, S.; Hoogenboom, R.; Fustin, C.A.; Gohy, J.M.W.; Schubert, U.S.

    2008-01-01

    Block copolymers of 2-ethyl-2-oxazoline (EtOx) and styrene were synthesized by a combination of cationic ring-opening polymerization (CROP) and atom transfer radical polymerization (ATRP). Initially, a detailed kinetic investigation for the ?-bromoisobutyrylbromide (BrEBBr) initiated CROP of EtOx

  19. 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

  1. Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Syed Shahabuddin

    2015-01-01

    Full Text Available Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydroxyphenylethane, a trifunctional core molecule, to give well-defined triple-arm star-branched polystyrene.

  2. 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.

  3. Surface-Initiated Graft Atom Transfer Radical Polymerization of Methyl Methacrylate from Chitin Nanofiber Macroinitiator under Dispersion Conditions

    Directory of Open Access Journals (Sweden)

    Ryo Endo

    2015-08-01

    Full Text Available Surface-initiated graft atom transfer radical polymerization (ATRP of methyl methacrylate (MMA from self-assembled chitin nanofibers (CNFs was performed under dispersion conditions. Self-assembled CNFs were initially prepared by regeneration from a chitin ion gel with 1-allyl-3-methylimidazolium bromide using methanol; the product was then converted into the chitin nanofiber macroinitiator by reaction with α-bromoisobutyryl bromide in a dispersion containing N,N-dimethylformamide. Surface-initiated graft ATRP of MMA from the initiating sites on the CNFs was subsequently carried out under dispersion conditions, followed by filtration to obtain the CNF-graft-polyMMA film. Analysis of the product confirmed the occurrence of the graft ATRP on the surface of the CNFs.

  4. Radical transfer between proteins: role of tyrosine, tryptophan and protein peroxyl radicals

    International Nuclear Information System (INIS)

    Irwin, J.A.; Ostdal, H.; Davies, M.J.

    1998-01-01

    Reaction of the Fe(III) forms of the heme proteins myoglobin (Mb) and horseradish peroxidase (HRP) with H 2 O 2 gives rise to high-oxidation-state heme-derived species which can be described as a Fe(IV)-oxo porphyrin radical-cation ('Compound 1'). In the case of Mb, the Fe(IV)-oxo porphyrin radical-cation undergoes rapid electron transfer with the surrounding protein to give protein (globin)-derived radicals and an Fe(lV)-oxo species ('Compound 2'). The globin-derived radicals have been shown to be located at two (or more) sites: Tyr-103 or Trp-14, with the latter radical known to react with oxygen to give a Trp-derived peroxyl radical (Mb-Trp-OO*). With HRP, the Fe(lV)-oxo porphyrin radical-cation carries out two successive one-electron oxidation reactions at the exposed heme edge to give firstly 'Compound 2' [the Fe(lV)oxo species] and then the resting Fe(III) state of the enzyme. n this study we have investigated whether the Trp-14 peroxyl radical from Mb and the Compound 1 and 2 species from HRP (in the absence and presence of free Tyr) can oxidise amino acids, peptides and proteins. Such reactions constitute intermolecular protein-to-protein radical transfer reactions and hence protein chain-oxidation. We have also examined whether these oxidants react with antioxidants. Reaction of these heme-protein derived oxidants with amino acids, proteins and antioxidants has been carried out at room temperature for defined periods of time before freeze-quenching to 77K to halt reaction. The radical species present in the reaction system at the time of freezing were subsequently examined by EPR spectroscopy at 77K. Three free amino acids, Tyr, Trp and Cys (with Cys the least efficient) have been shown to react rapidly with Mb-Trp-OO*, as evidenced by the loss of the characteristic EPR features of Mb-Trp-OO* on inclusion of increasing concentrations of the amino acids. All other amino acids are much less reactive. Evidence has also been obtained for (inefficient) hydrogen

  5. Controlled Grafting of Poly(methyl methacrylate) Brushes on Poly(vinylidene fluoride) Powders by Surface-initiated Atom Transfer Radical Polymerization

    Institute of Scientific and Technical Information of China (English)

    TANG Zhaoqi; LI Wei; LIU Lanqin; HUANG Lei; ZHOU Jin; YU Haiyin

    2009-01-01

    Controlled grafting of well-defined polymer brushes of methyl methacrylate (MMA) on the poly(vinylidene fluoride) (PVDF) powders was carded out by the surface-initiated atom transfer radical polymerization (ATRP). The ATRP initiator was anchored on the PVDF surface by alkaline treatment, followed by UV-induced bromination; then methyl methacrylate (MMA) was grafted onto the brominated PVDF by the ATRP technique. The chemical composition changes of PVDF were characterized by Fourier transform-infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). FT-IR and XPS results clearly indicated the successful graft of poly(methyl methacrylate) onto the PVDF surface.

  6. Preparation of poly(methyl methacrylate) grafted titanate nanotubes by in situ atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Gao Yuan; Zhou Yongfeng; Yan Deyue; Gao Xueping

    2008-01-01

    This paper reports the successful preparation of core-shell hybrid nanocomposites by a 'grafting from' approach based on in situ atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) from titanate nanotubes (TNTs). Transmission electron microscope (TEM) images of the products provide direct evidence for the formation of a core-shell structure, possessing a hard core of TNTs and a soft shell of poly-MMA (PMMA). Fourier-transform infrared spectroscopy (FT-IR), hydrogen nuclear magnetic resonance ( 1 H NMR), scanning electron microscopy (SEM), and thermal gravimetric analysis (TGA) were used to determine the chemical structure, morphology, and the grafted PMMA quantities of the resulting products. The grafted PMMA content was well controlled and increased with increasing monomer/initiator ratio. Further copolymerization of hydroxyethyl methacrylate (HEMA) with PMMA-coated TNTs as initiators was realized, illustrating the 'living' characteristics of the ATRP method used in this paper.

  7. Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

    Science.gov (United States)

    Matasović, Brunislav; Bonifačić, Marija

    2011-06-01

    Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals CO2-rad , rad CH 2OH, rad CH(CH 3)OH, and rad CH(CH 3)O - have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production 60Co γ-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U rad radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U rad radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of α-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism ( Matasović and Bonifačić, 2007). Thus, while both rad CH 2OH and rad CH(CH 3)OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm -3 concentrations, pH 7, brought about chain debromination to occur in the case of rad CH(CH 3)OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of α-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by U rad radicals have been estimated to amount to about ≥85 and 1200 dm 3 mol -1 s -1, respectively.

  8. Fabrication of ultrahydrophobic poly(lauryl acrylate) brushes on silicon wafer via surface-initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Oztuerk, Esra; Turan, Eylem [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey); Caykara, Tuncer, E-mail: caykara@gazi.edu.tr [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey)

    2010-11-15

    In this report, ultrahydrophobic poly(lauryl acrylate) [poly(LA)] brushes were synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP) of lauryl acrylate (LA) in N,N-dimethylformamide (DMF) at 90 deg. C. The formation of ultrahydrophobic poly(LA) films, whose thickness can be turned by changing polymerization time, is evidenced by using the combination of ellipsometry, X-ray photoelectron spectroscopy (XPS), grazing angle attenuated total reflectance-Fourier transform infrared spectroscopy (GATR-FTIR), atomic force microscopy (AFM), gel permeation chromatography (GPC), and water contact angle measurements. The SI-ATRP can be conducted in a well-controlled manner, as revealed by the linear kinetic plot, linear evolution of number-average molecular weights (M-bar{sub n}) versus monomer conversions, and the relatively narrow PDI (<1.28) of the grafted poly(LA) chains. The calculation of grafting parameters from experimental measurements indicated the synthesis of densely grafted poly(LA) films and allowed us to predict a 'brushlike' conformation for the chains in good solvent. The poly(LA) brushes exhibited high water contact angle of 163.3 {+-} 2.8{sup o}.

  9. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (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)

    2016-12-30

    Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: 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 {sup 1}H 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.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: 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 1 H 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.

  12. Crystalline TiO2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

    International Nuclear Information System (INIS)

    Zhao Yuancong; Tu Qiufen; Wang Jin; Huang Qiongjian; Huang Nan

    2010-01-01

    Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

  13. Crystalline TiO 2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

    Science.gov (United States)

    Zhao, Yuancong; Tu, Qiufen; Wang, Jin; Huang, Qiongjian; Huang, Nan

    2010-12-01

    Crystalline TiO 2 films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO 2 films by self-assembling, and the HUPA on TiO 2 films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO 2 films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

  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

    strategies for initiator grafting, physicochemical properties of polymer brushes and basic principles of quartz crystal microbalance technique (QCM) are discussed. In Chapter 2 various ATRP conditions are probed. The effects of solvent polarity, monomer concentration, initiator surface density, ligand nature......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...... and temperature on the kinetics of methyl methacrylate polymerization are elucidated. The strategy was based on the observation of dry polymer thickness versus time evolution by means of ellipsometry, profilometry and IR spectroscopy. An alternative approach, constituting Chapter 3, was based on optimization...

  15. Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Matasovic, Brunislav [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia); Bonifacic, Marija, E-mail: bonifacic@irb.h [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia)

    2011-06-15

    Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals {sup {center_dot}C}O{sub 2}{sup -}, {sup {center_dot}C}H{sub 2}OH, {sup {center_dot}C}H(CH{sub 3})OH, and {sup {center_dot}C}H(CH{sub 3})O{sup -} have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production {sup 60}Co {gamma}-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U{sup {center_dot}} radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U{sup {center_dot}} radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of {alpha}-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism (). Thus, while both {sup {center_dot}C}H{sub 2}OH and {sup {center_dot}C}H(CH{sub 3})OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm{sup -3} concentrations, pH 7, brought about chain debromination to occur in the case of {sup {center_dot}C}H(CH{sub 3})OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of {alpha}-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by U{sup {center_dot}} radicals have been estimated to amount to about {>=}85 and 1200 dm{sup 3} mol{sup -1} s{sup -1

  16. Synthesis of thermoresponsive poly(N-isopropylacrylamide) brush on silicon wafer surface via atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Turan, Eylem; Demirci, Serkan [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey); Caykara, Tuncer, E-mail: caykara@gazi.edu.t [Department of Chemistry, Faculty of Art and Science, Gazi University, 06500 Besevler, Ankara (Turkey)

    2010-08-31

    Thermoresponsive poly(N-isopropylacrylamide) [poly(NIPAM)] brush on silicon wafer surface was prepared by combining the self-assembled monolayer of initiator and atom transfer radical polymerization (ATRP). The resulting polymer brush was characterized by in situ reflectance Fourier transform infrared spectroscopy, atomic force microscopy and ellipsometry techniques. Gel permeation chromatography determination of the number-average molecular weight and polydispersity index of the brush detached from the silicon wafer surface suggested that the surface-initiated ATRP method can provide relatively homogeneous polymer brush. Contact angle measurements exhibited a two-stage increase upon heating over the board temperature range 25-45 {sup o}C, which is in contrast to the fact that free poly(NIPAM) homopolymer in aqueous solution exhibits a phase transition at ca. 34 {sup o}C within a narrow temperature range. The first de-wetting transition takes place at 27 {sup o}C, which can be tentatively attributed to the n-cluster induced collapse of the inner region of poly(NIPAM) brush close to the silicon surface; the second de-wetting transition occurs at 38 {sup o}C, which can be attributed to the outer region of poly(NIPAM) brush, possessing much lower chain density compared to that of the inner part.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-09-14

    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).

  18. Crystalline TiO{sub 2} grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Yuancong; Tu Qiufen; Wang Jin; Huang Qiongjian [Key Lab. of Advanced Technology for Materials, Education Ministry, School of Material Science and Technology of Southwest Jiaotong University, Chengdu, Sichuan (China); Huang Nan, E-mail: zhaoyc7320@163.com [Key Lab. of Advanced Technology for Materials, Education Ministry, School of Material Science and Technology of Southwest Jiaotong University, Chengdu, Sichuan (China)

    2010-12-15

    Crystalline TiO{sub 2} films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO{sub 2} films by self-assembling, and the HUPA on TiO{sub 2} films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO{sub 2} films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.

  19. Preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization for the selective recognition of tetracycline from aqueous medium

    International Nuclear Information System (INIS)

    Dai, Jiangdong; Pan, Jianming; Xu, Longcheng; Li, Xiuxiu; Zhou, Zhiping; Zhang, Rongxian; Yan, Yongsheng

    2012-01-01

    Highlights: ► Atom transfer radical emulsion polymerization is a “living” and green technique. ► Nanoparticles can overcome mass transfer limitations and improve accessibility. ► Molecular imprinted nanoparticles with magnetic property for fast separation. ► The performance of imprinted nanoparticles was investigated in detail. ► Nanoparticles were used to selective recognize Tetracycline from water medium. - Abstract: In the work, we reported an effective method for the preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization (ATREP), and then as-prepared magnetic molecularly imprinted nanoparticles (MMINs) were evaluated as adsorbents for selective recognition of tetracycline (TC) molecules from aqueous medium. The resulting nanoparticles were characterized by FT-IR, TGA, VSM, SEM and TEM. The results demonstrated MMINs with a narrow diameter distribution were cross-linked with modified Fe 3 O 4 particles, composed of imprinted layer and exhibited good magnetic sensitivity, magnetic and thermal stability. Batch rebinding studies were carried out to determine the specific adsorption equilibrium, kinetics, and selective recognition. The estimated adsorption capacity of MMINs towards TC by the Langmuir isotherm model was 12.10 mg g −1 at 298 K, which was 6.33 times higher than that of magnetic non-molecularly imprinted nanoparticles (MNINs). The kinetic property of MMINs was well-described by the pseudo-second-order rate equation. The results of selective recognition experiments demonstrated outstanding affinity and selectivity towards TC over competitive antibiotics. The reusability of MMINs showed no obviously deterioration at least five repeated cycles in performance. In addition, the MMINs prepared were successfully applied to the extraction of TC from the spiked pork sample.

  20. 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.

  1. Catalytic enantioselective alkene aminohalogenation/cyclization involving atom transfer.

    Science.gov (United States)

    Bovino, Michael T; Chemler, Sherry R

    2012-04-16

    Problem solved: the title reaction was used for the synthesis of chiral 2-bromo, chloro, and iodomethyl indolines and 2-iodomethyl pyrrolidines. Stereocenter formation is believed to occur by enantioselective cis aminocupration and C-X bond formation is believed to occur by atom transfer. The ultility of the products as versatile synthetic intermediates was demonstrated, as was a radical cascade cyclization sequence. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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.

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

    International Nuclear Information System (INIS)

    Wang, Jingjing; Wei, Jun

    2016-01-01

    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.

  4. Enantioselective H-atom transfer reaction: a strategy to synthesize formaldehyde aldol products.

    Science.gov (United States)

    Sibi, Mukund P; Patil, Kalyani

    2005-04-14

    [reaction: see text] Enantioselective radical alkylation of Baylis-Hillman adducts furnished aldol products in good yield and selectivity. The results illustrate that the selectivity in the hydrogen atom transfer is dependent on the size of the ester substituent, with smaller substituents providing better enantioselectivity.

  5. Preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization for the selective recognition of tetracycline from aqueous medium

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Jiangdong; Pan, Jianming; Xu, Longcheng; Li, Xiuxiu [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Zhou, Zhiping [School of Material Science and Engineering, Jiangsu University, Zhenjiang 212013 (China); Zhang, Rongxian [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Yan, Yongsheng, E-mail: djdxxx123@163.com [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing, 100191 (China)

    2012-02-29

    Highlights: Black-Right-Pointing-Pointer Atom transfer radical emulsion polymerization is a 'living' and green technique. Black-Right-Pointing-Pointer Nanoparticles can overcome mass transfer limitations and improve accessibility. Black-Right-Pointing-Pointer Molecular imprinted nanoparticles with magnetic property for fast separation. Black-Right-Pointing-Pointer The performance of imprinted nanoparticles was investigated in detail. Black-Right-Pointing-Pointer Nanoparticles were used to selective recognize Tetracycline from water medium. - Abstract: In the work, we reported an effective method for the preparation of molecularly imprinted nanoparticles with superparamagnetic susceptibility through atom transfer radical emulsion polymerization (ATREP), and then as-prepared magnetic molecularly imprinted nanoparticles (MMINs) were evaluated as adsorbents for selective recognition of tetracycline (TC) molecules from aqueous medium. The resulting nanoparticles were characterized by FT-IR, TGA, VSM, SEM and TEM. The results demonstrated MMINs with a narrow diameter distribution were cross-linked with modified Fe{sub 3}O{sub 4} particles, composed of imprinted layer and exhibited good magnetic sensitivity, magnetic and thermal stability. Batch rebinding studies were carried out to determine the specific adsorption equilibrium, kinetics, and selective recognition. The estimated adsorption capacity of MMINs towards TC by the Langmuir isotherm model was 12.10 mg g{sup -1} at 298 K, which was 6.33 times higher than that of magnetic non-molecularly imprinted nanoparticles (MNINs). The kinetic property of MMINs was well-described by the pseudo-second-order rate equation. The results of selective recognition experiments demonstrated outstanding affinity and selectivity towards TC over competitive antibiotics. The reusability of MMINs showed no obviously deterioration at least five repeated cycles in performance. In addition, the MMINs prepared were successfully

  6. Poly(n-isopropylacrylamide)-based hydrogel coatings on magnetite nanoparticles via atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Frimpong, Reynolds A; Hilt, J Zach [Department of Chemical and Materials Engineering, University of Kentucky, Lexington, KY 40506 (United States)], E-mail: hilt@engr.uky.edu

    2008-04-30

    Core magnetite (Fe{sub 3}O{sub 4}) nanoparticles have been functionalized with a model intelligent hydrogel system based on the temperature responsive polymer poly(n-isopropyl acrylamide) (PNIPAAm) to obtain magnetically responsive core-shell nanocomposites. Fe{sub 3}O{sub 4} nanoparticles were obtained from a one-pot co-precipitation method which provided either oleic acid (hydrophobic) or citric acid (hydrophilic) coated nanoparticles. Subsequent ligand exchange of these coatings with various bromine alkyl halides and a bromo silane provided initiating sites for functionalization with NIPAAm using atom transfer radical polymerization (ATRP). The bromine alkyl halides that were used were 2-bromo-2-methyl propionic acid (BMPA) and 2-bromopropionyl bromide (BPB). The bromo silane that was used was 3-bromopropyl trimethoxysilane (BPTS). The intelligent polymeric shell consists of NIPAAm crosslinked with poly(ethylene glycol) 400 dimethacrylate (PEG400DMA). Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used to confirm the presence of the polymeric shell. Dynamic light scattering (DLS) was used to characterize the nanocomposites for particle size changes with temperature. Their magnetic and temperature responsiveness show great promise for further biomedical applications. This platform for functionalizing magnetic nanoparticles with intelligent hydrogels promises to impact a wide range of medical and biological applications of magnetic nanoparticles.

  7. Poly(n-isopropylacrylamide)-based hydrogel coatings on magnetite nanoparticles via atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Frimpong, Reynolds A; Hilt, J Zach

    2008-01-01

    Core magnetite (Fe 3 O 4 ) nanoparticles have been functionalized with a model intelligent hydrogel system based on the temperature responsive polymer poly(n-isopropyl acrylamide) (PNIPAAm) to obtain magnetically responsive core-shell nanocomposites. Fe 3 O 4 nanoparticles were obtained from a one-pot co-precipitation method which provided either oleic acid (hydrophobic) or citric acid (hydrophilic) coated nanoparticles. Subsequent ligand exchange of these coatings with various bromine alkyl halides and a bromo silane provided initiating sites for functionalization with NIPAAm using atom transfer radical polymerization (ATRP). The bromine alkyl halides that were used were 2-bromo-2-methyl propionic acid (BMPA) and 2-bromopropionyl bromide (BPB). The bromo silane that was used was 3-bromopropyl trimethoxysilane (BPTS). The intelligent polymeric shell consists of NIPAAm crosslinked with poly(ethylene glycol) 400 dimethacrylate (PEG400DMA). Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used to confirm the presence of the polymeric shell. Dynamic light scattering (DLS) was used to characterize the nanocomposites for particle size changes with temperature. Their magnetic and temperature responsiveness show great promise for further biomedical applications. This platform for functionalizing magnetic nanoparticles with intelligent hydrogels promises to impact a wide range of medical and biological applications of magnetic nanoparticles

  8. All solid-state polymer electrolytes prepared from a hyper-branched graft polymer using atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Higa, Mitsuru; Fujino, Yukiko; Koumoto, Taihei; Kitani, Ryousuke; Egashira, Satsuki

    2005-01-01

    We propose an all solid-state (liquid free) polymer electrolyte (SPE) prepared from a hyper-branched graft copolymer. The graft copolymer consisting of a poly(methyl methacrylate) main chain and poly(ethylene glycol) methyl ether methacrylate side chains was synthesized by atom transfer radical polymerization changing the average chain distance between side chains, side chain length and branched chain length of the proposed structure of the graft copolymer. The ionic conductivity of the SPEs increases with increasing the side chain length, branched chain length and/or average distance between the side chains. The ionic conductivity of the SPE prepared from POEM 9 whose POEM content = 51 wt% shows 2 x 10 -5 S/cm at 30 deg. C. The tensile strength of the SPEs decreases with increases the side chain length, branched chain length and/or average distance between the side chains. These results indicate that a SPE prepared from the hyper-branched graft copolymer has potential to be applied to an all-solid polymer electrolyte

  9. Rational preparation of dibenzothiophene-imprinted polymers by surface imprinting technique combined with atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Yang, Wenming; Liu, Lukuan; Zhou, Zhiping; Liu, Hong; Xie, Binze; Xu, Wanzhen

    2013-01-01

    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.

  10. In situ development of self-reinforced cellulose nanocrystals based thermoplastic elastomers by atom transfer radical polymerization.

    Science.gov (United States)

    Yu, Juan; Wang, Chunpeng; Wang, Jifu; Chu, Fuxiang

    2016-05-05

    Recently, the utilization of cellulose nanocrystals (CNCs) as a reinforcing material has received a great attention due to its high elastic modulus. In this article, a novel strategy for the synthesis of self-reinforced CNCs based thermoplastic elastomers (CTPEs) is presented. CNCs were first surface functionalized with an initiator for surface-initiated atom transfer radical polymerization (SI-ATRP). Subsequently, SI-ATRP of methyl methacrylate (MMA) and butyl acrylate (BA) was carried out in the presence of sacrificial initiator to form CTPEs in situ. The CTPEs together with the simple blends of CNCs and linear poly(MMA-co-BA) copolymer (P(MMA-co-BA)) were characterized for comparative study. The results indicated that P(MMA-co-BA) was successfully grafted onto the surface of CNCs and the compatibility between CNCs and the polymer matrix in CTPEs was greatly enhanced. Specially, the CTPEs containing 2.15wt% CNCs increased Tg by 19.2°C and tensile strength by 100% as compared to the linear P(MMA-co-BA). Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Single-collision studies of hot atom energy transfer and chemical reaction

    International Nuclear Information System (INIS)

    Valentini, J.J.

    1991-01-01

    This report discusses research in the collision dynamics of translationally hot atoms, with funding with DOE for the project ''Single-Collision Studies of Hot Atom Energy Transfer and Chemical Reaction,'' Grant Number DE-FG03-85ER13453. The work reported here was done during the period September 9, 1988 through October 31, 1991. During this period this DOE-funded work has been focused on several different efforts: (1) experimental studies of the state-to-state dynamics of the H + RH → H 2 R reactions where RH is CH 4 , C 2 H 6 , or C 3 H 8 , (2) theoretical (quasiclassical trajectory) studies of hot hydrogen atom collision dynamics, (3) the development of photochemical sources of translationally hot molecular free radicals and characterization of the high resolution CARS spectroscopy of molecular free radicals, (4) the implementation of stimulated Raman excitation (SRE) techniques for the preparation of vibrationally state-selected molecular reactants

  12. Structure and Intramolecular Proton Transfer of Alanine Radical Cations

    International Nuclear Information System (INIS)

    Lee, Gab Yong

    2012-01-01

    The structures of the four lowest alanine conformers, along with their radical cations and the effect of ionization on the intramolecular proton transfer process, are studied using the density functional theory and MP2 method. The energy order of the radical cations of alanine differs from that of the corresponding neutral conformers due to changes in the basicity of the NH 2 group upon ionization. Ionization favors the intramolecular proton transfer process, leading to a proton-transferred radical-cation structure, [NH 3 + -CHCH 3 -COO·], which contrasts with the fact that a proton-transferred zwitterionic conformer is not stable for a neutral alanine in the gas phase. The energy barrier during the proton transfer process is calculated to be about 6 kcal/mol

  13. Reaction kinetics of hydrogen atom abstraction from isopentanol by the H atom and HO2˙ radical.

    Science.gov (United States)

    Parab, Prajakta Rajaram; Heufer, K Alexander; Fernandes, Ravi Xavier

    2018-04-25

    Isopentanol is a potential next-generation biofuel for future applications to Homogeneous Charge Compression Ignition (HCCI) engine concepts. To provide insights into the combustion behavior of isopentanol, especially to its auto-ignition behavior which is linked both to efficiency and pollutant formation in real combustion systems, detailed quantum chemical studies for crucial reactions are desired. H-Abstraction reaction rates from fuel molecules are key initiation steps for chain branching required for auto-ignition. In this study, rate constants are determined for the hydrogen atom abstraction reactions from isopentanol by the H atom and HO2˙ radical by implementing the CBS-QB3 composite method. For the treatment of the internal rotors, a Pitzer-Gwinn-like approximation is applied. On comparing the computed reaction energies, the highest exothermicity (ΔE = -46 kJ mol-1) is depicted for Hα abstraction by the H atom whereas the lowest endothermicity (ΔE = 29 kJ mol-1) is shown for the abstraction of Hα by the HO2˙ radical. The formation of hydrogen bonding is found to affect the kinetics of the H atom abstraction reactions by the HO2˙ radical. Further above 750 K, the calculated high pressure limit rate constants indicate that the total contribution from delta carbon sites (Cδ) is predominant for hydrogen atom abstraction by the H atom and HO2˙ radical.

  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 and characterization of TiO2/Ag/polymer ternary nanoparticles via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Park, Jung Tae; Koh, Joo Hwan; Seo, Jin Ah; Cho, Yong Soo; Kim, Jong Hak

    2011-01-01

    We report on the novel ternary hybrid materials consisting of semiconductor (TiO 2 ), metal (Ag) and polymer (poly(oxyethylene methacrylate) (POEM)). First, a hydrophilic polymer, i.e. POEM, was grafted from TiO 2 nanoparticles via the surface-initiated atom transfer radical polymerization (ATRP) technique. These TiO 2 -POEM brush nanoparticles were used to template the formation of Ag nanoparticles by introduction of a AgCF 3 SO 3 precursor and a NaBH 4 aqueous solution for reduction process. Successful grafting of polymeric chains from the surface of TiO 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.

  16. Electron transfer oxidation of DNA radicals by paranitroacetophenone

    Energy Technology Data Exchange (ETDEWEB)

    Whillans, D W; Adams, G E [Mount Vernon Hospital, Northwood (UK)

    1975-12-01

    The reaction of a typical electron-affinic sensitizer, paranitroacetophenone (PNAP) with the model compounds thymine, thymidine, thymidylic acid, deoxyribose and single and double-stranded DNA has been investigated by pulse radiolysis. Radicals formed by one-electron reduction of the bases and of DNA reacted rapidly and efficiently with PNAP by electron transfer. A small yield of transfer (< 10 per cent) was also observed arising from oxidation of the radicals formed by the small proportion of OH which reacted at the sugar moieties in DNA. In contrast, electron transfer oxidation by PNAP of radicals formed by the addition of OH to the base moieties, e.g. thymine, was not an efficient process. Further, addition of the sensitizer to the thymine OH-adduct proceeded at a rate that was too low to measure the pulse radiolysis. We conclude that, since the major sites of OH reaction by DNA are the heterocyclic bases (> 80 per cent), oxidation of the resultant radicals is unlikely to be a major step in the mechanism of sensitization by this typical hypoxic-cell sensitizer.

  17. Carbonate radical anion-induced electron transfer in bovine serum albumin

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, Ravi [Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India)]. E-mail: rjudrin@yahoo.com; Mukherjee, T. [Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

    2006-07-15

    Reaction of native and thermally denatured bovine serum albumin (BSA) with carbonate radical anion (CO{sub 3}{sup -} radical) has been studied using pulse radiolysis technique. Scavenging of CO{sub 3}{sup -} radical by native BSA and consequent electron transfer from tyrosine to tryptophan radical has been observed to occur with almost same rate constant (k{approx}1.7x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1}) at pH 8.8. Effect of structural changes, due to thermal denaturation, on scavenging of CO{sub 3}{sup -} radical and the electron transfer process have been studied and discussed in this paper.

  18. Time-resolved FTIR emission studies of laser photofragmentation and radical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Leone, S.R. [Univ. of Colorado, Boulder (United States)

    1993-12-01

    Recent studies have focused specifically on collision processes, such as single collision energy transfer, reaction dynamics, and radical reactions. The authors employ novel FTIR techniques in the study of single collision energy transfer processes using translationally fast H atom, as well as radical-radical reactions, e.g. CH{sub 3} + O, CF{sub 3} + H(D), and Cl + C{sub 2}H{sub 5}. The fast atoms permit unique high energy regions of certain transition states of combustion species to be probed for the first time.

  19. 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

  20. Formation of long-lived radicals on proteins by radical transfer from heme enzymes--a common process?

    DEFF Research Database (Denmark)

    Ostdal, H; Andersen, H J; Davies, Michael Jonathan

    1999-01-01

    concentrations were observed after limited digestion, although this effect was less marked with the HRP/H2O2/BSA system than with Fe(III)Mb/H2O2/BSA, consistent with different modes of radical transfer. More extensive digestion of BSA decreased the radical concentration to levels below those detected with native...... investigated using horseradish peroxidase (HRP)/H2O2, in the presence and absence of added tyrosine. Incubation of HRP with H2O2 and bovine or human serum albumins, in the presence and absence of tyrosine, gave long-lived albumin-derived radicals as detected by EPR spectroscopy. Evidence has been obtained...... for these albumin radicals being located on buried tyrosine residues on the basis of blocking experiments. The effect of protein conformation on radical transfer has been investigated using partial proteolytic digestion prior to protein oxidation. With HRP/H2O2/BSA and Fe(III)Mb/H2O2/BSA increased radical...

  1. 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.

  2. In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

    Science.gov (United States)

    Chen, Daqun; Hu, Weihua

    2017-04-18

    Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of the homogeneous polymerization and heterogeneous systems (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining the electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by the self-assembled monolayer of the ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information for eSI-ATRP and offers a powerful platform for in situ investigation of such complicated processes.

  3. Reactions of carbon radicals generated by 1,5-transposition of reactive centers

    Directory of Open Access Journals (Sweden)

    ZIVORAD CEKOVIC

    2005-03-01

    Full Text Available Radical intermediates can undergo specific reactions, such as intramolecular rearrangements, i.e., the transpositions of radical centers, which are not known in classical ionic organic reactions. 1,5-Transposition of a radical center to a non-activated carbon atom are of great synthetic importance. It can be successfully applied for the introduction of different functional groups (oxygen, nitrogen, sulfur, halogens onto a carbon atom remote from the present functional group. In addition to functionalization of a remote non-activated carbon atom, the formation of new C-C bonds on the d-carbon atom have also been achieved. 1,5-Transposition of the radical centers takes place from alkoxyl, aminyl and carbon radicals to a remote carbon atom. Relocation of the radical centers preferentially involves 1,5-transfer of a hydrogen atom, although migrations of some other groups are known. The reactions of the carbon radical generated by 1,5-relocation of the radical center are presented and their synthetic applications are reviewed.

  4. High-throughput optimization of nitroxide mediated radical polymerizations as basis for the synthesis of temperature-responsive copolymers

    NARCIS (Netherlands)

    Hoogenboom, R.; Becer, C.R.; Eggenhuisen, T.M.; Schubert, U.S.

    2008-01-01

    The development of controlled radical polymn. techniques, namely atom transfer radical polymn. (ATRP), reversible addn. fragmentation transfer (RAFT) and nitroxide mediated radical polymn. (NMP), have opened up unprecedented possibilities for the synthesis of well-defined macromol. architectures

  5. 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.

  6. 3D scaffolds from vertically aligned carbon nanotubes/poly(methyl methacrylate) composites via atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Tebikachew, Behabtu; Magina, Sandra; Mata, Diogo; Oliveira, Filipe J.; Silva, Rui F.; Barros-Timmons, Ana

    2015-01-01

    Vertically aligned carbon nanotubes (VACNTs) synthesized by Thermal Chemical Vapour Deposition (TCVD) were modified using an Ar:O 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

  7. Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

    2009-08-01

    The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

  8. 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

  9. High-performance liquid chromatographic method to evaluate the hydrogen atom transfer during reaction between 1,1-diphenyl-2-picryl-hydrazyl radical and antioxidants

    International Nuclear Information System (INIS)

    Boudier, Ariane; Tournebize, Juliana; Bartosz, Grzegorz; El Hani, Safae; Bengueddour, Rachid; Sapin-Minet, Anne; Leroy, Pierre

    2012-01-01

    Highlights: ► Both 1,1-diphenyl-2-picrylhydrazyl radical and its product measurement by HPLC. ► Lowest limit of detection by monitoring 1,1-diphenyl-2-picryl-hydrazine. ► Adsorption problem of the radical on HPLC parts have been pointed out. - Abstract: 1,1-Diphenyl-2-picrylhydrazyl (DPPH·) 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· 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· quenching rate and none of them permits to identify and measure 1,1-diphenyl-2-picryl-hydrazine (DPPH-H), the reduced product of DPPH· resulting from hydrogen atom transfer (HAT), which is the main mechanism of the reaction between DPPH· and AOs. We presently report an HPLC method devoted to the simultaneous measurement of DPPH· 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· onto materials of the HPLC system was pointed out. Consequently, the linearity range observed for DPPH· was restricted, thus a much lower limit of detection was obtained for DPPH-H than for DPPH· using standards (0.02 and 14 μM, respectively). The method was applied to three commonly used AOs, i.e. Trolox ® , 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 higher selectivity than colorimetry, and (ii) its help to investigate the mechanisms occurring with the free radical.

  10. 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. Copyright 2009 Wiley Periodicals, Inc.

  11. A peroxidase mimic with atom transfer radical polymerization activity constructed through the grafting of heme onto metal-organic frameworks.

    Science.gov (United States)

    Jiang, Wei; Pan, Yue; Yang, Jiebing; Liu, Yong; Yang, Yan; Tang, Jun; Li, Quanshun

    2018-07-01

    Atom transfer radical polymerization (ATRP) has been considered to be an efficient strategy for constructing functional macromolecules owing to its simple operation and versatile monomers, and thus it is of great significance to develop ideal catalysts with higher activity and perfect reusability. We constructed a peroxidase mimic through the grafting of heme onto metal-organic frameworks UiO-66-NH 2 (ZrMOF), namely Heme-ZrMOF. After the systematic characterization of structure, the composite Heme-ZrMOF was demonstrated to possess high peroxidase activity using 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulphonate) and 3,3',5,5'-tetramethylbenzidine as substrates. The enzyme mimic was then used as catalysts in the ATRP reactions of different monomers, in which favorable monomer conversion (44.6-98.0%) and product molecular weight (8600-25,600 g/mol) could be obtained. Compared to free heme, Heme-ZrMOF could efficiently achieve the easy separation of heme from the catalytic system and facilitate the ATRP reaction in an aqueous environment to avoid the utilization of organic solvents. In conclusion, the enzyme mimic Heme-ZrMOF could be potentially used as an effective catalyst for preparing well-defined polymers with biomedical applications. Copyright © 2018 Elsevier Inc. All rights reserved.

  12. Antifouling coatings via plasma polymerization and atom transfer radical polymerization on thin film composite membranes for reverse osmosis

    Science.gov (United States)

    Hirsch, Ulrike; Ruehl, Marco; Teuscher, Nico; Heilmann, Andreas

    2018-04-01

    A major drawback to otherwise highly efficient membrane-based desalination techniques like reverse osmosis (RO) is the susceptibility of the membranes to biofouling. In this work, a combination of plasma activation, plasma bromination and surface-initiated atom transfer radical polymerization (si-ATRP) of hydrophilic and zwitterionic monomers, namely hydroxyethyl methacrylate (HEMA), 2-methacryloyloxyethyl phosphorylcholine (MPC) and [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA), was applied to generate non-specific, anti-adhesive coatings on thin film composite (TFC) membranes. The antifouling effect of the coatings was shown by short-time batch as well as long-time steady state cultivation experiments with the microorganism Pseudomonas fluorescens. It could be shown that plasma functionalization and polymerization is possible on delicate thin film composite membranes without restricting their filtration performance. All modified membranes showed an increased resistance towards the adhesion of Pseudomonas fluorescens. On average, the biofilm coverage was reduced by 51.4-12.6% (for HEMA, SBMA, and MPC), the highest reduction was monitored for MPC with a biofilm reduction by 85.4%. The hydrophilic coatings applied did not only suppress the adhesion of Pseudomonas fluorescens, but also significantly increase the permeate flux of the membranes relative to uncoated membranes. The stability of the coatings was however not ideal and will have to be improved for future commercial use.

  13. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy.

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P; Nguyen, Huong T H; Dang, Andy; Tureček, František

    2018-01-16

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z 4 + H] +● fragment ion-radicals of the R-C ● H-CONH- type, initially formed by N-C α bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [ ● DAAR + H] + isomers and used to assign structures to the action spectra. The potential energy surface of [ ● DAAR + H] + isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [ ● XAAR + H] + ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone C α positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H] ● -ETD fragments containing Asp, Asn, Glu, and Gln residues. Graphical Abstract ᅟ.

  14. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P.; Nguyen, Huong T. H.; Dang, Andy; Tureček, František

    2018-01-01

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z4 + H]+● fragment ion-radicals of the R-C●H-CONH- type, initially formed by N-Cα bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [●DAAR + H]+ isomers and used to assign structures to the action spectra. The potential energy surface of [●DAAR + H]+ isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [●XAAR + H]+ ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone Cα positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H]●-ETD fragments containing Asp, Asn, Glu, and Gln residues. [Figure not available: see fulltext.

  15. Encapsulation of Gibbsite platelets with free radical and controlled radical emulsion polymerization approaches, a small review

    NARCIS (Netherlands)

    Loiko, O.P.; Spoelstra, A.B.; van Herk, A.M.; Meuldijk, J.; Heuts, J.P.A.

    2016-01-01

    Water-borne anisotropic polymer-Gibbsite latex particles were prepared by a conventional and an atom transfer radical polymerisation (ATRP) based starved-feed emulsion polymerisation without any chemical modification of the platelet surface. Anionic co-oligomers, synthesised via ATRP, were used in

  16. Thermodynamic and kinetic analysis of the reaction between biological catecholamines and chlorinated methylperoxy radicals

    Science.gov (United States)

    Dimić, Dušan S.; Milenković, Dejan A.; Marković, Jasmina M. Dimitrić; Marković, Zoran S.

    2018-05-01

    The antiradical potency of catecholamines (dopamine, epinephrine, norepinephrine, L-DOPA), metabolites of dopamine (homovanillic acid, 3-methoxytyramine and 3,4-dihydroxyphenylacetic acid) and catechol towards substituted methylperoxy radicals is investigated. The thermodynamic parameters, together with the kinetic approach, are used to determine the most probable mechanism of action. The natural bond orbital and quantum theory of atoms in molecules are utilised to explain the highest reactivity of trichloromethylperoxy radical. The preferred mechanism is dependent both on the thermodynamic and kinetic parameters . The number of chlorine atoms on radical, the presence of intra-molecular hydrogen bond and number of hydroxy groups attached to the aromatic ring significantly influence the mechanism. The results suggest that sequential proton loss electron transfer (SPLET) is the most probable for reaction with methylperoxy and hydrogen atom transfer (HAT) for reaction with trichloromethylperoxy radicals, with a gradual transition between SPLET and HAT for other two radicals. Due to the significant deprotonation of molecules containing the carboxyl group, the respective anions are also investigated. The HAT and SPLET mechanisms are highly competitive in reaction with MP radical, while the dominant mechanism towards chlorinated radicals is HAT. The reactions in methanol and benzene are also discussed.

  17. Designing of fluorescent and magnetic imprinted polymer for rapid, selective and sensitive detection of imidacloprid via activators regenerated by the electron transfer-atom transfer radical polymerization (ARGET-ATRP) technique

    Science.gov (United States)

    Kumar, Sunil; Karfa, Paramita; Madhuri, Rashmi; Sharma, Prashant K.

    2018-05-01

    In this work, we report on a dual-behavior electrochemical/optical sensor for sensitive determination of Imidacloprid by fluorescent dye (fluorescein, FL) and imprinted polymer modified europium doped superparamagnetic iron oxide nanoparticles (FL@SPIONs@MIP). The imidacloprid (IMD)-imprinted polymer was directly synthesized on the Eu-SPIONs surface via Activators regenerated by the electron transfer-atom transfer radical polymerization (ARGET-ATRP) technique. Preparation, characterization and application of the prepared FL@SPIONs@MIP were systematically investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), fluorescence spectroscopy and electrochemical techniques. The electrochemical experiments exhibited a remarkable selectivity of the prepared sensor towards IMD. Determination of IMD by the square wave stripping voltammetry method represented a wide linear range of 0.059-0.791 μg L-1 with a detection limit of 0.0125 μg L-1. In addition, the fluorescence method shows a linear range of 0.039-0.942 μg L-1 and LOD of 0.0108 μg L-1. The fluorescence property of prepared FL@SPIONs@MIP was used for rapid, on-spot but selective detection of IMD in real samples. The proposed electrode displayed excellent repeatability and long-term stability and was successfully applied for quantitative and trace level determination of IMD in several real samples.

  18. β-diketones containing oxygen atom in fluorinated radical

    International Nuclear Information System (INIS)

    Shivanyuk, A.F.; Kudryavtseva, L.S.; Lozinskij, M.O.; Neplyuev, V.M.; Fialkov, Yu.A.; Bratolyubova, A.G.

    1981-01-01

    The synthesis of a number of new aliphatic fluorinated β- diketones containing oxygen atom in fluorinated radical of linear or cyclic structure is described. The reaction of combination with aryldiazonium salts resulting in the formation of corresponding arylhydrazones of fluorinated triketones is studied. It is shown that as a result of arylhydrazone condensation with hydroxylamine, hydrazine and its substituted derivatives the fluorine-containing derivatives of isoxazol and pyrazol are formed [ru

  19. beta. -diketones containing oxygen atom in fluorinated radical

    Energy Technology Data Exchange (ETDEWEB)

    Shivanyuk, A.F.; Kudryavtseva, L.S.; Lozinskij, M.O.; Neplyuev, V.M.; Fialkov, Yu.A.; Bratolyubova, A.G. (AN Ukrainskoj SSR, Kiev. Inst. Organicheskoj Khimii)

    1981-10-01

    The synthesis of a number of new aliphatic fluorinated ..beta..-diketones containing oxygen atom in fluorinated radical of linear or cyclic structure is described. The reaction of combination with aryldiazonium salts resulting in the formation of corresponding arylhydrazones of fluorinated triketones is studied. It is shown that as a result of arylhydrazone condensation with hydroxylamine, hydrazine and its substituted derivatives the fluorine-containing derivatives of isoxazol and pyrazol are formed.

  20. Preparation of polystyrene brush film by radical chain-transfer polymerization and micromechanical properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Jing [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Chen Miao [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)], E-mail: miaochen99@yahoo.com; An Yanqing [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Liu Jianxi [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Yan Fengyuan [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)], E-mail: fyyan@lzb.ac.cn

    2008-12-30

    A radical chain-transfer polymerization technique has been applied to graft-polymerize brushes of polystyrene (PSt) on single-crystal silicon substrates. 3-Mercapto-propyltrimethoxysilane (MPTMS), as a chain-transfer agent for grafting, was immobilized on the silicon surface by a self-assembling process. The structure and morphology of the graft-functionalized silicon surfaces were characterized by the means of contact-angle measurement, ellipsometric thickness measurement, Fourier transformation infrared (FTIR) spectroscopy, and atomic force microscopy (AFM). The nanotribological and micromechanical properties of the as-prepared polymer brush films were investigated by frictional force microscopy (FFM), force-volume analysis and scratch test. The results indicate that the friction properties of the grafted polymer films can be improved significantly by the treatment of toluene, and the chemically bonded polystyrene film exhibits superior scratch resistance behavior compared with the spin-coated polystyrene film. The resultant polystyrene brush film is expected to develop as a potential lubrication coating for microelectromechanical systems (MEMS)

  1. Two-photon laser-induced fluorescence studies of HS radicals, DS radicals, and I atoms

    Energy Technology Data Exchange (ETDEWEB)

    Tiee, J J; Ferris, M J; Loge, G W; Wampler, F B

    1983-04-15

    A two-photon laser-induced excitation and fluorescence technique has been used to study the A /sup 2/..sigma../sup +/ - X/sup 2/PI transition of HS and DS radicals and various high-lying /sup 4/P/sup 0/, /sup 2/D/sup 0/, and /sup 4/D/sup 0/ states of the I atom. The two-photon excitation cross sections and detection sensitivity are discussed. 13 references, 5 figures.

  2. Reactions of the radical cations of aliphatic aldehydes in freon matrices

    International Nuclear Information System (INIS)

    Belevskij, V.N.; Belopushkin, S.I.; Feldman, V.I.

    1985-01-01

    ESR spectra of γ-irradiated solutions of acetic and propionic aldehydes in freon-11 and freon-113 affected by aldehyde concentration, temperature, and the action of light were studied. It is shown that the radical cations are converted into neutral radicals, and the cations CHsub(3)CHsub(2)CHOsup(+). are converted to RCO and CHsub(3)CHCHO due to ion-molecular reactions of proton transfer of hydrogen atom transfer. (author)

  3. Protein adsorption resistance of PVP-modified polyurethane film prepared by surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Yuan, Huihui; Qian, Bin; Zhang, Wei; Lan, Minbo

    2016-01-01

    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"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.

  4. 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.

  5. Ternary hybrid polymeric nanocomposites through grafting of polystyrene on graphene oxide-TiO_2 by surface initiated atom transfer radical polymerization (SI-ATRP)

    International Nuclear Information System (INIS)

    Kumar, Arvind; Bansal, Ankushi; Behera, Babita; Jain, Suman L.; Ray, Siddharth S.

    2016-01-01

    A ternary hybrid of graphene oxide-titania-polystyrene (GO-TiO_2-PS) nanocomposite is developed where polystyrene composition is regulated by controlling growth of polymer chains and nanoarchitectonics is discussed. Graphene Oxide-TiO_2 (GO-TiO_2) nanocomposite is prepared by in-situ hydrothermal method and the surface is anchored with α-bromoisobutyryl bromide to activate GO-TiO_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_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_2 with polystyrene. • PS is surface grafted on GO-TiO_2. • Polymer chain lengths are well regulated by SI-ATRP living polymerization. • Thermal stability of this hybrid is relatively high.

  6. Computational study of the structure-free radical scavenging relationship of procyanidins.

    Science.gov (United States)

    Mendoza-Wilson, Ana María; Castro-Arredondo, Sergio Ivan; Balandrán-Quintana, René Renato

    2014-10-15

    Procyanidins (PCs) are effective free radical scavengers, however, their antioxidant ability is variable because they have different degrees of polymerisation, are composed by distinct types of subunits and are very susceptible to changes in conformation. In this work the structure-free radical scavenging relationship of monomers, dimers and trimers of PCs was studied through the hydrogen atom transfer (HAT), sequential proton-loss electron-transfer (SPLET) and single electron transfer followed by proton transfer (SET-PT) mechanisms in aqueous phase, employing the Density Functional Theory (DFT) computational method. The structure-free radical scavenging relationship of PCs showed a very similar behaviour in HAT and SET-PT mechanisms, but very different in the SPLET mechanism. The structural factor that showed more effects on the ability of PCs to scavenge free radicals in aqueous phase was the conformation. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. 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.

  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. Poly(glycidyl methacrylate) grafted CdSe quantum dots by surface-initiated atom transfer radical polymerization: Novel synthesis, characterization, properties, and cytotoxicity studies

    International Nuclear Information System (INIS)

    Bach, Long Giang; Islam, Md. Rafiqul; Lee, Doh Chang; Lim, Kwon Taek

    2013-01-01

    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.

  10. Transfer of energy in an atom

    International Nuclear Information System (INIS)

    Chemin, J.F.

    2001-01-01

    In most cases the nucleus does not interact with the electron cloud because its energy range is far higher, but in some rare cases electrons from the electron cloud and the nucleus may exchange energy: an electron may de-excite by transferring a part of its energy to the nucleus that becomes itself excited (nuclear excitation by electronic transfer or NEET), conversely electrons can receive energy from the nucleus (bound internal conversion or BIC). For the first time both energy transfers have been observed: a BIC process on a tellurium-125 atom by a French team and a NEET process on a gold-197 atom by a Japanese team. (A.C.)

  11. Alkyl hydrogen atom abstraction reactions of the CN radical with ethanol

    Science.gov (United States)

    Athokpam, Bijyalaxmi; Ramesh, Sai G.

    2018-04-01

    We present a study of the abstraction of alkyl hydrogen atoms from the β and α positions of ethanol by the CN radical in solution using the Empirical Valence Bond (EVB) method. We have built separate 2 × 2 EVB models for the Hβ and Hα reactions, where the atom transfer is parameterized using ab initio calculations. The intra- and intermolecular potentials of the reactant and product molecules were modelled with the General AMBER Force Field, with some modifications. We have carried out the dynamics in water and chloroform, which are solvents of contrasting polarity. We have computed the potential of mean force for both abstractions in each of the solvents. They are found to have a small and early barrier along the reaction coordinate with a large energy release. Analyzing the solvent structure around the reaction system, we have found two solvents to have little effect on either reaction. Simulating the dynamics from the transition state, we also study the fate of the energies in the HCN vibrational modes. The HCN molecule is born vibrationally hot in the CH stretch in both reactions and additionally in the HCN bends for the Hα abstraction reaction. In the early stage of the dynamics, we find that the CN stretch mode gains energy at the expense of the energy in CH stretch mode.

  12. Preparation of high-capacity, weak anion-exchange membranes by surface-initiated atom transfer radical polymerization of poly(glycidyl methacrylate) and subsequent derivatization with diethylamine

    International Nuclear Information System (INIS)

    Qian, Xiaolei; Fan, Hua; Wang, Chaozhan; Wei, Yinmao

    2013-01-01

    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.

  13. Fluoropolymer materials and architectures prepared by controlled radical polymerizations

    DEFF Research Database (Denmark)

    Hansen, Natanya Majbritt Louie; Jankova Atanasova, Katja; Hvilsted, Søren

    2007-01-01

    This review initially summarizes the mechanisms, merits and limitations of the three controlled radical polymerizations: nitroxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP) or metal catalyzed living radical polymerization, and reversible addition–fragmentation chain...... transfer (RAFT) polymerization. This is followed by two parts, one dealing with homo- and copolymerizations of fluorinated methacrylates and acrylates, and a second where fluorinated styrenes, alone or in combination with other monomers, are the main issues. In these parts, initiators (including...... properties and functionalities that can be obtained from these novel fluorinated materials and architectures are especially emphasized. Thus, various amphiphilic, biocompatible or low energy materials, fluorinated nanoparticles and nanoporous films/membranes as well as materials for submicron and nanolevel...

  14. Role of plasma enhanced atomic layer deposition reactor wall conditions on radical and ion substrate fluxes

    Energy Technology Data Exchange (ETDEWEB)

    Sowa, Mark J., E-mail: msowa@ultratech.com [Ultratech/Cambridge NanoTech, 130 Turner Street, Building 2, Waltham, Massachusetts 02453 (United States)

    2014-01-15

    Chamber wall conditions, such as wall temperature and film deposits, have long been known to influence plasma source performance on thin film processing equipment. Plasma physical characteristics depend on conductive/insulating properties of chamber walls. Radical fluxes depend on plasma characteristics as well as wall recombination rates, which can be wall material and temperature dependent. Variations in substrate delivery of plasma generated species (radicals, ions, etc.) impact the resulting etch or deposition process resulting in process drift. Plasma enhanced atomic layer deposition is known to depend strongly on substrate radical flux, but film properties can be influenced by other plasma generated phenomena, such as ion bombardment. In this paper, the chamber wall conditions on a plasma enhanced atomic layer deposition process are investigated. The downstream oxygen radical and ion fluxes from an inductively coupled plasma source are indirectly monitored in temperature controlled (25–190 °C) stainless steel and quartz reactors over a range of oxygen flow rates. Etch rates of a photoresist coated quartz crystal microbalance are used to study the oxygen radical flux dependence on reactor characteristics. Plasma density estimates from Langmuir probe ion saturation current measurements are used to study the ion flux dependence on reactor characteristics. Reactor temperature was not found to impact radical and ion fluxes substantially. Radical and ion fluxes were higher for quartz walls compared to stainless steel walls over all oxygen flow rates considered. The radical flux to ion flux ratio is likely to be a critical parameter for the deposition of consistent film properties. Reactor wall material, gas flow rate/pressure, and distance from the plasma source all impact the radical to ion flux ratio. These results indicate maintaining chamber wall conditions will be important for delivering consistent results from plasma enhanced atomic layer deposition

  15. Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

    Directory of Open Access Journals (Sweden)

    Zong-Cheng Chen

    2014-09-01

    Full Text Available In this paper, we propose a simple one-pot methodology for proceeding from atom transfer reaction-induced conventional free radical polymerization (AT-FRP to atom transfer self-condensing vinyl polymerization (AT-SCVP through manipulation of the catalyst phase homogeneity (i.e., CuBr/2,2'-bipyridine (CuBr/Bpy in a mixture of styrene (St, 4-vinyl benzyl chloride (VBC, and ethyl 2-bromoisobutyrate. Tests of the solubilities of CuBr/Bpy and CuBr2/Bpy under various conditions revealed that both temperature and solvent polarity were factors affecting the solubility of these copper complexes. Accordingly, we obtained different polymer topologies when performing AT-SCVP in different single solvents. We investigated two different strategies to control the polymer topology in one-pot: varying temperature and varying solvent polarity. In both cases, different fractions of branching revealed the efficacy of varying the polymer topology. To diversify the functionality of the peripheral space, we performed chain extensions of the resulting hyperbranched poly(St-co-VBC macroinitiator (name as: hbPSt MI with either St or tBA (tert-butyl acrylate. The resulting hyperbranched core star polymer had high molecular weights (hbPSt-g-PSt: Mn = 25,000, Đ = 1.77; hbPSt-g-PtBA: Mn = 27,000, Đ = 1.98; hydrolysis of the tert-butyl groups of the later provided a hyperbranched core star polymer featuring hydrophilic poly(acrylic acid segments.

  16. Role of the reacting free radicals on the antioxidant mechanism of curcumin

    Energy Technology Data Exchange (ETDEWEB)

    Galano, Annia, E-mail: agalano@prodigy.net.mx [Universidad Autonoma Metropolitana-Iztapalapa, Departamento de Quimica, Area de Quimica Analitica, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, C.P. 09340, Mexico D.F. (Mexico); Alvarez-Diduk, Ruslan; Ramirez-Silva, Maria Teresa; Alarcon-Angeles, Georgina; Rojas-Hernandez, Alberto [Universidad Autonoma Metropolitana-Iztapalapa, Departamento de Quimica, Area de Quimica Analitica, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, C.P. 09340, Mexico D.F. (Mexico)

    2009-09-18

    Density functional theory is used to study the antioxidant mechanism of curcumin. Five different mechanisms are considered: single electron transfer (SET), radical adduct formation (RAF), H atom transfer from neutral curcumin (HAT), H atom transfer from deprotonated curcumin (HAT-D), and sequential proton loss electron transfer (SPLET). The influence of the environment is investigated for polar and non-polar surroundings. The apparent contradictions among previous experimental results are explained by the role of the nature of the reacting free radical on the relative importance of the above mentioned mechanism. It is proposed that the curcumin + DPPH reaction actually takes place mainly through the SPLET mechanism, while the reaction with {sup {center_dot}}OCH{sub 3}, and likely with other alkoxyl radicals, is governed by the HAT mechanism. Branching ratios for the {sup {center_dot}}OCH{sub 3} + curcumin reaction are reported for the first time. The calculated overall rate constants for this reaction are 1.16 x 10{sup 10} (benzene) and 5.52 x 10{sup 9} (water) L mol{sup -1} s{sup -1}. The role of phenolic groups on the antioxidant activity of curcumin has been experimentally confirmed.

  17. Atoms in molecules, an axiomatic approach. I. Maximum transferability

    Science.gov (United States)

    Ayers, Paul W.

    2000-12-01

    Central to chemistry is the concept of transferability: the idea that atoms and functional groups retain certain characteristic properties in a wide variety of environments. Providing a completely satisfactory mathematical basis for the concept of atoms in molecules, however, has proved difficult. The present article pursues an axiomatic basis for the concept of an atom within a molecule, with particular emphasis devoted to the definition of transferability and the atomic description of Hirshfeld.

  18. 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.

  19. Sugar Radical Formation by a Proton Coupled Hole Transfer in 2′-Deoxyguanosine Radical Cation (2′-dG•+): A Theoretical Treatment

    Science.gov (United States)

    Kumar, Anil; Sevilla, Michael D.

    2009-01-01

    Previous experimental and theoretical work has established that electronic excitation of a guanine cation radical in nucleosides or in DNA itself leads to sugar radical formation by deprotonation from the dexoxyribose sugar. In this work we investigate a ground electronic state pathway for such sugar radical formation in a hydrated one electron oxidized 2′-deoxyguanosine (dG•+ + 7H2O), using density functional theory (DFT) with the B3LYP functional and the 6-31G* basis set. We follow the stretching of the C5′-H bond in dG•+ to gain an understanding of the energy requirements to transfer the hole from the base to sugar ring and then to deprotonate to proton acceptor sites in solution and on the guanine ring. The geometries of reactant (dG•+ + 7H2O), transition state (TS) for deprotonation of C5′ site and product (dG(•C5′, N7-H+) + 7 H2O) were fully optimized. The zero point energy (ZPE) corrected activation energy (TS) for the proton transfer (PT) from C5′ is calculated to be 9.0 kcal/mol and is achieved by stretching the C5′-H bond by 0.13 Å from its equilibrium bond distance (1.099 Å). Remarkably, this small bond stretch is sufficient to transfer the “hole” (positive charge and spin) from guanine to the C5′ site on the deoxyribose group. Beyond the TS, the proton (H+) spontaneously adds to water to form a hydronium ion (H3O+) as an intermediate. The proton subsequently transfers to the N7 site of the guanine (product). The 9 kcal/mol barrier suggests slow thermal conversion of the cation radical to the sugar radical but also suggests that localized vibrational excitations would be sufficient to induce rapid sugar radical formation in DNA base cation radicals. PMID:19754084

  20. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu; Aly, Shawkat Mohammede; Usman, Anwar; Parida, Manas R.; Del Gobbo, Silvano; Alarousu, Erkki; Mohammed, Omar F.

    2015-01-01

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  1. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu

    2015-09-02

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  2. 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.

  3. Surface modification of polystyrene with atomic oxygen radical anions-dissolved solution

    International Nuclear Information System (INIS)

    Wang Lian; Yan Lifeng; Zhao Peitao; Torimoto, Yoshifumi; Sadakata, Masayoshi; Li Quanxin

    2008-01-01

    A novel approach to surface modification of polystyrene (PS) polymer with atomic oxygen radical anions-dissolved solution (named as O - water) has been investigated. The O - water, generated by bubbling of the O - (atomic oxygen radical anion) flux into the deionized water, was characterized by UV-absorption spectroscopy and electron paramagnetic resonance (EPR) spectroscopy. The O - water treatments caused an obvious increase of the surface hydrophilicity, surface energy, surface roughness and also caused an alteration of the surface chemical composition for PS surfaces, which were indicated by the variety of contact angle and material characterization by atomic force microscope (AFM) imaging, field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and attenuated total-reflection Fourier transform infrared (ATR-FTIR) measurements. Particularly, it was found that some hydrophilic groups such as hydroxyl (OH) and carbonyl (C=O) groups were introduced onto the polystyrene surfaces via the O - water treatment, leading to the increases of surface hydrophilicity and surface energy. The active oxygen species would react with the aromatic ring molecules on the PS surfaces and decompose the aromatic compounds to produce hydrophilic hydroxyl and carbonyl compounds. In addition, the O - water is also considered as a 'clean solution' without adding any toxic chemicals and it is easy to be handled at room temperature. Present method may suit to the surface modification of polymers and other heat-sensitive materials potentially

  4. Radical-Mediated Enzymatic Polymerizations

    Science.gov (United States)

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  5. Detection methods for atoms and radicals in the gas phase

    Science.gov (United States)

    Hack, W.

    This report lists atoms and free radicals in the gas phase which are of interest for environmental and flame chemistry and have been detected directly. The detection methods which have been used are discussed with respect to their range of application, specificity and sensitivity. In table 1, detection methods for the five atoms of group IV (C, Si, Ge, Sn, Pb) and about 60 radicals containing at least one atom of group IV are summarized (CH, Cd, Cf, CC1, CBr, Cn, Cs, CSe, CH2, CD2, Chf, Cdf, CHC1, CHBr, CF2, CC12, CBr2, CFC1, CFBr, CH3, CD3, CF3, CH2F, CH2C1, CH2Br, CHF2, CHC12, CHBr2, Hco, Fco, CH30, CD30, CH2OH, CH3S, Nco, CH4N, CH302, CF302; C2, C2N, C2H, C20, C2HO, C2H3, C2F3, C2H5, C2HsO, C2H4OH, CH3CO, CD3CO, C2H3O, C2H502, CH3COO2, C2H4N, C2H6N, C3; Si, SiF, SiF2, SiO, SiC, Si2; Ge, GeC, GeO, GeF, GeF2, GeCl2, Sn, SnF, SnO, SnF2, Pb, PbF, PbF2, PbO, PbS). In table 2 detection methods for about 25 other atoms and 60 radicals are listed: (H, D, O, O2, Oh, Od, HO2, DO2, F, Ci, Br, I, Fo, Cio, BrO, Io, FO2, C1O2, Li, Na, K, Rb, Cs, N, N3, Nh, Nd, Nf, Nci, NBr, NH2, ND2, Nhd, Nhf, NF2, NC12, N2H3, No, NO2, NO3, Hno, Dno, P, Ph, Pd, Pf, Pci, PH2, PD2, PF2, Po, As, AsO, AsS, Sb, Bi, S, S2, Sh, Sd, Sf, SF2, So, Hso, Dso, Sn, Se, Te, Se2, SeH, SeD, SeF, SeO, SeS, SeN, TeH, TeO, Bh, BH2, Bo, Bn, B02, Cd, Hg, UF5). The tables also cite some recent kinetic applications of the various methods.

  6. Exploring the dynamics of hydrogen atom release from the radical-radical reaction of O(3P) with C3H5

    International Nuclear Information System (INIS)

    Joo, Sun-Kyu; Kwon, Lee-Kyoung; Lee, Hohjai; Choi, Jong-Ho

    2004-01-01

    The gas-phase radical-radical reaction dynamics of O( 3 P)+C 3 H 5 →H( 2 S)+C 3 H 4 O was studied at an average collision energy of 6.4 kcal/mol in a crossed beam configuration. The ground-state atomic oxygen [O( 3 P)] and allyl radicals (C 3 H 5 ) were generated by the photolysis of NO 2 and the supersonic flash pyrolysis of allyl iodide, respectively. Nascent hydrogen atom products were probed by the vacuum-ultraviolet-laser induced fluorescence spectroscopy in the Lyman-α region centered at 121.6 nm. With the aid of the CBS-QB3 level of ab initio theory, it has been found that the barrierless addition of O( 3 P) to C 3 H 5 forms the energy-rich addition complexes on the lowest doublet potential energy surface, which are predicted to undergo a subsequent direct decomposition step leading to the reaction products H+C 3 H 4 O. The major counterpart C 3 H 4 O of the probed hydrogen atom is calculated to be acrolein after taking into account the factors of barrier height, reaction enthalpy, and the number of intermediates involved along the reaction pathway. The nascent H-atom Doppler profile analysis shows that the average center-of-mass translational energy of the H+C 3 H 4 O products and the fraction of the total available energy released as the translational energy were determined to be 3.83 kcal/mol and 0.054, respectively. On the basis of comparison with statistical calculations, the reaction proceeds through the formation of short-lived addition complexes rather than statistical, long-lived intermediates, and the polyatomic acrolein product is significantly internally excited at the moment of the decomposition

  7. Exploring the dynamics of hydrogen atom release from the radical-radical reaction of O(3P) with C3H5

    Science.gov (United States)

    Joo, Sun-Kyu; Kwon, Lee-Kyoung; Lee, Hohjai; Choi, Jong-Ho

    2004-05-01

    The gas-phase radical-radical reaction dynamics of O(3P)+C3H5→H(2S)+C3H4O was studied at an average collision energy of 6.4 kcal/mol in a crossed beam configuration. The ground-state atomic oxygen [O(3P)] and allyl radicals (C3H5) were generated by the photolysis of NO2 and the supersonic flash pyrolysis of allyl iodide, respectively. Nascent hydrogen atom products were probed by the vacuum-ultraviolet-laser induced fluorescence spectroscopy in the Lyman-α region centered at 121.6 nm. With the aid of the CBS-QB3 level of ab initio theory, it has been found that the barrierless addition of O(3P) to C3H5 forms the energy-rich addition complexes on the lowest doublet potential energy surface, which are predicted to undergo a subsequent direct decomposition step leading to the reaction products H+C3H4O. The major counterpart C3H4O of the probed hydrogen atom is calculated to be acrolein after taking into account the factors of barrier height, reaction enthalpy, and the number of intermediates involved along the reaction pathway. The nascent H-atom Doppler profile analysis shows that the average center-of-mass translational energy of the H+C3H4O products and the fraction of the total available energy released as the translational energy were determined to be 3.83 kcal/mol and 0.054, respectively. On the basis of comparison with statistical calculations, the reaction proceeds through the formation of short-lived addition complexes rather than statistical, long-lived intermediates, and the polyatomic acrolein product is significantly internally excited at the moment of the decomposition.

  8. Atmospheric reactions of methylcyclohexanes with Cl atoms and OH radicals: determination of rate coefficients and degradation products.

    Science.gov (United States)

    Ballesteros, Bernabé; Ceacero-Vega, Antonio A; Jiménez, Elena; Albaladejo, José

    2015-04-01

    As the result of biogenic and anthropogenic activities, large quantities of chemical compounds are emitted into the troposphere. Alkanes, in general, and cycloalkanes are an important chemical class of hydrocarbons found in diesel, jet and gasoline, vehicle exhaust emissions, and ambient air in urban areas. In general, the primary atmospheric fate of organic compounds in the gas phase is the reaction with hydroxyl radicals (OH). The oxidation by Cl atoms has gained importance in the study of atmospheric reactions because they may exert some influence in the boundary layer, particularly in marine and coastal environments, and in the Arctic troposphere. The aim of this paper is to study of the atmospheric reactivity of methylcylohexanes with Cl atoms and OH radicals under atmospheric conditions (in air at room temperature and pressure). Relative kinetic techniques have been used to determine the rate coefficients for the reaction of Cl atoms and OH radicals with methylcyclohexane, cis-1,4-dimethylcyclohexane, trans-1,4-dimethylcyclohexane, and 1,3,5-trimethylcyclohexane at 298 ± 2 K and 720 ± 5 Torr of air by Fourier transform infrared) spectroscopy and gas chromatography-mass spectrometry (GC-MS) in two atmospheric simulation chambers. The products formed in the reaction under atmospheric conditions were investigated using a 200-L Teflon bag and employing the technique of solid-phase microextraction coupled to a GC-MS. The rate coefficients obtained for the reaction of Cl atoms with the studied compounds are the following ones (in units of 10(-10) cm(3) molecule(-1) s(-1)): (3.11 ± 0.16), (2.89 ± 0.16), (2.89 ± 0.26), and (2.61 ± 0.42), respectively. For the reactions with OH radicals the determined rate coefficients are (in units of 10(-11) cm(3) molecule(-1) s(-1)): (1.18 ± 0.12), (1.49 ± 0.16), (1.41 ± 0.15), and (1.77 ± 0.23), respectively. The reported error is twice the standard deviation. A detailed

  9. Preparation of Mg(OH)_2 hybrid pigment by direct precipitation and graft onto cellulose fiber via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Wang, Xiao; Zhang, Yue; Lv, Lihua; Cui, Yongzhu; Wei, Chunyan; Pang, Guibing

    2016-01-01

    Graphical abstract: - Highlights: • Adsorbed anionic dye molecules are conducive to preferential growth of (0 0 1) plane of Mg(OH)_2 crystal for Mg(OH)_2 pigments. • Uniform coverage of nanosized Mg(OH)_2 pigments on fiber surface is achieved via surface-initiated ATRP. • About 4 wt% of Mg(OH)_2 pigment on fiber surface shortens nearly half of burning time of cellulose. - Abstract: 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.

  10. Electron affinities of atoms, molecules, and radicals

    International Nuclear Information System (INIS)

    Christodoulides, A.A.; McCorkle, D.L.; Christophorou, L.G.

    1982-01-01

    We review briefly but comprehensively the theoretical, semiempirical and experimental methods employed to determine electron affinities (EAs) of atoms, molecules and radicals, and summarize the EA data obtained by these methods. The detailed processes underlying the principles of the experimental methods are discussed very briefly. It is, nonetheless, instructive to recapitulate the definition of EA and those of the related quantities, namely, the vertical detachment energy, VDE, and the vertical attachment energy, VAE. The EA of an atom is defined as the difference in total energy between the ground state of the neutral atom (plus the electron at rest at infinity) and its negative ion. The EA of a molecule is defined as the difference in energy between the neutral molecule plus an electron at rest at infinity and the molecular negative ion when both, the neutral molecules and the negative ion, are in their ground electronic, vibrational and rotational states. The VDE is defined as the minimum energy required to eject the electron from the negative ion (in its ground electronic and nuclear state) without changing the internuclear separation; since the vertical transition may leave the neutral molecule in an excited vibrational/rotational state, the VDE, although the same as the EA for atoms is, in general, different (larger than), from the EA for molecules. Similarly, the VAE is defined as the difference in energy between the neutral molecule in its ground electronic, vibrational and rotational states plus an electron at rest at infinity and the molecular negative ion formed by addition of an electron to the neutral molecule without allowing a change in the intermolecular separation of the constituent nuclei; it is a quantity appropriate to those cases where the lowest negative ion state lies above the ground states of the neutral species and is less or equal to EA

  11. Cotton fibers encapsulated with homo- and block copolymers: synthesis by the atom transfer radical polymerization grafting-from technique and solid-state NMR dynamic investigations.

    Science.gov (United States)

    Castelvetro, Valter; Geppi, Marco; Giaiacopi, Simone; Mollica, Giulia

    2007-02-01

    Cotton fibers were modified by surface-initiated atom transfer radical polymerization of ethyl acrylate (EA) followed by copolymerization with styrene. Either ethyl 2-bromopropionate as a sacrificial free initiator or Cu(II) as a deactivator was used to optimize the EA grafting yield and to preserve the livingness of the chain ends for the subsequent growth of a poly(styrene) (PSty) block from the poly(ethyl acrylate) (PEA) grafts. The polymer-encapsulated cotton fibers were analyzed by Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry (DSC), thermogravimetric analysis, and solid-state NMR (high-resolution 13C cross-polarization magic angle spinning, 1H spin-lattice relaxation times, and 1H free induction decay analysis NMR). The latter allowed the detection of the dynamic modifications associated with the presence of homo- and block copolymer grafts. In particular, the results of the DSC and NMR investigations suggest a heterogeneous morphology of the g-PEA-b-PSty grafted skin, which could be described as an inner layer of g-PEA sandwiched between the semicrystalline cellulose of the core fiber and the high glass transition temperature PSty of the covalently linked outer layer. Such morphology results in a reduced molecular mobility of the PEA chains.

  12. Radical Chemistry and Charge Manipulation with an Atomic Force Microscope

    Science.gov (United States)

    Gross, Leo

    The fuctionalization of tips by atomic manipulation dramatically increased the resolution of atomic force microscopy (AFM). The combination of high-resolution AFM with atomic manipulation now offers the unprecedented possibility to custom-design individual molecules by making and breaking bonds with the tip of the microscope and directly characterizing the products on the atomic scale. We recently applied this technique to generate and study reaction intermediates and to investigate chemical reactions trigged by atomic manipulation. We formed diradicals by dissociating halogen atoms and then reversibly triggered ring-opening and -closing reactions via atomic manipulation, allowing us to switch and control the molecule's reactivity, magnetic and optical properties. Additional information about charge states and charge distributions can be obtained by Kelvin probe force spectroscopy. On multilayer insulating films we investigated single-electron attachment, detachment and transfer between individual molecules. EU ERC AMSEL (682144), EU project PAMS (610446).

  13. Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

    Science.gov (United States)

    Lin, Chen; Kumar, Manoj; Finney, Brian A; Francisco, Joseph S

    2017-09-28

    High level Brueckner doubles with triples correction method-based ab initio calculations have been used to investigate the nature of intramolecular hydrogen bonding and intramolecular hydrogen atom transfer in cis-malonaldehyde (MA) and its radical analogues. The radicals considered here are the ones that correspond to the homolytic cleavage of C-H bonds in cis-MA. The results suggest that cis-MA and its radical analogues, cis-MA RS , and cis-MA RA , both exist in planar geometry. The calculated intramolecular O-H⋯O=C bond in cis-MA is shorter than that in the radical analogues. The intramolecular hydrogen bond in cis-MA is stronger than in its radicals by at least 3.0 kcal/mol. The stability of a cis-malonaldehyde radical correlates with the extent of electron spin delocalization; cis-MA RA , in which the radical spin is more delocalized, is the most stable MA radical, whereas cis-MA RS , in which the radical spin is strongly localized, is the least stable radical. The natural bond orbital analysis indicates that the intramolecular hydrogen bonding (O⋯H⋯O) in cis-malonaldehyde radicals is stabilized by the interaction between the lone pair orbitals of donor oxygen and the σ * orbital of acceptor O-H bond (n → σ * OH ). The calculated barriers indicate that the intramolecular proton transfer in cis-MA involves 2.2 kcal/mol lower barrier than that in cis-MA RS .

  14. Surface-Initiated Atom Transfer Radical Polymerization of Magnetite Nanoparticles with Statistical Poly(tert-butyl acrylate-poly(poly(ethylene glycol methyl ether methacrylate Copolymers

    Directory of Open Access Journals (Sweden)

    Patcharin Kanhakeaw

    2015-01-01

    Full Text Available This work presented the surface modification of magnetite nanoparticle (MNP with poly[(t-butyl acrylate-stat-(poly(ethylene glycol methyl ether methacrylate] copolymers (P[(t-BA-stat-PEGMA] via a surface-initiated “grafting from” atom transfer radical polymerization (ATRP. Loading molar ratio of t-BA to PEGMA was systematically varied (100 : 0, 75 : 25, 50 : 50, and 25 : 75, resp. such that the degree of hydrophilicity of the copolymers, affecting the particle dispersibility in water, can be fine-tuned. The reaction progress in each step of the synthesis was monitored via Fourier transform infrared spectroscopy (FTIR. The studies in the reaction kinetics indicated that PEGMA had higher reactivity than that of t-BA in the copolymerizations. Gel permeation chromatography (GPC indicated that the molecular weights of the copolymers increased with the increase of the monomer conversion. Transmission electron microscopy (TEM revealed that the particles were spherical with averaged size of 8.1 nm in diameter. Dispersibility of the particles in water was apparently improved when the copolymers were coated as compared to P(t-BA homopolymer coating. The percentages of MNP and the copolymer in the composites were determined via thermogravimetric analysis (TGA and their magnetic properties were investigated via vibrating sample magnetometry (VSM.

  15. 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.

  16. Uranium Adsorbent Fibers Prepared by Atom-Transfer Radical Polymerization (ATRP) from Poly(vinyl chloride)- co -chlorinated Poly(vinyl chloride) (PVC- co -CPVC) Fiber

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Suree; Yue, Yanfeng; Kuo, Li-Jung; Mehio, Nada; Li, Meijun; Gill, Gary; Tsouris, Costas; Mayes, Richard T.; Saito, Tomonori; Dai, Sheng

    2016-04-20

    The need to secure future supplies of energy attracts researchers in several countries to a vast resource of nuclear energy fuel: uranium in seawater (estimated at 4.5 billion tons in seawater). In this study, we developed effective adsorbent fibers for the recovery of uranium from seawater via atom-transfer radical polymerization (ATRP) from a poly- (vinyl chloride)-co-chlorinated poly(vinyl chloride) (PVC-co-CPVC) fiber. ATRP was employed in the surface graft polymerization of acrylonitrile (AN) and tert-butyl acrylate (tBA), precursors for uranium-interacting functional groups, from PVC-co-CPVC fiber. The [tBA]/[AN] was systematically varied to identify the optimal ratio between hydrophilic groups (from tBA) and uranyl-binding ligands (from AN). The best performing adsorbent fiber, the one with the optimal [tBA]/[AN] ratio and a high degree of grafting (1390%), demonstrated uranium adsorption capacities that are significantly greater than those of the Japan Atomic Energy Agency (JAEA) reference fiber in natural seawater tests (2.42-3.24 g/kg in 42 days of seawater exposure and 5.22 g/kg in 49 days of seawater exposure, versus 1.66 g/kg in 42 days of seawater exposure and 1.71 g/kg in 49 days of seawater exposure for JAEA). Adsorption of other metal ions from seawater and their corresponding kinetics were also studied. The grafting of alternative monomers for the recovery of uranium from seawater is now under development by this versatile technique of ATRP.

  17. Migration of methyl and phenyl radicals, oxygen and sulphur atoms in certain diphenylthiophosphorane derivatives under electron impact

    International Nuclear Information System (INIS)

    Cauquis, G.; Divisia, B.; Ulrich, J.

    The fragmentation of various diphenylthiophosphoranes (Ph 2 P(S)R) subjected to electron impact gives rise to rearrangements dependent on the nature of the radical R. Migrations of phenyl or methyl radicals from phosphorus towards sulphur were thus observed for R=Ph, CH 3 , CH 2 Ph and NH 2 . When an electrophilic centre is formed, during a fragmentation, on a carbon in the α-position of the diphenylthiophosphoranyl radical, migrations of sulphur atoms and phenyl radicals take place from the phosphorus towards the carbon. This is found to be the case with certain fragmentations of diazo 5 and 6 compounds [fr

  18. Pyrones to pyrans: enantioselective radical additions to acyloxy pyrones.

    Science.gov (United States)

    Sibi, Mukund P; Zimmerman, Jake

    2006-10-18

    This paper describes a highly site-, diastereo-, and enantioselective intermolecular radical addition/hydrogen atom transfer to hydroxypyrone pyromeconic and kojic acids. The methodology can be extended to the formation of chiral quaternary centers. The products obtained are densely functionalized pyran moieties. The products contain structural features amenable for the introduction of additional substituents.

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

    Science.gov (United States)

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

    2017-10-19

    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.

  20. Complexes with charge transfer and ion-radical salts in catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Krylov, O V [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

    1978-01-01

    Considered are the data experimentally proving formation of complexes with charge transfer as intermediate complexes in homogeneous and heterogeneous catalysis. Catalytic activity correlations with charge transfer energy (and in heterogeneous catalysis with width of semiconductor forbidden band can be useful while selection of catalysts (MoO/sub 3//MgO; V/sub 2/O/sub 5//MgO; MoO/sub 3//Al/sub 2/O/sub 3/; V/sub 2/O/sub 5//Al/sub 2/O/sub 3/). A review of papers on catalytic activity of the previously prepared complexes with charge transfer and ion-radical salts is given. The use of alkali metal complexes with aromatic compounds showed their high activity in hydrogenation reactions and proved principle possibility of activation of hydrogen and hydrocarbons by the systems which do not contain transfer metals.

  1. Simulating Controlled Radical Polymerizations with mcPolymer—A Monte Carlo Approach

    Directory of Open Access Journals (Sweden)

    Georg Drache

    2012-07-01

    Full Text Available Utilizing model calculations may lead to a better understanding of the complex kinetics of the controlled radical polymerization. We developed a universal simulation tool (mcPolymer, which is based on the widely used Monte Carlo simulation technique. This article focuses on the software architecture of the program, including its data management and optimization approaches. We were able to simulate polymer chains as individual objects, allowing us to gain more detailed microstructural information of the polymeric products. For all given examples of controlled radical polymerization (nitroxide mediated radical polymerization (NMRP homo- and copolymerization, atom transfer radical polymerization (ATRP, reversible addition fragmentation chain transfer polymerization (RAFT, we present detailed performance analyses demonstrating the influence of the system size, concentrations of reactants, and the peculiarities of data. Different possibilities were exemplarily illustrated for finding an adequate balance between precision, memory consumption, and computation time of the simulation. Due to its flexible software architecture, the application of mcPolymer is not limited to the controlled radical polymerization, but can be adjusted in a straightforward manner to further polymerization models.

  2. FROM ATOM TRANSFER RADICAL ADDITION TO ATOM TRANSFER RADICAL POLYMERIZATION. (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...

  3. Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products.

    Science.gov (United States)

    Green, Amy M; Barber, Victoria P; Fang, Yi; Klippenstein, Stephen J; Lester, Marsha I

    2017-11-21

    Ozonolysis of alkenes, an important nonphotolytic source of hydroxyl (OH) radicals in the atmosphere, proceeds through unimolecular decay of Criegee intermediates. Here, we report a large kinetic isotope effect associated with the rate-limiting hydrogen-transfer step that releases OH radicals for a prototypical Criegee intermediate, CH 3 CHOO. IR excitation of selectively deuterated syn -CD 3 CHOO is shown to result in deuterium atom transfer and release OD radical products. Vibrational activation of syn -CD 3 CHOO is coupled with direct time-resolved detection of OD products to measure a 10-fold slower rate of unimolecular decay upon deuteration in the vicinity of the transition state barrier, which is confirmed by microcanonical statistical theory that incorporates quantum mechanical tunneling. The corresponding kinetic isotope effect of ∼10 is attributed primarily to the decreased probability of D-atom vs. H-atom transfer arising from tunneling. Master equation modeling is utilized to compute the thermal unimolecular decay rates for selectively and fully deuterated syn methyl-substituted Criegee intermediates under atmospheric conditions. At 298 K (1 atm), tunneling is predicted to enhance the thermal decay rate of syn -CH 3 CHOO compared with the deuterated species, giving rise to a significant kinetic isotope effect of ∼50.

  4. Scavenging of free-radical metabolites of aniline xenobiotics and drugs by amino acid derivatives: toxicological implications of radical-transfer reactions.

    Science.gov (United States)

    Michail, Karim; Baghdasarian, Argishti; Narwaley, Malyaj; Aljuhani, Naif; Siraki, Arno G

    2013-12-16

    We investigated a novel scavenging mechanism of arylamine free radicals by poly- and monoaminocarboxylates. Free radicals of arylamine xenobiotics and drugs did not react with oxygen in peroxidase-catalyzed reactions; however, they showed marked oxygen uptake in the presence of an aminocarboxylate. These free-radical intermediates were identified using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and electron paramagnetic resonance (EPR) spectrometry. Diethylenetriaminepentaacetic acid (DTPA), a polyaminocarboxylate, caused a concentration-dependent attenuation of N-centered radicals produced by the peroxidative metabolism of arylamines with the subsequent formation of secondary aliphatic carbon-centered radicals stemming from the cosubstrate molecule. Analogously, N,N-dimethylglycine (DMG) and N-methyliminodiacetate (MIDA), but not iminodiacetic acid (IDA), demonstrated a similar scavenging effect of arylamine-derived free radicals in a horseradish peroxidase/H2O2 system. Using human promyelocytic leukemia (HL-60) cell lysate as a model of human neutrophils, DTPA, MIDA, and DMG readily reduced anilinium cation radicals derived from the arylamines and gave rise to the corresponding carbon radicals. The rate of peroxidase-triggered polymerization of aniline was studied as a measure of nitrogen-radical scavenging. Although, IDA had no effect on the rate of aniline polymerization, this was almost nullified in the presence of DTPA and MIDA at half of the molar concentration of the aniline substrate, whereas a 20 molar excess of DMPO caused only a partial inhibition. Furthermore, the yield of formaldehyde, a specific reaction endproduct of the oxidation of aminocarboxylates by aniline free-radical metabolites, was quantitatively determined. Azobenzene, a specific reaction product of peroxidase-catalyzed free-radical dimerization of aniline, was fully abrogated in the presence of DTPA, as confirmed by GC/MS. Under aerobic conditions, a radical-transfer reaction

  5. Olefin copolymerization via controlled radical polymerization : copolymerization of methyl methacrylate and 1-octene

    NARCIS (Netherlands)

    Venkatesh, R.; Klumperman, B.

    2004-01-01

    The atom transfer radical (co)polymerization (ATRP) of methyl methacrylate (MMA) with 1-octene was investigated. Well controlled homopolymer of MMA was obtained with 2,2,2-trichoroethanol (TCE) and p-toluenesulfonyl chloride (pTsCl), although, uncontrolled copolymerization occurred when pTsCl was

  6. Novel atmospheric pressure plasma device releasing atomic hydrogen: reduction of microbial-contaminants and OH radicals in the air

    International Nuclear Information System (INIS)

    Nojima, Hideo; Park, Rae-Eun; Kwon, Jun-Hyoun; Suh, Inseon; Jeon, Junsang; Ha, Eunju; On, Hyeon-Ki; Kim, Hye-Ryung; Choi, KyoungHui; Lee, Kwang-Hee; Seong, Baik-Lin; Jung, Hoon; Kang, Shin Jung; Namba, Shinichi; Takiyama, Ken

    2007-01-01

    A novel atmospheric pressure plasma device releasing atomic hydrogen has been developed. This device has specific properties such as (1) deactivation of airborne microbial-contaminants, (2) neutralization of indoor OH radicals and (3) being harmless to the human body. It consists of a ceramic plate as a positive ion generation electrode and a needle-shaped electrode as an electron emission electrode. Release of atomic hydrogen from the device has been investigated by the spectroscopic method. Optical emission of atomic hydrogen probably due to recombination of positive ions, H + (H 2 O)n, generated from the ceramic plate electrode and electrons emitted from the needle-shaped electrode have been clearly observed in the He gas (including water vapour) environment. The efficacy of the device to reduce airborne concentrations of influenza virus, bacteria, mould fungi and allergens has been evaluated. 99.6% of airborne influenza virus has been deactivated with the operation of the device compared with the control test in a 1 m 3 chamber after 60 min. The neutralization of the OH radical has been investigated by spectroscopic and biological methods. A remarkable reduction of the OH radical in the air by operation of the device has been observed by laser-induced fluorescence spectroscopy. The cell protection effects of the device against OH radicals in the air have been observed. Furthermore, the side effects have been checked by animal experiments. The harmlessness of the device has been confirmed

  7. Oxidation of substituted alkyl radicals by IrCl62-, Fe(CN)63-, and MnO4- in aqueous solution. Electron transfer versus chlorine transfer from IrCl62-

    International Nuclear Information System (INIS)

    Steenken, S.; Neta, P.

    1982-01-01

    Alkyl radicals substituted at C/sub α/ by alkyl, carboxyl, hydroxyl, alkoxyl, and chlorine react in aqueous solutions with Ir/sup IV/Cl 6 2- to yield Ir(III) species. In the case of substitution by hydroxyl and alkoxyl, the rate constants are in the diffusion-controlled range ((4-6) x 10 9 M -1 s -1 ) and the reaction proceeds by electron transfer. In the case of ethyl, methyl, carboxymethyl, and chloromethyl radicals the rate constants range from 3.1 x 10 9 for ethyl to 2.8 x 10 7 M -1 s -1 for trichloromethyl and the reaction proceeds by chlorine transfer from IrCl 6 2- to the alkyl radical. With isopropyl and tert-butyll radicals the reaction proceeds by both electron and chlorine transfer. Alkyl radicals also react with Fe(CN) 6 3- . The rate constants increase strongly with increasing alkylation at C/sub α/ from 5 x 10 6 for methyl to 3.6 x 10 9 M -1 s -1 for tert-butyl, indicating that the transition state for the reaction is highly polar. Rate constants for reaction of MnO 4 - with alkyl radicals are of the order 10 9 M -1 s -1 . 4 figures, 1 table

  8. Preparation of polymer brushes grafted graphene oxide by atom transfer radical polymerization as a new support for trypsin immobilization and efficient proteome digestion.

    Science.gov (United States)

    Guo, Cong; Zhao, Xinyuan; Zhang, Wanjun; Bai, Haihong; Qin, Weijie; Song, Haifeng; Qian, Xiaohong

    2017-08-01

    Highly efficient protein digestion is one of the key issues in the "bottom-up" strategy-based proteomic studies. Compared with the time-consuming solution-based free protease digestion, immobilized protease digestion offers a promising alternative with obviously improved sample processing throughput. In this study, we proposed a new immobilized protease digestion strategy using two kinds of polymer-grafted graphene oxide (GO) conjugated trypsin. The polymer brush grafted GO was prepared using in situ polymer growth on initiator-functionalized GO using surface-initiated atom transfer radical polymerization (SI-ATRP) and characterized by AFM, TEM, TGA, and XPS. The polymer brush grafted GO supports three-dimensional trypsin immobilization, which not only increases the loading amount but also improves accessibility towards protein substrates. Both of the two types of immobilized trypsin provide 700 times shorter digestion time, while maintaining comparable protein/peptide identification scale compared with that of free trypsin digestion. More interestingly, combined application of the two types of immobilized trypsin with different surface-grafted polymers leads to at least 18.3/31.3% enhancement in protein/peptide identification compared with that obtained by digestion using a single type, indicating the potential of this digestion strategy for deeper proteome coverage using limited mass spectrometer machine hour. We expect these advantages may find valuable application in high throughput clinical proteomic studies, which often involve processing of a large number of samples. Graphical abstract Preparation of polymer brushes grafted and trypsin immobilized graphene oxide and its application in proteome digestion and mass spectrometry identification.

  9. The coordination and atom transfer chemistry of titanium porphyrin complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hays, James Allen [Iowa State Univ., Ames, IA (United States)

    1993-11-05

    Preparation, characterization, and reactivity of (η2- alkyne)(meso-tetratolylpoprphrinato)titanium(II) complexes are described, along with inetermetal oxygen atom transfer reactions involving Ti(IV) and Ti(III) porphyrin complexes. The η2- alkyne complexes are prepared by reaction of (TTP)TiCl2 with LiAlH4 in presence of alkyne. Structure of (OEP)Ti(η2-Ph-C≡C-Ph) (OEP=octaethylporphryin) was determined by XRD. The compounds undergo simple substitution to displace the alkyne and produce doubly substituted complexes. Structure of (TTP)Ti(4-picoline)2 was also determined by XRD. Reaction of (TTP)Ti=O with (OEP)Ti-Cl yields intermetal O/Cl exchange, which is a one-electron redox process mediated by O atom transfer. Also a zero-electron redox process mediated by atom transfer is observed when (TTP)TiCl2 is reacted with (OEP)Ti=O.

  10. A comparison of pulsed and continuous atom transfer between two magneto-optical traps

    International Nuclear Information System (INIS)

    Ram, S. P.; Tiwari, S. K.; Mishra, S. R.

    2010-01-01

    We present the experimental results for a comparison between pulsed and continuous transfer of cold 87 Rb atoms between a vapor chamber magneto-optical trap (VC-MOT) and an ultra-high vacuum magneto-optical trap (UHV-MOT) when using a resonant push beam. We find that employing repetitive cycles of a pulsed and unfocused push beam on an unsaturated VC-MOT cloud results in a significantly higher number of atoms transferred to the UHV-MOT than the number obtained with a continuous push beam focused on a continuous VC-MOT. In pulsed transfer, we find that both the VC-MOT loading duration and the push beam duration play important roles in the transfer process and govern the number of atoms transferred to the UHV-MOT. The parameters and processes affecting the transfer have been investigated and are discussed.

  11. Electron transfer rates and equilibria between substituted phenoxide ions and phenoxyl radicals

    International Nuclear Information System (INIS)

    Steenken, S.; Neta, P.

    1979-01-01

    The rate constants for electron transfer from a series of substituted isomeric dihydroxy- and diaminobenzenes to different substituted phenoxyl radicals were measured by observing the decay or buildup of one of the radicals invoved. In many cases the electron transfer reactions were reversible and the equilibrium constants could be calculated from the individual rate constants for attainment of equilibrium and from the concentrations of the species involved at equilibrium. From the equilibrium constants the one-electron redox potentials for 15 individual Q - ./Q 2- pairs were determined, using the value for hydroquinone (23 mV at pH 13.5) as a reference. The potential for catechol (43 mV) is near that of hydroquinone; resorcinol is oxidized much less readily (300 mV), while phenol is even a weaker reductant (>500mV). Methyl, methoxy, and hydroxy substituents decrease the redox potentials while acetyl and carboxyl substituents increase these values. Ascorbate has a potential (15mV) similar to that of hydroquinone, while TMPD (82mV) and p-phenylenediamine (183mV) are less easily oxidized

  12. A phenomenological model for collisional coherence transfer in an optically pumped atomic system

    Energy Technology Data Exchange (ETDEWEB)

    Khanbekyan, K; Bevilaqua, G; Mariotti, E; Moi, L [Universita degli Studi di Siena, Siena, 53100 (Italy); Khanbekyan, A; Papoyan, A, E-mail: karen.khanbekyan@gmail.com [Institute for Physical Research, National Academy of Sciences, Ashtarak 2 (Armenia)

    2011-03-14

    We consider a dual {Lambda}-system under double laser excitation to investigate the possibility of indirect coherence transfer between atomic ground states through an excited state. The atomic system is excited by a frequency modulated pump laser and probed by a low-power cw laser. All the decoherence mechanisms are discussed and taken into account. Adjustment of parameters of the two radiations aimed at maximization of coherence transfer is addressed. The study can help to understand the phenomena as collisional transfer of coherence and can find application in the experimental realization of atomic sensors.

  13. Reaction between aminoalkyl radicals and akyl halides: Dehalogenation by electron transfer?

    Science.gov (United States)

    Lalevée, J.; Fouassier, J. P.; Blanchard, N.; Ingold, K. U.

    2011-07-01

    Aminoalkyl radicals, such as Et2NCrad HCH3, have low oxidation potentials and are therefore powerful reducing agents. We have found that Et2NCrad HCH3 reacts with CCl4 and CBr4 in di-tert-butyl peroxide with bimolecular rate constants (measured by LFP) close, or equal, to the diffusion-controlled limit. For the less reactive halide, CH2Br2, the reaction rate is increased substantially by the addition of acetonitrile as a co-solvent. It is tentatively concluded that these reactions occur by electron-transfer from the aminoalkyl to the organohalide with formation of the iminium ion, Et2N+dbnd CHCH3 (NMR detection), halide ion and a halomethyl radical, e.g., rad CCl3 and rad CHCl2 (ESR, spin-trapping detection).

  14. 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.

  15. [Electron transfer, ionization and excitation in atomic collisions

    International Nuclear Information System (INIS)

    1991-01-01

    The research being carried out at Penn State by Winter and Alston addresses the fundamental atomic-collision processes of electron transfer, ionization, and excitation. Winter has focussed attention on intermediate and, more recently, higher collision energies -- proton energies of at least about 50 keV -- for which coupled-state approaches are appropriate. Alston has concentrated on perturbative approaches to symmetric ion-ion/atom collisions at high energies and to asymmetric collisions at intermediate to high energies

  16. Electron and Oxygen Atom Transfer Chemistry of Co(II) in a Proton Responsive, Redox Active Ligand Environment.

    Science.gov (United States)

    Cook, Brian J; Pink, Maren; Pal, Kuntal; Caulton, Kenneth G

    2018-05-21

    The bis-pyrazolato pyridine complex LCo(PEt 3 ) 2 serves as a masked form of three-coordinate Co II and shows diverse reactivity in its reaction with several potential outer sphere oxidants and oxygen atom transfer reagents. N-Methylmorpholine N-oxide (NMO) oxidizes coordinated PEt 3 from LCo(PEt 3 ) 2 , but the final cobalt product is still divalent cobalt, in LCo(NMO) 2 . The thermodynamics of a variety of oxygen atom transfer reagents, including NMO, are calculated by density functional theory, to rank their oxidizing power. Oxidation of LCo(PEt 3 ) 2 with AgOTf in the presence of LiCl as a trapping nucleophile forms the unusual aggregate [LCo(PEt 3 ) 2 Cl(LiOTf) 2 ] 2 held together by Li + binding to very nucleophilic chloride on Co(III) and triflate binding to those Li + . In contrast, Cp 2 Fe + effects oxidation to trivalent cobalt, to form (HL)Co(PEt 3 ) 2 Cl + ; proton and the chloride originate from solvent in a rare example of CH 2 Cl 2 dehydrochlorination. An unexpected noncomplementary redox reaction is reported involving attack by 2e reductant PEt 3 nucleophile on carbon of the 1e oxidant radical Cp 2 Fe + , forming a P-C bond and H + ; this reaction competes in the reaction of LCo(PEt 3 ) 2 with Cp 2 Fe + .

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

    International Nuclear Information System (INIS)

    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. (atomic and molecular physics)

  18. Enantioselective radical addition/trapping reactions with alpha,beta-disubstituted unsaturated imides. Synthesis of anti-propionate aldols.

    Science.gov (United States)

    Sibi, Mukund P; Petrovic, Goran; Zimmerman, Jake

    2005-03-02

    This manuscript describes a highly diastereo- and enantioselective intermolecular radical addition/hydrogen atom transfer to alpha,beta-disubstituted enoates. Additionally, we show that anti-propionate aldol-like products can be easily prepared from alpha-methyl-beta-acyloxyenoates in good yields and high diastereo- and enantioselectivities.

  19. Dynamical interaction of He atoms with metal surfaces: Charge transfer processes

    International Nuclear Information System (INIS)

    Flores, F.; Garcia Vidal, F.J.; Monreal, R.

    1993-01-01

    A self-consistent Kohn-Sham LCAO method is presented to calculate the charge transfer processes between a He * -atom and metal surfaces. Intra-atomic correlation effects are taken into account by considering independently each single He-orbital and by combining the different charge transfer processes into a set of dynamical rate equations for the different ion charge fractions. Our discussion reproduces qualitatively the experimental evidence and gives strong support to the method presented here. (author). 24 refs, 4 figs

  20. Charge transfer between O6+ and atomic hydrogen

    Science.gov (United States)

    Wu, Y.; Stancil, P. C.; Liebermann, H. P.; Buenker, R. J.; Schultz, D. R.; Hui, Y.

    2011-05-01

    The charge exchange process has been found to play a dominant role in the production of X-rays and/or EUV photons observed in cometary and planetary atmospheres and from the heliosphere. Charge transfer cross sections, especially state-selective cross sections, are necessary parameters in simulations of X-ray emission. In the present work, charge transfer due to collisions of ground state O6+(1s2 1 S) with atomic hydrogen has been investigated theoretically using the quantum-mechanical molecular-orbital close-coupling method (QMOCC). The multi-reference single- and double-excitation configuration interaction approach (MRDCI) has been applied to compute the adiabatic potential and nonadiabatic couplings, and the atomic basis sets used have been optimized with the method proposed previously to obtain precise potential data. Total and state-selective cross sections are calculated for energies between 10 meV/u and 10 keV/u. The QMOCC results are compared to available experimental and theoretical data as well as to new atomic-orbital close-coupling (AOCC) and classical trajectory Monte Carlo (CTMC) calculations. A recommended set of cross sections, based on the MOCC, AOCC, and CTMC calculations, is deduced which should aid in X-ray modeling studies.

  1. Kinetic of the gas-phase reactions of OH radicals and Cl atoms with Diethyl Ethylphosphonate and Triethyl Phosphate

    KAUST Repository

    Laversin, H.

    2015-11-30

    In this paper, the relative-rate technique has been used to obtain rate coefficients for the reaction of two organophosphorus compounds: Triethyl phosphate (TEP) and Diethyl ethylphosphonate (DEEP) with OH radicals and Cl atoms at atmospheric pressure and at different temperatures. The calculated rate constants were fitted to the Arrhenius expression over the temperature range 298 – 352 K. The following expressions (in cm3molecule-1s-1) were obtained for the reactions of OH and CL with DEEP and TEP: kOH+DEEP= (7.84±0.65)x10-14exp((1866±824)/T), kOH+TEP = (6.54±0.42)x10-14exp((1897±626)/T), kCl+DEEP = (5.27± 0.80)x10−11exp(765±140/T) and kCl+TEP = (5.23± 0.80)x10−11exp(736± 110/T). These results show that the reaction of the studied compounds with Cl atoms proceeds more rapidly than that with OH radicals. The related tropospheric lifetimes suggest that once emitted into the atmosphere, TEP and DEEP can be removed within a few hours in areas close to their emission sources. TEP and DEEP are principally removed by OH radicals. However, in coastal areas where the Cl atoms’ concentration is higher, TEP and DEEP removal by reaction with Cl atoms could be a competitive process.

  2. 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

  3. Synthesis, Characterization and Bulk Properties of Amphiphilic Copolymers Containing Fluorinated Methacrylates from Sequential Copper-Mediated Radical Polymerization

    DEFF Research Database (Denmark)

    Hansen, Natanya Majbritt Louie; Gerstenberg, Michael; Haddleton, David M.

    2008-01-01

    acrylate (MEA), and poly(ethylene glycol) methyl ether methacrylate (PEGMA) by Atom Transfer Radical Polymerization. A kinetic study of the 3FM homopolymerization initiated with ethyl bromoisobutyrate and Cu(I)Br/N-(n-propyl)-2-pyridylmethanimine reveals a living/ controlled polymerization in the range 80...

  4. Symmetric large momentum transfer for atom interferometry with BECs

    Science.gov (United States)

    Abend, Sven; Gebbe, Martina; Gersemann, Matthias; Rasel, Ernst M.; Quantus Collaboration

    2017-04-01

    We develop and demonstrate a novel scheme for a symmetric large momentum transfer beam splitter for interferometry with Bose-Einstein condensates. Large momentum transfer beam splitters are a key technique to enhance the scaling factor and sensitivity of an atom interferometer and to create largely delocalized superposition states. To realize the beam splitter, double Bragg diffraction is used to create a superposition of two symmetric momentum states. Afterwards both momentum states are loaded into a retro-reflected optical lattice and accelerated by Bloch oscillations on opposite directions, keeping the initial symmetry. The favorable scaling behavior of this symmetric acceleration, allows to transfer more than 1000 ℏk of total differential splitting in a single acceleration sequence of 6 ms duration while we still maintain a fraction of approx. 25% of the initial atom number. As a proof of the coherence of this beam splitter, contrast in a closed Mach-Zehnder atom interferometer has been observed with up to 208 ℏk of momentum separation, which equals a differential wave-packet velocity of approx. 1.1 m/s for 87Rb. The presented work is supported by the CRC 1128 geo-Q and the DLR with funds provided by the Federal Ministry of Economic Affairs and Energy (BMWi) due to an enactment of the German Bundestag under Grant No. DLR 50WM1552-1557 (QUANTUS-IV-Fallturm).

  5. Charge transfer and excitation in high-energy ion-atom collisions

    International Nuclear Information System (INIS)

    Schlachter, A.S.; Berkner, K.H.; McDonald, R.J.

    1986-11-01

    Coincidence measurements of charge transfer and simultaneous projectile electron excitation provide insight into correlated two-electron processes in energetic ion-atom collisions. Projectile excitation and electron capture can occur simultaneously in a collision of a highly charged ion with a target atom; this process is called resonant transfer and excitation (RTE). The intermediate excited state which is thus formed can subsequently decay by photon emission or by Auger-electron emission. Results are shown for RTE in both the K shell of Ca ions and the L shell of Nb ions, for simultaneous projectile electron loss and excitation, and for the effect of RTE on electron capture

  6. Kinetics of elementary atom and radical reactions

    International Nuclear Information System (INIS)

    Gordon, R.J.

    1990-06-01

    During the past three years we have been working on four problems in the general area of gas phase kinetics and energy transfer of small molecules. These are: (1) measurements of the fine structure populations of ground state oxygen atoms produced in photodissociation reactions; (2) quenching of the Rydberg B ( 1 Σ + ) state of CO; (3) vibrational relaxation of highly excited molecules; and (4) kinetics of hydrogen molecules. The first two topics, which involve transitions between different electronic states of the parent molecule, are a departure from our previous research interests. In the accompanying renewal proposal we discuss plans to pursue these new topics vigorously during the coming year. The third topic is a continuation of our long interest in the energy dependence of the rates laws governing vibrational-to-translational energy transfer of molecules having large initial amounts of vibrational excitation. The final topic is a continuation of our studies of the reaction of O( 3 P) + H 2 . In this work we measured the rate constant for the reaction O( 3 P) with deuterium and also analyzed spectroscopically different sources of vibrationally excited hydrogen for possible future work. We discuss each of these four studies in the following sections

  7. Single-electron transfer living radical copolymerization of SWCNT-g-PMMA via graft from approach

    Czech Academy of Sciences Publication Activity Database

    Jaisankar, S. N.; Haridharan, N.; Murali, A.; Ponyrko, Sergii; Špírková, Milena; Mandal, A. B.; Matějka, Libor

    2014-01-01

    Roč. 55, č. 13 (2014), s. 2959-2966 ISSN 0032-3861 R&D Projects: GA ČR GAP108/12/1459 Institutional support: RVO:61389013 Keywords : single electron transfer * single-walled carbon nanotubes * controlled radical polymerization Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.562, year: 2014

  8. Collisions involving energy transfer between atoms with large angular moments

    International Nuclear Information System (INIS)

    Vdovin, Yu.A.; Galitskij, V.M.

    1975-01-01

    Study is made of the collisions of excited and nonexcited atoms with a small resonance defect, assuming that the excited and ground states of each atom are bound via an allowed dipole transition and that intrinsic moments of states are great. In such an approximation the atomic interaction is defined by a dipole-dipole interaction operator. Equations for amplitudes are derived for two cases: (1) the first atom is in an excited state while the second is in the ground state and (2) the first atom is in the ground state while the second is in an excited state. The problem is solved in the approximation that the moments of the excited and ground states of each atom are equal. An expression for the excitation transfer cross section is written down. Analysis of this expression shows that the excitation transfer cross section at first increases with removal from the exact resonance and reaches resonance at lambda approximately 0.1 (lambda is a dimensionless parameter which is equal to the ratio of the resonance defect Δ to the interaction at spacings of the order of the Weisskopf radius). Only at lambda >0.16 does the cross section become smaller than the resonance one. This effect is due to the interaction Hamiltonian approximation adopted in the present study

  9. 1,2-Fluorine Radical Rearrangements: Isomerization Events in Perfluorinated Radicals.

    Science.gov (United States)

    Van Hoomissen, Daniel J; Vyas, Shubham

    2017-11-16

    Devising effective degradation technologies for perfluoroalkyl substances (PFASs) is an active area of research, where the molecular mechanisms involving both oxidative and reductive pathways are still elusive. One commonly neglected pathway in PFAS degradation is fluorine atom migration in perfluoroalkyl radicals, which was largely assumed to be implausible because of the high C-F bond strength. Using density functional theory calculations, it was demonstrated that 1,2-F atom migrations are thermodynamically favored when the fluorine atom migrated from a less branched carbon center to a more branched carbon center. Activation barriers for these rearrangements were within 19-29 kcal/mol, which are possible to easily overcome at elevated temperatures or in photochemically activated species in the gas or aqueous phase. It was also found that the activation barriers for the 1,2-F atom migration are lowered as much as by 10 kcal/mol when common oxidative degradation products such as HF assisted the rearrangements or if the resulting radical center was stabilized by vicinal π-bonds. Natural bond orbital analyses showed that fluorine moves as a radical in a noncharge-separated state. These findings add an important reaction to the existing knowledge of mechanisms for PFAS degradation and highlights the fact that 1,2-F atom shifts may be a small channel for isomerization of these compounds, but upon availability of mineralization products, this isomerization process could become more prominent.

  10. Kinetics and mechanism of the gas-phase reaction of Cl atoms and OH radicals with fluorobenzene at 296 K

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, MD

    2002-01-01

    Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with fluorobenzene, C6H5F, in 700 Torr of N-2 or air diluent at 296 K. Reaction of Cl atoms with C6H5F proceeds via two pathways: H-atom abstraction to give HCl and the C6H4F...... with Cl atoms via a mechanism which, at least in part, leads neither to production of C6H5Cl nor to reformation of C6H5F. As the steady-state Cl atom concentration is increased, the fraction of the C6H5F-Cl adduct undergoing reaction with Cl atoms increases causing an increase in the effective rate...

  11. Muon transfer from hot muonic hydrogen atoms to neon

    International Nuclear Information System (INIS)

    Jacot-Guillarmod, R.; Beer, G.A.; Knowles, P.E.; Mason, G.R.; Olin, A.; Beveridge, J.L.; Marshall, G.M.; Brewer, J.H.; Forster, B.M.; Huber, T.M.; Kammel, P.; Zmeskal, J.; Petitjean, C.

    1992-01-01

    A negative muon beam has been directed on adjacent solid layers of hydrogen and neon. Three targets differing by their deuterium concentration were investigated. Muonic hydrogen atoms can drift to the neon layer where the muon is immediately transferred. The time structure of the muonic neon X-rays follows the exponential law with a disappearance rate corresponding to the one of μ -p atoms in each target. The rates λ ppμ and λ pd can be extracted

  12. Collision dynamics of methyl radicals and highly vibrationally excited molecules using crossed molecular beams

    International Nuclear Information System (INIS)

    Chu, P.M.Y.

    1991-10-01

    The vibrational to translational (V→T) energy transfer in collisions between large highly vibrationally excited polyatomics and rare gases was investigated by time-of-flight techniques. Two different methods, UV excitation followed by intemal conversion and infrared multiphoton excitation (IRMPE), were used to form vibrationally excited molecular beams of hexafluorobenzene and sulfur hexafluoride, respectively. The product translational energy was found to be independent of the vibrational excitation. These results indicate that the probability distribution function for V→T energy transfer is peaked at zero. The collisional relaxation of large polyatomic molecules with rare gases most likely occurs through a rotationally mediated process. Photodissociation of nitrobenzene in a molecular beam was studied at 266 nm. Two primary dissociation channels were identified including simple bond rupture to produce nitrogen dioxide and phenyl radical and isomerization to form nitric oxide and phenoxy radical. The time-of-flight spectra indicate that simple bond rupture and isomerization occurs via two different mechanisms. Secondary dissociation of the phenoxy radicals to carbon monoxide and cyclopentadienyl radicals was observed as well as secondary photodissociation of phenyl radical to give H atom and benzyne. A supersonic methyl radical beam source is developed. The beam source configuration and conditions were optimized for CH 3 production from the thermal decomposition of azomethane. Elastic scattering of methyl radical and neon was used to differentiate between the methyl radicals and the residual azomethane in the molecular beam

  13. Improved simplified scheme of atom equivalents to calculate enthalpies of formation of alkyl radicals

    International Nuclear Information System (INIS)

    Castro, Eduardo A.

    2002-01-01

    An improved simplified method of atom equivalents is applied to the calculation of enthalpies of formation of several alkyl radicals. Some statistical mechanics and thermodynamic corrections are added to compare theoretical values with available experimental data. The estimation is quite satisfactory and the average error is similar to current experimental uncertainties, thus providing a direct and simple procedure for this sort of calculation when experimental results are unavailable or/and as an independent check when experimental data are in doubt. (Author) [es

  14. Free radical scavenging and COX-2 inhibition by simple colon metabolites of polyphenols: A theoretical approach.

    Science.gov (United States)

    Amić, Ana; Marković, Zoran; Marković, Jasmina M Dimitrić; Jeremić, Svetlana; Lučić, Bono; Amić, Dragan

    2016-12-01

    Free radical scavenging and inhibitory potency against cyclooxygenase-2 (COX-2) by two abundant colon metabolites of polyphenols, i.e., 3-hydroxyphenylacetic acid (3-HPAA) and 4-hydroxyphenylpropionic acid (4-HPPA) were theoretically studied. Different free radical scavenging mechanisms are investigated in water and pentyl ethanoate as a solvent. By considering electronic properties of scavenged free radicals, hydrogen atom transfer (HAT) and sequential proton loss electron transfer (SPLET) mechanisms are found to be thermodynamically probable and competitive processes in both media. The Gibbs free energy change for reaction of inactivation of free radicals indicates 3-HPAA and 4-HPPA as potent scavengers. Their reactivity toward free radicals was predicted to decrease as follows: hydroxyl>alkoxyls>phenoxyl≈peroxyls>superoxide. Shown free radical scavenging potency of 3-HPAA and 4-HPPA along with their high μM concentration produced by microbial colon degradation of polyphenols could enable at least in situ inactivation of free radicals. Docking analysis with structural forms of 3-HPAA and 4-HPPA indicates dianionic ligands as potent inhibitors of COX-2, an inducible enzyme involved in colon carcinogenesis. Obtained results suggest that suppressing levels of free radicals and COX-2 could be achieved by 3-HPAA and 4-HPPA indicating that these compounds may contribute to reduced risk of colon cancer development. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Physiology of free radicals

    Directory of Open Access Journals (Sweden)

    Stevanović Jelka

    2011-01-01

    Full Text Available Free radicals imply that every atom, molecule, ion, group of atoms, or molecules with one or several non-paired electrons in outer orbital. Among these are: nitrogenoxide (NO•, superoxide-anion-radical (O2•-, hydroxyl radical (OH•, peroxyl radical (ROO•, alcoxyl radical (RO• and hydroperoxyl radical (HO2•. However, reactive oxygen species also include components without non-paired electrons in outer orbital (so-called reactive non-radical agents, such as: singlet oxygen (1O2, peroxynitrite (ONOO-, hydrogen-peroxide (H2O2, hypochloric acid (eg. HOCl and ozone (O3. High concentrations of free radicals lead to the development of oxidative stress which is a precondition for numerous pathological effects. However, low and moderate concentrations of these matter, which occur quite normally during cell metabolic activity, play multiple significant roles in many reactions. Some of these are: regulation of signal pathways within the cell and between cells, the role of chemoattractors and leukocyte activators, the role in phagocytosis, participation in maintaining, changes in the position and shape of the cell, assisting the cell during adaption and recovery from damage (e.g.caused by physical effort, the role in normal cell growth, programmed cell death (apoptosis and cell ageing, in the synthesis of essential biological compounds and energy production, as well as the contribution to the regulation of the vascular tone, actually, tissue vascularization.

  16. Free radical scavenging potency of quercetin catecholic colonic metabolites: Thermodynamics of 2H+/2e- processes.

    Science.gov (United States)

    Amić, Ana; Lučić, Bono; Stepanić, Višnja; Marković, Zoran; Marković, Svetlana; Dimitrić Marković, Jasmina M; Amić, Dragan

    2017-03-01

    Reaction energetics of the double (2H + /2e - ), i.e., the first 1H + /1e - (catechol→ phenoxyl radical) and the second 1H + /1e - (phenoxyl radical→ quinone) free radical scavenging mechanisms of quercetin and its six colonic catecholic metabolites (caffeic acid, hydrocaffeic acid, homoprotocatechuic acid, protocatechuic acid, 4-methylcatechol, and catechol) were computationally studied using density functional theory, with the aim to estimate the antiradical potency of these molecules. We found that second hydrogen atom transfer (HAT) and second sequential proton loss electron transfer (SPLET) mechanisms are less energy demanding than the first ones indicating 2H + /2e - processes as inherent to catechol moiety. The Gibbs free energy change for reactions of inactivation of selected free radicals indicate that catecholic colonic metabolites constitute an efficient group of more potent scavengers than quercetin itself, able to deactivate various free radicals, under different biological conditions. They could be responsible for the health benefits associated with regular intake of flavonoid-rich diet. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. 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.

  18. Theoretical Investigation of Kinetic Processes in Small Radicals of Importance in Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, Millard [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Dagdigian, Paul J. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry

    2017-12-12

    Our group studies inelastic and reactive collisions of small molecules, focusing on radicals important in combustion environments. The goal is the better understanding of kinetic processes that may be difficult to access experimentally. An essential component is the accurate determination and fitting of potential energy surfaces (PESs). After fitting the ab initio points to obtain global PESs, we treat the dynamics using time-independent (close-coupling) methods. Cross sections and rate constants for collisions of are determined with our Hibridon program suite . We have studied energy transfer (rotationally, vibrationally, and/or electronically inelastic) in small hydrocarbon radicals (CH2 and CH3) and the CN radical. We have made a comparison with experimental measurements of relevant rate constants for collisions of these radicals. Also, we have calculated accurate transport properties using state-of-the-art PESs and to investigate the sensitivity to these parameters in 1-dimensional flame simulations. Of particular interest are collision pairs involving the light H atom.

  19. Synthesis of defined polyhedral oligosilsesquioxane-containing diblock and triblock methacrylate copolymers by atom transfer radical polymerization

    Czech Academy of Sciences Publication Activity Database

    Janata, Miroslav; Sikora, Antonín; Látalová, Petra; Čadová, Eva; Raus, Vladimír; Matějka, Libor; Vlček, Petr

    2013-01-01

    Roč. 128, č. 6 (2013), s. 4294-4301 ISSN 0021-8995 R&D Projects: GA ČR GAP106/12/0844; GA ČR GAP108/12/1459 Institutional support: RVO:61389013 Keywords : copolymers * nanostructured polymers * radical polymerization Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.640, year: 2013

  20. Hydroxyl-radical-induced oxidation of cyclic dipeptides: Reactions of free peptide radicals and their peroxyl radicals

    International Nuclear Information System (INIS)

    Mieden, O.J.

    1989-01-01

    In the course of this study investigations were carried out into the reactions of hydroxyl radicals and hydrogen atoms with cyclic dipeptides as well as the subsequent reactions of peptide radicals and their peroxyl radicals in aqueous solution. The radiolysis products formed in the absence and presence of oxygen or transient metal complexes were characterized and determined on a quantitative basis. The linking of information from product analyses to the kinetic data for transient species obtained by time-resolving UV/VIS and conductivity measurements (pulse radiolysis) as well as computer-assisted simulations of individual events during the reaction permitted an evaluation of the mechanisms underlying the various processes and an identification of interim products with short life-times, which did or did not belong to the group of radicals. Through the characterization of key reactions of radicals and peroxyl radicals of this substance class a major advance has been made towards a better understanding of the role of radicals in the peptide compound and the mechanisms involved in indirect radiation effects on long-chain peptides and proteins. (orig.) [de

  1. Correlation among Singlet-Oxygen Quenching, Free-Radical Scavenging, and Excited-State Intramolecular-Proton-Transfer Activities in Hydroxyflavones, Anthocyanidins, and 1-Hydroxyanthraquinones.

    Science.gov (United States)

    Nagaoka, Shin-Ichi; Bandoh, Yuki; Nagashima, Umpei; Ohara, Keishi

    2017-10-26

    Singlet-oxygen ( 1 O 2 ) quenching, free-radical scavenging, and excited-state intramolecular proton-transfer (ESIPT) activities of hydroxyflavones, anthocyanidins, and 1-hydroxyanthraquinones were studied by means of laser, stopped-flow, and steady-state spectroscopies. In hydroxyflavones and anthocyanidins, the 1 O 2 quenching activity positively correlates to the free-radical scavenging activity. The reason for this correlation can be understood by considering that an early step of each reaction involves electron transfer from the unfused phenyl ring (B-ring), which is singly bonded to the bicyclic chromen or chromenylium moiety (A- and C-rings). Substitution of an electron-donating OH group at B-ring enhances the electron transfer leading to activation of the 1 O 2 quenching and free-radical scavenging. In 3-hydroxyflavones, the OH substitution at B-ring reduces the activity of ESIPT within C-ring, which can be explained in terms of the nodal-plane model. As a result, the 1 O 2 quenching and free-radical scavenging activities negatively correlate to the ESIPT activity. A catechol structure at B-ring is another factor that enhances the free-radical scavenging in hydroxyflavones. In contrast to these hydroxyflavones, 1-hydroxyanthraquinones having an electron-donating OH substituent adjacent to the O-H---O═C moiety susceptible to ESIPT do not show a simple correlation between their 1 O 2 quenching and ESIPT activities, because the OH substitution modulates these reactions.

  2. Comparison between Two Bromine Containing Free Radical Initiators in PRESAGE®

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyeonsuk; Ryu, Dongmin; Ye, Sung-Joon [Seoul National University, Seoul (Korea, Republic of)

    2016-10-15

    PRESAGE® is an optically clear 3-D polyurethane dosimeter which contains a halogenated carbon as a free radical initiator and leucomalachite dye. The change of the optical density is known to be linear with respect to the absorbed dose and the sensitivity is related to the carbon–halogen bond dissociation energy of the free radical initiator. Although there are some studies regarding free radical initiators and dye materials, there’s a lack of reports about the effect of other elements like LMG solvent which can be added when there’s a difficulty mixing materials. Also, there are some studies about comparison between free radicals with different kind of halogen atoms but there’s a lack of studies of comparison between initiators with the same halogen atom. In this experiments, two kinds of halocarbon free radical initiator with the same halogen atom (bromine) as well as the effect of the LMG solvent were studied to use the dosimeter as a therapeutic purpose. Effective atomic numbers were also calculated. The initiators with the same halogen atom, CBr{sub 4} and C{sub 2}H{sub 2}Br{sub 4}, reacted totally differently. CBr{sub 4} was more sensitive to the radiation and emitted maximum 4 times more free radicals upon irradiation with no additional effective atomic number but the absorbance after irradiation was highly variable with time. For stable measurement, C{sub 2}H{sub 2}Br{sub 4} would be more appropriate as a free radical initiator.

  3. Excitation and charge transfer in low-energy hydrogen atom collisions with neutral iron

    Science.gov (United States)

    Barklem, P. S.

    2018-05-01

    Data for inelastic processes due to hydrogen atom collisions with iron are needed for accurate modelling of the iron spectrum in late-type stars. Excitation and charge transfer in low-energy Fe+H collisions is studied theoretically using a previously presented method based on an asymptotic two-electron linear combination of atomic orbitals model of ionic-covalent interactions in the neutral atom-hydrogen-atom system, together with the multi-channel Landau-Zener model. An extensive calculation including 166 covalent states and 25 ionic states is presented and rate coefficients are calculated for temperatures in the range 1000-20 000 K. The largest rates are found for charge transfer processes to and from two clusters of states around 6.3 and 6.6 eV excitation, corresponding in both cases to active 4d and 5p electrons undergoing transfer. Excitation and de-excitation processes among these two sets of states are also significant. Full Tables and rate coefficient data are only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/612/A90

  4. 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

    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...

  5. Redox properties of free radicals

    International Nuclear Information System (INIS)

    Neta, P.

    1981-01-01

    Results of electron transfer reactions observed and monitored by pulse radiolysis are reported. This technique allows determination of the first one-electron reduction or oxidation of a compound rather than the overall two-electron transfer usually reported. Pulse radiolysis allows the determination of absolute rate constants for reactions of free radicals and helps elucidate the mechanisms involved. Studies using this technique to study radicals derived from quinones, nitro compounds, pyridines, phenols, and anilines are reported. Radicals of biochemical interest arising from riboflavin, ascorbic acid, vitamin K 3 , vitamin E, MAD + , porphyrins, etc. have also been studied

  6. Muon substituted free radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Gygax, F.N.; Brinkman, G.A.; Louwrier, P.W.F.; McKenna, D.; Ramos, M.; Webster, B.C.

    1984-01-01

    Spin polarized energetic positive muons are injected as magnetic probes into unsaturated organic liquids. They are implemented via fast chemical processes ( -10 s) in various molecules. Of particular interest among these are muonium substituted free radicals. The technique allows determination of accurate rate coefficients for fast chemical reactions of radicals. Furthermore, radiochemical processes occuring in picoseconds after injection of the muon are studied. Of fundamental interest are also the structural and dynamical implications of substituting a proton by a muon, or in other terms, a hydrogen atom by a muonium atom. Selected examples for each of these three types of experiments are given. (Auth.)

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

    Energy Technology Data Exchange (ETDEWEB)

    Chanu, Sapam Ranjita; Rathod, Ketan D.; Natarajan, Vasant, E-mail: vasant@physics.iisc.ernet.in

    2016-08-26

    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. - Highlights: • Getter-source loaded magneto-optic trap (MOT). • Cold atomic beam generated by deflection from the MOT. • Use of two inclined beams for deflection.

  8. Watson-Crick Base Pair Radical Cation as a Model for Oxidative Damage in DNA.

    Science.gov (United States)

    Feketeová, Linda; Chan, Bun; Khairallah, George N; Steinmetz, Vincent; Maitre, Philippe; Radom, Leo; O'Hair, Richard A J

    2017-07-06

    The deleterious cellular effects of ionizing radiation are well-known, but the mechanisms causing DNA damage are poorly understood. The accepted molecular events involve initial oxidation and deprotonation at guanine sites, triggering hydrogen atom abstraction reactions from the sugar moieties, causing DNA strand breaks. Probing the chemistry of the initially formed radical cation has been challenging. Here, we generate, spectroscopically characterize, and examine the reactivity of the Watson-Crick nucleobase pair radical cation in the gas phase. We observe rich chemistry, including proton transfer between the bases and propagation of the radical site in deoxyguanosine from the base to the sugar, thus rupturing the sugar. This first example of a gas-phase model system providing molecular-level details on the chemistry of an ionized DNA base pair paves the way toward a more complete understanding of molecular processes induced by radiation. It also highlights the role of radical propagation in chemistry, biology, and nanotechnology.

  9. Photochemistry and reactivity of the phenyl radical-water system: a matrix isolation and computational study.

    Science.gov (United States)

    Mardyukov, Artur; Crespo-Otero, Rachel; Sanchez-Garcia, Elsa; Sander, Wolfram

    2010-08-02

    The reaction of the phenyl radical 1 with water has been investigated by using matrix isolation spectroscopy and quantum chemical calculations. The primary thermal product of the reaction between 1 and water is a weakly bound complex stabilized by an OH...pi interaction. This complex is photolabile, and visible-light irradiation (lambda>420 nm) results in hydrogen atom transfer from water to radical 1 and the formation of a highly labile complex between benzene and the OH radical. This complex is stable under the conditions of matrix isolation, however, continuous irradiation with lambda>420 nm light results in the complete destruction of the aromatic system and formation of an acylic unsaturated ketene. The mechanisms of all reaction steps are discussed in the light of ab initio and DFT calculations.

  10. The population transfer of high excited states of Rydberg lithium atoms in a microwave field

    International Nuclear Information System (INIS)

    Jiang Lijuan; Zhang Xianzhou; Ma Huanqiang; Jia Guangrui; Zhang Yonghui; Xia Lihua

    2012-01-01

    Using the time-dependent multilevel approach (TDMA), the properties of high excited Rydberg lithium atom have been obtained in the microwave field. The population transfer of lithium atom are studied on numerical calculation, quantum states are controlled and manipulated by microwave field. It shows that the population can be completely transferred to the target state by changing the chirped rate and field amplitude. (authors)

  11. Heavy Atom Substituents as Molecular Probes for Solvent Effects on the Dynamics of Short-lived Triplet Exciplexes

    OpenAIRE

    Winter, Gerhard; Steiner, Ulrich

    1980-01-01

    The influence of heavy atom substituents (Br, I) in the electron donor aniline on the electron transfer reaction with thiopyronine triplet is investigated by flash spectroscopy in solvents of different viscosity and polarity. Triplet quenching constants and radical yields are determined. The results are analysed in terms of decay constants of an intermediate triplet exciplex where the heavy atom substituents significantly enhance the intersystem crossing process leading to singlet ground stat...

  12. Hydroxyl-radical induced dechlorination of pentachlorophenol in water

    International Nuclear Information System (INIS)

    He Yongke; Wu Jilan; Fang Xingwang; Sonntag, C. von

    1998-01-01

    The hydroxyl-radical induced dechlorination of pentachlorophenol (PCP) in water has been investigated pulse radiolytically. Hydroxyl radicals react with PCP by both electron transfer and addition. The former process results in pentachlorophenoxyl radicals (PCP-O), the latter process followed by rapid HCl elimination gives birth to deprotonated hydroxytetrachlorophenoxyl radicals ( - O-TCP-O). These phenoxyl radicals exhibit maximum absorption around 452 nm, which hinders the proper estimation of the ratio of the two processes. However, these two processes cause different changes in conductivity. In basic solution, the electron transfer causes a conductivity increase due to the formation of OH - whereas an addition followed by HCl elimination results in a conductivity decrease. The concurrence of these two processes reduces the relative variation in conductivity, from which about 53% electron transfer is deduced

  13. Fe electron transfer and atom exchange in goethite: influence of Al-substitution and anion sorption.

    Science.gov (United States)

    Latta, Drew E; Bachman, Jonathan E; Scherer, Michelle M

    2012-10-02

    The reaction of Fe(II) with Fe(III) oxides and hydroxides is complex and includes sorption of Fe(II) to the oxide, electron transfer between sorbed Fe(II) and structural Fe(III), reductive dissolution coupled to Fe atom exchange, and, in some cases mineral phase transformation. Much of the work investigating electron transfer and atom exchange between aqueous Fe(II) and Fe(III) oxides has been done under relatively simple aqueous conditions in organic buffers to control pH and background electrolytes to control ionic strength. Here, we investigate whether electron transfer is influenced by cation substitution of Al(III) in goethite and the presence of anions such as phosphate, carbonate, silicate, and natural organic matter. Results from (57)Fe Mössbauer spectroscopy indicate that both Al-substitution (up to 9%) and the presence of common anions (PO(4)(3-), CO(3)(2-), SiO(4)(4-), and humic acid) does not inhibit electron transfer between aqueous Fe(II) and Fe(III) in goethite under the conditions we studied. In contrast, sorption of a long-chain phospholipid completely shuts down electron transfer. Using an enriched isotope tracer method, we found that Al-substitution in goethite (10%), does, however, significantly decrease the extent of atom exchange between Fe(II) and goethite (from 43 to 12%) over a month's time. Phosphate, somewhat surprisingly, appears to have little effect on the rate and extent of atom exchange between aqueous Fe(II) and goethite. Our results show that electron transfer between aqueous Fe(II) and solid Fe(III) in goethite can occur under wide range of geochemical conditions, but that the extent of redox-driven Fe atom exchange may be dependent on the presence of substituting cations such as Al.

  14. Radical cations in radiation chemistry of aldehydes. ESR study and quantum chemical analysis

    International Nuclear Information System (INIS)

    Belevskii, V.N.; Tyurin, D.A.; Chuvilkin, N.D.

    1998-01-01

    Quantum-chemical (MNDO-UHF) calculations of electronic, spin and energy characteristics of radical cations (RC) of ethanal, propanal, butanal, and pentanal and their distonic isomers were performed. The calculations both with 'frozen' (vertical ionization) and completely optimize geometry (adiabatic approximation) were made. It was been shown that the most positive charge and spin population are localized at O atoms and adjacent C atom as well as at aldehyde protons. The C-H bonds corresponding to those protons as well as neighboring C-O and C-C bonds are considerable weaker (longer) in radical cations as compared to their neutral precursors. That is why such reaction centers are apt to deprotonation with the formation of acyl radical as well as to α- and β-splitting (scission) which are well-known from aldehydes mass-spectra. Our calculations shown that distonic RC (products of intramolecular H-atom transfer) are more stable as compare to their classical isomers: e.g. the difference in energy ΔE = -0.95 eV, -1.2 eV, and -1.5 eV for tree distonic isomers of butanal RC as compare to classical isomer, ΔE -1.2 eV for distonic RC of ethanal. The results of calculations are effectively correlated with ESR data obtained in freonic solutions, X- and gamma-irradiated at 77 K and in liquid aldehydes, X-irradiated by using 2,4,6-tri-tert-burylnitrosobenzene (BNB) and t-BuNO (NtB) as a spin traps. (author)

  15. Improved Mechanical Performance Fracture Properties and Reliability of Radical-Cured Thermosets

    Energy Technology Data Exchange (ETDEWEB)

    Redline, Erica Marie [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Bolintineanu, Dan S. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Lane, J. Matthew [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Stevens, Mark J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Alam, Todd M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Celina, Mathias C. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2016-10-01

    The aim of this study was to alter polymerization chemistry to improve network homogeneity in free-radical crosslinked systems. It was hypothesized that a reduction in heterogeneity of the network would lead to improved mechanical performance. Experiments and simulations were carried out to investigate the connection between polymerization chemistry, network structure and mechanical properties. Experiments were conducted on two different monomer systems - the first is a single monomer system, urethane dimethacrylate (UDMA), and the second is a two-monomer system consisting of bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) in a ratio of 70/30 BisGMA/TEGDMA by weight. The methacrylate systems were crosslinked using traditional radical polymeriza- tion (TRP) with azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as an initiator; TRP systems were used as the control. The monomers were also cross-linked using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) as a type of controlled radical polymerization (CRP). FTIR and DSC were used to monitor reac- tion kinetics of the systems. The networks were analyzed using NMR, DSC, X-ray diffraction (XRD), atomic force microscopy (AFM), and small angle X-ray scattering (SAXS). These techniques were employed in an attempt to quantify differences between the traditional and controlled radical polymerizations. While a quantitative methodology for characterizing net- work morphology was not established, SAXS and AFM have shown some promising initial results. Additionally, differences in mechanical behavior were observed between traditional and controlled radical polymerized thermosets in the BisGMA/TEGDMA system but not in the UDMA materials; this finding may be the result of network ductility variations between the two materials. Coarse-grained molecular dynamics simulations employing a novel model of the CRP reaction were carried out for

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

    OpenAIRE

    Chanu, Sapam Ranjita; Rathod, Ketan D.; 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 ...

  17. Free radicals generated by radiolysis of aqueous solutions

    International Nuclear Information System (INIS)

    Schwarz, H.A.

    1981-01-01

    The free radicals produced in the radiolysis of aqueous solutions span the range of redox potentials from -2.9 to +2.65 volts. The identity and nature of these radicals were discussed. Most of the discussion was results obtained with low LET radiation sources ( 60 Co gamma radiation or electron accelerators). Water radiolysis provides the synthesis of many radicals and radical ions in aqueous solution. The primary radicals, e/sub aq/ - H, OH, are well characterized. The radical population can be made to be 90% pure OH (or O - ) if N 2 O solutions are irradiated, the remaining 10% being H atoms. 55% of the radicals can be converted to H atoms in acid solution or in neutral phosphate solutions(e/sub aq/ - reacts with H 2 PO 4- to produce H). The remaining 45% (OH radicals) are difficult to convert to H by reaction with H 2 , due to the slow rate of the reaction. About 100 atmospheres of H 2 are required to do the conversion in less than 10 - 6 sec. 3 figures, 3 tables. (DP)

  18. Photolysis of CH₃CHO at 248 nm: evidence of triple fragmentation from primary quantum yield of CH₃ and HCO radicals and H atoms.

    Science.gov (United States)

    Morajkar, Pranay; Bossolasco, Adriana; Schoemaecker, Coralie; Fittschen, Christa

    2014-06-07

    Radical quantum yields have been measured following the 248 nm photolysis of acetaldehyde, CH3CHO. HCO radical and H atom yields have been quantified by time resolved continuous wave Cavity Ring Down Spectroscopy in the near infrared following their conversion to HO2 radicals by reaction with O2. The CH3 radical yield has been determined using the same technique following their conversion into CH3O2. Absolute yields have been deduced for HCO radicals and H atoms through fitting of time resolved HO2 profiles, obtained under various O2 concentrations, to a complex model, while the CH3 yield has been determined relative to the CH3 yield from 248 nm photolysis of CH3I. Time resolved HO2 profiles under very low O2 concentrations suggest that another unknown HO2 forming reaction path exists in this reaction system besides the conversion of HCO radicals and H atoms by reaction with O2. HO2 profiles can be well reproduced under a large range of experimental conditions with the following quantum yields: CH3CHO + hν(248nm) → CH3CHO*, CH3CHO* → CH3 + HCO ϕ(1a) = 0.125 ± 0.03, CH3CHO* → CH3 + H + CO ϕ(1e) = 0.205 ± 0.04, CH3CHO*[Formula: see text]CH3CO + HO2 ϕ(1f) = 0.07 ± 0.01. The CH3O2 quantum yield has been determined in separate experiments as ϕ(CH₃) = 0.33 ± 0.03 and is in excellent agreement with the CH3 yields derived from the HO2 measurements considering that the triple fragmentation (R1e) is an important reaction path in the 248 nm photolysis of CH3CHO. From arithmetic considerations taking into account the HO2 and CH3 measurements we deduce a remaining quantum yield for the molecular pathway: CH3CHO* → CH4 + CO ϕ(1b) = 0.6. All experiments can be consistently explained with absence of the formerly considered pathway: CH3CHO* → CH3CO + H ϕ(1c) = 0.

  19. 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)

  20. Research concerning ionic and free radical reactions in radiation chemistry. Progress report, September 15, 1977--September 15, 1978

    International Nuclear Information System (INIS)

    Williams, T.F.

    1978-01-01

    One achievement during the past year was the development of cryogenic techniques to allow samples to be γ irradiated at 4 0 K and then transferred to the EPR spectrometer for subsequent observations at 10 to 15 0 K and above. The adduct methyl radical in γ-irradiated dimethyl sulfoxide-h 6 was detected by this means. A study of d-atom abstraction by trapped H and D atoms in 3-methylpenetane-d 14 at temperatures below 50 0 K was completed. Abstracts of reports published during the year are included

  1. Impact of OH Radical-Initiated H2CO3 Degradation in the Earth's Atmosphere via Proton-Coupled Electron Transfer Mechanism.

    Science.gov (United States)

    Ghoshal, Sourav; Hazra, Montu K

    2016-02-04

    The decomposition of isolated carbonic acid (H2CO3) molecule into CO2 and H2O (H2CO3 → CO2 + H2O) is prevented by a large activation barrier (>35 kcal/mol). Nevertheless, it is surprising that the detection of the H2CO3 molecule has not been possible yet, and the hunt for the free H2CO3 molecule has become challenging not only in the Earth's atmosphere but also on Mars. In view of this fact, we report here the high levels of quantum chemistry calculations investigating both the energetics and kinetics of the OH radical-initiated H2CO3 degradation reaction to interpret the loss of the H2CO3 molecule in the Earth's atmosphere. It is seen from our study that proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) are the two mechanisms by which the OH radical initiates the degradation of the H2CO3 molecule. Moreover, the PCET mechanism is potentially the important one, as the effective barrier, defined as the difference between the zero point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, for the PCET mechanism at the CCSD(T)/6-311++G(3df,3pd) level of theory is ∼3 to 4 kcal/mol lower than the effective barrier height associated with the HAT mechanism. The CCSD(T)/6-311++G(3df,3pd) level predicted effective barrier heights for the degradations of the two most stable conformers of H2CO3 molecule via the PCET mechanism are only ∼2.7 and 4.3 kcal/mol. A comparative reaction rate analysis at the CCSD(T)/6-311++G(3df,3pd) level of theory has also been carried out to explore the potential impact of the OH radical-initiated H2CO3 degradation relative to that from water (H2O), formic acid (FA), acetic acid (AA) and sulfuric acid (SA) assisted H2CO3 → CO2 + H2O decomposition reactions in both the Earth's troposphere and stratosphere. The comparison of the reaction rates reveals that, although the atmospheric concentration of the OH radical is

  2. Gold volatile species atomization and preconcentration in quartz devices for atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Arslan, Yasin [Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno (Czech Republic); Mehmet Akif Ersoy University, Faculty of Arts & Sciences, Chemistry Department, 15030 Burdur (Turkey); Musil, Stanislav; Matoušek, Tomáš; Kratzer, Jan [Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno (Czech Republic); Dědina, Jiří, E-mail: dedina@biomed.cas.cz [Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno (Czech Republic)

    2015-01-01

    The on-line atomization of gold volatile species was studied and the results were compared with thermodynamic calculations in several quartz atomizers, namely: diffusion flame, flame-in-gas-shield, flame-in-plain-tube, externally heated T-tube and externally heated flame-in-T-tube. Atomization mechanism in the explored devices is proposed, where volatile species are converted to thermodynamically stable AuH at elevated temperature over 500 °C and then atomized by an interaction with a cloud of hydrogen radicals. Because of its inherent simplicity and robustness, diffusion flame was employed as a reference atomizer. It yielded atomization efficiency of 70 to 100% and a very good long time reproducibility of peak area sensitivity: 1.6 to 1.8 s μg{sup −1}. Six and eleven times higher sensitivity, respectively, was provided by atomizers with longer light paths in the observation volume, i.e. externally heated T-tube and externally heated flame-in-T-tube. The latter one, offering limit of detection below 0.01 μg ml{sup −1}, appeared as the most prospective for on-line atomization. Insight into the mechanism of atomization of gold volatile species, into the fate of free atoms and into subsequent analyte transfer allowed to assess possibilities of in-atomizer preconcentration of gold volatile species: it is unfeasible with quartz atomizers but a sapphire tube atomizer could be useful in this respect. - Highlights: • On-line atomization of gold volatile species for AAS in quartz devices was studied. • Atomization mechanism was proposed and atomization efficiency was estimated. • Possibilities of in-atomizer preconcentration of gold volatile species were assessed.

  3. The kinetics of free radical metathetical and addition reactions in silane solutions

    International Nuclear Information System (INIS)

    Aloni, R.

    1976-12-01

    In this work radiolytic technique was employed for the initiation of free radical chainreactions in silane solution. The kinetic analysis of the chain mechanism in various solutions enabled the determination of the Arrhenius parameters for metathesis, addition and unimolecular decomposition reactions which make up the chainpropagation sequence in the systems studied. The following radical reactions were investigated: chlorine atom abstraction from chloromethanes by SiCl 3 and Et 3 Si radicals, and chlorine atom abstraction from chloroethanes by Et 3 Si radicals; unimolecular decomposition reactions and hydrogen atom abstraction, *from the solvent, of chloroethyl radicals in triethylsilane solutions; addition and abstraction reactions of Et 3 Si radicals with chloroolefins. Arrhenius parameters were determined for abstraction of chlorine atom from CH 3 Cl, CH 2 Cl 2 , CHCl 3 and CCl 4 , by SiCl 3 radicals and from CCl 4 , CHCl 3 , CH 2 Cl 2 , CCl 3 CN, C 2 Cl 5 H, sym-C 2 Cl 4 H 2 , asym-C 2 Cl 4 H 2 , 1.1.1-C 2 Cl 3 H 3 , 1.1.1-C 2 Dl 3 F 3 and 1.1-C 2 Cl 2 H 4 by Et 3 Si radicals. (author)

  4. Photo- and radiation chemical studies of intermediates involved in excited-state electron-transfer reactions

    International Nuclear Information System (INIS)

    Hoffman, M.Z.

    1985-01-01

    Excited-state inter- and intramolecular electron-transfer reactions lie at the heart of the most photochemical solar energy conversion schemes. The authors research, which has utilized the techniques of continuous and pulsed photolysis and radiolysis, has focused on three general aspects of these reactions involving transition metal coordination complexes and electron donor-acceptor complexes: i) the effect of solution medium on the properties and quenching of the excited states; ii) the control of the quantum yields of formation of redox products; iii) the mechanism by which reduced species interact with water to yield H 2 homogeneously and heterogeneously. EDTA is among the most popular sacrificial electron donors used in model systems. Its role is to scavenge the oxidized form of the photosensitizer in order to prevent its rapid reaction with the reduced form of the electron relay species that results from the electron-transfer quenching of the excited photosensitizer. In systems involving MV 2+ , the radicals resulting from the oxidation of EDTA can eventually lead to the generation of a second equivalent of MV + ; the reducing agent is believed to be a radical localized on the carbon atom alpha to the carboxylate group. The reaction of radiolytically-generated OH/H with EDTA produces this radical directly via H-abstraction or indirectly via deprotonation of the carbon atom adjacent to the nitrogen radical site in the oxidized amine moiety; it reduces MV 2+ with rate constants of 2.8 x 10 9 , 7.6 x 10 9 , and 8.5 x 10 6 M -1 s -1 at pH 12.5, 8.3, and 4.7, respectively. Degradative decarboxylation of EDTA-radicals and their back electron-transfer reactions are enhanced in acidic solution causing the yield of MV + to be severely diminished

  5. Free radical hydrogen atom abstraction from saturated hydrocarbons: A crossed-molecular-beams study of the reaction Cl + C{sub 3}H{sub 8} {yields} HCl + C{sub 3}H{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Blank, D.A.; Hemmi, N.; Suits, A.G.; Lee, Y.T. [Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    The abstraction of hydrogen atoms from saturated hydrocarbons are reactions of fundamental importance in combustion as well as often being the rate limiting step in free radical substitution reactions. The authors have begun studying these reactions under single collision conditions using the crossed molecular beam technique on beamline 9.0.2.1, utilizing VUV undulator radiation to selectively ionize the scattered hydrocarbon free radical products (C{sub x}H{sub 2x+1}). The crossed molecular beam technique involves two reactant molecular beams fixed at 90{degrees}. The molecular beam sources are rotatable in the plane defined by the two beams. The scattered neutral products travel 12.0 cm where they are photoionized using the VUV undulator radiation, mass selected, and counted as a function of time. In the authors initial investigations they are using halogen atoms as protypical free radicals to abstract hydrogen atoms from small alkanes. Their first study has been looking at the reaction of Cl + propane {r_arrow} HCl + propyl radical. In their preliminary efforts the authors have measured the laboratory scattering angular distribution and time of flight spectra for the propyl radical products at collision energies of 9.6 kcal/mol and 14.9 kcal/mol.

  6. Charge transfer between hydrogen(deuterium) ions and atoms in metal vapors

    International Nuclear Information System (INIS)

    Alvarez T, I.; Cisneros G, C.

    1981-01-01

    The current state of the experiments on charge transfer between hydrogen (deuterium) ions and atoms in metal vapors are given. Emphasis is given to describing different experimental techniques. The results of calculations if available, are compared with existing experimental data. (author)

  7. 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.

  8. Stepwise O-Atom Transfer in Heme-Based Tryptophan Dioxygenase: Role of Substrate Ammonium in Epoxide Ring Opening.

    Science.gov (United States)

    Shin, Inchul; Ambler, Brett R; Wherritt, Daniel; Griffith, Wendell P; Maldonado, Amanda C; Altman, Ryan A; Liu, Aimin

    2018-03-28

    Heme-based tryptophan dioxygenases are established immunosuppressive metalloproteins with significant biomedical interest. Here, we synthesized two mechanistic probes to specifically test if the α-amino group of the substrate directly participates in a critical step of the O atom transfer during catalysis in human tryptophan 2,3-dioxygenase (TDO). Substitution of the nitrogen atom of the substrate to a carbon (probe 1) or oxygen (probe 2) slowed the catalytic step following the first O atom transfer such that transferring the second O atom becomes less likely to occur, although the dioxygenated products were observed with both probes. A monooxygenated product was also produced from probe 2 in a significant quantity. Analysis of this new product by HPLC coupled UV-vis spectroscopy, high-resolution mass spectrometry, 1 H NMR, 13 C NMR, HSQC, HMBC, and infrared (IR) spectroscopies concluded that this monooxygenated product is a furoindoline compound derived from an unstable epoxyindole intermediate. These results prove that small molecules can manipulate the stepwise O atom transfer reaction of TDO and provide a showcase for a tunable mechanism by synthetic compounds. The product analysis results corroborate the presence of a substrate-based epoxyindole intermediate during catalysis and provide the first substantial experimental evidence for the involvement of the substrate α-amino group in the epoxide ring-opening step during catalysis. This combined synthetic, biochemical, and biophysical study establishes the catalytic role of the α-amino group of the substrate during the O atom transfer reactions and thus represents a substantial advance to the mechanistic comprehension of the heme-based tryptophan dioxygenases.

  9. Coherent population transfer and superposition of atomic states via stimulated Raman adiabatic passage using an excited-doublet four-level atom

    International Nuclear Information System (INIS)

    Jin Shiqi; Gong Shangqing; Li Ruxin; Xu Zhizhan

    2004-01-01

    Coherent population transfer and superposition of atomic states via a technique of stimulated Raman adiabatic passage in an excited-doublet four-level atomic system have been analyzed. It is shown that the behavior of adiabatic passage in this system depends crucially on the detunings between the laser frequencies and the corresponding atomic transition frequencies. Particularly, if both the fields are tuned to the center of the two upper levels, the four-level system has two degenerate dark states, although one of them contains the contribution from the excited atomic states. The nonadiabatic coupling of the two degenerate dark states is intrinsic, it originates from the energy difference of the two upper levels. An arbitrary superposition of atomic states can be prepared due to such nonadiabatic coupling effect

  10. Evidence of radicals created by plasma in bacteria in water

    International Nuclear Information System (INIS)

    Lee, Chae Bok; Na, Young Ho; Hong, Tae-Eun; Choi, Eun Ha; Uhm, Han S.; Baik, Ku Youn; Kwon, Gichung

    2014-01-01

    Heavy water (D 2 O) was introduced into a non-thermal plasma-jet (NTPJ) device to generate deuterium monoxide (OD) radicals at room temperature. Owing to the similar reactivity and low prevalence of deuterium in nature, OD radicals can be utilized to visualize the OH radical interactions with water and living cells. Escherichia coli in water were treated with OD radicals, and D atom incorporation into cells was visualized using time-of-flight SIMS and Nano-SIMS. The results show that D atoms from NTPJ reach the cytoplasm of E. coli in H 2 O, indicating the usefulness of this OD-tracking method for the study of radical interactions with living cells.

  11. Electron-electron interaction and transfer ionization in fast ion-atom collisions

    International Nuclear Information System (INIS)

    Voitkiv, A B

    2008-01-01

    Recently it was pointed out that electron capture occurring in fast ion-atom collisions can proceed via a mechanism which earlier was not considered. In the present paper we study this mechanism in more detail. Similarly as in radiative capture, where the electron transfer occurs due to the interaction with the radiation field and proceeds via emission of a photon, within this mechanism the electron capture is caused by the interaction with another atomic electron leading mainly to the emission of the latter. In contrast to the electron-electron Thomas capture, this electron-electron (E-E) mechanism is basically a first-order one having similarities to the kinematic and radiative capture channels. It also possesses important differences with the latter two. Leading to transfer ionization, this first-order capture mechanism results in the electron emission mainly in the direction opposite to the motion of the projectile ion. The same, although less pronounced, feature is also characteristic for the momenta of the target recoil ions produced via this mechanism. It is also shown that the action of the E-E mechanism is clearly seen in recent experimental data on the transfer ionization in fast proton-helium collisions.

  12. Charge transfer to the continuum by heavy ions in atomic hydrogen

    International Nuclear Information System (INIS)

    Sellin, I.A.

    1981-01-01

    Design and installation of an atomic hydrogen target for measurements of charge transfer to the continuum by heavy ions are discussed. The design consists of a tungsten gas cell operated at temperatures of 2500 to 2600 0 K. Initial testing is underway

  13. Pulse radiolysis of alkanes: a time-resolved EPR study - Part I. Alkyl radicals

    International Nuclear Information System (INIS)

    Shkrob, I.A.; Trifunac, A.D.

    1995-01-01

    Time-resolved EPR was applied to detect short-lived alkyl radicals in pulse radiolysis of liquid alkanes. Two problems were addressed: (i) the mechanism of radical formation and (ii) the mechanism of chemically-induced spin polarization in these radicals. (i) The ratio of yields of penultimate and interior radicals in n-alkanes at the instant of their generation was found to be ≅ 1.25 times greater than the statistical quantity. This higher-than-statistical production of penultimate radicals indicates that the proton transfer reaction involving excited radical cations must be a prevailing route of radical generation. The relative yields of hydrogen abstraction and fragmentation for various branched alkanes are estimated. It is concluded that the fragmentation occurs prior to the formation of radicals in an excited precursor species. (ii) The analysis of spin-echo kinetics in n-alkanes suggests that the alkyl radicals gain the emissive polarization in spur reactions. This initial polarization increases with shortening of the aliphatic chain. We suggest that the origin of this polarization is the ST mechanism operating in the pairs of alkyl radicals and hydrogen atoms generated in dissociation of excited alkane molecules. It is also found that a long-chain structure of alkyl radicals results in much higher rate of Heisenberg spin exchange relative to the recombination rate (up to 30 times). That suggests prominent steric effects in recombination or the occurrence of through-chain electron exchange. The significance of these results in the context of cross-linking in polyethylene and higher paraffins is discussed. (Author)

  14. Surface polyPEGylation of Eu"3"+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-01-01

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu"3"+ 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, Eu"3"+ 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

  15. DFT and time-resolved IR investigation of electron transfer between photogenerated 17- and 19-electron organometallic radicals

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James B.; Kling, Matthias F.; Sawyer, Karma R.; Andersen, Lars K.; Harris, Charles B.

    2008-04-30

    The photochemical disproportionation mechanism of [CpW(CO){sub 3}]{sub 2} in the presence of Lewis bases PR{sub 3} was investigated on the nano- and microsecond time-scales with Step-Scan FTIR time-resolved infrared spectroscopy. 532 nm laser excitation was used to homolytically cleave the W-W bond, forming the 17-electron radicals CpW(CO){sub 3} and initiating the reaction. With the Lewis base PPh{sub 3}, disproportionation to form the ionic products CpW(CO){sub 3}PPh{sub 3}{sup +} and CpW(CO){sub 3}{sup -} was directly monitored on the microsecond time-scale. Detailed examination of the kinetics and concentration dependence of this reaction indicates that disproportionation proceeds by electron transfer from the 19-electron species CpW(CO){sub 3}PPh{sub 3} to the 17-electron species CpW(CO){sub 3}. This result is contrary to the currently accepted disproportionation mechanism which predicts electron transfer from the 19-electron species to the dimer [CpW(CO){sub 3}]{sub 2}. With the Lewis base P(OMe){sub 3} on the other hand, ligand substitution to form the product [CpW(CO){sub 2}P(OMe){sub 3}]{sub 2} is the primary reaction on the microsecond time-scale. Density Functional Theory (DFT) calculations support the experimental results and suggest that the differences in the reactivity between P(OMe){sub 3} and PPh{sub 3} are due to steric effects. The results indicate that radical-to-radical electron transfer is a previously unknown but important process for the formation of ionic products with the organometallic dimer [CpW(CO){sub 3}]{sub 2} and may also be applicable to the entire class of organometallic dimers containing a single metal-metal bond.

  16. Transfer matrix treatment of atomic chemisorption on transition metal surface

    International Nuclear Information System (INIS)

    Mariz, A.M.; Koiller, B.

    1980-05-01

    The atomic adsorption of hydrogen on paramagnetic nickel 100 surface is studied, using the Green's function formalism and the transfer matrix technique, which allows the treatment of the geometry of the system in a simple manner. Electronic correlation at the adatom orbital in a self consistent Hartree-Fock approach is incorporated. The adsorption energy, local density of states and charge transfer between the solid and the adatom are calculated for different crystal structures (sc and fcc) and adatom positions at the surface. The results are discussed in comparison with other theories and with available experimental data, with satisfactory agreement. (Author) [pt

  17. Isotopic effects in the muon transfer from pmu and dmu to heavier atoms.

    Science.gov (United States)

    Dupays, Arnaud

    2004-07-23

    The results of accurate hyperspherical calculations of the muon-transfer rates from muonic protium and deuterium atoms to nitrogen, oxygen, and neon are reported. Very good agreement with measured rates is obtained and, for the three systems, the isotopic effect is perfectly reproduced. The transfer rate is higher for deuterium in the cases of nitrogen and neon due to constructive interferences between two transfer paths. The lower transfer rate for deuterium in the case of oxygen results from a large resonant contribution. Copyright 2004 The American Physical Society

  18. Can Carbamates Undergo Radical Oxidation in the Soil Environment? A Case Study on Carbaryl and Carbofuran.

    Science.gov (United States)

    Ćwieląg-Piasecka, Irmina; Witwicki, Maciej; Jerzykiewicz, Maria; Jezierska, Julia

    2017-12-19

    Radical oxidation of carbamate insecticides, namely carbaryl and carbofuran, was investigated with spectroscopic (electron paramagnetic resonance [EPR] and UV-vis) and theoretical (density functional theory [DFT] and ab initio orbital-optimized spin-component scaled MP2 [OO-SCS-MP2]) methods. The two carbamates were subjected to reaction with • OH, persistent DPPH • and galvinoxyl radical, as well as indigenous radicals of humic acids. The influence of fulvic acids on carbamate oxidation was also tested. The results obtained with EPR and UV-vis spectroscopy indicate that carbamates can undergo direct reactions with various radical species, oxidizing themselves into radicals in the process. Hence, they are prone to participate in the prolongation step of the radical chain reactions occurring in the soil environment. Theoretical calculations revealed that from the thermodynamic point of view hydrogen atom transfer is the preferred mechanism in the reactions of the two carbamates with the radicals. The activity of carbofuran was determined experimentally (using pseudo-first-order kinetics) and theoretically to be noticeably higher in comparison with carbaryl and comparable with gallic acid. The findings of this study suggest that the radicals present in soil can play an important role in natural remediation mechanisms of carbamates.

  19. Tin-free enantioselective radical reactions using silanes.

    Science.gov (United States)

    Sibi, Mukund P; Yang, Yong-Hua; Lee, Sunggi

    2008-12-04

    Readily available hexyl silane is an excellent choice as a H-atom donor and a chain carrier in Lewis acid mediated enantioselective radical reactions. Conjugate radical additions to alpha,beta-unsaturated imides at room temperature proceed in good yields and excellent enantioselectivities.

  20. One-electron transfer equilibria and redox potentials of radicals studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Meisel, D.; Czapski, G.

    1975-01-01

    The pulse radiolysis technique is utilized for measurements of the equilibrium constants for electron transfer between the durosemiquinone radical anion and oxygen, menadione, and indigodisulfonate. These equilibrium constants are in turn used for calculations of one-electron redox potentials for these systems. Each of these equilibrium constants was determined experimentally and independently and found to be self-consistent. Only for the reactions of the semiquinone radical ions with oxygen could the electron transfer reaction be followed directly. For the reactions between the various quinone-semiquinone systems substantial indirect evidence is presented that these equilibria are achieved rapidly. In those cases equilibrium constants were determined from studies of the effect of quinone concentrations on the relative yields of the semiquinones. A method for distinguishing between kinetic competition and equilibrium is outlined and its usefulness is emphasized. The DQ parallel DQ - (DQ = duroquinone) and IDS parallel IDS - (IDS = indigodisulfonate) systems were employed as reference couples as the redox potentials for those systems are either available in the literature (IDS parallel IDS - ) or may be calculated from available data (DQ parallel DQ - ). Taking E 7 1 , the redox potential for the first one-electron reduction step at pH 7, of DQ parallel DQ - as -0.235 V or of IDS parallelIDS - as -0.247 V both yield E 7 1 = -0.325 V for the O 2 parallel O 2 - system (1 atm of O 2 ) and E 2 1 = -0.20 V for the menadione system. (U.S.)

  1. Possible Involvement of Hydrosulfide in B12-Dependent Methyl Group Transfer

    Directory of Open Access Journals (Sweden)

    John I. Toohey

    2017-04-01

    Full Text Available Evidence from several fields of investigation lead to the hypothesis that the sulfur atom is involved in vitamin B12-dependent methyl group transfer. To compile the evidence, it is necessary to briefly review the following fields: methylation, the new field of sulfane sulfur/hydrogen sulfide (S°/H2S, hydrosulfide derivatives of cobalamins, autoxidation of hydrosulfide radical, radical S-adenosylmethionine methyl transfer (RSMT, and methionine synthase (MS. Then, new reaction mechanisms for B12-dependent methyl group transfer are proposed; the mechanisms are facile and overcome difficulties that existed in previously-accepted mechanisms. Finally, the theory is applied to the effect of S°/H2S in nerve tissue involving the “hypomethylation theory” that was proposed 50 years ago to explain the neuropathology resulting from deficiency of vitamin B12 or folic acid. The conclusions are consistent with emerging evidence that sulfane sulfur/hydrogen sulfide may be beneficial in treating Alzheimer’s disease.

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

    Indian Academy of Sciences (India)

    2014-02-08

    Feb 8, 2014 ... Laser Physics Applications Section, Raja Ramanna Centre for Advanced Technology,. Indore 452 013 ... Laser cooling; optical molasses; double-MOT; magnetic trapping; phase-space density. PACS Nos 52.55. ... this method, the transfer of laser-cooled atom cloud to magnetic trap is an important step,.

  3. Intracellular ROS protection efficiency and free radical-scavenging activity of curcumin.

    Directory of Open Access Journals (Sweden)

    Abolfazl Barzegar

    Full Text Available Curcumin has many pharmaceutical applications, many of which arise from its potent antioxidant properties. The present research examined the antioxidant activities of curcumin in polar solvents by a comparative study using ESR, reduction of ferric iron in aqueous medium and intracellular ROS/toxicity assays. ESR data indicated that the steric hindrance among adjacent big size groups within a galvinoxyl molecule limited the curcumin to scavenge galvinoxyl radicals effectively, while curcumin showed a powerful capacity for scavenging intracellular smaller oxidative molecules such as H₂O₂, HO•, ROO•. Cell viability and ROS assays demonstrated that curcumin was able to penetrate into the polar medium inside the cells and to protect them against the highly toxic and lethal effects of cumene hydroperoxide. Curcumin also showed good electron-transfer capability, with greater activity than trolox in aqueous solution. Curcumin can readily transfer electron or easily donate H-atom from two phenolic sites to scavenge free radicals. The excellent electron transfer capability of curcumin is because of its unique structure and different functional groups, including a β-diketone and several π electrons that have the capacity to conjugate between two phenyl rings. Therfore, since curcumin is inherently a lipophilic compound, because of its superb intracellular ROS scavenging activity, it can be used as an effective antioxidant for ROS protection within the polar cytoplasm.

  4. One electron transfer redox potentials of free radicals. I. The oxygen-superoxide system. Progress report, September 1, 1975--July 1, 1976

    International Nuclear Information System (INIS)

    Ilan, Y.A.; Czapski, G.; Meisel, D.

    1976-01-01

    The method of determination of Redox potentials of radicals, using the pulse radiolysis technique, is outlined. The method is based on the determination of equilibria constants of electron transfer reactions between the radicals and appropriate acceptors. The limitations of this technique are discussed. The redox potentials of several quinones--semi-quinones are calculated, as well as the standard redox potential of the peroxy radical. E 0 /sub O 2 /O 2 /sup -/ = -0.33 V and the redox oxidation properties of the peroxy radical in various systems and pH are discussed. The value determined for the redox potentials of O 2 /O 2 - is higher by more than 0.2 volts than earlier estimates, which has important implications on the possible role of O 2 - in biological processes of O 2 fixation

  5. Photolysis of CH3CHO at 248 nm: Evidence of triple fragmentation from primary quantum yield of CH3 and HCO radicals and H atoms

    Science.gov (United States)

    Morajkar, Pranay; Bossolasco, Adriana; Schoemaecker, Coralie; Fittschen, Christa

    2014-06-01

    Radical quantum yields have been measured following the 248 nm photolysis of acetaldehyde, CH3CHO. HCO radical and H atom yields have been quantified by time resolved continuous wave Cavity Ring Down Spectroscopy in the near infrared following their conversion to HO2 radicals by reaction with O2. The CH3 radical yield has been determined using the same technique following their conversion into CH3O2. Absolute yields have been deduced for HCO radicals and H atoms through fitting of time resolved HO2 profiles, obtained under various O2 concentrations, to a complex model, while the CH3 yield has been determined relative to the CH3 yield from 248 nm photolysis of CH3I. Time resolved HO2 profiles under very low O2 concentrations suggest that another unknown HO2 forming reaction path exists in this reaction system besides the conversion of HCO radicals and H atoms by reaction with O2. HO2 profiles can be well reproduced under a large range of experimental conditions with the following quantum yields: CH3CHO + hν248nm → CH3CHO*, CH3CHO* → CH3 + HCO ϕ1a = 0.125 ± 0.03, CH3CHO* → CH3 + H + CO ϕ1e = 0.205 ± 0.04, CH3CHO*{to 2pc{rArrfill}}limits^{o2}CH3CO + HO2 ϕ1f = 0.07 ± 0.01. The CH3O2 quantum yield has been determined in separate experiments as φ_{CH3} = 0.33 ± 0.03 and is in excellent agreement with the CH3 yields derived from the HO2 measurements considering that the triple fragmentation (R1e) is an important reaction path in the 248 nm photolysis of CH3CHO. From arithmetic considerations taking into account the HO2 and CH3 measurements we deduce a remaining quantum yield for the molecular pathway: CH3CHO* → CH4 + CO ϕ1b = 0.6. All experiments can be consistently explained with absence of the formerly considered pathway: CH3CHO* → CH3CO + H ϕ1c = 0.

  6. Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.

    Science.gov (United States)

    Choi, Gilbert J; Zhu, Qilei; Miller, David C; Gu, Carol J; Knowles, Robert R

    2016-11-10

    Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

  7. Eosin Y as a Direct Hydrogen Atom Transfer Photocatalyst for the Functionalization of C-H Bonds.

    Science.gov (United States)

    Fan, Xuan-Zi; Rong, Jia-Wei; Wu, Hao-Lin; Zhou, Quan; Deng, Hong-Ping; Tan, Jin Da; Xue, Cheng-Wen; Wu, Li-Zhu; Tao, Hai-Rong; Wu, Jie

    2018-05-02

    Eosin Y, a well-known economical alternative to metal catalysts in visible-light-driven single-electron transfer-based organic transformations, can behave as an effective direct hydrogen atom transfer catalyst for C-H activation. Using the alkylation of C-H bonds with electron-deficient alkenes as a model study revealed an extremely broad substrate scope, enabling easy access to a variety of important synthons. This eosin Y-based photocatalytic hydrogen atom transfer strategy is promising for diverse functionalization of a wide range of native C-H bonds in a green and sustainable manner. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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.

  9. Conditional Monte Carlo sampling to find branching architectures of polymers from radical polymerizations with transfer to polymer and recombination termination

    NARCIS (Netherlands)

    Iedema, P.D.; Wulkow, M.; Hoefsloot, H.C.J.

    2007-01-01

    A model is developed that predicts branching architectures of polymers from radical polymerization with transfer to polymer and termination by disproportionation and recombination, in a continuously stirred tank reactor (CSTR). It is a so-called conditional Monte Carlo (MC) method generating

  10. Surface polyPEGylation of Eu{sup 3+} doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Heng, Chunning [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Huang, Qiang; Mao, Liucheng; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Hui, Junfeng [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (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)

    2017-03-31

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu{sup 3+} 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, Eu{sup 3+} 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

  11. 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.

  12. Quantum Chemical Investigation on the Antioxidant Activity of Neutral and Anionic Forms of Juglone: Metal Chelation and Its Effect on Radical Scavenging Activity

    Directory of Open Access Journals (Sweden)

    Aymard Didier Fouegue Tamafo

    2017-01-01

    Full Text Available The chelation ability of divalent Mg, Ca, Fe, Co, Ni, Cu, Zn, and monovalent Cu ions by neutral and anionic forms of juglone has been investigated at DFT/B3LYP/6-31+G(d,p level of theory in gas and aqueous phases. It is noteworthy that only the 1 : 1 stoichiometry was considered herein. The effects of these metals on the radical scavenging activity of neutral juglone were evaluated via the usual descriptors of hydrogen atom transfer. According to our results, metal chelation by the two forms of juglone was spontaneous and exothermic in both media. Based on the binding energies, Cu(II ion showed the highest affinity for the ligands. QTAIM analyses identified the metal-ligand bonds as intermediate type interactions in all the chelates, except those of Ca and Mg. It was also found that the chelates were better radical scavengers than the ligands. In the gas phase, the scavenging activity of the compounds was found to be governed by direct hydrogen atom transfer, the Co(II chelate being the most reactive. In the aqueous phase also, the sequential proton loss electron transfer was preferred by all the molecules, while the Cu(II chelates were the most reactive.

  13. Fluorescence quenching of derivatives of anthracene by organic electron donors and acceptors in acetonitrile. Electron and proton transfer mechanism

    Science.gov (United States)

    Mac, Marek; Najbar, Jan; Wirz, Jakob

    1995-03-01

    Fluorescence quenching of anthracene derivatives by organic electron donors (amines) and acceptors was investigated using stationary fluorescence measurements. The dependence of log( kq) on Δ Get shows Rehm-Weller-type behavior. The formation of anion radicals of anthracene, bianthryl, and 9-cyanoanthracene was detected by flash photolysis in systems containing aromatic amines (aniline, 2-bromoaniline, 4-bromoaniline, N,N-dimethylaniline, 4-bromo-N,N-dimethylaniline, N,N-diethylaniline, and 1,4-diazabicyclo[2.2.2]octane). The radical yields decreased and triplet yields increased when bromo derivatives of amines were used as donor quenchers, indicating the heavy-atom effect on spin conversion within radical pairs. The importance of the heavy-atom effect decreased when the energy gap between the charge transfer and molecular triplet states was small. The formation of separated radicals decreased when primary amines were used as quenchers which indicated the existence of an additional path of deactivation of the radical pair. The behavior of amines as quenchers of bianthryl and anthracene is compared with that of inorganic anion quenchers.

  14. Aminoxyl (nitroxyl) radicals in the early decomposition of the nitramine RDX.

    Science.gov (United States)

    Irikura, Karl K

    2013-03-14

    The explosive nitramine RDX (1,3,5-trinitrohexahydro-s-triazine) is thought to decompose largely by homolytic N-N bond cleavage, among other possible initiation reactions. Density-functional theory (DFT) calculations indicate that the resulting secondary aminyl (R2N·) radical can abstract an oxygen atom from NO2 or from a neighboring nitramine molecule, producing an aminoxyl (R2NO·) radical. Persistent aminoxyl radicals have been detected in electron-spin resonance (ESR) experiments and are consistent with autocatalytic "red oils" reported in the experimental literature. When the O-atom donor is a nitramine, a nitrosamine is formed along with the aminoxyl radical. Reactions of aminoxyl radicals can lead readily to the "oxy-s-triazine" product (as the s-triazine N-oxide) observed mass-spectrometrically by Behrens and co-workers. In addition to forming aminoxyl radicals, the initial aminyl radical can catalyze loss of HONO from RDX.

  15. Reaction between protein radicals and other biomolecules

    DEFF Research Database (Denmark)

    Østdal, H.; Davies, M.J.; Andersen, Henrik Jørgen

    2002-01-01

    The present study investigates the reactivity of bovine serum albumin (BSA) radicals towards different biomolecules (urate, linoleic acid, and a polypeptide, poly(Glu-Ala-Tyr)). The BSA radical was formed at room temperature through a direct protein-to-protein radical transfer from H(2)O(2....... Subsequent analysis showed a decrease in the concentration of urate upon reaction with the BSA radical, while the BSA radical in the presence of poly(Glu-Ala-Tyr) resulted in increased formation of the characteristic protein oxidation product, dityrosine. Reaction between the BSA radical and a linoleic acid...

  16. Hot wire radicals and reactions

    International Nuclear Information System (INIS)

    Zheng Wengang; Gallagher, Alan

    2006-01-01

    Threshold ionization mass spectroscopy is used to measure radical (and stable gas) densities at the substrate of a tungsten hot wire (HW) reactor. We report measurements of the silane reaction probability on the HW and the probability of Si and H release from the HW. We describe a model for the atomic H release, based on the H 2 dissociation model. We note major variations in silicon-release, with dependence on prior silane exposure. Measured radical densities versus silane pressure yield silicon-silane and H-silane reaction rate coefficients, and the dominant radical fluxes to the substrate

  17. Photodynamically generated bovine serum albumin radicals

    DEFF Research Database (Denmark)

    Silvester, J A; Timmins, G S; Davies, Michael Jonathan

    1998-01-01

    Porphyrin-sensitized photoxidation of bovine serum albumin (BSA) results in oxidation of the protein at (at least) two different, specific sites: the Cys-34 residue giving rise to a thiyl radical (RS.); and one or both of the tryptophan residues (Trp-134 and Trp-214) resulting in the formation...... of tertiary carbon-centred radicals and disruption of the tryptophan ring system. In the case of porphyrins such as hematoporphyrin, which bind at specific sites on BSA, these species appear to arise via long-range transfer of damage within the protein structure, as the binding site is some distance from...... the ultimate site of radical formation. This transfer of damage is shown to depend on a number of factors including the conformation of the protein, the presence of blocking groups and pH. Alteration of the protein conformation results in radical formation at additional (or alternative) sites, as does blocking...

  18. Experimental evidence of state-selective charge transfer in inductively coupled plasma-atomic emission spectrometry

    International Nuclear Information System (INIS)

    Chan, George C.-Y.; Hieftje, Gary M.

    2004-01-01

    State-selective charge-transfer behavior was observed for Fe, Cr, Mn and Cu in inductively coupled plasma (ICP)-atomic emission spectrometry. Charge transfer from Ar + to Fe, Cr and Mn is state-selective because of inefficient collisional mixing of the quasiresonant charge-transfer energy levels with nearby levels. This low efficiency is the consequence of differences in electronic configuration of the core electrons. The reason for state-selective charge-transfer behavior to Cu is not clear, although a tentative explanation based on efficiency of intramultiplet and intermultiplet mixing for this special case is offered

  19. Surface PEGylation of mesoporous silica materials via surface-initiated chain transfer free radical polymerization: Characterization and controlled drug release.

    Science.gov (United States)

    Huang, Long; Liu, Meiying; Mao, Liucheng; Huang, Qiang; Huang, Hongye; Wan, Qing; Tian, Jianwen; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

    2017-12-01

    As a new type of mesoporous silica materials with large pore diameter (pore size between 2 and 50nm) and high specific surface areas, SBA-15 has been widely explored for different applications especially in the biomedical fields. The surface modification of SBA-15 with functional polymers has demonstrated to be an effective way for improving its properties and performance. In this work, we reported the preparation of PEGylated SBA-15 polymer composites through surface-initiated chain transfer free radical polymerization for the first time. The thiol group was first introduced on SBA-15 via co-condensation with γ-mercaptopropyltrimethoxysilane (MPTS), that were utilized to initiate the chain transfer free radical polymerization using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and itaconic acid (IA) as the monomers. The successful modification of SBA-15 with poly(PEGMA-co-IA) copolymers was evidenced by a series of characterization techniques, including 1 H NMR, FT-IR, TGA and XPS. The final SBA-15-SH- poly(PEGMA-co-IA) composites display well water dispersity and high loading capability towards cisplatin (CDDP) owing to the introduction of hydrophilic PEGMA and carboxyl groups. Furthermore, the CDDP could be released from SBA-15-SH-poly(PEGMA-co-IA)-CDDP complexes in a pH dependent behavior, suggesting the potential controlled drug delivery of SBA-15-SH-poly(PEGMA-co-IA). More importantly, the strategy should be also useful for fabrication of many other functional materials for biomedical applications owing to the advantages of SBA-15 and well monomer adoptability of chain transfer free radical polymerization. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Kinetics of the reaction of F atoms with O2 and UV spectrum of FO2 radicals in the gas phase at 295 K

    DEFF Research Database (Denmark)

    Ellermann, T.; Sehested, J.; Nielsen, O.J.

    1994-01-01

    The ultraviolet absorption spectrum of FO2 radicals and the kinetics of the reaction of F atoms with O2 have been studied in the gas phase at 295 K using pulse radiolysis combined with kinetic UV spectroscopy. At 230 nm, sigma(FO2) = (5.08 +/- 0.70) X 10(-18) cm2 molecule-1. The kinetics of the r......The ultraviolet absorption spectrum of FO2 radicals and the kinetics of the reaction of F atoms with O2 have been studied in the gas phase at 295 K using pulse radiolysis combined with kinetic UV spectroscopy. At 230 nm, sigma(FO2) = (5.08 +/- 0.70) X 10(-18) cm2 molecule-1. The kinetics...

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

    Indian Academy of Sciences (India)

    2014-02-08

    Feb 8, 2014 ... 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.

  2. Radical species involved in hotwire (catalytic) deposition of hydrogenated amorphous silicon

    International Nuclear Information System (INIS)

    Zheng Wengang; Gallagher, Alan

    2008-01-01

    Threshold ionization mass spectroscopy is used to measure the radicals that cause deposition of hydrogenated amorphous silicon by 'hotwire' (HW), or 'catalytic,' chemical vapor deposition. We provide the probability of silane (SiH 4 ) decomposition on the HW, and of Si and H release from the HW. The depositing radicals, and H atoms, are measured versus conditions to obtain their radical-silane reaction rates and contributions to film growth. A 0.01-3 Pa range of silane pressures and 1400-2400 K range of HW temperatures were studied, encompassing optimum device production conditions. Si 2 H 2 is the primary depositing radical under optimum conditions, accompanied by a few percent of Si atoms and a lot of H-atom reactions. Negligible SiH n radical production is observed and only a small flux of disilane is produced, but at the higher pressures some Si 3 H n is observed. A Si-SiH 4 reaction rate coefficient of 1.65 * 10 -11 cm 3 /s and a H + SiH 4 reaction rate coefficient of 5 * 10 -14 cm 3 /s are measured

  3. The fate of H atom adducts to 3'-uridine monophosphate.

    Science.gov (United States)

    Wang, Ran; Zhang, Ru Bo; Eriksson, Leif A

    2010-07-29

    The stabilities of the adducts deriving from H free radical addition to the O2, O4, and C5 positions of 3'-uridine monophosphate (3'UMP) are studied by the hybrid density functional B3LYP approach. Upon H atom addition at the O2 position, a concerted low-barrier proton-transfer process will initially occur, followed by the potential ruptures of the N-glycosidic or beta-phosphate bonds. The rupture barriers are strongly influenced by the rotational configuration of the phosphate group at the 3' terminal, and are influenced by bulk solvation effects. The O4-H adduct has the highest thermal stability, as the localization of the unpaired electron does not enable cleavage of either the C1'-N1 or the C3'-O(P) bonds. For the most stable adduct, with H atom added to the C5 position, the rate-controlled step is the H2'a abstraction by the C6 radical site, after which the subsequent strand rupture reactions proceed with low barriers. The main unpaired electron densities are presented for the transient species. Combined with previous results, it is concluded that the H atom adducts are more facile to drive the strand scission rather than N-glycosidic bond ruptures within the nucleic acid bases.

  4. Atomic reactor thermal engineering

    International Nuclear Information System (INIS)

    Kim, Gwang Ryong

    1983-02-01

    This book starts the introduction of atomic reactor thermal engineering including atomic reaction, chemical reaction, nuclear reaction neutron energy and soon. It explains heat transfer, heat production in the atomic reactor, heat transfer of fuel element in atomic reactor, heat transfer and flow of cooler, thermal design of atomic reactor, design of thermodynamics of atomic reactor and various. This deals with the basic knowledge of thermal engineering for atomic reactor.

  5. Repair Activity of trans-Resveratrol toward 2'-Deoxyguanosine Radicals.

    Science.gov (United States)

    Cheng, Xing; An, Ping; Li, Shujin; Zhou, Liping

    2018-04-26

    In the present study, the repair activity of trans-resveratrol toward 2'-deoxyguanosine (dGuo) radicals in polar and nonpolar solvents was studied using density functional theory. The hydrogen transfer/proton coupled electron transfer and single electron transfer (SET) mechanisms between trans-resveratrol and dGuo-radicals were considered. Taking into consideration the molar fraction of neutral trans-resveratrol (ROH) and anionic trans-resveratrol (RO - ), the overall rate constants for repairing dGuo-radicals by trans-resveratrol are 9.94 × 10 8 and 2.01 × 10 9 dm 3 mol -1 s -1 in polar and nonpolar solvents, respectively, and the overall rate constant of repairing cation radical (dGuo •+ ) by trans-resveratrol via an SET mechanism is 7.17 × 10 9 dm 3 mol -1 s -1 . The repair activity of RO - toward dGuo-radicals is better than that of ROH, but the repair activity of ROH toward dGuo •+ is better than that of RO - . Unfortunately, neither ROH nor RO - can repair the 2'-deoxyribose radicals of dGuo. It can therefore be concluded that trans-resveratrol is an effective antioxidant for repairing base radicals of dGuo and dGuo •+ . The study can help us understand the repair activity of trans-resveratrol toward dGuo radicals.

  6. Ultraviolet photodissociation dynamics of the benzyl radical.

    Science.gov (United States)

    Song, Yu; Zheng, Xianfeng; Lucas, Michael; Zhang, Jingsong

    2011-05-14

    Ultraviolet (UV) photodissociation dynamics of jet-cooled benzyl radical via the 4(2)B(2) electronically excited state is studied in the photolysis wavelength region of 228 to 270 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance enhanced multiphoton ionization (REMPI) techniques. In this wavelength region, H-atom photofragment yield (PFY) spectra are obtained using ethylbenzene and benzyl chloride as the precursors of benzyl radical, and they have a broad peak centered around 254 nm and are in a good agreement with the previous UV absorption spectra of benzyl. The H + C(7)H(6) product translational energy distributions, P(E(T))s, are derived from the H-atom TOF spectra. The P(E(T)) distributions peak near 5.5 kcal mol(-1), and the fraction of average translational energy in the total excess energy, , is ∼0.3. The P(E(T))s indicate the production of fulvenallene + H, which was suggested by recent theoretical studies. The H-atom product angular distribution is isotropic, with the anisotropy parameter β ≈ 0. The H/D product ratios from isotope labeling studies using C(6)H(5)CD(2) and C(6)D(5)CH(2) are reasonably close to the statistical H/D ratios, suggesting that the H/D atoms are scrambled in the photodissociation of benzyl. The dissociation mechanism is consistent with internal conversion of the electronically excited benzyl followed by unimolecular decomposition of the hot benzyl radical on the ground state.

  7. Thermal evolution of the morphology of Ni/Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface

    Energy Technology Data Exchange (ETDEWEB)

    Tomaszewska, Agnieszka; Huang, Xiao-Lan; Chang, Kuo-Wei; Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw

    2012-08-31

    The temperature-driven changes in morphology of the interface formed by room temperature (RT) deposition of Ni atoms onto an Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface were investigated by scanning tunneling microscopy. Roughly 70% of Ni deposition diffused into bulk substrate within the temperature range between RT and 573 K. The images as obtained after annealing up to 670 K correspond to the formation of nano-sized islands of nickel silicides. Two types of islands, large triangular islands typical of the whole range of applied coverage, and smaller islands of different shapes, coexist at Ni coverage higher than 1 monolayer. Annealing above 870 K led to the formation of a 7 Multiplication-Sign 7 phase in coexistence with small 5 Multiplication-Sign 5 domains at the expense of a complete disappearance of the {radical}3 Multiplication-Sign {radical}3 phase. Also, formation of Ni,Si alloy was observed at the temperature, along with segregation of bulk-dissolved Ni species onto the surface. - Highlights: Black-Right-Pointing-Pointer We examine changes in morphology of Ni/Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface upon annealing. Black-Right-Pointing-Pointer 70% of deposited Ni atoms diffuse into the bulk after annealing at 570 K. Black-Right-Pointing-Pointer A variety of nano-sized Ni, Si islands develops after annealing at 670 K. Black-Right-Pointing-Pointer 5 Multiplication-Sign 5 reconstruction as an evidence for mass transport during the island growth.

  8. Facile Synthesis of Well-Defined MDMO-PPV Containing (TriBlock—Copolymers via Controlled Radical Polymerization and CuAAC Conjugation

    Directory of Open Access Journals (Sweden)

    Neomy Zaquen

    2015-02-01

    Full Text Available A systematic investigation into the chain transfer polymerization of the so-called radical precursor polymerization of poly(p-phenylene vinylene (PPV materials is presented. Polymerizations are characterized by systematic variation of chain transfer agent (CTA concentration and reaction temperature. For the chain transfer constant, a negative activation energy of −12.8 kJ·mol−1 was deduced. Good control over molecular weight is achieved for both the sulfinyl and the dithiocarbamate route (DTC. PPVs with molecular weights ranging from thousands to ten thousands g·mol−1 were obtained. To allow for a meaningful analysis of the CTA influence, Mark–Houwink–Kuhn–Sakurada (MHKS parameters were determined for conjugated MDMO-PPV ([2-methoxy-5-(3',7'-dimethyloctyloxy]-1,4-phenylenevinylene to α = 0.809 and k = 0.00002 mL·g−1. Further, high-endgroup fidelity of the CBr4-derived PPVs was proven via chain extension experiments. MDMO-PPV-Br was successfully used as macroinitiator in atom transfer radical polymerization (ATRP with acrylates and styrene. A more polar PPV counterpart was chain extended by an acrylate in single-electron transfer living radical polymerization (SET-LRP. In a last step, copper-catalyzed azide alkyne cycloaddition (CuAAC was used to synthesize block copolymer structures. Direct azidation followed by macromolecular conjugation showed only partial success, while the successive chain extension via ATRP followed by CuAAC afforded triblock copolymers of the poly(p-phenylene vinylene-block-poly(tert-butyl acrylate-block-poly(ethylene glycol (PPV-b-PtBuA-b-PEG.

  9. Rate Constant of the Reaction between CH3O2 Radicals and OH Radicals Revisited.

    Science.gov (United States)

    Assaf, Emmanuel; Song, Bo; Tomas, Alexandre; Schoemaecker, Coralie; Fittschen, Christa

    2016-11-17

    The reaction between CH 3 O 2 and OH radicals has been studied in a laser photolysis cell using the reaction of F atoms with CH 4 and H 2 O for the simultaneous generation of both radicals, with F atoms generated through 248 nm photolysis of XeF 2 . An experimental setup combining cw-Cavity Ring Down Spectroscopy (cw-CRDS) and high repetition rate laser-induced fluorescence (LIF) to a laser photolysis cell has been used. The absolute concentration of CH 3 O 2 was measured by cw-CRDS, while the relative concentration of OH(v = 0) radicals was determined by LIF. To remove dubiety from the quantification of CH 3 O 2 by cw-CRDS in the near-infrared, its absorption cross section has been determined at 7489.16 cm -1 using two different methods. A rate constant of k 1 = (1.60 ± 0.4) × 10 -10 cm 3 s -1 has been determined at 295 K, nearly a factor of 2 lower than an earlier determination from our group ((2.8 ± 1.4) × 10 -10 cm 3 s -1 ) using CH 3 I photolysis as a precursor. Quenching of electronically excited I atoms (from CH 3 I photolysis) in collision with OH(v = 0) is suspected to be responsible for a bias in the earlier, fast rate constant.

  10. Quantum state population transfer of lithium atoms induced by frequency-chirped laser pulses

    International Nuclear Information System (INIS)

    Ma Huanqiang; Zhang Xianzhou; Jia Guangrui; Zhang Yonghui; Jiang Lijuan

    2011-01-01

    Using the time-dependent multilevel approach (TDMA) and B-splines function, we have calculated the five quantum state population transfer of rydberg lithium atoms. We also analyse the influence of the four major parameters of the frequency-chirped laser pulses field on transition. The result shows that the population can be completely transferred to the target state by changing the parameters of the laser pulse and achieve manual controls to a certain degree. (authors)

  11. Radiation-electrochemistry of the colloidal gold micro-electrode: Hydrogen formation by organic free radicals

    International Nuclear Information System (INIS)

    Westerhausen, J.; Henglein, A.; Lilie, J.

    1981-01-01

    Various organic free radicals as well as Ni + ions produce hydrogen in the presence of some 10 -4 M of colloidal gold. The gold catalyst was prepared via the reduction of HAuCl 4 either thermally by citrate or by γ-irradiation. The organic radicals were radiolytically produced. The mechanism of H 2 formation includes electron transfer from the organic radicals to the gold particles, storage of a large number of electrons per gold particle, conversion of the electrons into adsorbed H-atoms and desorption of the latter to form H 2 . - The rates of some of these steps were measured using the method of pulse radiolysis. 1-Hydroxy-1-methyl ethyl radicals, (CH 3 ) 2 COH, react with colloidal gold particles almost diffusion controlled provided that the gold particles are not charged with excess electrons. Charged gold particles react at a substantially lower rate. The stored electrons live seconds or even minutes depending on their number per gold particle. In the stationary state, up to 0.38 Coulomb of electrons could be stored per liter of a 2.9x10 -4 molar gold solution, each gold particle carrying about 39 electrons. A comparison is also made between the catalytic activities of colloidal gold and silver. Due to the relative fast conversion of electrons into adsorbed H-atoms, colloidal gold has less capacity for the storage of electrons than colloidal silver. - The dependence of the hydrogen yield on the pH of the solution, the concentration of gold, the size of the gold particles, the concentration of the polyvinyl alcohol stabilizer, and the intensity of radiation was also investigated. At high intensities, some of the radicals are destroyed in a gold catalysed disproportionation. (orig.)

  12. Chemical repair of trypsin-histidinyl radical

    International Nuclear Information System (INIS)

    Jovanovic, S.V.; Ruvarac, I.; Jankovic, I.; Josimovic, L.

    1991-01-01

    Oxyl radicals, such as hydroxyl, alkoxyl and peroxyl, react with biomolecules to produce bioradicals. Unless chemically repaired by suitable antioxidants, these bioradicals form stable products. This leads to loss of biological function of parent biomolecules with deleterious biological results, such as mutagenesis and cancer. Consequently, the understanding of the mechanisms of oxyl radical damage to biomolecules and chemical repair of such damage is crucial for the development of strategies for anticarcinogenesis and radioprotection. In this study the chemical repair of the histidinyl radical generated upon the trichloromethylperoxyl radical reaction with trypsin vas investigated by gamma radiolysis. The trypsin histidinyl radical is a resonance-stabilized heterocyclic free radical which was found to be unreactive with oxygen. The efficacy of the chemical repair of the trypsin-histidinyl radical by endogenous antioxidants which are electron donors (e.g. 5-hydroxytryptophan, uric acid) is compared to that of antioxidants which are H-atom donors (e. g. glutathione). 9 refs., 2 figs., 1 tab

  13. Ion-atom charge-transfer system for a heavy-ion-beam pumped laser

    International Nuclear Information System (INIS)

    Ulrich, A.; Gernhaeuser, R.; Kroetz, W.; Wieser, J.; Murnick, D.E.

    1994-01-01

    An Ar target to which Cs vapor could be added, excited by a pulsed beam of 100-MeV 32 S ions, was studied as a prototype ion-atom charge-transfer system for pumping short-wavelength lasers. Low-velocity Ar 2+ ions were efficiently produced; a huge increase in the intensity of the Ar II 4d-4p spectral lines was observed when Cs vapor was added to the argon. This observation is explained by a selective charge transfer of the Cs 6s electron into the upper levels of the observed transitions. A rate constant of (1.4±0.2)x10 -9 cm 3 /s for the transfer process was determined

  14. Proton-coupled electron transfer versus hydrogen atom transfer: generation of charge-localized diabatic states.

    Science.gov (United States)

    Sirjoosingh, Andrew; Hammes-Schiffer, Sharon

    2011-03-24

    The distinction between proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms is important for the characterization of many chemical and biological processes. PCET and HAT mechanisms can be differentiated in terms of electronically nonadiabatic and adiabatic proton transfer, respectively. In this paper, quantitative diagnostics to evaluate the degree of electron-proton nonadiabaticity are presented. Moreover, the connection between the degree of electron-proton nonadiabaticity and the physical characteristics distinguishing PCET from HAT, namely, the extent of electronic charge redistribution, is clarified. In addition, a rigorous diabatization scheme for transforming the adiabatic electronic states into charge-localized diabatic states for PCET reactions is presented. These diabatic states are constructed to ensure that the first-order nonadiabatic couplings with respect to the one-dimensional transferring hydrogen coordinate vanish exactly. Application of these approaches to the phenoxyl-phenol and benzyl-toluene systems characterizes the former as PCET and the latter as HAT. The diabatic states generated for the phenoxyl-phenol system possess physically meaningful, localized electronic charge distributions that are relatively invariant along the hydrogen coordinate. These diabatic electronic states can be combined with the associated proton vibrational states to generate the reactant and product electron-proton vibronic states that form the basis of nonadiabatic PCET theories. Furthermore, these vibronic states and the corresponding vibronic couplings may be used to calculate rate constants and kinetic isotope effects of PCET reactions.

  15. Zwitterion radicals and anion radicals from electron transfer and solvent condensation with the fingerprint developing agent ninhydrin.

    Science.gov (United States)

    Schertz, T D; Reiter, R C; Stevenson, C D

    2001-11-16

    Ninhydrin (the fingerprint developing agent) spontaneously dehydrates in liquid ammonia and in hexamethylphosphoramide (HMPA) to form indantrione, which has a sufficiently large solution electron affinity to extract an electron from the solvent (HMPA) to produce the indantrione anion radical. In liquid NH(3), the presence of trace amounts of amide ion causes the spontaneous formation of an anion radical condensation product, wherein the no. 2 carbon (originally a carbonyl carbon) becomes substituted with -NH(2) and -OH groups. In HMPA, the indantrione anion radical spontaneously forms condensation products with the HMPA to produce a variety of zwitterionic radicals, wherein the no. 2 carbon becomes directly attached to a nitrogen of the HMPA. The mechanisms for the formation of the zwitterionic paramagnetic condensation products are analogous to that observed in the reaction of ninhydrin with amino acids to yield Ruhemann's Purple, the contrast product in fingerprint development. The formation of anion and zwitterionic radical condensation products from ninhydrin and nitrogen-containing solvents may represent an example of a host of analogous polyketone-solvent reactions.

  16. Separation of photo-induced radical pair in cryptochrome to a functionally critical distance

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Domratcheva, Tatiana; Schulten, Klaus

    2014-01-01

    Cryptochrome is a blue light receptor that acts as a sensor for the geomagnetic field and assists many animals in long-range navigation. The magnetoreceptor function arises from light-induced formation of a radical pair through electron transfer between a flavin cofactor (FAD) and a triad...... of tryptophan residues. Here, this electron transfer is investigated by quantum chemical and classical molecular dynamics calculations. The results reveal how sequential electron transfer, assisted by rearrangement of polar side groups in the cryptochrome interior, can yield a FAD-Trp radical pair state...... step can overcome in speed both recombination (electron back-transfer) and proton transfer involving the radical pair reached after primary electron transfer....

  17. Atomic collisions research with excited atomic species

    International Nuclear Information System (INIS)

    Hoogerland, M.D.; Gulley, R.J.; Colla, M.; Lu, W.; Milic, D.; Baldwin, K.G.H.; Buckman, S.J.

    1999-01-01

    Measurements and calculations of fundamental atomic collision and spectroscopic properties such as collision cross sections, reaction rates, transition probabilities etc. underpin the understanding and operation of many plasma and gas-discharge-based devices and phenomena, for example plasma processing and deposition. In almost all cases the complex series of reactions which sustains the discharge or plasma, or produces the reactive species of interest, has a precursor electron impact excitation, attachment, dissociation or ionisation event. These processes have been extensively studied in a wide range of atomic and molecular species and an impressive data base of collision cross sections and reaction rates now exists. However, most of these measurements are for collisions with stable atomic or molecular species which are initially in their ground electronic state. Relatively little information is available for scattering from excited states or for scattering from unstable molecular radicals. Examples of such species would be metastable excited rare gases, which are often used as buffer gases, or CF 2 radicals formed by electron impact dissociation in a CF 4 plasma processing discharge. We are interested in developing experimental techniques which will enable the quantitative study of such exotic atomic and molecular species. In this talk I would like to outline one such facility which is being used for studies of collisions with metastable He(2 3 S) atoms

  18. Leghemoglobin-derived radicals. Evidence for multiple protein-derived radicals and the initiation of peribacteroid membrane damage

    DEFF Research Database (Denmark)

    Moreau, S; Davies, Michael Jonathan; Mathieu, C

    1996-01-01

    , with the consequent generation of lipid-derived radicals. The formation of such radicals may result in the depletion of membrane antioxidants and the initiation of lipid peroxidation. This transfer of damage from the heme center via the protein surface to neighboring membranes may be of considerable biological......-derived phenoxyl radical present at Tyr-133 in the soybean protein and Tyr-138 in the lupin protein. To obtain further information on these protein radicals and their potential interaction with the physiologically important peribacteroid membrane (which surrounds the microsymbiont in vivo), EPR spin trapping......); these radicals may be side chain- or alpha-carbon-derived, their exact sites have not been determined. Some of these radicals are on the protein surface and may be key intermediates in the formation of protein dimers. These radicals have been shown to be capable of reacting with peribacteroid membrane fractions...

  19. Pyrimidine nucleobase radical reactivity in DNA and RNA

    Science.gov (United States)

    Greenberg, Marc M.

    2016-11-01

    Nucleobase radicals are major products of the reactions between nucleic acids and hydroxyl radical, which is produced via the indirect effect of ionizing radiation. The nucleobase radicals also result from hydration of cation radicals that are produced via the direct effect of ionizing radiation. The role that nucleobase radicals play in strand scission has been investigated indirectly using ionizing radiation to generate them. More recently, the reactivity of nucleobase radicals resulting from formal hydrogen atom or hydroxyl radical addition to pyrimidines has been studied by independently generating the reactive intermediates via UV-photolysis of synthetic precursors. This approach has provided control over where the reactive intermediates are produced within biopolymers and facilitated studying their reactivity. The contributions to our understanding of pyrimidine nucleobase radical reactivity by this approach are summarized.

  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. Glutathione--hydroxyl radical interaction: a theoretical study on radical recognition process.

    Directory of Open Access Journals (Sweden)

    Béla Fiser

    Full Text Available Non-reactive, comparative (2 × 1.2 μs molecular dynamics simulations were carried out to characterize the interactions between glutathione (GSH, host molecule and hydroxyl radical (OH(•, guest molecule. From this analysis, two distinct steps were identified in the recognition process of hydroxyl radical by glutathione: catching and steering, based on the interactions between the host-guest molecules. Over 78% of all interactions are related to the catching mechanism via complex formation between anionic carboxyl groups and the OH radical, hence both terminal residues of GSH serve as recognition sites. The glycine residue has an additional role in the recognition of OH radical, namely the steering. The flexibility of the Gly residue enables the formation of further interactions of other parts of glutathione (e.g. thiol, α- and β-carbons with the lone electron pair of the hydroxyl radical. Moreover, quantum chemical calculations were carried out on selected GSH/OH(• complexes and on appropriate GSH conformers to describe the energy profile of the recognition process. The relative enthalpy and the free energy changes of the radical recognition of the strongest complexes varied from -42.4 to -27.8 kJ/mol and from -21.3 to 9.8 kJ/mol, respectively. These complexes, containing two or more intermolecular interactions, would be the starting configurations for the hydrogen atom migration to quench the hydroxyl radical via different reaction channels.

  2. Mechanistic Insights into Radical-Mediated Oxidation of Tryptophan from ab Initio Quantum Chemistry Calculations and QM/MM Molecular Dynamics Simulations.

    Science.gov (United States)

    Wood, Geoffrey P F; Sreedhara, Alavattam; Moore, Jamie M; Wang, John; Trout, Bernhardt L

    2016-05-12

    An assessment of the mechanisms of (•)OH and (•)OOH radical-mediated oxidation of tryptophan was performed using density functional theory calculations and ab initio plane-wave Quantum Mechanics/Molecular Mechanics (QM/MM) molecular dynamics simulations. For the (•)OH reactions, addition to the pyrrole ring at position 2 is the most favored site with a barrierless reaction in the gas phase. The subsequent degradation of this adduct through a H atom transfer to water was intermittently observed in aqueous-phase molecular dynamics simulations. For the (•)OOH reactions, addition to the pyrrole ring at position 2 is the most favored pathway, in contrast to the situation in the model system ethylene, where concerted addition to the double bond is preferred. From the (•)OOH position 2 adduct QM/MM simulations show that formation of oxy-3-indolanaline occurs readily in an aqueous environment. The observed transformation starts from an initial rupture of the O-O bond followed by a H atom transfer with the accompanying loss of an (•)OH radical to solution. Finally, classical molecular dynamics simulations were performed to equate observed differential oxidation rates of various tryptophan residues in monoclonal antibody fragments. It was found that simple parameters derived from simulation correlate well with the experimental data.

  3. The energy dependence of selective hydrogen atom abstraction by H(D) atoms in the photolysis of neopentane - ethane mixtures at 77 K

    International Nuclear Information System (INIS)

    Miyazaki, T.; Fueki, K.

    1980-01-01

    Selective hydrogen - atom - abstraction reaction by H or D atom has been studied in a neo C 5 H 12 - C 2 H 6 (less than 1 mol %) mixture at 77 K by ESR spectroscopy. The H (or D) atom produced by the photolysis of HI (or DI) reacts with neo - C 2 H 12 and C 2 H 6 to form neo - C 5 H 11 and C 2 H 5 radicals. In order to obtain H atoms with different kinetic energies, the photolysis was performed with different lights of 313, 254 and 229 nm. The selective formation of the C 2 H 5 radical by the reaction of the H (or D) atom with C 2 H 6 becomes more effective with the decrease in the energy of the H (or D) atom. The formation of the neo - C 5 H 11 radical by the reaction of the H (or D) atom with neo - C 2 H 12 becomes more effective with the increase in the energy of the H (or D) atom. (A.R.H.) [pt

  4. Fluorescence lifetime measurement of radical ions

    International Nuclear Information System (INIS)

    Ichinose, Nobuyuki; Kinugasa, Jun-ichiro; Hagiri, Masahide; Nakayama, Toshihiro; Murakami, Hiroshi; Kishimoto, Maki; Daido, Hiroyuki

    2004-01-01

    One-photonic excitation of a charge transfer complex of hexamethoxybenzene (HMB) and nitrosonium tetrafluoroborate (NO + BF 4 - ) in acetonitrile afforded fluorescences emission from excited radical cation of HMB (HMB + *). Lifetime of the excited radical ion species was measured to be 7 ps by the pump-probe transient absorption technique. The lifetime was much shorter than that of free radical ion (63 ps), indicating the presence of an interaction between HMB + * and NO in the excited complex. (author)

  5. Effects of Molecular Iodine and 4-tert-Butylcatechol Radical Inhibitor on the Radical Polymerization of Styrene

    Directory of Open Access Journals (Sweden)

    Mojtaba Bozorg

    2017-05-01

    Full Text Available The presence of molecular iodine was studied in relation the molecular weight and molecular weight distribution of polystyrene, produced by radical poly merization. Radical polymerization of styrene initiated by 2,2׳-azobisisobutyronitrile (AIBN was performed at 70°C in the presence of molecular iodine. The synthesized polymers were characterized by gel permeation chromatography (GPC and proton- nuclear magnetic resonance (1H NMR techniques. The results of these reactions including conversion data, number-average molecular weight and molecular weight distribution were compared with those obtained for styrene radical polymerization initiated by AIBN at the same temperature in the absence of molecular iodine. It was found that the presence of iodine had a profound effect on the molecular weight and its distribution in the produced polystyrene. This was attributed to the ability of iodine to control the polymerization of styrene initiated by AIBN via reverse iodine transfer polymerization (RITP mechanism. The polymer produced by this method had a molecular weight of 10600 g/mol with a molecular weight polydispersity index of 1.3. Due to the importance of induction period in reverse iodine transfer radical polymerization, increasing the temperature to 120°C during the induction period resulted in shorter induction periods and the produced species led to better control of the molecular weight. Also, due to the role of iodine molecules as a radical inhibitor, the presence of a secondary radical inhibitor, i.e. 4-tert-butylcatechol, along with the iodine was investigated in radical polymerization of polystyrene initiated by AIBN. It was observed that the secondary radical inhibitor prevented the consumption of the iodine molecules by the radicals produced from decomposition of the AIBN initiator; therefore, alkyl halides were not produced during the induction period.

  6. The Unimolecular Reactions of CF3CHF2 Studied by Chemical Activation: Assignment of Rate Constants and Threshold Energies to the 1,2-H Atom Transfer, 1,1-HF and 1,2-HF Elimination Reactions, and the Dependence of Threshold Energies on the Number of F-Atom Substituents in the Fluoroethane Molecules.

    Science.gov (United States)

    Smith, Caleb A; Gillespie, Blanton R; Heard, George L; Setser, D W; Holmes, Bert E

    2017-11-22

    The recombination of CF 3 and CHF 2 radicals in a room-temperature bath gas was used to prepare vibrationally excited CF 3 CHF 2 * molecules with 101 kcal mol -1 of vibrational energy. The subsequent 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions were observed as a function of bath gas pressure by following the CHF 3 , CF 3 (F)C: and C 2 F 4 product concentrations by gas chromatography using a mass spectrometer as the detector. The singlet CF 3 (F)C: concentration was measured by trapping the carbene with trans-2-butene. The experimental rate constants are 3.6 × 10 4 , 4.7 × 10 4 , and 1.1 × 10 4 s -1 for the 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions, respectively. These experimental rate constants were matched to statistical RRKM calculated rate constants to assign threshold energies (E 0 ) of 88 ± 2, 88 ± 2, and 87 ± 2 kcal mol -1 to the three reactions. Pentafluoroethane is the only fluoroethane that has a competitive H atom transfer decomposition reaction, and it is the only example with 1,1-HF elimination being more important than 1,2-HF elimination. The trend of increasing threshold energies for both 1,1-HF and 1,2-HF processes with the number of F atoms in the fluoroethane molecule is summarized and investigated with electronic-structure calculations. Examination of the intrinsic reaction coordinate associated with the 1,1-HF elimination reaction found an adduct between CF 3 (F)C: and HF in the exit channel with a dissociation energy of ∼5 kcal mol -1 . Hydrogen-bonded complexes between HF and the H atom migration transition state of CH 3 (F)C: and the F atom migration transition state of CF 3 (F)C: also were found by the calculations. The role that these carbene-HF complexes could play in 1,1-HF elimination reactions is discussed.

  7. COMPUTATIONAL STUDY OF INTERSTELLAR GLYCINE FORMATION OCCURRING AT RADICAL SURFACES OF WATER-ICE DUST PARTICLES

    International Nuclear Information System (INIS)

    Rimola, Albert; Sodupe, Mariona; Ugliengo, Piero

    2012-01-01

    Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH . radical and H 3 O + surface defects. The coupling of incoming CO molecules with the surface OH . radicals on the ice clusters yields the formation of the COOH . radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol –1 and –22 kcal mol –1 , respectively. The COOH . radicals couple with incoming NH=CH 2 molecules (experimentally detected in the ISM) to form the NHCH 2 COOH . radical glycine through energy barriers of 12 kcal mol –1 , exceedingly high at ISM cryogenic temperatures. Nonetheless, when H 3 O + is present, one proton may be barrierless transferred to NH=CH 2 to give NH 2 =CH 2 + . This latter may react with the COOH . radical to give the NH 2 CH 2 COOH +. glycine radical cation which can then be transformed into the NH 2 CHC(OH) 2 +. species (the most stable form of glycine in its radical cation state) or into the NH 2 CHCOOH . neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh-physical conditions of the ISM may trigger reactions of cosmochemical interest. The relevance of surface H 3 O

  8. Computational Study of Interstellar Glycine Formation Occurring at Radical Surfaces of Water-ice Dust Particles

    Science.gov (United States)

    Rimola, Albert; Sodupe, Mariona; Ugliengo, Piero

    2012-07-01

    Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH• radical and H3O+ surface defects. The coupling of incoming CO molecules with the surface OH• radicals on the ice clusters yields the formation of the COOH• radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol-1 and -22 kcal mol-1, respectively. The COOH• radicals couple with incoming NH=CH2 molecules (experimentally detected in the ISM) to form the NHCH2COOH• radical glycine through energy barriers of 12 kcal mol-1, exceedingly high at ISM cryogenic temperatures. Nonetheless, when H3O+ is present, one proton may be barrierless transferred to NH=CH2 to give NH2=CH2 +. This latter may react with the COOH• radical to give the NH2CH2COOH+• glycine radical cation which can then be transformed into the NH2CHC(OH)2 +• species (the most stable form of glycine in its radical cation state) or into the NH2CHCOOH• neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh-physical conditions of the ISM may trigger reactions of cosmochemical interest. The relevance of surface H3O+ ions to facilitate chemical

  9. Some reactions of oxidizing radicals with enzymes in aqueous solution

    International Nuclear Information System (INIS)

    Cundall, R.B.; Bisby, R.H.; Hoe, S.T.; Sims, H.E.; Anderson, R.F.

    1979-01-01

    A range of oxidizing radicals including some inorganic radical anions and the superoxide radical, can be generated by radiolysis of aqueous solutions. These radicals are more selective in their reactions with amino acids than the hydroxyl radical. Factors controlling the apparent reactivity of radical anions with proteins, such as free radical equilibria and ion-binding, are described. The superoxide radical inactivates papain by reaction with the cysteine residue. This reaction has been studied in solutions subjected to radiations of varying linear energy transfer. (Auth.)

  10. Electron spin resonance of spin-trapped radicals of amines and polyamines. Hydroxyl radical reactions in aqueous solutions and. gamma. radiolysis in the solid state

    Energy Technology Data Exchange (ETDEWEB)

    Mossoba, M.M.; Rosenthal, I.; Riesz, P. (National Cancer Inst., Bethesda, MD (USA))

    1982-06-15

    The reactions of hydroxyl radicals with methylamine, dimethylamine, trimethylamine, diethylamine, sec-butylamine, ethylene-diamine, 1,3-diaminopropane, putrescine, cadaverine, 1,7-diaminoheptane, ornithine, spermidine, spermine, agmatine, and arcaine in aqueous solutions have been investigated by spin-trapping and esr. Hydroxyl radicals were generated by the uv photolysis of H/sub 2/O/sub 2/ and 2-methyl-2-nitrosopropane (MNP) was used as the spin-trap. The effects of ionizing radiation on the same polyamines in the polycrystalline state were also investigated. The free radicals produced by ..gamma..-radiolysis of these solids at room temperature in the absence of air were identified by dissolution in aqueous solutions of MNP. The predominant reaction of OH radicals with amines and polyamines below pH 7 was the abstraction of hydrogen atoms from a carbon that is not adjacent to the protonated amino group. For agmatine and arcaine which contain guanidinium groups abstraction occurred from the ..cap alpha..-CH. Dimethylamine was oxidized to the dimethylnitroxyl radical by H/sub 2/O/sub 2/ in the dark. ..gamma..-Radiolysis of polyamines in the polycrystalline state generated radicals due to H-abstraction from either the ..cap alpha..-Ch or from a carbon atom in the middle of the alkyl chain. The deamination radical was obtained from ornithine.

  11. Atomic collisions related to atomic laser isotope separation

    International Nuclear Information System (INIS)

    Shibata, Takemasa

    1995-01-01

    Atomic collisions are important in various places in atomic vapor laser isotope separation (AVLIS). At a vaporization zone, many atomic collisions due to high density have influence on the atomic beam characteristics such as velocity distribution and metastable states' populations at a separation zone. In the separation zone, a symmetric charge transfer between the produced ions and the neutral atoms may degrade selectivity. We have measured atomic excitation temperatures of atomic beams and symmetric charge transfer cross sections for gadolinium and neodymium. Gadolinium and neodymium are both lanthanides. Nevertheless, results for gadolinium and neodymium are very different. The gadolinium atom has one 5d electron and neodymium atom has no 5d electron. It is considered that the differences are due to existence of 5d electron. (author)

  12. Generation and propagation of radical reactions on proteins

    DEFF Research Database (Denmark)

    Hawkins, C L; Davies, Michael Jonathan

    2001-01-01

    The oxidation of proteins by free radicals is thought to play a major role in many oxidative processes within cells and is implicated in a number of human diseases as well as ageing. This review summarises information on the formation of radicals on peptides and proteins and how radical damage may...... be propagated and transferred within protein structures. The emphasis of this article is primarily on the deleterious actions of radicals generated on proteins, and their mechanisms of action, rather than on enzymatic systems where radicals are deliberately formed as transient intermediates. The final section...

  13. Excitation and charge transfer in low-energy hydrogen atom collisions with neutral oxygen

    Science.gov (United States)

    Barklem, P. S.

    2018-02-01

    Excitation and charge transfer in low-energy O+H collisions is studied; it is a problem of importance for modelling stellar spectra and obtaining accurate oxygen abundances in late-type stars including the Sun. The collisions have been studied theoretically using a previously presented method based on an asymptotic two-electron linear combination of atomic orbitals (LCAO) model of ionic-covalent interactions in the neutral atom-hydrogen-atom system, together with the multichannel Landau-Zener model. The method has been extended to include configurations involving excited states of hydrogen using an estimate for the two-electron transition coupling, but this extension was found to not lead to any remarkably high rates. Rate coefficients are calculated for temperatures in the range 1000-20 000 K, and charge transfer and (de)excitation processes involving the first excited S-states, 4s.5So and 4s.3So, are found to have the highest rates. Data are available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/vizbin/qcat?J/A+A/610/A57. The data are also available at http://https://github.com/barklem/public-data

  14. Radical abundance how a revolution in nanotechnology will change civilization

    CERN Document Server

    Drexler, K Eric

    2013-01-01

    K. Eric Drexler is the founding father of nanotechnology--the science of engineering on a molecular level. In Radical Abundance, he shows how rapid scientific progress is about to change our world. Thanks to atomically precise manufacturing, we will soon have the power to produce radically more of what people want, and at a lower cost. The result will shake the very foundations of our economy and environment. Already, scientists have constructed prototypes for circuit boards built of millions of precisely arranged atoms. The advent of this kind of atomic precision promises to change the way we make things--cleanly, inexpensively, and on a global scale. It allows us to imagine a world where solar arrays cost no more than cardboard and aluminum foil, and laptops cost about the same. A provocative tour of cutting edge science and its implications by the field's founder and master, Radical Abundance offers a mind-expanding vision of a world hurtling toward an unexpected future.

  15. Effect of water and ethanol radicals on the protein part of human hemoglobin

    International Nuclear Information System (INIS)

    Szweda-Lewandowska, Z.; Puchala, M.

    1989-01-01

    This paper studies the changes in the tryptophan fluorescence in human hemoglobin induced by ·OH, e aq - , H atoms and ethanol radicals. Measurements of irradiated hemoglobin performed in phosphate buffer, pH 7, indicate that the processes of unfolding a protein are induced with the highest efficiency by the ·OH radicals. A destructive action of e aq - is more evident in the absence of the ·OH radicals. Fluorescence measurements carried out after incubation of irradiated hemoglobin in Gdn·HCl solution reveal the tryptophan residues destruction, which is relatively small (at 2.5 kGy maximum fluorescence decrease was about 23%) and caused by the ·OH radicals. Within the dose range, the participation of the e aq - , H atoms and ethanol radicals in hemoglobin tryptophan residue destruction can be neglected. (author)

  16. Product study of 1-adamantyl and 1-bicyclo[2.2.2]octyl radicals in hydrocarbon solvents. An unusually large hydrogen isotope effect

    International Nuclear Information System (INIS)

    Engel, P.S.; Chae, W.K.; Baughman, S.A.; Marschke, G.E.; Lewis, E.S.; Timberlake, J.W.; Luedtke, A.E.

    1983-01-01

    1-Adamantyl (ada.) and 1-bicyclo[2.2.2]octyl (bo.) radicals have been generated by photolysis of the corresponding azoalkanes in various hydrocarbon solvents. Both radicals abstract hydrogen readily from saturated hydrocarbons and they add to aromatic rings much faster than tert-butyl. does. Despite its reactivity, ada. is remarkably selective in hydrogen atom abstraction, preferring a benzylic hydrogen 25:1 over a cyclohexane hydrogen. The effect of solvent viscosity indicates that formation of the radical dimers biada and bibo occurs in the solvent cage. The most striking result of this work is a deuterium isotope effect of 25 for hydrogen transfer from cyclohexane to ada. at 65 0 C. Steric compression in the transition state is postulated to cause an unusually large tunnel correction and hence a large k/sub H//k/sub D/. 6 tables

  17. Quasi-four-body treatment of charge transfer in the collision of protons with atomic helium: I. Thomas related mechanisms

    Science.gov (United States)

    Safarzade, Zohre; Fathi, Reza; Shojaei Akbarabadi, Farideh; Bolorizadeh, Mohammad A.

    2018-04-01

    The scattering of a completely bare ion by atoms larger than hydrogen is at least a four-body interaction, and the charge transfer channel involves a two-step process. Amongst the two-step interactions of the high-velocity single charge transfer in an anion-atom collision, there is one whose amplitude demonstrates a peak in the angular distribution of the cross sections. This peak, the so-called Thomas peak, was predicted by Thomas in a two-step interaction, classically, which could also be described through three-body quantum mechanical models. This work discusses a four-body quantum treatment of the charge transfer in ion-atom collisions, where two-step interactions illustrating a Thomas peak are emphasized. In addition, the Pauli exclusion principle is taken into account for the initial and final states as well as the operators. It will be demonstrated that there is a momentum condition for each two-step interaction to occur in a single charge transfer channel, where new classical interactions lead to the Thomas mechanism.

  18. Atomic layer deposited oxide films as protective interface layers for integrated graphene transfer

    Science.gov (United States)

    Cabrero-Vilatela, A.; Alexander-Webber, J. A.; Sagade, A. A.; Aria, A. I.; Braeuninger-Weimer, P.; Martin, M.-B.; Weatherup, R. S.; Hofmann, S.

    2017-12-01

    The transfer of chemical vapour deposited graphene from its parent growth catalyst has become a bottleneck for many of its emerging applications. The sacrificial polymer layers that are typically deposited onto graphene for mechanical support during transfer are challenging to remove completely and hence leave graphene and subsequent device interfaces contaminated. Here, we report on the use of atomic layer deposited (ALD) oxide films as protective interface and support layers during graphene transfer. The method avoids any direct contact of the graphene with polymers and through the use of thicker ALD layers (≥100 nm), polymers can be eliminated from the transfer-process altogether. The ALD film can be kept as a functional device layer, facilitating integrated device manufacturing. We demonstrate back-gated field effect devices based on single-layer graphene transferred with a protective Al2O3 film onto SiO2 that show significantly reduced charge trap and residual carrier densities. We critically discuss the advantages and challenges of processing graphene/ALD bilayer structures.

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

    International Nuclear Information System (INIS)

    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

  20. The mechanism of three-body process of energy transfer from excited xenon atoms to molecules

    International Nuclear Information System (INIS)

    Wojciechowski, K.; Forys, M.

    1999-01-01

    The mechanism of energy transfer from Xe(6 s[3/2] 1 ) resonance state (E=8.44 eV) and higher excited Xe(6p, 6p', 6 d) atoms produced in pulse radiolysis to molecules have been discussed. The analysis of the kinetic data for these processes shows that in the sensitized photolysis and radiolysis of Xe-M mixtures the excited atoms decay in 'ordinary' two-body reaction: Xe(6s[3/2] 1 0 )+M→products (r.1) and in fast 'accelerated' third order process: Xe(6s[3/2] 1 0 )+M+Xe→products (r.2) The discussion shows that three-body process occurs via reactions: Xe(6s[3/2] 1 0 )+Xe k w ↔ k d Xe 2 ** (r.2a) Xe 2 **+M k q →[Xe 2 M]*→products (r.2b) It was shown that this mechanism concerns also higher excited Xe atoms and can explain a similar process in He-M mixtures and suggests that it is a general mechanism of energy transfer in all irradiated rare gas-molecule systems

  1. Nuclear prehistory influence on transfer velocity of 54Mn impurity 'hot' atoms in irradiated metallic iron

    International Nuclear Information System (INIS)

    Alekseev, I.E.

    2007-01-01

    Influence of nuclear prehistory on transfer velocity of 54 Mn impurity 'hot'-atoms - got by different nuclear channels: 56 Fe(d, α), 54 Fe(n,p) in irradiated metallic iron - is studied. Irradiation of targets were carried out in U-120 accelerator (energy range 7.3/5.3 MeV, deuteron beam current makes up 5 μA). Mean density of thermal neutron (WWR-M reactor) makes up 8.6·10 13 neutron·cm -2 ·s -1 . It is shown, that transfer velocity of 54 Mn 'hot' atoms is defining by rate of radiation damage of targets in the irradiation process at that a key importance has a bombarding particles type applied for radioactive label getting

  2. Research concerning ionic and free radical reactions in radiation chemistry. Progress report, September 15, 1976--September 15, 1977

    International Nuclear Information System (INIS)

    Williams, T.F.

    1977-01-01

    Progress is reported on ESR studies of fluorocarbon radicals and intermediate radicals. A detailed study was made of the dimethyl, diethyl, and di-n-propyl carbonates. Studies were continued on hydrogen-atom abstraction reactions at low temperatures with view to evaluating the contribution from quantum-mechanical tunneling. Detection of the transient dimer radical anion of acetonitrile in the upper crystalline phase at -50 0 C is reported. Abstracts of current reports are included on electron attachment to fluorocarbons hydrogen atom abstraction by methyl radicals. EPR spectra of the tetrafluoroethylene radical anion, and addition of tetrafluoroethylene to the tetrafluoroethylene radical anion

  3. 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

    2017-04-18

    We report the synthesis, characterization, and reactivity of [LFe 3 (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 Fe 3 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. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Free radical scavenging injectable hydrogels for regenerative therapy

    Energy Technology Data Exchange (ETDEWEB)

    Komeri, Remya [Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Science Division, BMT Wing, Thiruvananthapuram 695 012, Kerala State (India); Thankam, Finosh Gnanaprakasam [Dept. of Biomedical Sciences, Creighton University, 2500 California Plaza, Omaha NE68178 (United States); Muthu, Jayabalan, E-mail: mjayabalan52@gmail.com [Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Science Division, BMT Wing, Thiruvananthapuram 695 012, Kerala State (India)

    2017-02-01

    Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07 kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. - Graphical abstract: Injectable hydrogel with inherent free radical scavenging property for regenerative tissue engineering application. - Highlights: • Novel injectable hydrogel (PEAX-P) is prepared using D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer

  5. Free radical scavenging injectable hydrogels for regenerative therapy

    International Nuclear Information System (INIS)

    Komeri, Remya; Thankam, Finosh Gnanaprakasam; Muthu, Jayabalan

    2017-01-01

    Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07 kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. - Graphical abstract: Injectable hydrogel with inherent free radical scavenging property for regenerative tissue engineering application. - Highlights: • Novel injectable hydrogel (PEAX-P) is prepared using D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer

  6. 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

  7. Controlled radical polymerization of an acrylamide containing L-alanine moiety via ATRP.

    Science.gov (United States)

    Rafiee, Zahra

    2016-02-01

    Homopolymerization of an optically active acrylamide having an amino acid moiety in the side chain, N-acryloyl-L-alanine (AAla) was carried out via atom transfer radical polymerization (ATRP) at room temperature using 2-hydroxyethyl-2'-methyl-2'-bromopropionate (HMB) or sodium-4-(bromomethyl)benzoate (SBB) as initiator in pure water, methanol/water mixture and pure methanol solvents. The polymerization reaction resulted in the optically active biocompatible amino acid-based homopolymer in good yield with narrow molecular weight distribution. The number average molecular weight increased with conversion and polydispersity was low. The structure and molecular weight of synthesized polymer were characterized by (1)H NMR, FT-IR spectroscopic techniques and size-exclusion chromatography.

  8. The form of electron-atom excitation amplitudes at high momentum transfers in the Faddeev-Watson approximation

    International Nuclear Information System (INIS)

    Catalan, G.; Roberts, M.J.

    1979-01-01

    A form of the off-shell Coulomb T matrix, which has a well defined on-shell limit, is used in the Faddeev-Watson multiple-scattering expansion for a direct three-body collision process. Using the excitation of atomic hydrogen by electron impact as an example, approximations to the second-order terms, which are valid for high momentum transfers of the incident electron, are derived. It is shown how the resulting asymptotic behaviour of the second-order Faddeev-Watson approximation is related to the high momentum transfer limit of the second Born approximation. The results are generalised to the excitation of more complex atoms. The asymptotic forms of the Faddeev-Watson and Born approximations are compared with other theories and with measurements of differential cross sections and angular correlation parameters for the excitation of H(2p) and He(2 1 P). The results indicate that the Faddeev-Watson approximation converges more rapidly at high momentum transfers than does the Born approximation. (author)

  9. Studies of radiation-produced radicals and radical ions. Progress report, June 1, 1981-August 31, 1982

    International Nuclear Information System (INIS)

    Williams, T.F.

    1982-01-01

    The discovery and characterization of novel radical ions produced by the γ irradiation of solids continues to be a fertile field for investigation. This Progress Report describes the generation and ESR identification of several new paramagnetic species, some of which have long been sought as important intermediates in radiation chemistry. We have also contributed to a general theoretical problem in ESR spectroscopy. Solid-state studies of electron attachment reactions, both non-dissociative and dissociative, reveal interesting structural and chemical information about the molecular nature of these processes for simple compounds. In particular, ESR measurements of the spin distribution in the products allow a fairly sharp distinction to be drawn between radical anions and radical-anion pairs or adducts. Dimer radical anion formation can also take place but the crystal structure plays a role in this process, as expected. Some radical anions undergo photolysis to give radical-anion pairs which may then revert back to the original radical anion by a thermal reaction. The chemistry of these reversible processes is made more intricate by a competing reaction in which the radical abstracts a hydrogen atom from a neighboring molecule. However, the unraveling of this complication has also served to extend our knowledge of the role of quantum tunneling in chemical reactions. The results of this investigation testify to the potential of solid-state techniques for the study of novel and frangible radical ions. Progress in this field shows no sign of abating, as witness the recent discovery of perfluorocycloalkane radical anions and alkane radical cations

  10. 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.

  11. Prospects of radical-interacting porphyrin photosensitizers and their possible use in photodynamic therapy

    Science.gov (United States)

    Gal, Dezso; Shuliakovskaya, T.; Vidoczy, Tamas; Elzemzam, Saleh; Vasvari, Gabor; Suemegi, L.; Kuti, Zsolt

    1994-03-01

    Based on literature data obtained in various fields with respect to studies on the role of free radicals in biology and on the kinetics of triplet-doublet interactions, it is suggested that excited photosensitizers react in vivo with free radicals formed in malignant tissues during photodynamic therapy (PDT) and this interaction competes with sensitizer-radical + molecule and the singlet oxygen mediated effects. Experimental results by laser flash photolysis and electron spin resonance revealed that sensitizer applied in PDT react with stable free radicals presumably both by energy transfer and electron transfer.

  12. Electron spin resonance of spin-trapped radicals of amines and polyamines

    International Nuclear Information System (INIS)

    Mossoba, M.M.; Rosenthal, Ionel; Riesz, Peter

    1982-01-01

    The reactions of hydroxyl radicals with methylamine, dimethylamine, trimethylamine, diethylamine, sec-butylamine, ethylene-diamine, 1,3-diaminopropane, putrescine, cadaverine, 1,7-diaminoheptane, ornithine, spermidine, spermine, agmatine, and arcaine in aqueous solutions have been investigated by spin-trapping and esr. Hydroxyl radicals were generated by the uv photolysis of H 2 O 2 and 2-methyl-2-nitrosopropane (MNP) was used as the spin-trap. The effects of ionizing radiation on the same polyamines in the polycrystalline state were also investigated. The free radicals produced by ν-radiolysis of these solids at room temperature in the absence of air were identified by dissolution in aqueous solutions of MNP. The predominant reaction of OH radicals with amines and polyamines below pH 7 was the abstraction of hydrogen atoms from a carbon that is not adjacent to the protonated amino group. For agmatine and arcaine which contain guanidinium groups abstraction occurred from the α-CH. Dimethylamine was oxidized to the dimethylnitroxyl radical by H 2 O 2 in the dark. ν-Radiolysis of polyamines in the polycrystalline state generated radicals due to H-abstraction from either the α-Ch or from a carbon atom in the middle of the alkyl chain. The deamination radical was obtained from ornithine

  13. Relative stability of radicals derived from artemisinin: A semiempirical and DFT study

    Science.gov (United States)

    Arantes, C.; de Araujo, M. T.; Taranto, A. G.; de M. Carneiro, J. W.

    The semiempirical AM1 and PM3 methods, as well as the density functional (DFT/B3LYP) approach using the 6-31g(d) basis set, were employed to calculate the relative stability of intermediate radicals derived from artemisinin, a sesquiterpene lactone having an endoperoxide bridge that is essential for its antimalarial activity. The compounds studied have their nonperoxidic oxygen atom of the trioxane ring and/or the carbonyl group replaced by a CH2 unit. Relative stabilities were calculated by means of isodesmic equations using artemisinin as reference. It was found that replacement of oxygen atoms decreases the relative stability of the anionic radical intermediates. In contrast, for compounds with inverted stereochemistry the intermediate radicals were found to be more stable than those with the artemisinin-like stereochemistry. These relative stabilities may modulate the antimalarial potency. Radicals centered on carbon are always more stable than the corresponding radicals centered on oxygen.

  14. Polarization transfer from polarized nuclear spin to μ- spin in muonic atom

    International Nuclear Information System (INIS)

    Kuno, Yoshitaka; Nagamine, Kanetada; Yamazaki, Toshimitsu.

    1987-02-01

    A theoretical study of polarization transfer from an initially-polarized nuclear spin to a μ - spin in a muonic atom is given. The switching of the hyperfine interaction at excited muonic states as well as at the ground 1s state is taken into account. The upper state of hyperfine doublet at the muonic 1s state is considered to proceed down to the lower state. It is found that as the hyperfine interaction becomes effective at higher excited muonic orbitals, a less extent of polarization is transferred from the nuclear spin to the μ - spin. The theoretical values obtained are compared with the recent experiment of μ - repolarization in a polarized 209 Bi target. (author)

  15. State-selective charge transfer cross sections for light ion impact of atomic hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, D. R. [University of North Texas; Stancil, Phillip C. [University of Georgia, Athens; Havener, C. C. [Oak Ridge National Laboratory (ORNL)

    2015-01-01

    Owing to the utility of diagnosing plasma properties such as impurity concentration and spatial distribution, and plasma temperature and rotation, by detection of photon emission following capture of electrons from atomic hydrogen to excited states of multiply charged ions, new calculations of state-selective charge transfer involving light ions have been carried out using the atomic orbital close-coupling and the classical trajectory Monte Carlo methods. By comparing these with results of other approaches applicable in a lower impact energy regime, and by benchmarking them using key experimental data, knowledge of the cross sections can be made available across the range parameters needed by fusion plasma diagnostics.

  16. Bibliography on electron transfer processes in ion-ion/atom/molecule collisions (updated 1993)

    International Nuclear Information System (INIS)

    Tawara, H.

    1993-04-01

    Following our previous compilations [IPPJ-AM-45 (1986), NIFS-DATA-7 (1990)], bibliographic information on experimental and theoretical studies on electron transfer processes in ion-ion/atom/molecule collisions is up-dated. The references published through 1980-1992 are included. For easy finding references for particular combination of collision partners, a simple list is also provided. (author) 1542 refs

  17. RATE CONSTANTS FOR THE REACTIONS OF OH RADICALS AND CL ATOMS WITH DI-N-PROPYL ETHER AND DI-N-BUTYL ETHER AND THEIR DEUTERATED ANALOGS. (R825252)

    Science.gov (United States)

    Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d14, di-n-butyl ether and di-n-butyl ether-d18 have been measured at 296 ? 2 K and atmos...

  18. Distribution of free radical products among the bases of x-irradiated DNA model systems: an ESR study

    International Nuclear Information System (INIS)

    Spalletta, R.A.

    1984-01-01

    Exposure of solid state DNA to ionizing radiation results in an ESR spectrum that has been attributed to a nonstoichiometric distribution of free radicals among the bases. At low temperatures radical cations appear to be stabilized on the purines while radical anions are stabilized on the pyrimidines. This distribution could arise from at least two different mechanisms. The first, charge transfer, involves the transfer of electrons and/or holes between stacked bases. In the second, saturation asymmetry, the free radical distribution arises from differences in the dose saturation characteristics of individual bases. The present study addresses the relative importance of charge transfer versus saturation asymmetry in the production of these population differences. Radicals formed by dissolving irradiated polycrystalline pyrimidines in aqueous solutions containing NtB or PBN spin traps were analyzed using ESR. The relative importance of the two free radical production and distribution mechanisms was assessed using DNA model systems. Saturation asymmetry plays a significant role in determining the free radical population while charge transfer was unambiguously observed in only one, the complex of dAMP and TMP. The results demonstrate that any quantitative analysis of charge transfer must take saturation asymmetry into account

  19. COMPUTATIONAL STUDY OF INTERSTELLAR GLYCINE FORMATION OCCURRING AT RADICAL SURFACES OF WATER-ICE DUST PARTICLES

    Energy Technology Data Exchange (ETDEWEB)

    Rimola, Albert; Sodupe, Mariona [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra (Spain); Ugliengo, Piero, E-mail: albert.rimola@uab.cat [Dipartimento di Chimica, NIS Centre of Excellence and INSTM (Materials and Technology National Consortium), UdR Torino, Universita di Torino, Via P. Giuria 7, 10125 Torino (Italy)

    2012-07-20

    Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH{sup .} radical and H{sub 3}O{sup +} surface defects. The coupling of incoming CO molecules with the surface OH{sup .} radicals on the ice clusters yields the formation of the COOH{sup .} radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol{sup -1} and -22 kcal mol{sup -1}, respectively. The COOH{sup .} radicals couple with incoming NH=CH{sub 2} molecules (experimentally detected in the ISM) to form the NHCH{sub 2}COOH{sup .} radical glycine through energy barriers of 12 kcal mol{sup -1}, exceedingly high at ISM cryogenic temperatures. Nonetheless, when H{sub 3}O{sup +} is present, one proton may be barrierless transferred to NH=CH{sub 2} to give NH{sub 2}=CH{sub 2}{sup +}. This latter may react with the COOH{sup .} radical to give the NH{sub 2}CH{sub 2}COOH{sup +.} glycine radical cation which can then be transformed into the NH{sub 2}CHC(OH){sub 2}{sup +.} species (the most stable form of glycine in its radical cation state) or into the NH{sub 2}CHCOOH{sup .} neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh

  20. Radical-induced oxidation of RAFT agents : a kinetic study

    NARCIS (Netherlands)

    Li, Changxi; He, Junpo; Zhou, Yanwu; Gu, Yuankai; Yang, Yuliang

    2011-01-01

    Radical-induced oxidn. of reversible addn.-fragmentation chain transfer (RAFT) agents is studied with respect to the effect of mol. structure on oxidn. rate. The radicals are generated by homolysis of either azobisisobutyronitrile or alkoxyamine and transformed in situ immediately into peroxy

  1. Towards an improved prediction of the free radical scavenging potency of flavonoids: the significance of double PCET mechanisms.

    Science.gov (United States)

    Amić, Ana; Marković, Zoran; Dimitrić Marković, Jasmina M; Stepanić, Višnja; Lučić, Bono; Amić, Dragan

    2014-01-01

    The 1H(+)/1e(-) and 2H(+)/2e(-) proton-coupled electron transfer (PCET) processes of free radical scavenging by flavonoids were theoretically studied for aqueous and lipid environments using the PM6 and PM7 methods. The results reported here indicate that the significant contribution of the second PCET mechanism, resulting in the formation of a quinone/quinone methide, effectively discriminates the active from inactive flavonoids. The predictive potency of descriptors related to the energetics of second PCET mechanisms (the second O-H bond dissociation enthalpy (BDE2) related to hydrogen atom transfer (HAT) mechanism, and the second electron transfer enthalpy (ETE2) related to sequential proton loss electron transfer (SPLET) mechanism) are superior to the currently used indices, which are related to the first 1H(+)/1e(-) processes, and could serve as primary descriptors in development of the QSAR (quantitative structure-activity relationships) of flavonoids. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Energy transfers between N_2(A"3Σ) nitrogen metastable molecules and oxygen atoms and molecules

    International Nuclear Information System (INIS)

    De Souza, Antonio Rogerio

    1985-01-01

    This research thesis aims at determining reaction coefficients for energy transfers between nitrogen in its metastable status and oxygen atoms and molecules, the variation of these coefficients with respect to temperature (mainly in the 200-400 K range), products formed and more particularly branching rates of O("1S) oxygen and of NO_2. Reaction coefficients are experimentally determined by using the technique of post-discharge in flow. The experimental set-up is described and the study of the best operating conditions is reported. In the next part, the author reports the study of the energy transfer between nitrogen in its metastable status N_2(A) and oxygen molecules. Reaction coefficients are determined for the first three vibrational levels. The author then reports the study of the transfer of N_2(A) molecules on oxygen atoms in their fundamental status. Reactions coefficients and their variations are determined for the three first vibrational levels. The author describes the dissociation method and the method of detection of atomic oxygen. A kinetic model is proposed for the analysis of formed products during a post-discharge in flow, and the branching rate for the formation of O("1S) oxygen between 190 and 365 K is determined. The author finally discusses publications on the role of these reactions in the interpretation of some atmospheric phenomena

  3. Antioxidant mechanism of bilirubin: both HAT and SET are possible

    International Nuclear Information System (INIS)

    Adhikari, Soumyakanti; Joshi, Ravi; Mukherjee, Tulsi

    2008-01-01

    Bilirubin (BR) plays two extreme roles in physiology, one hand it is a toxic metabolite while at micromolar concentration it acts as antioxidant. It has been observed that hydroxyl, glutathiyl and Linoleic peroxyl radicals abstract hydrogen atom from bilirubin, whereas N 3 , Br 2 , CCl 3 OO, NO 2 radicals react via single electron transfer action. Our study demonstrates that oxidation of bilirubin occurs via both hydrogen atom transfer and single electron transfer depending on the nature of the radical. (author)

  4. Intramolecular addition of benzylic radicals onto ketenimines. Synthesis of 2-alkylindoles.

    Science.gov (United States)

    Alajarín, Mateo; Vidal, Angel; Ortín, María-Mar

    2003-12-07

    The inter- and intramolecular addition of free radicals onto ketenimines is studied. All the attempts to add intermolecularly several silicon, oxygen or carbon centered radicals to N-(4-methylphenyl)-C,C-diphenyl ketenimine were unsuccessful. In contrast, the intramolecular addition of benzylic radicals, generated from xanthates, onto the central carbon of a ketenimine function with its N atom linked to the ortho position of the aromatic ring occurred under a variety of reaction conditions. These intramolecular cyclizations provide a novel radical-mediated synthesis of 2-alkylindoles.

  5. Light element atom, molecule and radical behaviour in the divertor and edge plasma regions. Summary report of the 1. research coordination meeting

    International Nuclear Information System (INIS)

    Braams, B.J.

    2010-01-01

    The first research coordination meeting of the Coordinated Research Project (CRP) on Light Element Atom, Molecule and Radical Behaviour in the Divertor and Edge Plasma Regions was held 18-20 November 2009 at IAEA headquarters, bringing together experts representing 14 institutions. Participants summarized their recent and ongoing work pertinent to the research project. The specific objectives of the CRP and a detailed work plan were formulated. The discussions, conclusions and recommendations of the meeting are summarized in this report. (author)

  6. Near-Infrared Free-Radical and Free-Radical-Promoted Cationic Photopolymerizations by In-Source Lighting Using Upconverting Glass.

    Science.gov (United States)

    Kocaarslan, Azra; Tabanli, Sevcan; Eryurek, Gonul; Yagci, Yusuf

    2017-11-13

    A method is presented for the initiation of free-radical and free-radical-promoted cationic photopolymerizations by in-source lighting in the near-infrared (NIR) region using upconverting glass (UCG). This approach utilizes laser irradiation of UCG at 975 nm in the presence of fluorescein (FL) and pentamethyldiethylene triamine (PMDETA). FL excited by light emitted from the UCG undergoes electron-transfer reactions with PMDETA to form free radicals capable of initiating polymerization of methyl methacrylate. To execute the corresponding free-radical-promoted cationic polymerization of cyclohexene oxide, isobutyl vinyl ether, and N-vinyl carbazole, it was necessary to use FL, dimethyl aniline (DMA), and diphenyliodonium hexafluorophosphate as sensitizer, coinitiator, and oxidant, respectively. Iodonium ions promptly oxidize DMA radicals formed to the corresponding cations. Thus, cationic polymerization with efficiency comparable to the conventional irradiation source was achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Transfer behavior of quantum states between atoms in photonic crystal coupled cavities

    International Nuclear Information System (INIS)

    Zhang Ke; Li Zhiyuan

    2010-01-01

    In this article, we discuss the one-excitation dynamics of a quantum system consisting of two two-level atoms each interacting with one of two coupled single-mode cavities via spontaneous emission. When the atoms and cavities are tuned into resonance, a wide variety of time-evolution behaviors can be realized by modulating the atom-cavity coupling strength g and the cavity-cavity hopping strength λ. The dynamics is solved rigorously via the eigenproblem of an ordinary coupled linear system and simple analytical solutions are derived at several extreme situations of g and λ. In the large hopping limit where g >λ, the time-evolution behavior of the system is characterized by the usual slowly varying carrier envelope superimposed upon a fast and violent oscillation. At a certain instant, the energy is fully transferred from the one quantum subsystem to the other. When the two interaction strengths are comparable in magnitude, the dynamics acts as a continuous pulse having irregular frequency and line shape of peaks and valleys, and the complicated time-evolution behaviors are ascribed to the violent competition between all the one-excitation quantum states. The coupled quantum system of atoms and cavities makes a good model to study cavity quantum electrodynamics with great freedoms of many-body interaction.

  8. [Electron transfer, ionization, and excitation in atomic collisions

    International Nuclear Information System (INIS)

    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 + 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

  9. Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

    Science.gov (United States)

    Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

    2017-11-21

    Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

  10. Interactions between simple radicals and water

    International Nuclear Information System (INIS)

    Crespo-Otero, Rachel; Sanchez-Garcia, Elsa; Suardiaz, Reynier; Montero, Luis A.; Sander, Wolfram

    2008-01-01

    The interactions of the simple radicals CH 3 , NH 2 , OH, and F with water have been studied by DFT (UB3LYP/6-311++G(2d,2p)) and ab initio (RHF-UCCSD(T)/6-311++G(2d,2p)) methods. In this order the number of lone pairs (from zero to three), the electronegativity, and the strength of the X-H bonds increase (X = C, N, and O). The various minima of the radical-water complexes were located using the multiple minima hypersurface (MMH) approach which had previously been proven to be useful for closed-shell molecules. The role of the unpaired electron in hydrogen bonding was investigated using the natural bond orbital (NBO) analysis. A considerable contribution of the unpaired electron to the complex stabilization was only found for the methyl radical and the fluorine atom, whereas in the aminyl and the hydroxyl radical the role of the unpaired electron is negligible

  11. Sulfate radical-based water treatment in presence of chloride: formation of chlorate, inter-conversion of sulfate radicals into hydroxyl radicals and influence of bicarbonate.

    Science.gov (United States)

    Lutze, Holger V; Kerlin, Nils; Schmidt, Torsten C

    2015-04-01

    Sulfate radical (SO4(-)) based oxidation is discussed as a potential water treatment option and is already used in ground water remediation. However, the complex SO4(-) chemistry in various matrices is poorly understood. In that regard, the fast reaction of SO4(-) with Cl(-) is of high importance since Cl(-) belongs to the main constituents in aqueous environments. This reaction yields chlorine atoms (Cl) as primary products. Cl initiate a cascade of subsequent reactions with a pH dependent product pattern. At low pH ( 5 Cl mainly react with water yielding hydroxyl radicals. Thus, at moderate Cl(-) concentrations (mM range) the SO4(-)-based process may be converted into a conventional (hydroxyl radical -based) advanced oxidation process. The conversion of SO4(-) into OH, however, is interrupted in presence of bicarbonate by scavenging of Cl. Copyright © 2014. Published by Elsevier Ltd.

  12. Muon level crossing resonance spectroscopy applied to free-radical formation

    International Nuclear Information System (INIS)

    Venkateswaran, K.; Barnabas, M.V.; Walker, D.C.

    1989-01-01

    Muon Level Crossing Resonance Spectroscopy has been used to explore two aspects of muonium chemistry: unique free radicals and muonated radical yields. (1) A variety of new free-radicals have been seen by LCR. For instance, in thioacetamide the only radical produced from muonium is the S sm-bullet radical formed when Mu adds to the C of the C=S bond. In allylbenzene a whole range of radicals form with substantial yields (two side-chain and three ring additions); whereas in styrene, 85% of the radicals have Mu bonded to the end C of the side-chain and there is no meta-adduct at all. (2) Absolute yields of the radicals formed by interaction of muonium atoms in water with acrylamide as a solute (and with benzene in n-hexane) have shown that all muons not directly incorporated into diamagnetic molecules (such as MuH) appear as muonated free radicals. i.e. the missing fraction is found

  13. The natural food colorant Peonidin from cranberries as a potential radical scavenger - A DFT based mechanistic analysis.

    Science.gov (United States)

    Rajan, Vijisha K; Hasna, C K; Muraleedharan, K

    2018-10-01

    A theoretical evaluation of the antioxidant property of a natural food colorant Peonidin has been performed. The most suitable mechanism for explaining the radical scavenging capacity of Peonidin is the Hydrogen Atom Transfer and the most active site for radical formation is position 3 and is confirmed through Mulliken charge analysis, pKa value evaluation, Bond Dissociation Energy values, and Natural Bond Orbital analysis. Position 3 and 5 in Peonidin exists in blood as deprotonated as their pKa values are lower than the pH of blood. Peonidin is highly reactive than Quercetin and less stable than flavan-3-ols due to the small band gap. Global descriptor analysis shows that PN prefers to accept electrons than to donate. The effect of number of OH groups and the nature of substituents are well explained through this work. Copyright © 2018 Elsevier Ltd. All rights reserved.

  14. Synchrotron-based valence shell photoionization of CH radical

    Energy Technology Data Exchange (ETDEWEB)

    Gans, B., E-mail: berenger.gans@u-psud.fr, E-mail: christian.alcaraz@u-psud.fr; Falvo, C. [Institut des Sciences Moléculaires d’Orsay (ISMO), CNRS, Univ. Paris-Sud, Université Paris-Saclay, F-91405 Orsay (France); Holzmeier, F.; Röder, A. [Institut of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg (Germany); Krüger, J.; Garcia, G. A. [Synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin BP 48, F-91192 Gif sur Yvette Cedex (France); Lopes, A.; Alcaraz, C., E-mail: berenger.gans@u-psud.fr, E-mail: christian.alcaraz@u-psud.fr [Laboratoire de Chimie Physique, UMR 8000 CNRS—Univ. Paris-Sud, Univ. Paris-Saclay, Bât. 350, Centre Universitaire Paris-Sud, F-91405 Orsay Cedex (France); Fittschen, C. [Université Lille, CNRS, UMR 8522–PC2A–Physicochimie des Processus de Combustion et de l’Atmosphère, F-59000 Lille (France); Loison, J.-C. [Institut des Sciences Moléculaires, UMR 5255 CNRS—Université de Bordeaux, Bât. A12, 351 cours de la Libération, F-33405 Talence Cedex (France)

    2016-05-28

    We report the first experimental observations of X{sup +} {sup 1}Σ{sup +}←X {sup 2}Π and a{sup +} {sup 3}Π←X {sup 2}Π single-photon ionization transitions of the CH radical performed on the DESIRS beamline at the SOLEIL synchrotron facility. The radical was produced by successive hydrogen-atom abstractions on methane by fluorine atoms in a continuous microwave discharge flow tube. Mass-selected ion yields and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The ion yield appears to be strongly affected by vibrational and electronic autoionizations, which allow the observation of high Rydberg states of the neutral species. The photoelectron spectra enable the first direct determinations of the adiabatic ionization potential and the energy of the first triplet state of the cation with respect to its singlet ground state. This work also brings valuable information on the complex electronic structure of the CH radical and its cation and adds new observations to complement our understanding of Rydberg states and autoionization processes.

  15. Analysis of conformations and ESR spectra of free radicals in carbohydrates

    International Nuclear Information System (INIS)

    Abaghyan, G.V.; Abaghyan, A.G.; Apresyan, A.S.

    1998-01-01

    The conformations of free radicals arising when the unpaired electron is localized on carbon atoms in pyranose ring of carbohydrate molecule are considered. On the base of the analysis of expected conformations of radicals a possible contribution of β-protons in hyperfine structure of ESP spectra is predicted. The results of conformational analysis for different types of free radicals are in satisfactory agreement with the corresponding experimental data for the liquid phase. 17 refs

  16. Bibliography on electron transfer processes in ion-ion/atom/molecule collisions, updated 1990

    International Nuclear Information System (INIS)

    Tawara, H.

    1990-08-01

    Following a previous compilation, new bibliographic information on experimental and theoretical studies on electron transfer processes in ion-ion/atom/molecule collisions is up-dated. The references published through 1989 are surveyed. For easy finding references for particular combination of collision partners, a simple list is also provided. Furthermore, for convenience, a copy of the previous compilation (IPPJ-AM-45 (1986)) is included. (author) 1363 refs

  17. Matrix effect on hydrogen-atom tunneling of organic molecules in cryogenic solids

    International Nuclear Information System (INIS)

    Ichikawa, Tsuneki

    2000-01-01

    Although the tunneling of atoms through potential energy barriers separating the reactant and reaction systems is not paid much attention in organic reactions, this plays an important role in reactions including the transfer of light atoms. Atomic tunneling is especially important for chemical reactions at low temperatures, since the thermal activation of reactant systems is very slow process in comparison with the tunneling. One of the typical reactions of atomic tunneling is hydrogen-atom abstraction from alkanes in cryogenic solids exposed to high-energy radiation. Irradiation of alkane molecules causes the homolytic cleavage of C-H bonds, which results in the pairwise formation of free hydrogen atoms and organic free radicals. Since the activation energies for the abstraction of hydrogen atoms from alkane molecules by free hydrogen atoms are higher than 5 kcal/mol, the lifetime of free hydrogen atoms at 77 K is estimated from the Arrhenius equation of k=vexp(-E a /RT) to be longer than 10 hrs. However, except for solid methane, free hydrogen atoms immediately convert to alkyl radicals even at 4.2 K by hydrogen-atom tunneling from alkane molecules to the free hydrogen atoms. The rate of hydrogen atom tunneling does not necessary increase with decreasing activation energy or the peak height of the potential energy barrier preventing the tunneling. Although the activation energy is the lowest at the tertiary carbon of alkanes, hydrogen atom tunneling from branched alkanes with tertiary carbon at the antepenultimate position of the carbon skeleton is the fastest at the secondary penultimate carbon. Based on our experimental results, we have proposed that the peculiarity of the hydrogen-atom abstraction in cryogenic solids comes from the steric hindrance by matrix molecules to the deformation of alkane molecules from the initial sp 3 to the final sp 2 configurations. The steric hindrance causes the increase of the height of the potential energy barrier for the

  18. Energy-Transfer Kinetics for Xe (6p[1/2]0) Atoms in Kr, Ar, Ne, and He.

    Science.gov (United States)

    He, Shan; Liu, Dong; Li, Xueyang; Chu, Junzhi; Guo, Jingwei; Liu, Jinbo; Hu, Shu; Sang, Fengting; Jin, Yuqi

    2018-06-11

    The kinetic processes for the Xe (6p[1/2] 0 ) atoms in Kr, Ar, Ne, and He buffer gases were studied. We found that Kr, Ar, and Ne atoms can be used to switch the amplified spontaneous emission (ASE) channel from 3408 nm (6p[1/2] 0 -6s'[1/2] 1 ) to 3680 nm (5d[1/2] 1 -6p[1/2] 1 ), while Xe and He atoms do not show such a phenomenon. This ASE channel switch is mainly ascribed to the fast transfer of 6p[1/2] 0 → 5d[1/2] 1 . On the basis of the rate equations for two-state coupling (energy-transfer processes between the two states are very rapid), the reason why the ASE channel switch effect normally coincides with a double exponential decay of the spontaneous emission at 828 nm (6p[1/2] 0 -6s[3/2] 1 ) is explained. The actual situations in Xe, Ar, Ne, and He follow this rule. However, the strictly single exponential decay of the spontaneous emission at 828 nm and strong ASE channel switch effect simultaneously emerge in Kr. This indicates that the transfer of 6p[1/2] 0 → 5d[1/2] 1 in Kr does not occur via two-state coupling, but via two steps of near-resonance collision through the 5s[3/2] 2 (Kr) state as the intermediate state (6p[1/2] 0 → 5s[3/2] 2 (Kr) → 5d[1/2] 1 ). In addition, we found Xe (6p[1/2] 0 ) atoms strongly tend to reach the 6p[3/2] 2 , 6p[3/2] 1 , and 6p[5/2] 2 states through the 5s[3/2] 2 (Kr) state as the intermediate state in Kr. The 5s[3/2] 2 (Kr) state plays a very important role in the energy-transfer kinetics for the Xe (6p[1/2] 0 ) atoms. Kr is probably an excellent buffer gas for laser systems based on Xe.

  19. Radical C-H functionalization to construct heterocyclic compounds.

    Science.gov (United States)

    Yu, Jin-Tao; Pan, Changduo

    2016-02-07

    Heterocyclic compounds are widely present in natural products, pharmaceuticals and bioactive molecules. Thus, organic and pharmaceutical chemists have been making extensive efforts to construct those heterocyclic frameworks through developing versatile and efficient synthetic strategies. The direct C-H functionalization via the radical pathway has emerged as a promising and dramatic approach towards heterocycles with high atom- and step-economy. Heterocyclic compounds such as coumarins, furans, benzofurans, xanthones, benzothiazoles, indoles, indolines, oxindoles, quinolines, isoquinolines, quinoxaline, and phenanthridines have been successfully synthesized by C-H functionalization through the radical pathway. In this review, recent advances on radical C-H functionalization to construct heterocyclic compounds are highlighted with discussions.

  20. PREFACE: Light element atom, molecule and radical behaviour in the divertor and edge plasma regions

    Science.gov (United States)

    Braams, Bastiaan J.; Chung, Hyun-Kung

    2015-01-01

    This volume of Journal of Physics: Conference Series contains contributions by participants in an International Atomic Energy Agency (IAEA) Coordinated Research Project (CRP) on "Light element atom, molecule and radical behaviour in the divertor and edge plasma regions" (in magnetic fusion devices). Light elements are the dominant impurity species in fusion experiments and in the near-wall plasma they occur as atoms or ions and also as hydrides and other molecules and molecular ions. Hydrogen (H or D, and T in a reactor) is the dominant species in fusion experiments, but all light elements He - O and Ne are of interest for various reasons. Helium is a product of the D+T fusion reaction and is introduced in experiments for transport studies. Lithium is used for wall coating and also as a beam diagnostic material. Beryllium is foreseen as a wall material for the ITER experiment and is used on the Joint European Torus (JET) experiment. Boron may be used as a coating material for the vessel walls. Carbon (graphite or carbon-fiber composite) is often used as the target material for wall regions subject to high heat load. Nitrogen may be used as a buffer gas for edge plasma cooling. Oxygen is a common impurity in experiments due to residual water vapor. Finally, neon is another choice as a buffer gas. Data for collisional and radiative processes involving these species are important for plasma modelling and for diagnostics. The participants in the CRP met 3 times over the years 2009-2013 for a research coordination meeting. Reports and presentation materials for these meetings are available through the web page on coordinated research projects of the (IAEA) Atomic and Molecular Data Unit [1]. Some of the numerical data generated in the course of the CRP is available through the ALADDIN database [2]. The IAEA takes the opportunity to thank the participants in the CRP for their dedicated efforts in the course of the CRP and for their contributions to this volume. The IAEA

  1. On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide

    DEFF Research Database (Denmark)

    Sánchez, Marina; Alkorta, Ibon; Elguero, José

    2014-01-01

    for the hydrogen, oxygen and carbon atoms as well as for the methyl group at the level of time-dependent density functional theory with the B3LYP exchange-correlation functional employing a large Gaussian basis set. We find that the atomic or group contributions are not transferable among these three molecules....

  2. Abstraction of iodine from aromatic iodides by alkyl radicals: steric and electronic effects.

    Science.gov (United States)

    Dolenc, Darko; Plesnicar, Bozo

    2006-10-13

    Abstraction of the iodine atom from aryl iodides by alkyl radicals takes place in some cases very efficiently despite the unfavorable difference in bond dissociation energies of C-I bonds in alkyl and aryl iodides. The abstraction is most efficient in iodobenzenes, ortho-substituted with bulky groups. The ease of abstraction can be explained by the release of steric strain during the elimination of the iodine atom. The rate of abstraction correlates fairly well with the strain energy, calculated by density functional theory (DFT) and Hartree-Fock (HF) methods as a difference in the total energy of ortho and para isomers. However, besides the steric bulk, the presence of some other functional groups in an ortho substituent also influences the rate. The stabilization of the transition state, resembling a 9-I-2 iodanyl radical, by electron-withdrawing groups seems to explain a positive sign of the Hammett rho value in the radical abstraction of halogen atoms.

  3. Olefin copolymerization using atom transfer radical polymerization (ATRP)

    NARCIS (Netherlands)

    Venkatesh, R.; Klumperman, B.

    2003-01-01

    Olefin copolymers of alpha-olefins with polar monomers with various architectures remain an ultimate goal in polyolefin engineering. The present paper is a more detailed study on the copolymn. of alpha-olefins (1-octene) with acrylates (Me acrylate). Comparison of reaction kinetics between free

  4. Enhanced binding capacity of boronate affinity adsorbent via surface modification of silica by combination of atom transfer radical polymerization and chain-end functionalization for high-efficiency enrichment of cis-diol molecules

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Wei; He, Maofang; Wang, Chaozhan; Wei, Yinmao, E-mail: ymwei@nwu.edu.cn

    2015-07-30

    Boronate affinity materials have been widely used for specific separation and preconcentration of cis-diol molecules, but most do not have sufficient capacity due to limited binding sites on the material surface. In this work, we prepared a phenylboronic acid-functionalized adsorbent with a high binding capacity via the combination of surface-initiated atom transfer radical polymerization (SI-ATRP) and chain-end functionalization. With this method, the terminal chlorides of the polymer chains were used fully, and the proposed adsorbent contains dense boronic acid polymers chain with boronic acid on the chain end. Consequently, the proposed adsorbent possesses excellent selectivity and a high binding capacity of 513.6 μmol g{sup −1} for catechol and 736.8 μmol g{sup −1} for fructose, which are much higher than those of other reported adsorbents. The dispersed solid-phase extraction (dSPE) based on the prepared adsorbent was used for extraction of three cis-diol drugs (i.e., epinephrine, isoprenaline and caffeic acid isopropyl ester) from plasma; the eluates were analyzed by HPLC-UV. The reduced amount of adsorbent (i.e., 2.0 mg) could still eliminate interferences efficiently and yielded a recovery range of 85.6–101.1% with relative standard deviations ranging from 2.5 to 9.7% (n = 5). The results indicated that the proposed strategy could serve as a promising alternative to increase the density of surface functional groups on the adsorbent; thus, the prepared adsorbent has the potential to effectively enrich cis-diol substances in real samples. - Highlights: • Boronate adsorbent is prepared via ATRP and chain-end functionalization. • The adsorbent has quite high binding capacity for cis-diols. • Binding capacity is easily manipulated by ATRP condition. • Chain-end functionalization can improve binding capacity significantly. • Reduced adsorbent is consumed in dispersed solid-phase extraction of cis-diols.

  5. Simple preparation of thiol-ene particles in glycerol and surface functionalization by thiol-ene chemistry (TEC) and surface chain transfer free radical polymerization (SCT-FRP)

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Chiaula, Valeria; Yu, Liyun

    2018-01-01

    functionalization of excess thiol groups via photochemical thiol-ene chemistry (TEC) resulting in a functional monolayer. In addition, surface chain transfer free radical polymerization (SCT-FRP) was used for the first time to introduce a thicker polymer layer on the particle surface. The application potential...

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

    International Nuclear Information System (INIS)

    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)

  7. 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....

  8. Mechanisms of free radical-induced damage to DNA.

    Science.gov (United States)

    Dizdaroglu, Miral; Jaruga, Pawel

    2012-04-01

    Endogenous and exogenous sources cause free radical-induced DNA damage in living organisms by a variety of mechanisms. The highly reactive hydroxyl radical reacts with the heterocyclic DNA bases and the sugar moiety near or at diffusion-controlled rates. Hydrated electron and H atom also add to the heterocyclic bases. These reactions lead to adduct radicals, further reactions of which yield numerous products. These include DNA base and sugar products, single- and double-strand breaks, 8,5'-cyclopurine-2'-deoxynucleosides, tandem lesions, clustered sites and DNA-protein cross-links. Reaction conditions and the presence or absence of oxygen profoundly affect the types and yields of the products. There is mounting evidence for an important role of free radical-induced DNA damage in the etiology of numerous diseases including cancer. Further understanding of mechanisms of free radical-induced DNA damage, and cellular repair and biological consequences of DNA damage products will be of outmost importance for disease prevention and treatment.

  9. Linear energy transfer (LET) effects in the radiation-induced inactivation of papain

    International Nuclear Information System (INIS)

    Bisby, R.H.; Cundall, R.B.; Sims, H.E.; Burns, W.G.

    1977-01-01

    The inactivation of dilute aqueous solutions of papain by radiations of varying linear energy transfer has been studied in N 2 , N 2 0 and O 2 -saturated solutions. The results obtained with low LET radiation are very similar to those previously reported by Lin et al (Radiation Res.;62:438(1975)). The additional data obtained at higher LET, when radical product yields are reduced and the yield of hydrogen peroxide is increased, show that the hydrogen atom is more important in the inactivation of papain than previously considered. (author)

  10. Atomic fusion, Gerrard atomic fusion

    International Nuclear Information System (INIS)

    Gerrard, T.H.

    1980-01-01

    In the approach to atomic fusion described here the heat produced in a fusion reaction, which is induced in a chamber by the interaction of laser beams and U.H.F. electromagnetic beams with atom streams, is transferred to a heat exchanger for electricity generation by a coolant flowing through a jacket surrounding the chamber. (U.K.)

  11. High-temperature shock tube and modeling studies on the reactions of methanol with D-atoms and CH3-radicals.

    Science.gov (United States)

    Peukert, S L; Michael, J V

    2013-10-10

    The shock tube technique has been used to study the hydrogen abstraction reactions D + CH3OH → CH2O + H + HD (A) and CH3 + CH3OH → CH2O + H + CH4 (B). For reaction A, the experiments span a T-range of 1016 K ≤ T ≤ 1325 K, at pressures 0.25 bar ≤ P ≤ 0.46 bar. The experiments on reaction B, CH3 + CH3OH, cover a T-range of 1138 K ≤ T ≤ 1270 K, at pressures around 0.40 bar. Reflected shock tube experiments, monitoring the depletion of D-atoms by applying D-atom atomic resonance absorption spectrometry (ARAS), were performed on reaction A using gas mixtures of C2D5I and CH3OH in Kr bath gas. C2D5I was used as precursor for D-atoms. For reaction B, reflected shock tube experiments monitoring H-atom formation with H-ARAS, were carried out using gas mixtures of diacetyl ((CH3CO)2) and CH3OH in Kr bath gas. (CH3CO)2 was used as the source of CH3-radicals. Detailed reaction models were assembled to fit the D-atom and H-atom time profiles in order to obtain experimental rate constants for reactions A and B. Total rate constants from the present experiments on D + CH3OH and CH3 + CH3OH can be represented by the Arrhenius equations kA(T) = 1.51 × 10(-10) exp(-3843 K/T) cm(3) molecules(-1) s(-1) (1016 K ≤ T ≤ 1325 K) and kB(T) = 9.62 × 10(-12) exp(-7477 K/T) cm(3) molecules(-1) s(-1) (1138 K ≤ T ≤ 1270 K). The experimentally obtained rate constants were compared with available rate data from the literature. The results from quantum chemical studies on reaction A were found to be in good agreement with the present results. The present work represents the first direct experimental study on these bimolecular reactions at combustion temperatures and is important to the high-temperature oxidation of CH3OH.

  12. Entanglement transfer between bipartite systems

    International Nuclear Information System (INIS)

    Bougouffa, Smail; Ficek, Zbigniew

    2012-01-01

    The problem of a controlled transfer of an entanglement initially encoded into two two-level atoms that are successively sent through two single-mode cavities is investigated. The atoms and the cavity modes form a four-qubit system and we demonstrate the conditions under which the initial entanglement encoded into the atoms can be completely transferred to other pairs of qubits. We find that in the case of non-zero detuning between the atomic transition frequencies and the cavity mode frequencies, no complete transfer of the initial entanglement is possible to any of the other pairs of qubits. In the case of exact resonance and equal coupling strengths of the atoms to the cavity modes, an initial maximally entangled state of the atoms can be completely transferred to the cavity modes. Complete transfer of the entanglement is restricted to the cavity modes, with transfer to the other pairs being limited to 50%. We find that complete transfer of an initial entanglement to other pairs of qubits may take place if the initial state is not the maximally entangled state and the atoms couple to the cavity modes with unequal strengths. Depending on the ratio between the coupling strengths, optimal entanglement can be created between the atoms and one of the cavity modes.

  13. Polar-Nonpolar Radical Copolymerization under Li+ Catalysis

    Science.gov (United States)

    2008-09-21

    bonds or aromatic rings. Thus, we propose that a transfer of a methyl radical from CB11Me12C to IB triggers a radical polymerization chain that yields ...b-PIB and the resulting CB11Me11 byproduct concurrently triggers a cationic polymerization chain that yields l-PIB terminated with a carborate anion...tetrahydrofuran and passed through a column of alumina about five times to remove the bulk of the catalyst. A Soxhlet apparatus was used to recover

  14. Radioprotective effects of dimethyl sulfoxide in golden hamster embryo cells exposed to gamma rays at 77 K. I. Radical formation as studied by electron spin resonance

    International Nuclear Information System (INIS)

    Miyazaki, T.; Hayakawa, Y.; Suzuki, K.; Suzuki, M.; Watanabe, M.

    1990-01-01

    Formation of free radicals in golden hamster embryo (GHE) cells in the frozen living state by gamma irradiation has been studied by electron spin resonance spectroscopy at 4.2 and 77 K. The relative yields of H atoms, OH radicals, and organic radicals trapped in the irradiated GHE cells are 12, 72, and 16%, respectively, of total radical yields. When dimethylsulfoxide (DMSO) is added to GHE cells at 77 K, a large quantity of CH2SOCH3 radicals (DMSO radicals) are formed after gamma irradiation. The yields of OH radicals are not affected by the addition of DMSO. When the GHE cell-DMSO mixtures are irradiated with gamma rays at 77 K and then warmed to 111 K, the OH radicals decay, whereas the DMSO radicals do not increase complementarily. Moreover, the decay rates of the OH radicals at 111 K do not depend upon the concentration of DMSO. Thus OH radicals do not react with DMSO during warming of the irradiated sample. When H atoms are produced by gamma irradiation of acid ice at 60 K, the decay rates of the H atoms at 77 K increase with increasing DMSO concentration, indicating that DMSO reacts with H atoms (CH3SOCH3 + H----.CH2SOCH3 + H2) at 77 K by quantum-mechanical tunneling. When the GHE cell-DMSO mixture is irradiated with gamma rays at 77 or 4.2 K in the dark, DMSO ions are produced in addition to DMSO radicals. Therefore it is concluded that DMSO does not scavenge OH radicals, but does capture H atoms, holes and/or electrons in the gamma-irradiated cells, resulting in the remarkable formation of DMSO radicals. This scavenger effect of DMSO may be related to the radioprotection of DMSO against cell killing

  15. An Atomic Gravitational Wave Interferometric Sensor (AGIS)

    Energy Technology Data Exchange (ETDEWEB)

    Dimopoulos, Savas; /Stanford U., Phys. Dept.; Graham, Peter W.; /SLAC; Hogan, Jason M.; Kasevich, Mark A.; /Stanford U., Phys. Dept.; Rajendran, Surjeet; /SLAC /Stanford U., Phys. Dept.

    2008-08-01

    We propose two distinct atom interferometer gravitational wave detectors, one terrestrial and another satellite-based, utilizing the core technology of the Stanford 10m atom interferometer presently under construction. Each configuration compares two widely separated atom interferometers run using common lasers. The signal scales with the distance between the interferometers, which can be large since only the light travels over this distance, not the atoms. The terrestrial experiment with baseline {approx} 1 km can operate with strain sensitivity {approx} 10{sup -19}/{radical}Hz in the 1 Hz-10 Hz band, inaccessible to LIGO, and can detect gravitational waves from solar mass binaries out to megaparsec distances. The satellite experiment with baseline {approx} 1000 km can probe the same frequency spectrum as LISA with comparable strain sensitivity {approx} 10{sup -20}/{radical}Hz. The use of ballistic atoms (instead of mirrors) as inertial test masses improves systematics coming from vibrations, acceleration noise, and significantly reduces spacecraft control requirements. We analyze the backgrounds in this configuration and discuss methods for controlling them to the required levels.

  16. Mulliken-Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical

    International Nuclear Information System (INIS)

    Rosokha, S.V.; Newton, M.D.; Head-Gordon, M.; Kochi, J.K.

    2006-01-01

    The paramagnetic [1:1] encounter complex (TCNE) 2 -dot is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor (TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE) 2 -dot by its intervalence absorption band at the solvent-dependent wavelength of λ IV ∼1500nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of H DA =1000cm -1 . The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of H DA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy (λ) and the electronic coupling element (H DA ) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes

  17. The mechanisms of radical formation in L-α-alanine

    International Nuclear Information System (INIS)

    Bugay, A.A.; Onischuk, V.A.; Petrenko, T.L.; Teslenko, V.V.

    2000-01-01

    Modeling of radical transformations in L-α-alanine after irradiation was performed for isolated radicals and for clusters. Special attention was devoted to the explanation of the experimental results concerning selective proton transfer and behavior of cation-radicals because a unique interpretation of the corresponding experiments is very difficult. Both semi-empirical and ab initio methods were used depending on the size of system under investigation. The results obtained show the usefulness of the computer simulation for processes in rather complex materials used in dosimetry

  18. The use of iteration factors in the solution of the NLTE line transfer problem-II. Multilevel atom

    International Nuclear Information System (INIS)

    Kuzmanovska-Barandovska, O.; Atanackovic, O.

    2010-01-01

    The iteration factors method (IFM) developed in Paper I (Atanackovic-Vukmanovic and Simonneau, 1994) to solve the NLTE line transfer problem for a two-level atom model, is extended here to deal with a multilevel atom case. At the beginning of each iteration step, for each line transition, angle and frequency averaged depth-dependent iteration factors are computed from the formal solution of radiative transfer (RT) equation and used to close the system of the RT equation moments, non-linearly coupled with the statistical equilibrium (SE) equations. Non-linear coupling of the atomic level populations and the corresponding line radiation field intensities is tackled in two ways. One is based on the linearization of the equations with respect to the relevant variables, and the other on the use of the old (known from the previous iteration) level populations in the line-opacity-like terms of the SE equations. In both cases the use of quasi-invariant iteration factors provided very fast and accurate solution. The properties of the proposed procedures are investigated in detail by applying them to the solution of the prototype multilevel RT problem of Avrett and Loeser , and compared with the properties of some other methods.

  19. Transverse flow reactor studies of the dynamics of radical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Macdonald, R.G. [Argonne National Laboratory, IL (United States)

    1993-12-01

    Radical reactions are in important in combustion chemistry; however, little state-specific information is available for these reactions. A new apparatus has been constructed to measure the dynamics of radical reactions. The unique feature of this apparatus is a transverse flow reactor in which an atom or radical of known concentration will be produced by pulsed laser photolysis of an appropriate precursor molecule. The time dependence of individual quantum states or products and/or reactants will be followed by rapid infrared laser absorption spectroscopy. The reaction H + O{sub 2} {yields} OH + O will be studied.

  20. Investigation of polar and stereoelectronic effects on pure excited-state hydrogen atom abstractions from phenols and alkylbenzenes.

    Science.gov (United States)

    Pischel, Uwe; Patra, Digambara; Koner, Apurba L; Nau, Werner M

    2006-01-01

    The fluorescence quenching of singlet-excited 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by 22 phenols and 12 alkylbenzenes has been investigated. Quenching rate constants in acetonitrile are in the range of 10(8)-10(9) M(-1)s(-1) for phenols and 10(5)-10(6) M(-1)s(-1) for alkylbenzenes. In contrast to the quenching of triplet-excited benzophenone, no exciplexes are involved, so that a pure hydrogen atom transfer is proposed as quenching mechanism. This is supported by (1) pronounced deuterium isotope effects (kH/kD ca 4-6), which were observed for phenols and alkylbenzenes, and (2) a strongly endergonic thermodynamics for charge transfer processes (electron transfer, exciplex formation). In the case of phenols, linear free energy relationships applied, which led to a reaction constant of rho = -0.40, suggesting a lower electrophilicity of singlet-excited DBO than that of triplet-excited ketones and alkoxyl radicals. The reactivity of singlet-excited DBO exposes statistical, steric, polar and stereoelectronic effects on the hydrogen atom abstraction process in the absence of complications because of competitive exciplex formation.

  1. Cross sections for energy transfer in collisions between two excited sodium atoms

    International Nuclear Information System (INIS)

    Huennekens, J.; Gallagher, A.

    1983-01-01

    We have measured cross sections, sigma/sub n/L, for the excitation transfer process Na(3P)+Na(3P)→Na(3S)+Na(nL), where nL is the 4D or 5S level. Our results are sigma/sub 4D/ = 23 A 2 +- 35% and sigma/sub 5S/ = 16 A 2 +- 35% at Tapprox.600 K. To obtain these cross sections we have used pulsed excitation and measured the intensities of 4D, 5S, and 3P fluorescence emissions, and the spatial distribution of excited atoms resulting from radiation diffusion, as well as the excited atom density as a function of time. Additionally, we have accounted for (time-dependent) radiation trapping of 3P and nL level radiation and for the resulting anisotropies of these fluorescence emissions. Comparisons of our results with theory have been made, and their relevance to other experiments is discussed

  2. Electron transfer to sulfides:

    International Nuclear Information System (INIS)

    Meneses, Ana Belen; Antonello, Sabrina; Arevalo, Maria Carmen; Maran, Flavio

    2005-01-01

    The problem of characterizing the steps associated with the dissociative reduction of sulfides has been addressed. The electrochemical reduction of diphenylmethyl para-methoxyphenyl sulfide in N,N-dimethylformamide, on both glassy carbon and mercury electrodes, was chosen as a test system. The electrode process involves the slow heterogeneous outer-sphere electron transfer to the sulfide, the fast cleavage of the C-S bond, the reduction of the ensuing carbon radical, and the self-protonation triggered by the generation of the strong base Ph 2 CH - . The latter reaction is rather slow, in agreement with the large intrinsic barriers characterizing proton transfers between CH-acids and carbon bases. The dissociative reduction was studied in the presence of an exogenous acid. The results, obtained by convolution analysis, point to a stepwise DET mechanism in which the ET step is accompanied by rather large reorganization energy. Similar results were obtained on both electrode materials. Analysis of the heterogeneous electron transfer and associated C-S bond cleavage indicate that the reduction of this and other sulfides lies between the stepwise dissociative electron transfers leading to the formation of stiff π* radical anions and those going through the intermediacy of loose σ* radical anions

  3. Preparation of Transparent Bulk TiO2/PMMA Hybrids with Improved Refractive Indices via an in Situ Polymerization Process Using TiO2 Nanoparticles Bearing PMMA Chains Grown by Surface-Initiated Atom Transfer Radical Polymerization.

    Science.gov (United States)

    Maeda, Satoshi; Fujita, Masato; Idota, Naokazu; Matsukawa, Kimihiro; Sugahara, Yoshiyuki

    2016-12-21

    Transparent TiO 2 /PMMA hybrids with a thickness of 5 mm and improved refractive indices were prepared by in situ polymerization of methyl methacrylate (MMA) in the presence of TiO 2 nanoparticles bearing poly(methyl methacrylate) (PMMA) chains grown using surface-initiated atom transfer radical polymerization (SI-ATRP), and the effect of the chain length of modified PMMA on the dispersibility of modified TiO 2 nanoparticles in the bulk hybrids was investigated. The surfaces of TiO 2 nanoparticles were modified with both m-(chloromethyl)phenylmethanoyloxymethylphosphonic acid bearing a terminal ATRP initiator and isodecyl phosphate with a high affinity for common organic solvents, leading to sufficient dispersibility of the surface-modified particles in toluene. Subsequently, SI-ATRP of MMA was achieved from the modified surfaces of the TiO 2 nanoparticles without aggregation of the nanoparticles in toluene. The molecular weights of the PMMA chains cleaved from the modified TiO 2 nanoparticles increased with increases in the prolonging of the polymerization period, and these exhibited a narrow distribution, indicating chain growth controlled by SI-ATRP. The nanoparticles bearing PMMA chains were well-dispersed in MMA regardless of the polymerization period. Bulk PMMA hybrids containing modified TiO 2 nanoparticles with a thickness of 5 mm were prepared by in situ polymerization of the MMA dispersion. The transparency of the hybrids depended significantly on the chain length of the modified PMMA on the nanoparticles, because the modified PMMA of low molecular weight induced aggregation of the TiO 2 nanoparticles during the in situ polymerization process. The refractive indices of the bulk hybrids could be controlled by adjusting the TiO 2 content and could be increased up to 1.566 for 6.3 vol % TiO 2 content (1.492 for pristine PMMA).

  4. Study of elementary transfer mechanisms during a collision between a swift multi-charged heavy ion and a neutral atom

    International Nuclear Information System (INIS)

    Jardin, P.

    1995-01-01

    This work is dedicated to the study of the energy transfer mechanisms which occur during a collision between a swift multicharged heavy ion and a neutral atom. The elementary energy energy transfer mechanisms (scattering, excitation, ionization, capture) and their consequences on the target velocity after the collision (recoil velocity) are recalled in the first chapter. In the case of small projectile diffusion angles, we show that the recoil velocity component, transverse to the incident projectile direction, results principally from the diffusion mechanism, while the longitudinal component is due essentially to the mass transfer and the inelastic energy transfer mechanisms. Since the target recoil velocities are very small, we have built an experimental set-up which reduces the impreciseness on their measurement due to the target thermal spread using, as targets, cooled atoms of a supersonic jet (temperature 44+ (6.7 MeV/A) + Ar => Xe 44 + Ar q+ +qe - (q ranging from 1 to 7); Xe 44+ (6.7 MeV/A) + He => Xe 44+ He 1+,2+ +1e - ,2e - . We show that it is possible to interpret the recoil velocity in terms of kinetic energy transferred to the target and to the electrons ejected from the target. (author)

  5. RADICAL SCAVENGING ACTIVITY OF SOME NATURAL ...

    African Journals Online (AJOL)

    Hydrogen atom transfer (HAT) and one-electron transfer mechanisms have ... In this work, the structural, electronic and molecular properties were ..... modification to tune the electronic and charge transport properties of solar cell materials:.

  6. Vinylimidazole-Based Asymmetric Ion Pair Comonomers: Synthesis, Polymerization Studies and Formation of Ionically Crosslinked PMMA

    NARCIS (Netherlands)

    Jana, S.; Vasantha, V.A.; Stubbs, L.P.; Parthiban, A.; Vancso, Gyula J.

    2013-01-01

    Vinylimidazole-based asymmetric ion pair comonomers (IPCs) which are free from nonpolymerizable counter ions have been synthesized, characterized and polymerized by free radical polymerization (FRP), atom transfer radical polymerization (ATRP), and reversible addition-fragmentation chain transfer

  7. Free radical reactions of monochloramine and hydroxylamine in aqueous solution

    International Nuclear Information System (INIS)

    Johnson, H.D.; Cooper, William J.; Mezyk, Stephen P.; Bartels, David M.

    2002-01-01

    The use of Advanced Oxidation Technologies to destroy organic contaminants in drinking water may be impacted by the presence of disinfection chemicals such as monochloramine (NH 2 Cl). To allow a quantitative evaluation of the effect of NH 2 Cl on the destruction of organics in water rate constants for its reaction with the hydrated electron, the hydroxyl radical and the hydrogen atom were determined in this study. The corresponding values of (2.2±0.2)x10 10 , (2.8±0.2)x10 9 , and (1.2±0.1)x10 9 M -1 s -1 , respectively, were incorporated into a kinetic computer model whose predictions were in good agreement with experimental chloramine removal under large scale, steady-state electron-beam irradiation conditions. Rate constants were also determined for the reaction of the hydroxyl radical and hydrogen atom with the chloramine hydration product hydroxylamine to supplement established literature data. Hydroxyl radical rate constants for the basic (NH 2 OH) and acidic (NH 3 OH + ) forms were determined as (8.5±0.4)x10 9 and ≤5x10 7 M -1 s -1 , respectively, while for hydrogen atom reaction, corresponding rate constants of (4.5±0.1)x10 7 and (3.6±1.5)x10 5 M -1 s -1 were found

  8. Unimolecular reaction dynamics of free radicals

    International Nuclear Information System (INIS)

    Terry A. Miller

    2006-01-01

    Free radical reactions are of crucial importance in combustion and in atmospheric chemistry. Reliable theoretical models for predicting the rates and products of these reactions are required for modeling combustion and atmospheric chemistry systems. Unimolecular reactions frequently play a crucial role in determining final products. The dissociations of vinyl, CH2= CH, and methoxy, CH3O, have low barriers, about 13,000 cm-1 and 8,000 cm-1, respectively. Since barriers of this magnitude are typical of free radicals these molecules should serve as benchmarks for this important class of reactions. To achieve this goal, a detailed understanding of the vinyl and methoxy radicals is required. Results for dissociation dynamics of vinyl and selectively deuterated vinyl radical are reported. Significantly, H-atom scrambling is shown not to occur in this reaction. A large number of spectroscopic experiments for CH3O and CHD2O have been performed. Spectra recorded include laser induced fluorescence (LIF), laser excited dispersed fluorescence (LEDF), fluorescence dip infrared (FDIR) and stimulated emission pumping (SEP). Such results are critical for implementing dynamics experiments involving the dissociation of methoxy

  9. Charge transfer of O3+ ions with atomic hydrogen

    International Nuclear Information System (INIS)

    Wang, J.G.; Stancil, P.C.; Turner, A.R.; Cooper, D.L.

    2003-01-01

    Charge transfer processes due to collisions of ground state O 3+ (2s 2 2p 2 P) ions with atomic hydrogen are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method. The MOCC calculations utilize ab initio adiabatic potentials and nonadiabatic radial and rotational coupling matrix elements obtained with the spin-coupled valence-bond approach. Total and state-selective cross sections and rate coefficients are presented. Comparison with existing experimental and theoretical data shows our results to be in better agreement with the measurements than the previous calculations, although problems with some of the state-selective measurements are noted. Our calculations demonstrate that rotational coupling is not important for the total cross section, but for state-selective cross sections, its relevance increases with energy. For the ratios of triplet to singlet cross sections, significant departures from a statistical value are found, generally in harmony with experiment

  10. Charge transfer of O3+ ions with atomic hydrogen

    Science.gov (United States)

    Wang, J. G.; Stancil, P. C.; Turner, A. R.; Cooper, D. L.

    2003-01-01

    Charge transfer processes due to collisions of ground state O3+(2s22p 2P) ions with atomic hydrogen are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method. The MOCC calculations utilize ab initio adiabatic potentials and nonadiabatic radial and rotational coupling matrix elements obtained with the spin-coupled valence-bond approach. Total and state-selective cross sections and rate coefficients are presented. Comparison with existing experimental and theoretical data shows our results to be in better agreement with the measurements than the previous calculations, although problems with some of the state-selective measurements are noted. Our calculations demonstrate that rotational coupling is not important for the total cross section, but for state-selective cross sections, its relevance increases with energy. For the ratios of triplet to singlet cross sections, significant departures from a statistical value are found, generally in harmony with experiment.

  11. Charge transfer incollisions of Li3+ and Be4+ ions with atomic hydrogen at low impact energy

    International Nuclear Information System (INIS)

    Ohyama, T.; Itikawa, Y.

    1981-08-01

    Total charge transfer cross sections are calculated for the collisions of Li 3+ and Be 4+ ions with H(1s) atoms in the low energy region (E 3+ -H system, a reasonable agreement is found between the present calculation and the recent experiment. (author)

  12. Radical fragmentation of six-membered oxygen-containing heterocycles

    International Nuclear Information System (INIS)

    Petryaev, E.P.; Kosobutskij, V.S.; Shadyro, O.I.

    1982-01-01

    Using chromatography, the composition and radiation-chemical yields of final products of desctruction of six-member saturated oxygen-containing heterocycles (the effect of #betta#-radiation on aqueous solutions of tetrahydropyran, 1,3-dioxane, 2,2 dimethyl-1,3 dioxane, 1,4-dioxane, paraldehyde) have been determined. It is established that the identified products are formed at the expense of decomposition of primary radicals of the initial compounds and point to the realization of the following fragmentation ways: 1) #betta#-scattering, 2) #betta#-scattering with a subsequent 1,5 migration of an H atom, 3) simultaneous rupture of two vicinal, relative to the radical center, bonds. A formation mechanism of the substances desctruction products is suggested. Material balance of the product yields of 1,3-dioxane radical synchronous decomposition is presented

  13. Electron transfer reactions

    CERN Document Server

    Cannon, R D

    2013-01-01

    Electron Transfer Reactions deals with the mechanisms of electron transfer reactions between metal ions in solution, as well as the electron exchange between atoms or molecules in either the gaseous or solid state. The book is divided into three parts. Part 1 covers the electron transfer between atoms and molecules in the gas state. Part 2 tackles the reaction paths of oxidation states and binuclear intermediates, as well as the mechanisms of electron transfer. Part 3 discusses the theories and models of the electron transfer process; theories and experiments involving bridged electron transfe

  14. Muon transfer rates in collisions of hydrogen isotope mesic atoms on 'bare' nuclei. Multichannel adiabatic approach

    International Nuclear Information System (INIS)

    Korobov, V.I.; Melezhik, V.S.; Ponomarev, L.I.

    1992-01-01

    A numerical scheme for solving the problem of slow collisions in the three-body adiabatic approach is applied for calculation of muon transfer rates in collisions of hydrogen isotope atoms on bare nuclei. It is demonstrated that the multichannel adiabatic approach allows one to reach high accuracy results (∼3%) estimating the cross sections of charge transfer processes which are the best ones up to date. The method is appliable in a wide range of energies (0.001-50 eV) which is of interest for analysis of muon catalysed fusion experiments. 20 refs.; 3 figs.; 5 tabs

  15. Cyanide Ligand Assembly by Carbon Atom Transfer to an Iron Nitride

    International Nuclear Information System (INIS)

    Martinez, Jorge L.; Pink, Maren

    2017-01-01

    The new iron(IV) nitride complex PhB( i Pr 2 Im) 3 Fe≡N reacts with two equivalents of bis(diisopropylamino)cyclopropenylidene (BAC) to provide PhB( i Pr 2 Im) 3 Fe(CN)(N 2 )(BAC). This unusual example of a four-electron reaction involves carbon atom transfer from BAC to create a cyanide ligand along with the alkyne i Pr 2 N-C≡C-N i Pr 2 . The iron complex is in equilibrium with an N 2 - free species. Further reaction with CO leads to formation of a CO analogue, which can be independently prepared using NaCN as the cyanide source, while reaction with B(C 6 F 5 ) 3 provides the cyanoborane derivative.

  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. Transients observed in the low temperature photolysis of alkyl radicals and divalent sulfur substrates

    International Nuclear Information System (INIS)

    Adam, F.C.

    1976-01-01

    The 253.7 nm photolysis of the isometric butyl radicals is described. These radicals are produced by electron capture during the γ-radiolysis of the corresponding butyl chlorides diluted in a rigid glass of 3-methylpentane-d14 at 77K. Thus t-butyl gives an equilibrium mixture of i-butyl and methyl radicals. Solvent radicals, M, are also produced and these obscure the former species in 3-MP-h14. Likewise sec-butyl radicals give rise to the ethyl, n-butyl, methyl and small amounts of the i-butyl radicals. Solvent radicals also rearrange and degrade in the photolytic beam, and the mechanism by which these processes occur is discussed. The procedure has also been used to study the formation and photolability of the alkyl thinyl and perthyl radicals occuring in the photolysis of RSH, RSR and RSSR. The thinyl radical is found to be unstable and gives the alkyl radical and atomic sulfur while the perthiyl radical is stable to radiation > 240 nm. (author)

  18. Radical clashes : what tangible interaction is made of

    NARCIS (Netherlands)

    Dijk, van J.; Mousette, C.; Kuenen, C.D.; Hummels, C.C.M.

    2013-01-01

    Driven by a critique of Ishii et al's recent vision of Radical Atoms we call for a debate on the different conceptual paradigms underlying the TEI community and its activities. TEI was initiated to share and connect different perspectives, but we feel conceptual debate is lacking. To fuel this

  19. Atomic Covalent Functionalization of Graphene

    Science.gov (United States)

    Johns, James E.; Hersam, Mark C.

    2012-01-01

    Conspectus Although graphene’s physical structure is a single atom thick, two-dimensional, hexagonal crystal of sp2 bonded carbon, this simple description belies the myriad interesting and complex physical properties attributed to this fascinating material. Because of its unusual electronic structure and superlative properties, graphene serves as a leading candidate for many next generation technologies including high frequency electronics, broadband photodetectors, biological and gas sensors, and transparent conductive coatings. Despite this promise, researchers could apply graphene more routinely in real-world technologies if they could chemically adjust graphene’s electronic properties. For example, the covalent modification of graphene to create a band gap comparable to silicon (~1 eV) would enable its use in digital electronics, and larger band gaps would provide new opportunities for graphene-based photonics. Towards this end, researchers have focused considerable effort on the chemical functionalization of graphene. Due to its high thermodynamic stability and chemical inertness, new methods and techniques are required to create covalent bonds without promoting undesirable side reactions or irreversible damage to the underlying carbon lattice. In this Account, we review and discuss recent theoretical and experimental work studying covalent modifications to graphene using gas phase atomic radicals. Atomic radicals have sufficient energy to overcome the kinetic and thermodynamic barriers associated with covalent reactions on the basal plane of graphene but lack the energy required to break the C-C sigma bonds that would destroy the carbon lattice. Furthermore, because they are atomic species, radicals substantially reduce the likelihood of unwanted side reactions that confound other covalent chemistries. Overall, these methods based on atomic radicals show promise for the homogeneous functionalization of graphene and the production of new classes of two

  20. Reductive Umpolung of Carbonyl Derivatives with Visible-Light Photoredox Catalysis: Direct Access to Vicinal Diamines and Amino Alcohols via α-Amino Radicals and Ketyl Radicals

    KAUST Repository

    Fava, Eleonora; Millet, Anthony; Nakajima, Masaki; Loescher, Sebastian; Rueping, Magnus

    2016-01-01

    Visible-light-mediated photoredox-catalyzed aldimine-aniline and aldehyde-aniline couplings have been realized. The reductive single electron transfer (SET) umpolung of various carbonyl derivatives enabled the generation of intermediary ketyl and α-amino radical anions, which were utilized for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols. Anilines can be coupled with aldimines or aldehydes in a visible-light-mediated photoredox-catalyzed process. Reductive single electron transfer (SET) umpolung of the carbonyl derivatives leads to the generation of intermediary ketyl and α-amino radical anions, which were used for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols.

  1. Reductive Umpolung of Carbonyl Derivatives with Visible-Light Photoredox Catalysis: Direct Access to Vicinal Diamines and Amino Alcohols via α-Amino Radicals and Ketyl Radicals

    KAUST Repository

    Fava, Eleonora

    2016-05-02

    Visible-light-mediated photoredox-catalyzed aldimine-aniline and aldehyde-aniline couplings have been realized. The reductive single electron transfer (SET) umpolung of various carbonyl derivatives enabled the generation of intermediary ketyl and α-amino radical anions, which were utilized for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols. Anilines can be coupled with aldimines or aldehydes in a visible-light-mediated photoredox-catalyzed process. Reductive single electron transfer (SET) umpolung of the carbonyl derivatives leads to the generation of intermediary ketyl and α-amino radical anions, which were used for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols.

  2. Exploring the Role of Persulfate in the Activation Process: Radical Precursor Versus Electron Acceptor.

    Science.gov (United States)

    Yun, Eun-Tae; Yoo, Ha-Young; Bae, Hyokwan; Kim, Hyoung-Il; Lee, Jaesang

    2017-09-05

    This study elucidates the mechanism behind persulfate activation by exploring the role of various oxyanions (e.g., peroxymonosulfate, periodate, and peracetate) in two activation systems utilizing iron nanoparticle (nFe 0 ) as the reducing agent and single-wall carbon nanotubes (CNTs) as electron transfer mediators. Since the tested oxyanions serve as both electron acceptors and radical precursors in most cases, oxidative degradation of organics was achievable through one-electron reduction of oxyanions on nFe 0 (leading to radical-induced oxidation) and electron transfer mediation from organics to oxyanions on CNTs (leading to oxidative decomposition involving no radical formation). A distinction between degradative reaction mechanisms of the nFe 0 /oxyanion and CNT/oxyanion systems was made in terms of the oxyanion consumption efficacy, radical scavenging effect, and EPR spectral analysis. Statistical study of substrate-specificity and product distribution implied that the reaction route induced on nFe 0 varies depending on the oxyanion (i.e., oxyanion-derived radical), whereas the similar reaction pathway initiates organic oxidation in the CNT/oxyanion system irrespective of the oxyanion type. Chronoamperometric measurements further confirmed electron transfer from organics to oxyanions in the presence of CNTs, which was not observed when applying nFe 0 instead.

  3. Teaching Semantic Radicals Facilitates Inferring New Character Meaning in Sentence Reading for Nonnative Chinese Speakers

    Directory of Open Access Journals (Sweden)

    Thi Phuong Nguyen

    2017-10-01

    Full Text Available This study investigates the effects of teaching semantic radicals in inferring the meanings of unfamiliar characters among nonnative Chinese speakers. A total of 54 undergraduates majoring in Chinese Language from a university in Hanoi, Vietnam, who had 1 year of learning experience in Chinese were assigned to two experimental groups that received instructional intervention, called “old-for-new” semantic radical teaching, through two counterbalanced sets of semantic radicals, with one control group. All of the students completed pre- and post-tests of a sentence cloze task where they were required to choose an appropriate character that fit the sentence context among four options. The four options shared the same phonetic radicals but had different semantic radicals. The results showed that the pre-test and post-test score increases were significant for the experimental groups, but not for the control group. Most importantly, the experimental groups successfully transferred the semantic radical strategy to figure out the meanings of unfamiliar characters containing semantic radicals that had not been taught. The results demonstrate the effectiveness of teaching semantic radicals for lexical inference in sentence reading for nonnative speakers, and highlight the ability of transfer learning to acquire semantic categories of sub-lexical units (semantic radicals in Chinese characters among foreign language learners.

  4. Rate constants for the reactions of free radicals with oxygen in solution

    International Nuclear Information System (INIS)

    Maillard, B.; Ingold, K.U.; Scaiano, J.C.

    1983-01-01

    The kinetics of the rections of several free radicals with oxygen have been examined in solution at 300 K using laser flash photolysis techniques. The reactions of resonance-stabilized radicals are only slightly slower than those of nonstabilized radicals: for example, for tert-butyl (in cyclohexane), 4.93 x 10 9 ; benzyl, 2.36 x 10 9 (in cyclohexane); cyclohexadienyl (in benzene), 1.64 x 10 9 M -1 s -1 . The reaction of butyl-tin (n-Bu 3 Sn.) radicals is unusually fast (7.5 x 10 9 M -1 s -1 ), a fact that has been tentatively attributed to a relaxation of spin selection rules due to heavy atom effects. 1 table

  5. Attenuation of hydrogen radicals traveling under flowing gas conditions through tubes of different materials

    International Nuclear Information System (INIS)

    Grubbs, R.K.; George, S.M.

    2006-01-01

    Hydrogen radical concentrations traveling under flowing gas conditions through tubes of different materials were measured using a dual thermocouple probe. The source of the hydrogen radicals was a toroidal radio frequency plasma source operating at 2.0 and 3.3 kW for H 2 pressures of 250 and 500 mTorr, respectively. The dual thermocouple probe was comprised of exposed and covered Pt/Pt13%Rh thermocouples. Hydrogen radicals recombined efficiently on the exposed thermocouple and the energy of formation of H 2 heated the thermocouple. The second thermocouple was covered by glass and was heated primarily by the ambient gas. The dual thermocouple probe was translated and measured temperatures at different distances from the hydrogen radical source. These temperature measurements were conducted at H 2 flow rates of 35 and 75 SCCM (SCCM denotes cubic centimeter per minute at STP) inside cylindrical tubes made of stainless steel, aluminum, quartz, and Pyrex. The hydrogen radical concentrations were obtained from the temperatures of the exposed and covered thermocouples. The hydrogen concentration decreased versus distance from the plasma source. After correcting for the H 2 gas flow using a reference frame transformation, the hydrogen radical concentration profiles yielded the atomic hydrogen recombination coefficient, γ, for the four materials. The methodology of measuring the hydrogen radical concentrations, the analysis of the results under flowing gas conditions, and the determination of the atomic hydrogen recombination coefficients for various materials will help facilitate the use of hydrogen radicals for thin film growth processes

  6. Low energy cross section data for ion-molecule reactions in hydrogen systems and for charge transfer of multiply charged ions with atoms and molecules

    International Nuclear Information System (INIS)

    Okuno, Kazuhiko

    2007-04-01

    Systematic cross section measurements for ion-molecule reactions in hydrogen systems and for charge transfer of multiply charged ions in low energy collisions with atoms and molecules have been performed continuously by the identical apparatus installed with an octo-pole ion beam guide (OPIG) since 1980 till 2004. Recently, all of accumulated cross section data for a hundred collision systems has been entered into CMOL and CHART of the NIFS atomic and molecular numerical database together with some related cross section data. In this present paper, complicated ion-molecule reactions in hydrogen systems are revealed and the brief outlines of specific properties in low energy charge transfer collisions of multiply charged ions with atoms and molecules are introduced. (author)

  7. Radiation chemistry of aromatic dimer radical cations

    International Nuclear Information System (INIS)

    Okamoto, Kazumasa; Tagawa, Seiichi

    2009-01-01

    π-π Interactions of aromatic molecules are paid attention much in many fields, especially biology, chemistry, and applied physics, represented as protein, DNA, electron donor-accepter complexes, charge transfers, and self assembly molecules. Aromatic molecules including benzene rings are the simplest case to study the π-π interactions. To interpret the charge resonance (CR) structure in the dimer radical cations, spectroscopic and ESR methods have been carried out. The spectroscopic study on the dimer radical ion of molecules with two chromophores would be profitable to identify the electronic and configurational properties. In this article, dynamics of the dimer radical cation of benzenes, polystyrenes, and resist polymers is described on the basis of direct observation of CR band by the nanosecond pulse radiolysis and low temperature γ-radiolysis methods. (author)

  8. Pion-transfer (n,d) and (d, 3He) reactions leading to deeply bound pionic atoms

    International Nuclear Information System (INIS)

    Toki, H.; Hirenzaki, S.; Yamazaki, T.

    1990-11-01

    Theoretical studies are given on the (n,d) and (d, 3 He) reactions leading to deeply bound pionic atoms in heavy nuclei of configuration [(nl) π ·j n -1 ]J. The cross sections for various pionic and neutron-hole configurations in the case of a 208 Pb target are calculated at incident energies 300-1000 MeV/u by using the effective number approach and the eikonal approximation for distortion. The effective number with a pion in the 1s or 2p state and a neutron hole in the i 13/2 orbit peaks around the same incident energy (T n =600 MeV) as the elementary cross section n+n→d+π - , where the momentum transfer matches the angular-momentum transfer of L=5∼7. The DWIA cross section for (n,d) producing a pion in the 1s or 2p orbit at T n =600 MeV is found to be around 42 or 75 μb/sr, respectively. At T n =350 MeV, where the momentum transfer is small, quasi-substitutional states of configurations [(2p) π (3p 1/2 ) n -1 ]L=0 and [(2p) π (3p 3/2 ) n -1 ]L=0 are preferentially populated with cross sections of 190 and 380 μb/sr, respectively. The (d, 3 He) cross sections are estimated to be an order of magnitude smaller than the (n,d) cross sections. Thus, the (n,d) and (d, 3 He) reactions are found to be suited for the production of deeply bound pionic atoms. (author)

  9. Hydride generation – in-atomizer collection of Pb in a quartz trap-and-atomizer device for atomic absorption spectrometry – an interference study

    Energy Technology Data Exchange (ETDEWEB)

    Novotný, Pavel [Institute of Analytical Chemistry of the ASCR, v.v.i., Veveří 97, 602 00 Brno (Czech Republic); High School in Hořice, Husova 1414, 508 01 Hořice (Czech Republic); Kratzer, Jan, E-mail: jkratzer@biomed.cas.cz [Institute of Analytical Chemistry of the ASCR, v.v.i., Veveří 97, 602 00 Brno (Czech Republic)

    2013-01-01

    Interferences of selected hydride forming elements (As, Sb, Bi, Se and Sn) on lead determination by hydride generation atomic absorption spectrometry were extensively studied in both on-line atomization and preconcentration (collection) modes. The commonly used on-line atomization mode was found free of significant interferences, whereas strong interference from Bi was observed when employing the preconcentration mode with plumbane collection in a quartz trap-and-atomizer device. Interference of Bi seems to take place in the preconcentration step. Interference of Bi in the collection mode cannot be reduced by increased hydrogen radical amount in the trap and/or the atomizer. - Highlights: ► Interference study on Pb determination by in-atomizer trapping was performed for the first time. ► Bi was found as a severe interferent in the preconcentration mode (Pb:Bi ratio 1:100). ► No interference was found in the on-line atomization (no preconcentration). ► Bi interference occurs during preconcentration.

  10. Electronic states of aryl radical functionalized graphenes: Density functional theory study

    Science.gov (United States)

    Tachikawa, Hiroto; Kawabata, Hiroshi

    2016-06-01

    Functionalized graphenes are known as a high-performance molecular device. In the present study, the structures and electronic states of the aryl radical functionalized graphene have been investigated by the density functional theory (DFT) method to elucidate the effects of functionalization on the electronic states of graphene (GR). Also, the mechanism of aryl radical reaction with GR was investigated. The benzene, biphenyl, p-terphenyl, and p-quaterphenyl radicals [denoted by (Bz) n (n = 1-4), where n means numbers of benzene rings in aryl radical] were examined as aryl radicals. The DFT calculation of GR-(Bz) n (n = 1-4) showed that the aryl radical binds to the carbon atom of GR, and a C-C single bond was formed. The binding energies of aryl radicals to GR were calculated to be ca. 6.0 kcal mol-1 at the CAM-B3LYP/6-311G(d,p) level. It was found that the activation barrier exists in the aryl radical addition: the barrier heights were calculated to be 10.0 kcal mol-1. The electronic states of GR-(Bz) n were examined on the basis of theoretical results.

  11. Photoionization of atoms and molecules

    International Nuclear Information System (INIS)

    Samson, J.A.R.

    1976-01-01

    A literature review on the present state of knowledge in photoionization is presented. Various experimental techniques that have been developed to study photoionization, such as fluorescence and photoelectron spectroscopy, mass spectroscopy, are examined. Various atoms and molecules were chosen to illustrate these techniques, specifically helium and xenon atoms and hydrogen molecules. Specialized photoionization such as in positive and negative ions, excited states, and free radicals is also treated. Absorption cross sections and ionization potentials are also discussed

  12. On rings generating supernilpotent and special atoms | France ...

    African Journals Online (AJOL)

    We study prime rings which generate supernilpotent (respectively special) atoms, that is, atoms of the lattice of all supernilpotent (respectively special) radicals. A prime ring A is called a **-ring if the smallest special class containing A is closed under semiprime homomorphic images of A. A semiprime ring A whose every ...

  13. Selective hydrogen atom abstraction by hydrogen atoms in photolysis and radiolysis of alkane mixtures at 770 K

    International Nuclear Information System (INIS)

    Miyazaki, T.; Kinugawa, K.; Eguchi, M.; Guedes, S.M.L.

    1977-01-01

    Selective hydrogen atom abstraction reaction by H atoms, has been found in Isobutane, 2,2,3,3-tetramethylbutane(TMB), cyclopropane matrices besides neopentane matrix. The selective hydrogen atom abstraction reaction in neopentane-isobutane mixture is affected by the difference of kinetic energies of H atoms. The reaction occurs more favorably with decreasing the kinetic energy of H atoms. Competitive reaction between c-C 6 H 12 and Hi for H atoms has been studied in the radiolysis and photolysis of neo-C 5 H 12 HI mixture at 77 K. The rate constants of these reactions in neopentane matrix are quite different from these of thermal H atom reaction, but similar to those of hot H atom reaction. Importance of the selective hydrogen atom abstraction reaction by H atoms is pointed out in the radical formation in the radiolysis of pure TMB at 77 K [pt

  14. Fe atoms trapped on graphene as a potential efficient catalyst for room-temperature complete oxidation of formaldehyde: a first-principles investigation

    KAUST Repository

    Guo, Huimin

    2017-03-24

    We investigated the oxidation of formaldehyde, one of the major indoor air pollutants, into CO2 and H2O over Fe atoms trapped in defects on graphene by first-principles based calculations. These trapped Fe atoms are not only stable to withstand interference from the reaction environments but are also efficient in catalyzing the reactions between coadsorbed O-2 and formaldehyde. The oxidation of formaldehyde starts with the formation of a peroxide-like intermediate and continues by its dissociation into. eta(1)-OCHO coadsorbed with an OH radical. Then, the adsorbed OCHO undergoes conformational changes and hydride transfer, leading to the formation of H2O and CO2. Subsequent adsorption of O2 or formaldehyde facilitates desorption of H2O and a new reaction cycle initiates. The calculated barriers for formation and dissociation of the peroxide-like intermediate are 0.43 and 0.40 eV, respectively, and those for conformation changes and hydride transfer are 0.47 and 0.13 eV, respectively. These relatively low barriers along the reaction path suggest the potential high catalytic performance of trapped Fe atoms for formaldehyde oxidation.

  15. Fe atoms trapped on graphene as a potential efficient catalyst for room-temperature complete oxidation of formaldehyde: a first-principles investigation

    KAUST Repository

    Guo, Huimin; Li, Min; Liu, Xin; Meng, Changgong; Linguerri, Roberto; Han, Yu; Chambaud, Gilberte

    2017-01-01

    We investigated the oxidation of formaldehyde, one of the major indoor air pollutants, into CO2 and H2O over Fe atoms trapped in defects on graphene by first-principles based calculations. These trapped Fe atoms are not only stable to withstand interference from the reaction environments but are also efficient in catalyzing the reactions between coadsorbed O-2 and formaldehyde. The oxidation of formaldehyde starts with the formation of a peroxide-like intermediate and continues by its dissociation into. eta(1)-OCHO coadsorbed with an OH radical. Then, the adsorbed OCHO undergoes conformational changes and hydride transfer, leading to the formation of H2O and CO2. Subsequent adsorption of O2 or formaldehyde facilitates desorption of H2O and a new reaction cycle initiates. The calculated barriers for formation and dissociation of the peroxide-like intermediate are 0.43 and 0.40 eV, respectively, and those for conformation changes and hydride transfer are 0.47 and 0.13 eV, respectively. These relatively low barriers along the reaction path suggest the potential high catalytic performance of trapped Fe atoms for formaldehyde oxidation.

  16. Simultaneous electrochemical-electron spin resonance studies of carotenoid cation radicals and dications

    International Nuclear Information System (INIS)

    Khaled, M.; Hadjipetrou, A.; Xinhai Chen; Kispert, L.

    1989-01-01

    Carotenoids are present in the chloroplasts of photosynthetic green plants and serve as photoprotect devices and antenna pigments, and active role in the photosynthetic electron-transport chain with the carotenoid cation radical as an integral part of the electron-transfer process. The research reported herein has confirmed that carotenoid cation radicals have a lifetime that is sensitive to solvent, being longest in CH 2 Cl 2 and are best prepared electrochemically. Semiempirical AM1 and INDO calculations of the trans and cis isomers of β-carotene, canthaxanthin and β-apo-8'-carotenal cation radicals predicted the unresolved EPR line whose linewidth varies to a measurable degree with carotenoid, which subsequent experimental observations affirmed. Simultaneous electrochemical - electron spin resonance studies of carotenoid cation radicals and dications have shown the radicals detected by EPR are formed by the one electron oxidation of the carotenoid, that dimers are not formed upon decay of the radical cations and an estimate of the rate of comproportionation as a function of carotenoid can be given. The formal rate constant K' for heterogenous electron transfer rate at the electrode surface has been deduced from rotating disc experiments. Upon deuteration, and in the presence of excess β-carotene, the half-life for decay of the carotenoid radical cation increased an order of magnitude due to the reaction between diffusion carotenoid dications and carotenoids to form additional radical cations. The carotenoid diffusion coefficients deduced by chronocoulometry substantiates this measurement. The produces formed upon electrochemical studies are being studied by HPLC and the isomers formed thermally are being separated. Additional radical reactions are currently being studied by EPR and electrochemical methods

  17. Free radical scavenging injectable hydrogels for regenerative therapy.

    Science.gov (United States)

    Komeri, Remya; Thankam, Finosh Gnanaprakasam; Muthu, Jayabalan

    2017-02-01

    Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Synthesis of Amphiphilic Copolymwers by Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Hansen, Natanya Majbritt Louie

    2007-01-01

    Fluorerede polymerer besidder en række enestående egenskaber såsom god biokom-patibilitet og lav overfladeenergi såvel som god kemisk og termisk stabilitet. Målsæt-ningen for denne afhandling var at fremstille fluorerede polymerer og copolymerer, der potentielt kunne finde anvendelse som...... egenskaber der genfindes i homopolymerer af den dominerende monomer i copolymeren. Som indikation af de nye materialers mulige vekselvirkning med omgivelserne udførtes omfattende studier af kontaktvinkler. Film fremstillet af de fluorerede copolymerer og polymerer udviste øget hydrofobicitet (vandafvisning...

  19. GRADIENT COPOLYMERS BY ATOM TRANSFER RADICAL COPOLYMERIZATION. (R826735)

    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...

  20. REVERSE ATOM TRANSFER RADICAL POLYMERIZATION IN MINIEMULSION. (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...

  1. COPPER(I)-CATALYZED ATOM TRANSFER RADICAL POLYMERIZATIONS. (R826735)

    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...

  2. TRANSITION METAL CATALYZED ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    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...

  3. 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

  4. Heterogeneous Single-Atom Catalyst for Visible-Light-Driven High-Turnover CO2 Reduction: The Role of Electron Transfer.

    Science.gov (United States)

    Gao, Chao; Chen, Shuangming; Wang, Ying; Wang, Jiawen; Zheng, Xusheng; Zhu, Junfa; Song, Li; Zhang, Wenkai; Xiong, Yujie

    2018-03-01

    Visible-light-driven conversion of CO 2 into chemical fuels is an intriguing approach to address the energy and environmental challenges. In principle, light harvesting and catalytic reactions can be both optimized by combining the merits of homogeneous and heterogeneous photocatalysts; however, the efficiency of charge transfer between light absorbers and catalytic sites is often too low to limit the overall photocatalytic performance. In this communication, it is reported that the single-atom Co sites coordinated on the partially oxidized graphene nanosheets can serve as a highly active and durable heterogeneous catalyst for CO 2 conversion, wherein the graphene bridges homogeneous light absorbers with single-atom catalytic sites for the efficient transfer of photoexcited electrons. As a result, the turnover number for CO production reaches a high value of 678 with an unprecedented turnover frequency of 3.77 min -1 , superior to those obtained with the state-of-the-art heterogeneous photocatalysts. This work provides fresh insights into the design of catalytic sites toward photocatalytic CO 2 conversion from the angle of single-atom catalysis and highlights the role of charge kinetics in bridging the gap between heterogeneous and homogeneous photocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Thermal stability of carbonyl radicals. Part II. Reactions of methylglyoxyl and methylglyoxylperoxy radicals at 1 bar in the temperature range 275-311 K.

    Science.gov (United States)

    Jagiella, Stefan; Zabel, Friedhelm

    2008-04-07

    Reactions of methylglyoxyl and methylglyoxylperoxy radicals were investigated at a total pressure of 1 bar in oxygen. Methylglyoxyl radicals were generated by stationary photolysis of Br2-CH3C(O)C(O)H-NO2-O2-N2 mixtures at wavelengths > or =480 nm and of Cl2-CH3C(O)C(O)H-NO2-O2-N2 mixtures in the wavelength range 315-460 nm. In the bromine system, rate constant ratios for the reactions CH3C(O)CO --> CH3CO + CO (kdis) and CH3C(O)CO + O2 --> CH3C(O)C(O)O2 (kO2) were measured as a function of temperature in the range 275-311 K. Assuming the constant value kO2 = 5.1 x 10(-12) cm3 molecule(-1) s(-1) for our reaction conditions, kdis = 1.2 x 10(10.0+/-0.7) x exp(-11.7 +/- 3.8 kJ mol(-1)/RT) s(-1) (2sigma errors) was obtained for ptot = 1 bar (M = O2), in good agreement with the kinetic parameters calculated by Méreau et al. [R. Méreau, M.-T. Rayez, J.-C. Rayez, F. Caralp and R. Lesclaux, Phys. Chem. Chem. Phys., 2001, 3, 4712]. CH3C(O)C(O)O2 radicals oxidise NO2, forming NO3, CH3CO and CO2. This experimental result is supported by DFT and ab initio calculations. Possible mechanisms for the observed formation of several % of ketene and bromoacetyl peroxynitrate are discussed. Use of Cl rather than Br atoms to abstract the aldehydic H atom from methylglyoxal leads to chemically activated CH3C(O)CO radicals, thus substantially increasing the fraction of CH3C(O)CO radicals that decompose rather than add O2.

  6. Hole transfer in DNA studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Majima, T.; Kawai, K.; Takada, T.

    2003-01-01

    Attention has been paid to charge transfer in DNA with respect to oxidation damage of DNA and nano bio-devices such as DNA molecular wire. We report hole transfer in DNA during pulse radiolysis of molecule-conjugated DNA (M-DNA). Direct measurement of the charge transfer in DNA has never been reported due to the low extinction coefficient of nucleobase radical ions and to difficult definition of nucleobases. We have used M-DNA in which M radical cation has enough extinction coefficient and distinct absorption. Radical cation was generated in M-DNA during pulse radiolysis in water, and hole transfer through DNA was monitored by time-resolved transient absorption spectra of the radical cations. Hole was generated in Py-DNA by pulse radiolysis in water. Hole transfer to Py through DNA was monitored by transient absorption of Py'+ at 465 nm. The hole hopping rate (k) from G-region to Py was determined to be 104 s-1 which decreased with intervening A-T base-pairs between Py and G-region. We suppose that G(-H+)-radical and C(+H+) basepair can alive in DNA more than 100 us and that this long lifetime is responsible to the long-distance hole transfer. The dependence of k against the distance between the G-region and Py led to the slope of 0.3 Angstroms-1 which is due to multi-step k with the smaller distance dependence. On the other hand, beta = 0.6 Angstroms-1 was found for the single-step k in DNA. On the basis of pulse radiolytic studied on various molecule-conjugated DNA, we found that hole transfer between two chromophores (A and B)-conjugated DNA increased with decreasing the distance between A and B and was accelerated slightly with increasing the number of Gs of the bridge between A and B, and that k was modulated by the bridged base sequences. We also found that weak distance dependent hole transfer in DNA by adenine hopping mechanism

  7. Molecular weight growth in Titan's atmosphere: branching pathways for the reaction of 1-propynyl radical (H3CC≡C˙) with small alkenes and alkynes.

    Science.gov (United States)

    Kirk, Benjamin B; Savee, John D; Trevitt, Adam J; Osborn, David L; Wilson, Kevin R

    2015-08-28

    The reaction of small hydrocarbon radicals (i.e.˙CN, ˙C2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC[triple bond, length as m-dash]C˙), a likely product from the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (-H = 27%, -CH3 = 73%) and (-H = 14%, -CH3 = 86%), respectively. Together, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.

  8. Sign of the electron exchange coupling in random radical encounter pairs in solution

    International Nuclear Information System (INIS)

    Thurnauer, M.C.; Chiu, T.M.; Trifunac, A.D.

    1985-01-01

    An important parameter in the study of reacting radical systems is the electron exchange interaction, J. The properties of interest are the sign and magnitude of J, and its functional dependence on distance between radicals. One source of information about J is from understanding the Chemically Induced Dynamic Electron Polarization (CIDEP) which is observed in the EPR spectra of reactive radical systems. For radicals reacting in solution to form new covalent bonds, it has generally been found that J O. It is suggested that F-pairs react at a separation greater than that at which spin correlated (geminate) pairs of the same radicals are formed, so that the intervening solvent molecules become involved in the exchange interaction giving rise to J>O via some sort of superexchange process. This is an interesting proposition since superexchange via solvent molecules may play a role in rates of long-distance electron transfer reactions and in the electron transfer reactions of photosynthesis. However, the model suggested runs contrary to all F-air radicals are produced. In order to clarify this important point, the authors present here a definitive study in which we examine several systems of radgenerated independently (exclusive F-pairs) by pulsed laser photolysis and pulsed radiolicals generatedysis in aqueous, alcoholic and hydrocarbon solvents

  9. Radical scavenging activity of some natural tropolones by density functional theory

    Directory of Open Access Journals (Sweden)

    A. G. Al-Sehemi

    2017-07-01

    Full Text Available The ground state neutral geometries of some natural tropolones, i.e. stipitatonic acid (AF1, stipitalide (AF2, stipitaldehydic acid (AF3 and methyl stipitate (AF4 have been optimized by using Density Functional Theory (DFT at B3LYP/6-31G*, B3LYP/6-31G**, B3LYP/6-31+G* and B3LYP/6-31+G** levels of theory. The excited state geometries of AF1-AF4 were optimized by adopting the Time Dependent Density Functional Theory (TDDFT at the same levels of theory. The frequencies and cation species of AF1-AF4 were also computed at all the above mentioned levels of theory. We shed light on the electro-optical and molecular properties, e.g. energy gaps, highest occupied molecular orbitals, lowest unoccupied molecular orbitals, absorption wavelengths, electronegativity (χ, hardness (η, electrophilicity (ω, softness (S, electrophilicity index (ωi and the radical scavenging activity (RSA. Hydrogen atom transfer (HAT and one-electron transfer mechanisms have been discussed to shed light on the RSA. The smallest ionization potential and bond dissociation energy of AF4 are revealing that this compound would have more RSA than those of other counterparts.

  10. Chemical determination of free radical-induced damage to DNA.

    Science.gov (United States)

    Dizdaroglu, M

    1991-01-01

    Free radical-induced damage to DNA in vivo can result in deleterious biological consequences such as the initiation and promotion of cancer. Chemical characterization and quantitation of such DNA damage is essential for an understanding of its biological consequences and cellular repair. Methodologies incorporating the technique of gas chromatography/mass spectrometry (GC/MS) have been developed in recent years for measurement of free radical-induced DNA damage. The use of GC/MS with selected-ion monitoring (SIM) facilitates unequivocal identification and quantitation of a large number of products of all four DNA bases produced in DNA by reactions with hydroxyl radical, hydrated electron, and H atom. Hydroxyl radical-induced DNA-protein cross-links in mammalian chromatin, and products of the sugar moiety in DNA are also unequivocally identified and quantitated. The sensitivity and selectivity of the GC/MS-SIM technique enables the measurement of DNA base products even in isolated mammalian chromatin without the necessity of first isolating DNA, and despite the presence of histones. Recent results reviewed in this article demonstrate the usefulness of the GC/MS technique for chemical determination of free radical-induced DNA damage in DNA as well as in mammalian chromatin under a vast variety of conditions of free radical production.

  11. Charge Transfer Processes in Collisions of Si4+ Ions with He Atoms at Intermediate Energies

    Science.gov (United States)

    Suzuki, R.; Watanabe, A.; Sato, H.; Gu, J. P.; Hirsch, G.; Buenker, R. J.; Kimura, M.; Stancil, P. C.

    Charge transfer in collisions of Si4+ ions with He atoms below 100 keV/u is studied by using a molecular orbital representation within both the semiclassical and quantal representations. Single transfer reaction Si4++He →Si3++He+ has been studied by a number of theoretical investigations. In addition to the reaction (1), the first semiclassical MOCC calculations are performed for the double transfer channel Si4++HE→Si2++He2+ Nine molecular states that connect both with single and double electron transfer processes are considered in the present model. Electronic states and corresponding couplings are determined by the multireference single- and double- excitation configuration interaction method. The present cross sections tie well with the earlier calculations of Stancil et al., Phys. Rev. A 55, 1064 (1997) at lower energies, but show a rather different magnitude from those of Bacchus-Montabonel and Ceyzeriat, Phys. Rev. A 58, 1162 (1998). The present rate constant is found to be significantly different from the experimental finding of Fang and Kwong, Phys. Rev. A 59, 342 (1996) at 4,600 K, and hence does not support the experiment.

  12. Radical fashion and radical fashion innovation

    NARCIS (Netherlands)

    Zhang, D.; Benedetto, Di A.C.

    2010-01-01

    This is a study of the related concepts of radical fashion and radical fashion innovation. Radical fashions are defined here as those that may never enter the market at all, and exist primarily on runway shows, in exhibitions and in publicity; by contrast, radical fashion innovations may be very

  13. Stable Isotope Fractionation Caused by Glycyl Radical Enzymes during Bacterial Degradation of Aromatic Compounds

    Science.gov (United States)

    Morasch, Barbara; Richnow, Hans H.; Vieth, Andrea; Schink, Bernhard; Meckenstock, Rainer U.

    2004-01-01

    Stable isotope fractionation was studied during the degradation of m-xylene, o-xylene, m-cresol, and p-cresol with two pure cultures of sulfate-reducing bacteria. Degradation of all four compounds is initiated by a fumarate addition reaction by a glycyl radical enzyme, analogous to the well-studied benzylsuccinate synthase reaction in toluene degradation. The extent of stable carbon isotope fractionation caused by these radical-type reactions was between enrichment factors (ɛ) of −1.5 and −3.9‰, which is in the same order of magnitude as data provided before for anaerobic toluene degradation. Based on our results, an analysis of isotope fractionation should be applicable for the evaluation of in situ bioremediation of all contaminants degraded by glycyl radical enzyme mechanisms that are smaller than 14 carbon atoms. In order to compare carbon isotope fractionations upon the degradation of various substrates whose numbers of carbon atoms differ, intrinsic ɛ (ɛintrinsic) were calculated. A comparison of ɛintrinsic at the single carbon atoms of the molecule where the benzylsuccinate synthase reaction took place with compound-specific ɛ elucidated that both varied on average to the same extent. Despite variations during the degradation of different substrates, the range of ɛ found for glycyl radical reactions was reasonably narrow to propose that rough estimates of biodegradation in situ might be given by using an average ɛ if no fractionation factor is available for single compounds. PMID:15128554

  14. Oxidation of carbon monoxide, hydrogen peroxide and water at a boron doped diamond electrode: the competition for hydroxyl radicals.

    Science.gov (United States)

    Kisacik, Izzet; Stefanova, Ana; Ernst, Siegfried; Baltruschat, Helmut

    2013-04-07

    Boron doped diamond (BDD) electrodes have an extremely high over-voltage for oxygen evolution from water, which favours its use in oxidation processes of other compounds at high potentials. We used a rotating ring disc (RRDE) assembly and differential electrochemical mass spectrometry (DEMS) in order to monitor the consumption or the production of species in the course of the electrode processes. By intercepting the intermediate of the electrochemical water oxidation with chemical reactions we demonstrate clearly, albeit indirectly, that in the water oxidation process at BDD above 2.5 V the first step is the formation of ˙OH radicals. The electro-oxidation of CO to CO2 at BDD electrodes proceeds only via a first attack by ˙OH radicals followed by a further electron transfer to the electrode. At potentials below the onset of oxygen evolution from water, H2O2 is oxidised by a direct electron transfer to the BDD electrode, while at higher potentials, two different reactions paths compete for the ˙OH radicals formed in the first electron transfer from water: one, where these ˙OH radicals react with each other followed by further electron transfers leading to O2 on the one hand and one, where ˙OH radicals react with other species like H2O2 or CO with subsequent electron transfers on the other hand.

  15. EPR Spectroscopy of Radical Ions of a 2,3-Diamino-1,4-naphthoquinone Derivative.

    Science.gov (United States)

    Tarábek, Ján; Wen, Jin; Dron, Paul I; Pospíšil, Lubomír; Michl, Josef

    2018-05-18

    We report the electron paramagnetic resonance spectra of the radical cation and radical anion of 1,2,2,3-tetramethyl-2,3-dihydro-1 H-naphtho[2,3- d]imidazole-4,9-dione (1) and its doubly 13 C labeled analogue 2, of interest for singlet fission. The hyperfine coupling constants are in excellent agreement with density functional theory calculations and establish the structures beyond doubt. Unlike the radical cation 1 •+ , the radical anion 1 •- and its parent 1 have pyramidalized nitrogen atoms and inequivalent methyl groups 15 and 16, in agreement with the calculations. The distinction is particularly clear with the labeled analogue 2 •- .

  16. Charge transfer processes in collisions of Si{sup 4+} ions with He atoms at intermediate energies

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, R. [Hitotsubashi Univ., Tokyo (Japan). Computer Center; Watanabe, A. [Dept. of Information Sciences, Ochanomizu Univ., Tokyo (Japan); Sato, H. [Graduate School of Humanities and Sciences, Ochanomizu Univ., Tokyo (Japan); Gu, J.P.; Hirsch, G.; Buenker, R.J. [Wuppertal Univ. (Gesamthochschule) (Germany). Lehrgebiet Theoretische Chemie; Kimura, M. [Graduate School of Science and Engineering, Yamaguchi Univ., Ube (Japan); Stancil, P.C. [Georgia Univ., Athens, GA (United States). Dept. of Physics

    2001-07-01

    Charge transfer in collisions of Si{sup 4+} ions with He atoms below 100 keV/u is studied by using a molecular orbital representation within both the semiclassical and quantal representations. Single transfer reaction Si{sup 4+} + He {yields} Si{sup 3+} + He{sup +} has been studied by a number of theoretical investigations. In addition to the reaction (1), the first semiclassical MOCC calculations are performed for the double transfer channel Si{sup 4+} + He {yields} Si{sup 2+} + He{sup 2+}. Nine molecular states that connect both with single and double electron transfer processes are considered in the present model. Electronic states and corresponding couplings are determined by the multireference single- and double- excitation configuration interaction method. The present cross sections tie well with the earlier calculations of Stancil et al., (1997) at lower energies, but show a rather different magnitude from those of Bacchus-Montabonel and Ceyzeriat, (1998). The present rate constant is found to be significantly different from the experimental finding of Fang and Kwong, (1996) at 4,600 K, and hence does not support the experiment. (orig.)

  17. Low-energy charge transfer for collisions of Si3+ with atomic hydrogen

    Science.gov (United States)

    Bruhns, H.; Kreckel, H.; Savin, D. W.; Seely, D. G.; Havener, C. C.

    2008-06-01

    Cross sections of charge transfer for Si3+ ions with atomic hydrogen at collision energies of ≈40-2500eV/u were carried out using a merged-beam technique at the Multicharged Ion Research Facility at Oak Ridge National Laboratory. The data span an energy range in which both molecular orbital close coupling (MOCC) and classical trajectory Monte Carlo (CTMC) calculations are available. The influence of quantum mechanical effects of the ionic core as predicted by MOCC is clearly seen in our results. However, discrepancies between our experiment and MOCC results toward higher collision energies are observed. At energies above 1000 eV/u good agreement is found with CTMC results.

  18. Free radicals formed by H(Mu) addition to triphenylene and dodecahydrotriphenylene

    Energy Technology Data Exchange (ETDEWEB)

    Brodovitch, Jean-Claude [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Ghandi, Khashayar [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); McKenzie, Iain [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Percival, Paul W. [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada)]. E-mail: percival@sfu.ca; Schueth, Joachim [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada)

    2006-03-31

    Muonium has been used as an H atom analogue to investigate the free radicals formed by H addition to the fused polyaromatic hydrocarbon triphenylene. Although there are three inequivalent sites of attack in this molecule, only two radicals were detected. Muon and proton hyperfine constants were determined by transverse field {mu}SR and LCR, respectively. With the help of quantum calculations, all the signals can be assigned to radicals formed by Mu addition to C-H sites, while there is no evidence for addition to the tertiary carbons at ring junctions. To force attack on a tertiary carbon, a complementary study was conducted on the dodecahydrotriphenylene molecule. As expected, only one radical is formed. From LCR measurements the number of non-equivalent protons are interpreted as the results of the conformational effect of the saturated side rings.

  19. Free radicals formed by H(Mu) addition to triphenylene and dodecahydrotriphenylene

    International Nuclear Information System (INIS)

    Brodovitch, Jean-Claude; Ghandi, Khashayar; McKenzie, Iain; Percival, Paul W.; Schueth, Joachim

    2006-01-01

    Muonium has been used as an H atom analogue to investigate the free radicals formed by H addition to the fused polyaromatic hydrocarbon triphenylene. Although there are three inequivalent sites of attack in this molecule, only two radicals were detected. Muon and proton hyperfine constants were determined by transverse field μSR and LCR, respectively. With the help of quantum calculations, all the signals can be assigned to radicals formed by Mu addition to C-H sites, while there is no evidence for addition to the tertiary carbons at ring junctions. To force attack on a tertiary carbon, a complementary study was conducted on the dodecahydrotriphenylene molecule. As expected, only one radical is formed. From LCR measurements the number of non-equivalent protons are interpreted as the results of the conformational effect of the saturated side rings

  20. ESR study on hydrogen-atom abstraction in cryogenic organic solids

    International Nuclear Information System (INIS)

    Ichikawa, Tsuneki

    1995-01-01

    The present paper summarizes our recent results on the hydrogen-atom abstraction from protiated alkane molecule by deuterium atoms in cryogenic deuterated organic solids, obtained by the X-band ESR and electron spin-echo measurements of the product alkyl radicals at cryogenic temperatures. (J.P.N.)

  1. Functionalized graphene quantum dots loaded with free radicals combined with liquid chromatography and tandem mass spectrometry to screen radical scavenging natural antioxidants from Licorice and Scutellariae.

    Science.gov (United States)

    Wang, Guoying; Niu, XiuLi; Shi, Gaofeng; Chen, Xuefu; Yao, Ruixing; Chen, Fuwen

    2014-12-01

    A novel screening method was developed for the detection and identification of radical scavenging natural antioxidants based on a free radical reaction combined with liquid chromatography with tandem mass spectrometry. Functionalized graphene quantum dots were prepared for loading free radicals in the complex screening system. The detection was performed with and without a preliminary exposure of the samples to specific free radicals on the functionalized graphene quantum dots, which can facilitate charge transfer between free radicals and antioxidants. The difference in chromatographic peak areas was used to identify potential antioxidants. This is a novel approach to simultaneously evaluate the antioxidant power of a component versus a free radical, and to identify it in a vegetal matrix. The structures of the antioxidants in the samples were identified using tandem mass spectrometry and comparison with standards. Fourteen compounds were found to possess potential antioxidant activity, and their free radical scavenging capacities were investigated. The order of scavenging capacity of 14 compounds was compared according to their free radical scavenging rate. 4',5,6,7-Tetrahydroxyflavone (radical scavenging rate: 0.05253 mL mg(-1) s(-1) ) showed the strongest capability for scavenging free radicals. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Deciphering free-radical code of radiation effects

    International Nuclear Information System (INIS)

    Volovyk, S.; Bazyka, D.; Loganovsky, K.; Bebeshko, V.

    2007-01-01

    Complete text of publication follows. Objective: Ionizing radiation is fundamental environmental factor for life origin and evolution. Free radicals, primordial 'sea' for life conceiving and existence, induced by cosmic and terrestrial background radiation, are evolutionally archetypal, ubiquitous, and omnipotent in physiological- pathophysiological dichotomy. Classical free-radical paradigm in radiation biology and medicine, focused in essence on oxidative damage, needs new conceptualization and generalization. Methods: Suggested novel insights into free radicals dual immanent nature and functions in organism systems are based on original concepts of radicals dynamic charge transfer (CT) - redox ambivalence (interactional nucleo-, electro-, and ambiphilicity spectrum); pertinent chemical reactivity and selectivity delocalization model; physiological functional ambivalence and complementarity, and dynamic free-radical homeostasis. Results: Subtle perturbations in radicals CT spatiotemporal homeodynamics, in responsive signaling / controlling networks, concomitant alterations in genes expression, transcription, and apoptosis, redox control of mitochondrial ET chain, telomere/telomerase balance, DNA CT, circadian clock, hemispheric biochemical dominance/accentuation, including alteration of nitric oxide-superoxide complementarity, membranes permeability, neurotransmission pattern, synaptic circuitry, etc under radiation exposure have more fundamental impact on organism systems (especially CNS and CVS) deterioration than simple radicals inflicted oxidative (nitrosative) damage of cellular constituents. Conclusions: This novel conceptualization of free-radical paradigm constitutes new dimension in deciphering molecular mechanisms of radiation effects on subtle borderline norm-pathology and continuity-discontinuity dichotomy in organisms systems disorders - CT(redox)omics, which involves investigation of CT, redox, and spin states of free radicals, DNA bases

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

    International Nuclear Information System (INIS)

    1998-01-01

    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 + , Li 2+ , Be 3+ , B 4+ , C 5+ , and the H + + Na system

  4. Effects of dipole—dipole interaction on entanglement transfer

    International Nuclear Information System (INIS)

    Guo Hong; Xiong Hengna

    2008-01-01

    A system consisting of two different atoms interacting with a two-mode vacuum, where each atom is resonant only with one cavity mode, is considered. The effects of dipole—dipole (dd) interaction between two atoms on the atom-atom entanglement and mode-mode entanglement are investigated. For a weak dd interaction, when the atoms are initially separable, the entanglement between them can be induced by the dd interaction, and the entanglement transfer between the atoms and the modes occurs efficiently; when the atoms are initially entangled, the entanglement transfer is almost not influenced by the dd interaction. However, for a strong dd interaction, it is difficult to transfer the entanglement from the atoms to the modes, but the atom-atom entanglement can be maintained when the atoms are initially entangled

  5. Structure reactivity relationship in the reaction of DNA guanyl radicals with hydroxybenzoates

    Energy Technology Data Exchange (ETDEWEB)

    Do, Trinh T.; Tang, Vicky J.; Aguilera, Joseph A. [Department of Radiology University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0610 (United States); Milligan, Jamie R., E-mail: jmilligan@ucsd.ed [Department of Radiology University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0610 (United States)

    2010-11-15

    In DNA, guanine bases are the sites from which electrons are most easily removed. As a result of hole migration to this stable location on guanine, guanyl radicals are major intermediates in DNA damage produced by the direct effect of ionizing radiation (ionization of the DNA itself and not through the intermediacy of water radicals). We have modeled this process by employing gamma irradiation in the presence of thiocyanate ions, a method which also produces single electron oxidized guanyl radicals in plasmid DNA in aqueous solution. The stable products formed in DNA from these radicals are detected as strand breaks after incubation with the FPG protein. When a phenolic compound is present in the solution during gamma irradiation, the formation of guanyl radical species is decreased by electron donation from the phenol to the guanyl radical. We have quantified the rate of this reaction for four different phenolic compounds bearing carboxylate substituents as proton acceptors. A comparison of the rates of these reactions with the redox strengths of the phenolic compounds reveals that salicylate reacts ca. 10-fold faster than its structural analogs. This observation is consistent with a reaction mechanism involving a proton coupled electron transfer, because intra-molecular transfer of a proton from the phenolic hydroxyl group to the carboxylate group is possible only in salicylate, and is favored by the strong 6-membered ring intra-molecular hydrogen bond in this compound.

  6. Energy flux of hot atoms

    International Nuclear Information System (INIS)

    Wotzak, G.P.; Kostin, M.D.

    1976-01-01

    The process in which hot atoms collide with thermal atoms of a gas, transfer kinetic energy to them, and produce additional hot atoms is investigated. A stochastic method is used to obtain numerical results for the spatial and time dependent energy flux of hot atoms in a gas. The results indicate that in hot atom systems a front followed by an intense energy flux of hot atoms may develop

  7. Strong isotope effects on the charge transfer in slow collisions of He2+ with atomic hydrogen, deuterium, and tritium

    NARCIS (Netherlands)

    Stolterfoht, N.; Cabrera-Trujillo, R.; Oehrn, Y.; Deumens, E.; Hoekstra, R.; Sabin, J. R.

    2007-01-01

    Probabilities and cross sections for charge transfer by He2+ impact on atomic hydrogen (H), deuterium (D), and tritium (T) at low collision energies are calculated. The results are obtained using an ab initio theory, which solves the time-dependent Schrodinger equation. For the H target, excellent

  8. Crossed-beam reaction of carbon atoms with hydrocarbon molecules. IV. Chemical dynamics of methylpropargyl radical formation, C4H5, from reaction of C(3Pj) with propylene, C3H6 (X1A)

    International Nuclear Information System (INIS)

    Kaiser, R.I.; Stranges, D.; Bevsek, H.M.; Lee, Y.T.; Suits, A.G.

    1997-01-01

    The reaction between ground state carbon atoms and propylene, C 3 H 6 , was studied at average collision energies of 23.3 and 45.0 kJmol -1 using the crossed molecular beam technique. Product angular distributions and time-of-flight spectra of C 4 H 5 at m/e=53 were recorded. Forward-convolution fitting of the data yields a maximum energy release as well as angular distributions consistent with the formation of methylpropargyl radicals. Reaction dynamics inferred from the experimental results suggest that the reaction proceeds on the lowest 3 A surface via an initial addition of the carbon atom to the π-orbital to form a triplet methylcyclopropylidene collision complex followed by ring opening to triplet 1,2-butadiene. Within 0.3 endash 0.6 ps, 1,2-butadiene decomposes through carbon endash hydrogen bond rupture to atomic hydrogen and methylpropargyl radicals. The explicit identification of C 4 H 5 under single collision conditions represents a further example of a carbon endash hydrogen exchange in reactions of ground state carbon with unsaturated hydrocarbons. This versatile machine represents an alternative pathway to build up unsaturated hydrocarbon chains in combustion processes, chemical vapor deposition, and in the interstellar medium. copyright 1997 American Institute of Physics

  9. Quenching reactions of electronically excited atoms

    International Nuclear Information System (INIS)

    Setser, D.W.

    2001-01-01

    The two-body, thermal quenching reactions of electronically excited atoms are reviewed using excited states of Ar, Kr, and Xe atoms as examples. State-specific interstate relaxation and excitation-transfer reactions with atomic colliders are discussed first. These results then are used to discuss quenching reactions of excited-state atoms with diatomic and polyatomic molecules, the latter have large cross sections, and the reactions can proceed by excitation transfer and by reactive quenching. Excited states of molecules are not considered; however, a table of quenching rate constants is given for six excited-state molecules in an appendix

  10. Hydrogen-transfer and charge transfer in photochemical and high energy radiation induced reactions: effects of thiols. Final report, February 1, 1960-january 31, 1979

    International Nuclear Information System (INIS)

    Cohen, S.G.

    1980-03-01

    Absorption of ultraviolet or visible light, or high energy radiation, may lead to highly reactive free radicals. Thiols affect the reactions of these radicals in the following ways: (1) transfer of hydrogen from sulfur of the thiol to a substrate radical, converting the radical to a stable molecule, and the thiol to a reactive thiyl radical; and (2) transfer of hydrogen from a substrate radical or molecule to thiyl, regenerating thiol. The thiol is thus used repeatedly and a single molecule may affect the consequences of many quanta. Three effects may ensue, depending upon the system irradiated: (1) the substrate radicals may be converted by thiol-thiyl to the original molecules, and protection against radiation damage is afforded. (2) The radicals may be converted to molecules not identical with the starting materials, and in both cases damage caused by radical combination processes is prevented. (3) Product yields may be increased where the initial radicals might otherwise regenerate starting materials. It was shown that rates of reaction of excited species can be correlated with triplet energies and reduction potentials, and with ionization potentials, that amines are very reactive toward excited carbonyl compounds of all types, and that yields of products from these reactions can be increased by thiols, leading to increased efficiency in utilization of light

  11. Ab initio molecular dynamics of the reaction of quercetin with superoxide radical

    International Nuclear Information System (INIS)

    Lespade, Laure

    2016-01-01

    Highlights: • Ab initio molecular dynamics is performed to describe the reaction of quercetin and superoxide. • The reaction occurs near the sites 4′ and 7 when the system contains sufficiently water molecules. • The difference of reactivity of superoxide compared to commonly used radicals as DPPH · or ABTS ·+ is explained. - Abstract: Superoxide plays an important role in biology but in unregulated concentrations it is implicated in a lot of diseases such as cancer or atherosclerosis. Antioxidants like flavonoids are abundant in plant and are good scavengers of superoxide radical. The modeling of superoxide scavenging by flavonoids from the diet still remains a challenge. In this study, ab initio molecular dynamics of the reaction of the flavonoid quercetin toward superoxide radical has been carried out using Car–Parrinello density functional theory. The study has proven different reactant solvation by modifying the number of water molecules surrounding superoxide. The reaction consists in the gift of a hydrogen atom of one of the hydroxyl groups of quercetin to the radical. When it occurs, it is relatively fast, lower than 100 fs. Calculations show that it depends largely on the environment of the hydroxyl group giving its hydrogen atom, the geometry of the first water layer and the presence of a certain number of water molecules in the second layer, indicating a great influence of the solvent on the reactivity.

  12. Dissociative Photoionization of the Elusive Vinoxy Radical.

    Science.gov (United States)

    Adams, Jonathan D; Scrape, Preston G; Lee, Shih-Huang; Butler, Laurie J

    2017-08-24

    These experiments report the dissociative photoionization of vinoxy radicals to m/z = 15 and 29. In a crossed laser-molecular beam scattering apparatus, we induce C-Cl bond fission in 2-chloroacetaldehyde by photoexcitation at 157 nm. Our velocity measurements, combined with conservation of angular momentum, show that 21% of the C-Cl photofission events form vinoxy radicals that are stable to subsequent dissociation to CH 3 + CO or H + ketene. Photoionization of these stable vinoxy radicals, identified by their velocities, which are momentum-matched with the higher-kinetic-energy Cl atom photofragments, shows that the vinoxy radicals dissociatively photoionize to give signal at m/z = 15 and 29. We calibrated the partial photoionization cross section of vinoxy to CH 3 + relative to the bandwidth-averaged photoionization cross section of the Cl atom at 13.68 eV to put the partial photoionization cross sections on an absolute scale. The resulting bandwidth-averaged partial cross sections are 0.63 and 1.3 Mb at 10.5 and 11.44 eV, respectively. These values are consistent with the upper limit to the cross section estimated from a study by Savee et al. on the O( 3 P) + propene bimolecular reaction. We note that the uncertainty in these values is primarily dependent on the signal attributed to C-Cl primary photofission in the m/z = 35 (Cl + ) time-of-flight data. While the value is a rough estimate, the bandwidth-averaged partial photoionization cross section of vinoxy to HCO + calculated from the signal at m/z = 29 at 11.53 eV is approximately half that of vinoxy to CH 3 + . We also present critical points on the potential energy surface of the vinoxy cation calculated at the G4//B3LYP/6-311++G(3df,2p) level of theory to support the observation of dissociative ionization of vinoxy to both CH 3 + and HCO + .

  13. Kinetic study on hot-wire-assisted atomic layer deposition of nickel thin films

    International Nuclear Information System (INIS)

    Yuan, Guangjie; Shimizu, Hideharu; Momose, Takeshi; Shimogaki, Yukihiro

    2014-01-01

    High-purity Ni films were deposited using hot-wire-assisted atomic layer deposition (HW-ALD) at deposition temperatures of 175, 250, and 350 °C. Negligible amount of nitrogen or carbon contamination was detected, even though the authors used NH 2 radical as the reducing agent and nickelocene as the precursor. NH 2 radicals were generated by the thermal decomposition of NH 3 with the assist of HW and used to reduce the adsorbed metal growth precursors. To understand and improve the deposition process, the kinetics of HW-ALD were analyzed using a Langmuir-type model. Unlike remote-plasma-enhanced atomic layer deposition, HW-ALD does not lead to plasma-induced damage. This is a significant advantage, because the authors can supply sufficient NH 2 radicals to deposit high-purity metallic films by adjusting the distance between the hot wire and the substrate. NH 2 radicals have a short lifetime, and it was important to use a short distance between the radical generation site and substrate. Furthermore, the impurity content of the nickel films was independent of the deposition temperature, which is evidence of the temperature-independent nature of the NH 2 radical flux and the reactivity of the NH 2 radicals

  14. Oxidation of caffeine by phosphate radical anion in aqueous ...

    Indian Academy of Sciences (India)

    Unknown

    reactions in our body generate reactive oxygen species mainly comprising free radicals .... caffeine might be acting as a sensitizer to transfer energy to PDP to produce phosphate ... The lifetime of the excited singlet 21 state of caffeine is of the.

  15. Engaging unactivated alkyl, alkenyl and aryl iodides in visible-light-mediated free radical reactions

    Science.gov (United States)

    Nguyen, John D.; D'Amato, Erica M.; Narayanam, Jagan M. R.; Stephenson, Corey R. J.

    2012-10-01

    Radical reactions are a powerful class of chemical transformations. However, the formation of radical species to initiate these reactions has often required the use of stoichiometric amounts of toxic reagents, such as tributyltin hydride. Recently, the use of visible-light-mediated photoredox catalysis to generate radical species has become popular, but the scope of these radical precursors has been limited. Here, we describe the identification of reaction conditions under which photocatalysts such as fac-Ir(ppy)3 can be utilized to form radicals from unactivated alkyl, alkenyl and aryl iodides. The generated radicals undergo reduction via hydrogen atom abstraction or reductive cyclization. The reaction protocol utilizes only inexpensive reagents, occurs under mild reaction conditions, and shows exceptional functional group tolerance. Reaction efficiency is maintained upon scale-up and decreased catalyst loading, and the reaction time can be significantly shortened when the reaction is performed in a flow reactor.

  16. Intermolecular Hydrogen Transfer in Isobutane Hydrate

    Directory of Open Access Journals (Sweden)

    Takeshi Sugahara

    2012-05-01

    Full Text Available Electron spin resonance (ESR spectra of butyl radicals induced with γ-ray irradiation in the simple isobutane (2-methylpropane hydrate (prepared with deuterated water were investigated. Isothermal annealing results of the γ-ray-irradiated isobutane hydrate reveal that the isobutyl radical in a large cage withdraws a hydrogen atom from the isobutane molecule through shared hexagonal-faces of adjacent large cages. During this “hydrogen picking” process, the isobutyl radical is apparently transformed into a tert-butyl radical, while the sum of isobutyl and tert-butyl radicals remains constant. The apparent transformation from isobutyl to tert-butyl radicals is an irreversible first-order reaction and the activation energy was estimated to be 35 ± 3 kJ/mol, which was in agreement with the activation energy (39 ± 5 kJ/mol of hydrogen picking in the γ-ray-irradiated propane hydrate with deuterated water.

  17. Symmetric charge transfer cross section of uranium

    International Nuclear Information System (INIS)

    Shibata, Takemasa; Ogura, Koichi

    1995-03-01

    Symmetric charge transfer cross section of uranium was calculated under consideration of reaction paths. In the charge transfer reaction a d 3/2 electron in the U atom transfers into the d-electron site of U + ( 4 I 9/2 ) ion. The J value of the U atom produced after the reaction is 6, 5, 4 or 3, at impact energy below several tens eV, only resonant charge transfer in which the product atom is ground state (J=6) takes place. Therefore, the cross section is very small (4-5 x 10 -15 cm 2 ) compared with that considered so far. In the energy range of 100-1000eV the cross section increases with the impact energy because near resonant charge transfer in which an s-electron in the U atom transfers into the d-electron site of U + ion. Charge transfer cross section between U + in the first excited state (289 cm -1 ) and U in the ground state was also obtained. (author)

  18. Effect of solid phase on the selectivity of alkyl radical formation by gamma-irradiation of branched alkanes

    International Nuclear Information System (INIS)

    Koizumi, Hitoshi; Hashino, Masatoshi; Ichikawa, Tsuneki; Yoshida, Hiroshi

    1992-01-01

    ESR and electron spin echo measurements of alkyl radicals generated by γ-irradiation of glassy and crystalline branched alkanes C 10 ∼ C 13 have been carried out to elucidate the effect of molecular structure and solid phase on the selectivity of alkyl radical formation. Alkyl radicals generated and stabilized at 77 K in the glassy alkanes are secondary penultimate radicals. Tertiary radicals and secondary radicals other than the penultimate one are not generated either by hydrogen abstraction or from ionized or excited molecules. In the crystalline alkanes, however, a small amount of secondary internal radicals are generated in addition to the predominant formation of the secondary penultimate radicals. It is concluded that the detachment of C-H hydrogen preferentially takes place at the location where the motion of carbon atoms assisting the detachment of the C-H hydrogen easily occurs. (author)

  19. The polar 2e/12c bond in phenalenyl-azaphenalenyl hetero-dimers: Stronger stacking interaction and fascinating interlayer charge transfer

    Energy Technology Data Exchange (ETDEWEB)

    Zhong, Rong-Lin; Li, Zhi-Ru, E-mail: hlxu@nenu.edu.cn, E-mail: lzr@jlu.edu.cn [Institute of Theoretical Chemistry, Jilin University, Changchun 130023 (China); Xu, Hong-Liang, E-mail: hlxu@nenu.edu.cn, E-mail: lzr@jlu.edu.cn [Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, Jilin 130024 (China)

    2016-08-07

    An increasing number of chemists have focused on the two-electron/multicenter bond (2e/mc) that was first introduced to interpret the bonding mechanism of radical dimers. Herein, we report the polar two-electron/twelve center (2e/12c) bonding character in a series of phenalenyl-azaphenalenyl radical hetero-dimers. Interestingly, the bonding energy of weaker polar hetero-dimer (P-TAP) is dominated by the overlap of the two different singly occupied molecular orbital of radicals, while that of stronger polar hetero-dimer (P-HAP) is dominated by the electrostatic attraction. Results show that the difference between the electronegativity of the monomers plays a prominent role in the essential attribution of the polar 2e/12c bond. Correspondingly, a stronger stacking interaction in the hetero-dimer could be effectively achieved by increasing the difference of nitrogen atoms number between the monomers. It is worthy of note that an interesting interlayer charge transfer character is induced in the polar hetero-dimers, which is dependent on the difference between the electronegativity of the monomers. It is our expectation that the new knowledge about the bonding nature of radical hetero-dimers might provide important information for designing radical based functional materials with various applications.

  20. Valence isomerization of hexamethyl(dewar benzene) radical cation. Pulse radiolytic investigation

    International Nuclear Information System (INIS)

    Gebicki, J.; Marcinek, A.; Mayer, J.

    1989-01-01

    Organic radical ions are important intermediates in a wide variety of electron-transfer reactions. Both the steady-state and time-resolved techniques have been extensively applied to probe various aspects of their chemistry. We have recently established that low-temperature pulse radiolysis can be successfully applied to the kinetic study of radical ion transformations with very low activation barriers. The target of the present investigation is the hexamethyl(Dewar benzene) (HMDB)-hexamethylbenzene (HMDB) system. Studies by the CIDNP technique indicated the presence of two distinguishable radical cations in the system HMDB-HMB. This view has not been supported by a nanosecond spectroscopic observation which failed to reveal any evidence for a radical cation other than HMB sm-bullet+ . The aim of this work is to present spectroscopic evidence for two different radical cations HMDB sm-bullet+ -HMB sm-bullet+ and the activation barrier for their interconversion

  1. Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions.

    Science.gov (United States)

    Mitra, Mainak; Nimir, Hassan; Demeshko, Serhiy; Bhat, Satish S; Malinkin, Sergey O; Haukka, Matti; Lloret-Fillol, Julio; Lisensky, George C; Meyer, Franc; Shteinman, Albert A; Browne, Wesley R; Hrovat, David A; Richmond, Michael G; Costas, Miquel; Nordlander, Ebbe

    2015-08-03

    Two new pentadentate {N5} donor ligands based on the N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) framework have been synthesized, viz. [N-(1-methyl-2-benzimidazolyl)methyl-N-(2-pyridyl)methyl-N-(bis-2-pyridyl methyl)amine] (L(1)) and [N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L(2)), where one or two pyridyl arms of N4Py have been replaced by corresponding (N-methyl)benzimidazolyl-containing arms. The complexes [Fe(II)(CH3CN)(L)](2+) (L = L(1) (1); L(2) (2)) were synthesized, and reaction of these ferrous complexes with iodosylbenzene led to the formation of the ferryl complexes [Fe(IV)(O)(L)](2+) (L = L(1) (3); L(2) (4)), which were characterized by UV-vis spectroscopy, high resolution mass spectrometry, and Mössbauer spectroscopy. Complexes 3 and 4 are relatively stable with half-lives at room temperature of 40 h (L = L(1)) and 2.5 h (L = L(2)). The redox potentials of 1 and 2, as well as the visible spectra of 3 and 4, indicate that the ligand field weakens as ligand pyridyl substituents are progressively substituted by (N-methyl)benzimidazolyl moieties. The reactivities of 3 and 4 in hydrogen-atom transfer (HAT) and oxygen-atom transfer (OAT) reactions show that both complexes exhibit enhanced reactivities when compared to the analogous N4Py complex ([Fe(IV)(O)(N4Py)](2+)), and that the normalized HAT rates increase by approximately 1 order of magnitude for each replacement of a pyridyl moiety; i.e., [Fe(IV)(O)(L(2))](2+) exhibits the highest rates. The second-order HAT rate constants can be directly related to the substrate C-H bond dissociation energies. Computational modeling of the HAT reactions indicates that the reaction proceeds via a high spin transition state.

  2. Reaction of hydrogen atoms with acrylaldehyde

    International Nuclear Information System (INIS)

    Koda, Seiichiro; Nakamura, Kazumoto; Hoshino, Takashi; Hikita, Tsutomu

    1978-01-01

    The reaction of hydrogen atoms with acrylaldehyde was investigated in a fast flow reactor equipped with a time-of-flight type mass spectrometer under reduced pressure. Main reaction products were carbon monoxide, ethylene, ethane, methane, and propanal. Consideration of the distributions of the reaction products under various reaction conditions showed that hydrogen atoms attacked the C=C double bond, especially its inner carbon side under reduced pressure. Resulting hot radicals caused subsequent reactions. The relative value of the apparent bimolecular rate constant of the reaction against that of trans-2-butene with hydrogen atoms was 1.6+-0.2, which supported the above-mentioned initial reaction. (auth.)

  3. Transfer-free synthesis of graphene-like atomically thin carbon films on SiC by ion beam mixing technique

    Science.gov (United States)

    Zhang, Rui; Chen, Fenghua; Wang, Jinbin; Fu, Dejun

    2018-03-01

    Here we demonstrate the synthesis of graphene directly on SiC substrates at 900 °C using ion beam mixing technique with energetic carbon cluster ions on Ni/SiC structures. The thickness of 7-8 nm Ni films was evaporated on the SiC substrates, followed by C cluster ion bombarding. Carbon cluster ions C4 were bombarded at 16 keV with the dosage of 4 × 1016 atoms/cm2. After thermal annealing process Ni silicides were formed, whereas C atoms either from the decomposition of the SiC substrates or the implanted contributes to the graphene synthesis by segregating and precipitating process. The limited solubility of carbon atoms in silicides, involving SiC, Ni2Si, Ni5Si2, Ni3Si, resulted in diffusion and precipitation of carbon atoms to form graphene on top of Ni and the interface of Ni/SiC. The ion beam mixing technique provides an attractive production method of a transfer-free graphene growth on SiC and be compatible with current device fabrication.

  4. Mechanism of formation and spatial distribution of lead atoms in quartz tube atomizers

    Science.gov (United States)

    Johansson, M.; Baxter, D. C.; Ohlsson, K. E. A.; Frech, W.

    1997-05-01

    The cross-sectional and longitudinal spatial distributions of lead atoms in a quartz tube (QT) atomizers coupled to a gas chromatograph have been investigated. A uniform analyte atom distribution over the cross-section was found in a QT having an inner diameter (i.d.) of 7 mm, whereas a 10 mm i.d. QT showed an inhomogeneous distribution. These results accentuate the importance of using QTs with i.d.s below 10 mm to fulfil the prerequirement of the Beer—Lambert law to avoid bent calibration curves. The influence of the make up gas on the formation of lead atoms from alkyllead compounds has been studied, and carbon monoxide was found equally efficient in promoting free atom formation as hydrogen. This suggests that hydrogen radicals are not essential for mediating the atomization of alkyllead in QT atomizers at ˜ 1200 K. Furthermore, thermodynamic equilibrium calculations describing the investigated system were performed supporting the experimental results. Based on the presented data, a mechanism for free lead atom formation in continuously heated QT atomizers is proposed; thermal atomization occurs under thermodynamic equilibrium conditions in a reducing gas. The longitudinal atom distribution has been further investigated applying other make up gases, N 2 and He. These results show the effect of the influx of atmospheric oxygen on the free lead atom formation. Calculations of the partial pressure of oxygen in the atomizer gas phase assuming thermodynamic equilibrium have been undertaken using a convective-diffusional model.

  5. The Rise of Radicals in Bioinorganic Chemistry.

    Science.gov (United States)

    Gray, Harry B; Winkler, Jay R

    2016-10-01

    Prior to 1950, the consensus was that biological transformations occurred in two-electron steps, thereby avoiding the generation of free radicals. Dramatic advances in spectroscopy, biochemistry, and molecular biology have led to the realization that protein-based radicals participate in a vast array of vital biological mechanisms. Redox processes involving high-potential intermediates formed in reactions with O 2 are particularly susceptible to radical formation. Clusters of tyrosine (Tyr) and tryptophan (Trp) residues have been found in many O 2 -reactive enzymes, raising the possibility that they play an antioxidant protective role. In blue copper proteins with plastocyanin-like domains, Tyr/Trp clusters are uncommon in the low-potential single-domain electron-transfer proteins and in the two-domain copper nitrite reductases. The two-domain muticopper oxidases, however, exhibit clusters of Tyr and Trp residues near the trinuclear copper active site where O 2 is reduced. These clusters may play a protective role to ensure that reactive oxygen species are not liberated during O 2 reduction.

  6. Thermal 18F atom addition to olefins

    International Nuclear Information System (INIS)

    Rogers, P.J.M.

    1986-01-01

    The addition of thermal 18 F atoms to olefins was investigated using various substrate molecules. The 18 F atoms were produced by the 19 F(n,2n) 18 F nuclear reaction with >10 5 eV of energy which is removed by multiple collisions with SF 6 molecules before reaction occurs with an olefin. By varying the SF 6 /substrate mole ratio it was demonstrated that the fraction of non-thermal reactions is dependent upon the frequency of non-reactive energy reducing collisions with SF 6 . The rate constants for addition and abstraction reactions with propene, cis-1-chloropropene and trans-1-chloropropene were determined. The substitution of a C1 atom for the olefinic H atom in the C 1 position does not affect the rate of 18 F bond formation but it changes the orientation of attack. The 18 F atom prefers the terminal carbon-in propene and propene-d 6 by a factor of 1.35 while the preference is less than 0.5 for the terminal carbon in cis-1-chloropropene and trans-1-chloropropene. The addition of 18 F atoms to olefins creates vibrationally excited fluoroalkyl radicals which can either decompose or stabilize by collision with another molecule. The rate constants for decomposition of excited CH 3 CHCHC1F radicals formed by 18 F addition to cis-1-chloropropene and trans-1-chloropropene are competitive with C 1 -C 2 bond rotation. The 18 F atoms add to the parent molecule with retention of geometry and a memory of the geometry persists as demonstrated by the cis-1-fluoropropene/trans-1-fluoropropene decomposition product ratio

  7. 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.

  8. Magnetic Resonance Studies of Proton Loss from Carotenoid Radical Cations

    Energy Technology Data Exchange (ETDEWEB)

    Kispert, Lowell D [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Focsan, A Ligia [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Konovalova, Tatyana A [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawrence, Jesse [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Bowman, Michael K [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Molnar, Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Deli, Jozsef [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2007-06-11

    Carotenoids, intrinsic components of reaction centers and pigment-protein complexes in photosynthetic membranes, play a photoprotective role and serve as a secondary electron donor. Before optimum use of carotenoids can be made in artificial photosynthetic systems, their robust nature in living materials requires extensive characterization of their electron transfer, radical trapping ability, stability, structure in and on various hosts, and photochemical behavior. Pulsed ENDOR and 2D-HYSCORE studies combined with DFT calculations reveal that photo-oxidation of natural zeaxanthin (I) and violaxanthin (II) on silica-alumina produces not only the carotenoid radical cations (Car•+) but also neutral radicals (#Car•) by proton loss from the methyl groups at positions 5 or 5', and possibly 9 or 9' and 13 or 13'. Notably, the proton loss favored in I at the 5 position by DFT calculations, is unfavorable in II due to the epoxide at the 5, 6 position. DFT calculations predict the isotropic methyl proton couplings of 8-10 MHz for Car•+ which agree with the ENDOR for carotenoid α-conjugated radical cations. Large α-proton hyperfine coupling constants (>10 MHz) determined from HYSCORE are assigned from the DFT calculations to neutral carotenoid radicals. Proton loss upon photolysis was also examined as a function of carotenoid polarity [Lycopene (III) versus 8'-apo-β-caroten-8'-al (IV)]; hydrogen bonding [Lutein (V) versus III]; host [silica-alumina versus MCM-41 molecular sieve]; and substituted metal in MCM-41. Loss of H+ from the 5(5'), 9(9') or 13(13') methyl positions has importance in photoprotection. Photoprotection involves nonphotochemical quenching (NPQ) in which 1Ch1* decays via energy transfer to the carotenoid which returns to the ground state by thermal dissipation; or via electron transfer to form a charge transfer state (I •+…Chl•-), lower in energy than 1Chl*. Formation of I •+ results in bond

  9. Zeaxanthin Radical Cation Formation in Minor Light-Harvesting Complexes of Higher Plant Antenna

    Energy Technology Data Exchange (ETDEWEB)

    Avenson, Thomas H.; Ahn, Tae Kyu; Zigmantas, Donatas; Niyogi, Krishna K.; Li, Zhirong; Ballottari, Matteo; Bassi, Roberto; Fleming, Graham R.

    2008-01-31

    Previous work on intact thylakoid membranes showed that transient formation of a zeaxanthin radical cation was correlated with regulation of photosynthetic light-harvesting via energy-dependent quenching. A molecular mechanism for such quenching was proposed to involve charge transfer within a chlorophyll-zeaxanthin heterodimer. Using near infrared (880-1100 nm) transient absorption spectroscopy, we demonstrate that carotenoid (mainly zeaxanthin) radical cation generation occurs solely in isolated minor light-harvesting complexes that bind zeaxanthin, consistent with the engagement of charge transfer quenching therein. We estimated that less than 0.5percent of the isolated minor complexes undergo charge transfer quenching in vitro, whereas the fraction of minor complexes estimated to be engaged in charge transfer quenching in isolated thylakoids was more than 80 times higher. We conclude that minor complexes which bind zeaxanthin are sites of charge transfer quenching in vivo and that they can assume Non-quenching and Quenching conformations, the equilibrium LHC(N)<--> LHC(Q) of which is modulated by the transthylakoid pH gradient, the PsbS protein, and protein-protein interactions.

  10. Radiolytic production and thermal decay kinetics of free radicals in n-alkoxyazoxybenzenes

    International Nuclear Information System (INIS)

    Tria, J.J.

    1977-01-01

    Free radical production and decay over several temperature ranges have been studied by ESR for three members of the series of n-alkoxyazoxybenzenes, those with one, two and seven carbon atoms respectively in the alkoxy chain: p,p'-azoxydianisole (PAA), p,p'-azoxydiphenetole (PAP) and 4,4'-bis-heptyloxyazoxybenzene (HAB). Radical yields per 100 ev absorbed at room temperature were: PAA 0.018, 0.019; PAP 0.033, 0.046; HAB 0.10, 0.14 for powder and single crystal samples respectively. Radicals present at room temperature and above are believed to be formed by loss of hydrogen from the benzene rings and the alkoxy groups, with more of the latter (probably α-alkoxy radicals) occurring as the alkoxy group becomes longer, based on the poorly resolved powder spectra. No cyclohexadienyl radicals or alkoxy radicals were seen. Decay of radicals between room temperature and the first liquid crystal phase transition occurred in a ''stepwise'' manner without radical conversions and was analyzed according to a model due to Waite (Phys. Rev., 107, 463 (1957) for diffusion-controlled reaction of randomly distributed reactants with a significant activation energy for the reaction step. Thermodynamic data are included for PAA powder samples and for toluene-grown single crystals. Reactions are postulated for the higher radical yields in powder samples of the three compounds irradiated at 77 0 K

  11. Investigating radical cation chain processes in the electrocatalytic Diels-Alder reaction.

    Science.gov (United States)

    Imada, Yasushi; Okada, Yohei; Chiba, Kazuhiro

    2018-01-01

    Single electron transfer (SET)-triggered radical ion-based reactions have proven to be powerful options in synthetic organic chemistry. Although unique chain processes have been proposed in various photo- and electrochemical radical ion-based transformations, the turnover number, also referred to as catalytic efficiency, remains unclear in most cases. Herein, we disclose our investigations of radical cation chain processes in the electrocatalytic Diels-Alder reaction, leading to a scalable synthesis. A gram-scale synthesis was achieved with high current efficiency of up to 8000%. The reaction monitoring profiles showed sigmoidal curves with induction periods, suggesting the involvement of intermediate(s) in the rate determining step.

  12. Radical-mediated reduction of the dithiocarbamate group under tin-free conditions.

    Science.gov (United States)

    McMaster, Claire; Bream, Robert N; Grainger, Richard S

    2012-06-28

    Reductive desulfurisation of dithiocarbamates is conveniently achieved using H(3)PO(2)-Et(3)N-ACCN in refluxing dioxane. Fused and spirocyclic β-lactams, prepared through 4-exo trig carbamoyl radical cyclisation-dithiocarbamate group transfer reactions, are reduced without fragmentation of the strained 4-membered ring. Diethyl tetraacetyl-d-glucopyranosyl dithiocarbamate is selectively reduced with or without acyloxy group migration depending on reaction conditions and choice of reductant. Deuterium incorporation from D(3)PO(2)-Et(3)N is observed for a system involving a nucleophilic radical intermediate, but not in the case of the electrophilic radical obtained through acyloxy group migration on a glucose derivative.

  13. Reaction between peroxynitrite and boronates: EPR spin-trapping, HPLC analyses, and quantum mechanical study of the free radical pathway

    Science.gov (United States)

    Sikora, Adam; Zielonka, Jacek; Lopez, Marcos; Dybala-Defratyka, Agnieszka; Joseph, Joy; Marcinek, Andrzej; Kalyanaraman, Balaraman

    2013-01-01

    Recently we showed that peroxynitrite (ONOO−) reacts directly and rapidly with aromatic and aliphatic boronic acids (k ≈ 106 M−1s−1). Product analyses and substrate consumption data indicated that ONOO− reacts stoichiometrically with boronates, yielding the corresponding phenols as the major product (~85–90%), and the remaining products (10–15%) were proposed to originate from free radical intermediates (phenyl and phenoxyl radicals). Here we investigated in detail the minor, free radical pathway of boronate reaction with ONOO−. The electron paramagnetic resonance (EPR) spin-trapping technique was used to characterize the free radical intermediates formed from the reaction between boronates and ONOO−. Using 2-methyl-2-nitrosopropane (MNP) and 5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide (DEPMPO) spin traps, phenyl radicals were trapped and detected. Although phenoxyl radicals were not detected, the positive effects of molecular oxygen, and inhibitory effects of hydrogen atom donors (acetonitrile, and 2-propanol) and general radical scavengers (GSH, NADH, ascorbic acid and tyrosine) on the formation of phenoxyl radical-derived nitrated product, suggest that phenoxyl radical was formed as the secondary species. We propose that the initial step of the reaction involves the addition of ONOO− to the boron atom in boronates. The anionic intermediate undergoes both heterolytic (major pathway) and homolytic (minor pathway) cleavage of the peroxy (O-O) bond to form phenol and nitrite as a major product (via a non-radical mechanism), or a radical pair PhB(OH)2O•−…•NO2 as a minor product. It is conceivable that phenyl radicals are formed by the fragmentation of PhB(OH)2O•− radical anion. According to the DFT quantum mechanical calculations, the energy barrier for the dissociation of PhB(OH)2O•− radical anion to form phenyl radicals is only a few kcal/mol, suggesting rapid and spontaneous fragmentation of PhB(OH)2O•− radical anion

  14. Synthesis by ATRP of triblock copolymers with densely grafted styrenic end blocks from a polyisobutylene macroinitiator

    DEFF Research Database (Denmark)

    Truelsen, Jens Høg; Kops, Jørgen; Pedersen, Walther Batsberg

    2000-01-01

    A macroinitiator was prepared from a triblock copolymer of polyisobutylene (PIB) with end blocks of poly(p-methylstyrene) (P(p-MeS)) by bromination to obtain initiating bromomethyl groups for atom transfer radical polymerization (ATRP). Controlled polymerization of styrene and p-acetoxystyrene yi......A macroinitiator was prepared from a triblock copolymer of polyisobutylene (PIB) with end blocks of poly(p-methylstyrene) (P(p-MeS)) by bromination to obtain initiating bromomethyl groups for atom transfer radical polymerization (ATRP). Controlled polymerization of styrene and p...

  15. Formation of an intermediate radical cation in the nanosecond pulse radiolysis of malachite green leucocyanide in organic solvents

    International Nuclear Information System (INIS)

    Grodkowski, J.; Bobrowski, K.; Mehnert, R.; Brede, O.

    1989-01-01

    The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl 4 and acetone with 13 ns electron pulses. Two species with absorption maxima at 620 and 480 nm were observed. The latter was attributed to the malachite green leucocyanide radical cation (MGCN +radical ) and the former to the known carbonium ion of malachite green dye (MG + ). Observation of the consecutive charge transfer via the schemes: DCE +radical → BPh +radical → MGCN +radical and DCE +radical → MGCN +radical → TMPD +radical , allowed to estimate the ionization potential of MGCN molecule in the range 6.9 eV MGCN +radical radical cation is located in the ''aniline'' part of the molecule. (author)

  16. Heavy atoms as molecular probes in studying the solvent dependence of the dynamics of triplet exciplexes

    International Nuclear Information System (INIS)

    Steiner, U.; Winter, G.

    1981-01-01

    Electron transfer reactions between thiopyronine triplet (acceptor 3 A + ) and the electron donors (D), aniline, p-Br-aniline and p-I-aniline, are investigated by flash spectroscopy in solvents of different viscosity and polarity. Due to the heavy-atom effect the radical yield becomes very sensitive to the solvent influence, which can be explained by the dynamic properties of a triplet exciplex ( 3 (AD + )) formed as a primary product in the reaction between acceptor triplet and donor. Whereas on variation of solvent viscosity the solvent cage effect on the dissociation of 3 (AD + ) is observed, a change in solvent polarity is suggested to affect the radiationless deactivation of 3 (AD + ) to the ground state of the components. (author)

  17. Molecular Insights into Variable Electron Transfer in Amphibian Cryptochrome

    DEFF Research Database (Denmark)

    Sjulstok, Emil; Lüdemann, Gesa; Kubař, Tomáš

    2018-01-01

    are mutated, radical-pair formation is still observed. In this study, we computationally investigate electron-transfer pathways in the X. laevis cryptochrome DASH by extensively equilibrating a previously established homology model using molecular dynamics simulations and then mutating key amino acids......Cryptochrome proteins are activated by the absorption of blue light, leading to the formation of radical pairs through electron transfer in the active site. Recent experimental studies have shown that once some of the amino acid residues in the active site of Xenopus laevis cryptochrome DASH...... involved in the electron transfer. The electron-transfer pathways are then probed by using tight-binding density-functional theory. We report the alternative electron-transfer pathways resolved at the molecular level and, through comparison of amino acid sequences for cryptochromes from different species...

  18. Ab initio molecular dynamics of the reaction of quercetin with superoxide radical

    Energy Technology Data Exchange (ETDEWEB)

    Lespade, Laure, E-mail: l.lespade@ism.u-bordeaux1.fr

    2016-08-22

    Highlights: • Ab initio molecular dynamics is performed to describe the reaction of quercetin and superoxide. • The reaction occurs near the sites 4′ and 7 when the system contains sufficiently water molecules. • The difference of reactivity of superoxide compared to commonly used radicals as DPPH{sup ·} or ABTS{sup ·+} is explained. - Abstract: Superoxide plays an important role in biology but in unregulated concentrations it is implicated in a lot of diseases such as cancer or atherosclerosis. Antioxidants like flavonoids are abundant in plant and are good scavengers of superoxide radical. The modeling of superoxide scavenging by flavonoids from the diet still remains a challenge. In this study, ab initio molecular dynamics of the reaction of the flavonoid quercetin toward superoxide radical has been carried out using Car–Parrinello density functional theory. The study has proven different reactant solvation by modifying the number of water molecules surrounding superoxide. The reaction consists in the gift of a hydrogen atom of one of the hydroxyl groups of quercetin to the radical. When it occurs, it is relatively fast, lower than 100 fs. Calculations show that it depends largely on the environment of the hydroxyl group giving its hydrogen atom, the geometry of the first water layer and the presence of a certain number of water molecules in the second layer, indicating a great influence of the solvent on the reactivity.

  19. 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

    2017-08-28

    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( 2 S) atoms with SO 2 (X̃ 1 A ' ) molecules is presented here. For such a study, a double many-body expansion potential energy surface previously reported for HSO 2 ( 2 A) is used. This work was motivated by recent experiments by Ma et al. studying collisions of H + SO 2 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 HSO 2 ). 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 SO 2 with relatively low vibrational excitation energy, while indirect ones dominate the conversion from translational energy to high values of the vibrational counterpart.

  20. Solvent driving force ensures fast formation of a persistent and well-separated radical pair in plant cryptochrome

    DEFF Research Database (Denmark)

    Lüdemann, Gesa; Solov'yov, Ilia; Kubar, Tomás

    2015-01-01

    upon the electron transfer. This approach allows us to follow the time evolution of the electron transfer in an unbiased fashion and to reveal the molecular driving force which ensures fast electron transfer in cryptochrome guaranteeing formation of a persistent radical pair suitable...

  1. Matrix-isolation and computational study of H{sub 2}CCCl and H{sub 2}CCBr radicals

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Cheng; Duarte, Luís; Khriachtchev, Leonid, E-mail: leonid.khriachtchev@helsinki.fi [Department of Chemistry, University of Helsinki, P.O. Box 55, FI-00014 Helsinki (Finland)

    2016-08-21

    We report on two new radicals, H{sub 2}CCCl and H{sub 2}CCBr, prepared in low-temperature noble-gas matrices and characterized using infrared spectroscopy. These radicals are made by UV photolysis of HCCCl and HCCBr and subsequent thermal annealing to mobilize hydrogen atoms in the matrices and promote their reaction with the residual precursor molecules. Three characteristic infrared bands are observed for each radical. The assignments are supported by quantum chemical calculations at the B3LYP and CCSD(T) levels of theory with the def2-TZVPPD basis set.

  2. Multiple-electron processes in fast ion-atom collisions

    International Nuclear Information System (INIS)

    Schlachter, A.S.

    1989-03-01

    Research in atomic physics at the Lawrence Berkeley Laboratory Super-HILAC and Bevalac accelerators on multiple-electron processes in fast ion-atom collisions is described. Experiments have studied various aspects of the charge-transfer, ionization, and excitation processes. Examples of processes in which electron correlation plays a role are resonant transfer and excitation and Auger-electron emission. Processes in which electron behavior can generally be described as uncorrelated include ionization and charge transfer in high-energy ion-atom collisions. A variety of experiments and results for energies from 1 MeV/u to 420 MeV/u are presented. 20 refs., 15 figs

  3. Transfer Hydrogenation in Open-Shell Nucleotides — A Theoretical Survey

    Directory of Open Access Journals (Sweden)

    Florian Achrainer

    2014-12-01

    Full Text Available The potential of a larger number of sugar models to act as dihydrogen donors in transfer hydrogenation reactions has been quantified through the calculation of hydrogenation energies of the respective oxidized products. Comparison of the calculated energies to hydrogenation energies of nucleobases shows that many sugar fragment radicals can reduce pyrimidine bases such as uracil in a strongly exothermic fashion. The most potent reducing agent is the C3' ribosyl radical. The energetics of intramolecular transfer hydrogenation processes has also been calculated for a number of uridinyl radicals. The largest driving force for such a process is found for the uridin-C3'-yl radical, whose rearrangement to the C2'-oxidized derivative carrying a dihydrouracil is predicted to be exothermic by 61.1 kJ/mol in the gas phase.

  4. Nitrogen atom transfer mediated by a new PN3P-pincer nickel core via a putative nitrido nickel intermediate

    KAUST Repository

    Yao, Changguang

    2018-02-13

    A 2nd generation PN3P-pincer azido nickel complex (PN3P)Ni(N3) reacts with isocyanides to afford monosubstituted carbodiimides under irradiation, presumably via a transient nitrido intermediate. The resulting species can further generate unsymmetrical carboddimides and the PN3P nickel halide complex, accomplishing a synthetic cycle for a complete nitrogen atom transfer reaction.

  5. Nitrogen atom transfer mediated by a new PN3P-pincer nickel core via a putative nitrido nickel intermediate

    KAUST Repository

    Yao, Changguang; Wang, Xiufang; Huang, Kuo-Wei

    2018-01-01

    A 2nd generation PN3P-pincer azido nickel complex (PN3P)Ni(N3) reacts with isocyanides to afford monosubstituted carbodiimides under irradiation, presumably via a transient nitrido intermediate. The resulting species can further generate unsymmetrical carboddimides and the PN3P nickel halide complex, accomplishing a synthetic cycle for a complete nitrogen atom transfer reaction.

  6. Low-Energy Charge Transfer in Multiply-Charged Ion-Atom Collisions Studied with the Combined SCVB-MOCC Approach

    OpenAIRE

    Cooper, D. L.; Stancil, P. C.; Turner, A. R.; Wang, J. G.; Clarke, N. J.; Zygelman, B.

    2002-01-01

    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...

  7. Comparison of Polymer Networks Synthesized by Conventional Free Radical and RAFT Copolymerization Processes in Supercritical Carbon Dioxide

    OpenAIRE

    Patricia Pérez-Salinas; Gabriel Jaramillo-Soto; Alberto Rosas-Aburto; Humberto Vázquez-Torres; María Josefa Bernad-Bernad; Ángel Licea-Claverie; Eduardo Vivaldo-Lima

    2017-01-01

    There is a debate in the literature on whether or not polymer networks synthesized by reversible deactivation radical polymerization (RDRP) processes, such as reversible addition-fragmentation radical transfer (RAFT) copolymerization of vinyl/divinyl monomers, are less heterogeneous than those synthesized by conventional free radical copolymerization (FRP). In this contribution, the syntheses by FRP and RAFT of hydrogels based on 2-hydroxyethylene methacrylate (HEMA) and ethylene glycol dimet...

  8. Download this PDF file

    African Journals Online (AJOL)

    place by H atomes transfer to the DPPH radical,. Structural differencies of chemical compounds bear- ing the transferable hydrogen atome and present in each extract may reasonably explain the varied be- haviour of the extracts as suggested by Brand-. Williams et al., (1995) when analysing the antiradicalar efficacy of 20 ...

  9. Charge-transfer modified embedded atom method dynamic charge potential for Li-Co-O system.

    Science.gov (United States)

    Kong, Fantai; Longo, Roberto C; Liang, Chaoping; Nie, Yifan; Zheng, Yongping; Zhang, Chenxi; Cho, Kyeongjae

    2017-11-29

    To overcome the limitation of conventional fixed charge potential methods for the study of Li-ion battery cathode materials, a dynamic charge potential method, charge-transfer modified embedded atom method (CT-MEAM), has been developed and applied to the Li-Co-O ternary system. The accuracy of the potential has been tested and validated by reproducing a variety of structural and electrochemical properties of LiCoO 2 . A detailed analysis on the local charge distribution confirmed the capability of this potential for dynamic charge modeling. The transferability of the potential is also demonstrated by its reliability in describing Li-rich Li 2 CoO 2 and Li-deficient LiCo 2 O 4 compounds, including their phase stability, equilibrium volume, charge states and cathode voltages. These results demonstrate that the CT-MEAM dynamic charge potential could help to overcome the challenge of modeling complex ternary transition metal oxides. This work can promote molecular dynamics studies of Li ion cathode materials and other important transition metal oxides systems that involve complex electrochemical and catalytic reactions.

  10. Radical anion structure of β-halogen-substituted acetamides in X-ray-irradiated single crystals: an INDO and EPR study

    International Nuclear Information System (INIS)

    Samskog, P.O.; Kispert, L.D.

    1984-01-01

    The anion radicals of bromodifluoroacetamide and chlorodifluoroacetamide are investigated by using the INDO method and EPR spectroscopy. INDO calculations for the anions give a spin density distribution in agreement with that suggested from experiment. Results of the analyses show that the unpaired electron occupies the sigma* orbital composed of the rho orbitals, along the C/sub β/-X bond, on the carbon and the unique halogen atoms. The results are compared to the radical anion in trifluoroacetamide. The electronic structure of SCF 2 CONH 2 - radical anions is a π-radical anion when X = F and a sigma*-radical anion when X = Cl and Br. 2 figures, 4 tables

  11. ATOM TRANSFER RADICAL POLYMERIZATION IN SUPERCRITICAL CARBON DIOXIDE. (R826735)

    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...

  12. Scattering of State-Selected and Oriented Hydroxyl Radicals by Halogen Hydrides and Xenon

    NARCIS (Netherlands)

    Moise, A.V.

    2007-01-01

    The interaction of the OH radical with atoms and other molecules is relevant for many physical and chemical processes involved in atmospheric, combustion and interstellar chemistry. Various experimental and theoretical studies have revealed information concerning the interaction of the hydroxyl

  13. Etude de la fixation d'atomes de brome dans les traces latentes d'ions

    Science.gov (United States)

    Vareille, J. C.; Moliton, J. P.; Decossas, J. L.; Teyssier, J. L.; Delaunay, B.

    1981-09-01

    We show that the branching of bromide atoms is possible on chemically active sites produced by Kr 8+, Cl 6+ and He 2+ ion irradiation on cellulose triacetate. The number of fixed atoms increases with ion fluence and atomic number. These results are in good agreement with those concerning radical yield around the ions' path.

  14. Electron spin resonance studies of γ-irradiated phosphite and phosphate esters. Identification of phosphinyl, phosphonyl, phosphoranyl, and phosphine dimer cation radicals

    International Nuclear Information System (INIS)

    Kerr, C.M.L.; Webster, K.; Williams, F.

    1975-01-01

    The powder ESR spectra of several γ-irradiated phosphorus esters at 77 0 K were analyzed into their distinguishable radical components, each spectrum being generally a composite of anisotropic features from a number of alkyl and phosphorus-centered radicals. Resolution of overlapping spectra was achieved in some instances by radiation-chemical experiments designed to suppress or enhance the products of electron capture relative to the radicals formed by other mechanisms. The radiation chemistry of dialkyl phosphites, (RO) 2 P(O)H, is influenced by the ease with which the P--H bond in these compounds is broken, the principal radicals being the phosphonyl species (RO) 2 PO and ROP(O)O - . Both of these species are thought to be the secondary products of hydrogen atom abstraction by the alkyl radical R which is produced by dissociative electron capture. A similar primary step was found to apply for the trialkyl phosphates, (RO) 3 PO, but in this case only carbon-centered radicals are formed by secondary H-atom abstraction processes. Results for the pyrophosphite differ from those for the trialkyl phosphites in showing the absence of alkyl radicals or their phosphoranyl adducts and the formation of the phosphonyl species (EtO) 2 PO, the latter being produced presumably by cleavage of the P--O--P bridge. The ESR parameters for each of the four main groups of phosphorus-centered radicals are summarized and the electronic structures of these radicals are discussed briefly

  15. Complementary Strategies for Directed C(sp3 )-H Functionalization: A Comparison of Transition-Metal-Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer.

    Science.gov (United States)

    Chu, John C K; Rovis, Tomislav

    2018-01-02

    The functionalization of C(sp 3 )-H bonds streamlines chemical synthesis by allowing the use of simple molecules and providing novel synthetic disconnections. Intensive recent efforts in the development of new reactions based on C-H functionalization have led to its wider adoption across a range of research areas. This Review discusses the strengths and weaknesses of three main approaches: transition-metal-catalyzed C-H activation, 1,n-hydrogen atom transfer, and transition-metal-catalyzed carbene/nitrene transfer, for the directed functionalization of unactivated C(sp 3 )-H bonds. For each strategy, the scope, the reactivity of different C-H bonds, the position of the reacting C-H bonds relative to the directing group, and stereochemical outcomes are illustrated with examples in the literature. The aim of this Review is to provide guidance for the use of C-H functionalization reactions and inspire future research in this area. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Quantitative Structure--Activity Relationship (QSAR) for the Oxidation of Trace Organic Contaminants by Sulfate Radical.

    Science.gov (United States)

    Xiao, Ruiyang; Ye, Tiantian; Wei, Zongsu; Luo, Shuang; Yang, Zhihui; Spinney, Richard

    2015-11-17

    The sulfate radical anion (SO4•–) based oxidation of trace organic contaminants (TrOCs) has recently received great attention due to its high reactivity and low selectivity. In this study, a meta-analysis was conducted to better understand the role of functional groups on the reactivity between SO4•– and TrOCs. The results indicate that compounds in which electron transfer and addition channels dominate tend to exhibit a faster second-order rate constants (kSO4•–) than that of H–atom abstraction, corroborating the SO4•– reactivity and mechanisms observed in the individual studies. Then, a quantitative structure activity relationship (QSAR) model was developed using a sequential approach with constitutional, geometrical, electrostatic, and quantum chemical descriptors. Two descriptors, ELUMO and EHOMO energy gap (ELUMO–EHOMO) and the ratio of oxygen atoms to carbon atoms (#O:C), were found to mechanistically and statistically affect kSO4•– to a great extent with the standardized QSAR model: ln kSO4•– = 26.8–3.97 × #O:C – 0.746 × (ELUMO–EHOMO). In addition, the correlation analysis indicates that there is no dominant reaction channel for SO4•– reactions with various structurally diverse compounds. Our QSAR model provides a robust predictive tool for estimating emerging micropollutants removal using SO4•– during wastewater treatment processes.

  17. Reaction mechanisms and kinetics of the iminovinylidene radical with NO: Ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Hsiao, Ming-Kai; Chung, Yi-Hua; Hung, Yu-Ming; Chen, Hui-Lung, E-mail: chl3@faculty.pccu.edu.tw [Department of Chemistry and Institute of Applied Chemistry, Chinese Culture University, Taipei 111, Taiwan (China)

    2014-05-28

    The nitric oxide (NO) is a notorious compound for polluting environment. Recent year, removing nitric oxide from the atmosphere becomes a focus of the investigation. In our work, we study the iminovinylidene (HNCC) radical reacted with NO molecule. The mechanism and kinetic for reaction of the HNCC radical with the NO molecule is investigated via considering the possible channels of the N and O atoms of NO attacking the N and C atoms of the HNCC based on the high level ab initio molecular orbital calculations in conjunction with variational TST and RRKM calculations. The species involved have been optimized at the B3LYP/6-311++G(3df,2p) level and their single-point energies are refined by the CCSD(T)/aug-cc-PVQZ//B3LYP/6-311++G(3df,2p) method. The calculated potential energy surfaces indicated that energetically the most favorable channel for the HNCC + NO reaction was predicted to be the formation of HNC+CNO (P8) product via the addition reaction of the C atom of HNCC radical and the N atom of NO with the head to head orientation. To rationalize the scenario of the calculated results, we also employ the Fukui functions and HSAB theory to seek for a possible explanation. In addition, the reaction rate constants were calculated using VariFlex code, and the results show that the total rate coefficient, k{sub total}, at Ar pressure 760 Torr can be represented with an equation: k{sub total} = 6.433 × 10{sup −11} T {sup 0.100} exp(0.275 kcal mol{sup −1}/RT) at T = 298–3000 K, in units of cm{sup 3} molecule{sup −1} s{sup −1}.

  18. The nature of resonance in allyl ions and radical.

    Science.gov (United States)

    Linares, Mathieu; Humbel, Stéphane; Braïda, Benoît

    2008-12-18

    A recent valence bond scheme based on Lewis structures, the valence bond BOND (VBB) method (BOND: Breathing Orbitals Naturally Delocalized) method (Linares, M.; Braida, B.; Humbel, S. J. Phys. Chem. A 2006, 110, 2505-2509), is applied to explore the nature of resonance in allyl systems. Whereas allyl radical is correctly described by the resonance between the two traditional Lewis structures, a third "long-bonded" structure, which apparently creates a pi bond between the two distant carbon atoms, appears to plays an important role in allyl ions description. The similar vertical resonance energy (VRE) for both allyl ions is rather moderate (approximately 37 kcal/mol) in the two-structure description but is significantly enhanced when the long-bonded structure is included into the VBB wave function (by up to 20 kcal/mol). The allyl radical is much less resonant and is correctly described by the traditional two-structure picture. The development of VBB Lewis structures into "pure" valence bond determinants enlightens the role of the third structure in the description of allyl ions. The existence of a long bond between the two distant carbon atoms is clearly ruled out. Charge equilibration effect is shown to be a minor factor. The third structure is finally attributed to one- and three-electron bonding character revealed in the pi systems of the cation and anion, respectively. This makes these systems two surprising examples of odd electron bonding within a singlet state. Last, the two-structure description of allyl radical is improved by addition of missing ionic structures.

  19. Hydrogen transfer reactions of interstellar Complex Organic Molecules

    Science.gov (United States)

    Álvarez-Barcia, S.; Russ, P.; Kästner, J.; Lamberts, T.

    2018-06-01

    Radical recombination has been proposed to lead to the formation of complex organic molecules (COMs) in CO-rich ices in the early stages of star formation. These COMs can then undergo hydrogen addition and abstraction reactions leading to a higher or lower degree of saturation. Here, we have studied 14 hydrogen transfer reactions for the molecules glyoxal, glycoaldehyde, ethylene glycol, and methylformate and an additional three reactions where CHnO fragments are involved. Over-the-barrier reactions are possible only if tunneling is invoked in the description at low temperature. Therefore the rate constants for the studied reactions are calculated using instanton theory that takes quantum effects into account inherently. The reactions were characterized in the gas phase, but this is expected to yield meaningful results for CO-rich ices due to the minimal alteration of reaction landscapes by the CO molecules. We found that rate constants should not be extrapolated based on the height of the barrier alone, since the shape of the barrier plays an increasingly larger role at decreasing temperature. It is neither possible to predict rate constants based only on considering the type of reaction, the specific reactants and functional groups play a crucial role. Within a single molecule, though, hydrogen abstraction from an aldehyde group seems to be always faster than hydrogen addition to the same carbon atom. Reactions that involve heavy-atom tunneling, e.g., breaking or forming a C-C or C-O bond, have rate constants that are much lower than those where H transfer is involved.

  20. Thermo-responsive and fluorescent cellulose nanocrystals grafted with polymer brushes

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Weibing [Nanjing Forestry Univ. (China); Georgia Inst. of Technology, Atlanta, GA (United States); Huang, Fang [Georgia Inst. of Technology, Atlanta, GA (United States); Pan, Shaobo [Georgia Inst. of Technology, Atlanta, GA (United States); Mu, Wei [Georgia Inst. of Technology, Atlanta, GA (United States); Meng, Xianzhi [Georgia Inst. of Technology, Atlanta, GA (United States); Yang, Haitao [Hubei Univ. of Technology, Wuhan (China); Xu, Zhaoyang [Nanjing Forestry Univ. (China); Ragauskas, Arthur J. [Georgia Inst. of Technology, Atlanta, GA (United States); Deng, Yulin [Georgia Inst. of Technology, Atlanta, GA (United States)

    2014-11-24

    Fluorescent and thermo-responsive cellulose nanocrystals (CNCs) with tuned polymer brushes were preparedviasurface initiated activators generated by electron transfer for atom transfer radical polymerization.

  1. Magnetic Resonance Studies of Proton Loss from Carotenoid Radical Cations

    International Nuclear Information System (INIS)

    Kispert, Lowell D.; Focsan, A. Ligia; Konovalova, Tatyana A.; Lawrence, Jesse; Bowman, Michael K.; Dixon, David A.; Molnar, Peter; Deli, Jozsef

    2007-01-01

    Carotenoids, intrinsic components of reaction centers and pigment-protein complexes in photosynthetic membranes, play a photoprotective role and serve as a secondary electron donor. Before optimum use of carotenoids can be made in artificial photosynthetic systems, their robust nature in living materials requires extensive characterization of their electron transfer, radical trapping ability, stability, structure in and on various hosts, and photochemical behavior. Pulsed ENDOR and 2D-HYSCORE studies combined with DFT calculations reveal that photo-oxidation of natural zeaxanthin (I) and violaxanthin (II) on silica-alumina produces not only the carotenoid radical cations (Car ·+ ) but also neutral radicals ((number s ign)Car · ) by proton loss from the methyl groups at positions 5 or 5(prime), and possibly 9 or 9(prime) and 13 or 13(prime). Notably, the proton loss favored in I at the 5 position by DFT calculations, is unfavorable in II due to the epoxide at the 5, 6 position. DFT calculations predict the isotropic methyl proton couplings of 8-10 MHz for Car # center d ot# + which agree with the ENDOR for carotenoid π-conjugated radical cations. Large α-proton hyperfine coupling constants (>10 MHz) determined from HYSCORE are assigned from the DFT calculations to neutral carotenoid radicals. Proton loss upon photolysis was also examined as a function of carotenoid polarity (Lycopene (III) versus 8(prime)-apo-β-caroten-8(prime)-al (IV)); hydrogen bonding (Lutein (V) versus III); host (silica-alumina versus MCM-41 molecular sieve); and substituted metal in MCM-41. Loss of H + from the 5(5(prime)), 9(9(prime)) or 13(13(prime)) methyl positions has importance in photoprotection. Photoprotection involves nonphotochemical quenching (NPQ) in which 1 Ch1* decays via energy transfer to the carotenoid which returns to the ground state by thermal dissipation; or via electron transfer to form a charge transfer state (I # center d ot# + ...Chl # center d ot# - ), lower in

  2. Direct Aldehyde C-H Arylation and Alkylation via the Combination of Nickel, Hydrogen Atom Transfer, and Photoredox Catalysis.

    Science.gov (United States)

    Zhang, Xiaheng; MacMillan, David W C

    2017-08-23

    A mechanism that enables direct aldehyde C-H functionalization has been achieved via the synergistic merger of photoredox, nickel, and hydrogen atom transfer catalysis. This mild, operationally simple protocol transforms a wide variety of commercially available aldehydes, along with aryl or alkyl bromides, into the corresponding ketones in excellent yield. This C-H abstraction coupling technology has been successfully applied to the expedient synthesis of the medicinal agent haloperidol.

  3. Electron transfer in organic glass. Distance and energy dependence

    International Nuclear Information System (INIS)

    Krongauz, V.V.

    1992-01-01

    The authors have investigated the distance and energy dependence of electron transfer in rigid organic glasses containing randomly dispersed electron donor and electron acceptor molecules. Pulsed radiolysis by an electron beam from a linear accelerator was used for ionization resulting in charge deposition on donor molecules. The disappearance kinetics of donor radical anions due to electron transfer to acceptor was monitored spectroscopically by the change in optical density at the wavelength corresponding to that of donor radical anion absorbance. It was found that the rate of the electron transfer observed experimentally was higher than that computed using the Marcus-Levich theory assuming that the electron-transfer activation barrier is equal to the binding energy of electron on the donor molecule. This discrepancy between the experimental and computed results suggests that the open-quotes inertclose quotes media in which electron-transfer reaction takes place may be participating in the process, resulting in experimentally observed higher electron-transfer rates. 32 refs., 3 figs., 2 tabs

  4. Double C-H activation of ethane by metal-free SO2*+ radical cations.

    Science.gov (United States)

    de Petris, Giulia; Cartoni, Antonella; Troiani, Anna; Barone, Vincenzo; Cimino, Paola; Angelini, Giancarlo; Ursini, Ornella

    2010-06-01

    The room-temperature C-H activation of ethane by metal-free SO(2)(*+) radical cations has been investigated under different pressure regimes by mass spectrometric techniques. The major reaction channel is the conversion of ethane to ethylene accompanied by the formation of H(2)SO(2)(*+), the radical cation of sulfoxylic acid. The mechanism of the double C-H activation, in the absence of the single activation product HSO(2)(+), is elucidated by kinetic studies and quantum chemical calculations. Under near single-collision conditions the reaction occurs with rate constant k=1.0 x 10(-9) (+/-30%) cm(3) s(-1) molecule(-1), efficiency=90%, kinetic isotope effect k(H)/k(D)=1.1, and partial H/D scrambling. The theoretical analysis shows that the interaction of SO(2)(*+) with ethane through an oxygen atom directly leads to the C-H activation intermediate. The interaction through sulfur leads to an encounter complex that rapidly converts to the same intermediate. The double C-H activation occurs by a reaction path that lies below the reactants and involves intermediates separated by very low energy barriers, which include a complex of the ethyl cation suitable to undergo H/D scrambling. Key issues in the observed reactivity are electron-transfer processes, in which a crucial role is played by geometrical constraints. The work shows how mechanistic details disclosed by the reactions of metal-free electrophiles may contribute to the current understanding of the C-H activation of ethane.

  5. Golden mean energy equals highest atomic electron orbital energy

    Energy Technology Data Exchange (ETDEWEB)

    Malinowski, Leonard J. [Interdisciplinary Research Club, P.O. Box 371, Monroeville, PA 15146 (United States)], E-mail: LJMalinowski@gmail.com

    2009-12-15

    The golden mean numerical value {phi} = 0.5({radical}5 - 1) has been given a physical manifestation through E infinity theory. This short paper relates the golden mean energy 0.618034 MeV to atomic electron orbitals.

  6. Some aspects of radiation-induced free-radical chemistry of biologically important molecules

    International Nuclear Information System (INIS)

    Sonntag, C. von

    1992-01-01

    Biologically relevant material is usually associated with considerable amounts of water. When ionizing radiation interacts with such material one must consider two modes of energy deposition: the direct effect (ionizing radiation is absorbed by the biomolecules) and the indirect effect (ionizing radiation is absorbed by the surrounding water). In the direct effect, radical cations plus electrons, and excited states of the biomolecules are formed. In the indirect effect the water is decomposed resulting in the formation of the water radicals OH,H and e aq - . These reactive intermediates then interact with the biomolecules. When such systems are irradiated oxygen is often present. As a result of this, the radicals formed in the biomolecules by the various routes are converted into the corresponding peroxyl radicals. In certain cases, e.g. with the nucleobases of DNA, radical cations can be produced in dilute aqueous solutions by radiation-generated SO 4 - radicals, and the fate of these nucleobase radical cations studied by pulse radiolysis and product analysis. Attention will be drawn to the fact that frequently some of the reaction products of the radical cations with water are identical to those formed by OH radical attack, but that there are also marked differences. Similarly, protonation of radical anions (formed by the reaction of solvated electrons with the biomolecules) and the reaction of H-atoms with these molecules can lead to radical intermediates with considerably differing characteristics. Our present knowledge of the variety of reactions of the peroxyl radicals occurring in aqueous solutions will be briefly discussed, emphasizing the large variety of HO 2 /O 2 - elimination reactions and pointing to the reversibility of the oxygen addition (RO 2 →R + O 2 ) in some systems recently studied. (author)

  7. Fast multilevel radiative transfer

    Science.gov (United States)

    Paletou, Frédéric; Léger, Ludovick

    2007-01-01

    The vast majority of recent advances in the field of numerical radiative transfer relies on approximate operator methods better known in astrophysics as Accelerated Lambda-Iteration (ALI). A superior class of iterative schemes, in term of rates of convergence, such as Gauss-Seidel and Successive Overrelaxation methods were therefore quite naturally introduced in the field of radiative transfer by Trujillo Bueno & Fabiani Bendicho (1995); it was thoroughly described for the non-LTE two-level atom case. We describe hereafter in details how such methods can be generalized when dealing with non-LTE unpolarised radiation transfer with multilevel atomic models, in monodimensional geometry.

  8. Muonic atoms with vacant electron shells

    International Nuclear Information System (INIS)

    Bacher, R.; Gotta, D.; Simons, L.M.; Missimer, J.; Mukhopadhyay, N.C.

    1985-01-01

    We show that the cascade in muonic atoms with Z<20 ejects sufficient atomic electrons to ionize an isolated muonic atom completely. In gases, the rates with which electrons refill the atomic shell can be accurately deduced from measured and calculated electron transfer cross sections. Thus, we can conclude that completely ionized muonic atoms can be prepared in gases, and that they remain isolated for long enough times at attainable pressures to facilitate studies of fundamental interactions in muonic atoms

  9. Efficiency of ablative plasma energy transfer into a massive aluminum target using different atomic number ablators

    Czech Academy of Sciences Publication Activity Database

    Kasperczuk, A.; Pisarczyk, T.; Chodukowski, T.; Kalinowska, Z.; Stepniewski, W.; Jach, K.; Swierczynski, R.; Renner, Oldřich; Šmíd, Michal; Ullschmied, Jiří; Cikhart, J.; Klír, D.; Kubeš, P.; Řezáč, K.; Krouský, Eduard; Pfeifer, Miroslav; Skála, Jiří

    2015-01-01

    Roč. 33, č. 3 (2015), s. 379-386 ISSN 0263-0346 R&D Projects: GA MŠk ED1.1.00/02.0061; GA MŠk(CZ) LD14089 EU Projects: European Commission(XE) 284464 - LASERLAB-EUROPE Grant - others:ELI Beamlines(XE) CZ.1.05/1.1.00/02.0061; AVČR(CZ) M100101208 Institutional support: RVO:68378271 ; RVO:61389021 Keywords : ablator atomic number * crater volume * laser energy transfer * plasma ablative pressure Subject RIV: BL - Plasma and Gas Discharge Physics; BH - Optics, Masers, Lasers (UFP-V) Impact factor: 1.649, year: 2015

  10. Kinetics and Mechanism of the Gas-Phase Reaction of Selected Carbonyls with Cl Atoms between 250 and 340 K

    Science.gov (United States)

    Hasson, A. S.; Algrim, L.; Abdelhamid, A.; Tyndall, G. S.; Orlando, J. J.

    2013-12-01

    Carbonyls are important products from the gas phase degradation of most volatile organic compounds. Their atmospheric reactions therefore have a significant impact on atmospheric composition, particularly in aged air masses. While the reactions of short-chain linear carbonyls are well understood, the chemistry of larger (> C6) and branched carbonyl is more uncertain. To provide insight into these reactions, the reactions of three carbonyls (methyl isopropyl ketone, MIK; di-isopropyl ketone, DIK; and diethyl ketone, DEK) with chlorine atoms were investigated between 250 and 340 K and 1 atm in the presence and absence of NOx and an HO2 source (methanol). Experiments were performed in a photochemical reactor using a combination of long-path Fourier transform infra-red spectroscopy, proton transfer reaction mass spectrometry and gas chromatography with flame ionization detection. The kinetics were studied using the relative rate technique with butanone and isopropanol as the reference compounds. The Arrhenius expression for the three rate coefficients was determined to be k(DEK+Cl) = 3.87 x 10-11e(2 × 7 kJ/mol)/RT cm3 molecules-1 s-1 , k(MIPK+Cl) = 7.20 x 10-11e(0.2× 8 kJ/mol)/RT cm3 molecules-1 s-1 , and k(DIPK+Cl) = 3.33 x 10-10e(-3× 8 kJ/mol)/RT cm3 molecules-1 s-1 . Measured reaction products accounted for 38-72 % of the reacted carbon and were consistent with strong deactivation of the carbon atom adjacent to the carbonyl group with respect to H-atom abstraction by Cl atoms. The product distributions also provide insight into radical recycling from the organic peroxy + HO2 reaction, and the relative rates of isomerization, fragmentation and reaction with O2 for carbonyl-containing alkoxy radicals. Implications of these results will be discussed.

  11. Low Energy Charge Transfer for Collisions of Si3+ with Atomic Hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Bruhns, H. [Columbia University; Kreckel, H. [Columbia University; Savin, D. W. [Columbia University; Seely, D. G. [Albion College; Havener, Charles C [ORNL

    2008-01-01

    Cross sections of charge transfer for Si{sup 3+} ions with atomic hydrogen at collision energies of {approx} 40-2500 eV/u were carried out using a merged-beam technique at the Multicharged Ion Research Facility at Oak Ridge National Laboratory. The data span an energy range in which both molecular orbital close coupling (MOCC) and classical trajectory Monte Carlo (CTMC) calculations are available. The influence of quantum mechanical effects of the ionic core as predicted by MOCC is clearly seen in our results. However, discrepancies between our experiment and MOCC results toward higher collision energies are observed. At energies above 1000 eV/u good agreement is found with CTMC results.

  12. Absolute photoionization cross-section of the methyl radical.

    Science.gov (United States)

    Taatjes, Craig A; Osborn, David L; Selby, Talitha M; Meloni, Giovanni; Fan, Haiyan; Pratt, Stephen T

    2008-10-02

    The absolute photoionization cross-section of the methyl radical has been measured using two completely independent methods. The CH3 photoionization cross-section was determined relative to that of acetone and methyl vinyl ketone at photon energies of 10.2 and 11.0 eV by using a pulsed laser-photolysis/time-resolved synchrotron photoionization mass spectrometry method. The time-resolved depletion of the acetone or methyl vinyl ketone precursor and the production of methyl radicals following 193 nm photolysis are monitored simultaneously by using time-resolved synchrotron photoionization mass spectrometry. Comparison of the initial methyl signal with the decrease in precursor signal, in combination with previously measured absolute photoionization cross-sections of the precursors, yields the absolute photoionization cross-section of the methyl radical; sigma(CH3)(10.2 eV) = (5.7 +/- 0.9) x 10(-18) cm(2) and sigma(CH3)(11.0 eV) = (6.0 +/- 2.0) x 10(-18) cm(2). The photoionization cross-section for vinyl radical determined by photolysis of methyl vinyl ketone is in good agreement with previous measurements. The methyl radical photoionization cross-section was also independently measured relative to that of the iodine atom by comparison of ionization signals from CH3 and I fragments following 266 nm photolysis of methyl iodide in a molecular-beam ion-imaging apparatus. These measurements gave a cross-section of (5.4 +/- 2.0) x 10(-18) cm(2) at 10.460 eV, (5.5 +/- 2.0) x 10(-18) cm(2) at 10.466 eV, and (4.9 +/- 2.0) x 10(-18) cm(2) at 10.471 eV. The measurements allow relative photoionization efficiency spectra of methyl radical to be placed on an absolute scale and will facilitate quantitative measurements of methyl concentrations by photoionization mass spectrometry.

  13. Sub-millitesla magnetic field effects on the recombination reaction of flavin and ascorbic acid radicals

    Energy Technology Data Exchange (ETDEWEB)

    Evans, Emrys W.; Henbest, Kevin B.; Timmel, Christiane R., E-mail: christiane.timmel@chem.ox.ac.uk, E-mail: stuart.mackenzie@chem.ox.ac.uk [Department of Chemistry, Centre for Advanced Electron Spin Resonance, University of Oxford, Oxford (United Kingdom); Kattnig, Daniel R.; Hore, P. J.; Mackenzie, Stuart R., E-mail: christiane.timmel@chem.ox.ac.uk, E-mail: stuart.mackenzie@chem.ox.ac.uk [Physical and Theoretical Chemistry Laboratory, Department of Chemistry, University of Oxford, Oxford (United Kingdom)

    2016-08-28

    Even though the interaction of a <1 mT magnetic field with an electron spin is less than a millionth of the thermal energy at room temperature (k{sub B}T), it still can have a profound effect on the quantum yields of radical pair reactions. We present a study of the effects of sub-millitesla magnetic fields on the photoreaction of flavin mononucleotide with ascorbic acid. Direct control of the reaction pathway is achieved by varying the rate of electron transfer from ascorbic acid to the photo-excited flavin. At pH 7.0, we verify the theoretical prediction that, apart from a sign change, the form of the magnetic field effect is independent of the initial spin configuration of the radical pair. The data agree well with model calculations based on a Green’s function approach that allows multinuclear spin systems to be treated including the diffusive motion of the radicals, their spin-selective recombination reactions, and the effects of the inter-radical exchange interaction. The protonation states of the radicals are uniquely determined from the form of the magnetic field-dependence. At pH 3.0, the effects of two chemically distinct radical pair complexes combine to produce a pronounced response to ∼500 μT magnetic fields. These findings are relevant to the magnetic responses of cryptochromes (flavin-containing proteins proposed as magnetoreceptors in birds) and may aid the evaluation of effects of weak magnetic fields on other biologically relevant electron transfer processes.

  14. Pulse radiolysis studies of intramolecular electron transfer in model peptides and proteins. 7. Trp -> TyrO radical transformation in hen egg-white lysozyme. Effects of pH, temperature, Trp62 oxidation and inhibitor binding

    DEFF Research Database (Denmark)

    Bobrowski, K.; Holcman, J.; Poznanski, J.

    1997-01-01

    Intramolecular long-range electron transfer (LRET) in hen egg-white lysozyme (HEWL) accompanying Trp --> TyrO radical transformation was investigated in aqueous solution by pulse radiolysis as a function of pH (5.2-7.4) and temperature (283-328K). The reaction was induced by highly selective...... below its denaturation temperature. Selective oxidation by ozone of the Trp62 indole side-chain in HEWL to N'-formylkynurenine (NFKyn62-HEWL) caused a large drop in the initial yield of Trp(.) radicals, G(Trp(.))(i). This was accompanied by a relatively small decrease in k(5) but selective oxidation...

  15. Fast multilevel radiative transfer

    International Nuclear Information System (INIS)

    Paletou, Frederic; Leger, Ludovick

    2007-01-01

    The vast majority of recent advances in the field of numerical radiative transfer relies on approximate operator methods better known in astrophysics as Accelerated Lambda-Iteration (ALI). A superior class of iterative schemes, in term of rates of convergence, such as Gauss-Seidel and successive overrelaxation methods were therefore quite naturally introduced in the field of radiative transfer by Trujillo Bueno and Fabiani Bendicho [A novel iterative scheme for the very fast and accurate solution of non-LTE radiative transfer problems. Astrophys J 1995;455:646]; it was thoroughly described for the non-LTE two-level atom case. We describe hereafter in details how such methods can be generalized when dealing with non-LTE unpolarised radiation transfer with multilevel atomic models, in monodimensional geometry

  16. 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Observation of OH radicals produced by pulsed discharges on the surface of a liquid

    Science.gov (United States)

    Kanazawa, Seiji; Kawano, Hirokazu; Watanabe, Satoshi; Furuki, Takashi; Akamine, Shuichi; Ichiki, Ryuta; Ohkubo, Toshikazu; Kocik, Marek; Mizeraczyk, Jerzy

    2011-06-01

    The hydroxyl radical (OH) plays an important role in plasma chemistry at atmospheric pressure. OH radicals have a higher oxidation potential compared with other oxidative species such as free radical O, atomic oxygen, hydroperoxyl radical (HO2), hydrogen peroxide(H2O2) and ozone. In this study, surface discharges on liquids (water and its solutions) were investigated experimentally. A pulsed streamer discharge was generated on the liquid surface using a point-to-plane electrode geometry. The primary generation process of OH radicals is closely related to the streamer propagation, and the subsequent secondary process after the discharge has an influence on the chemical reaction. Taking into account the timescale of these processes, we investigated the behavior of OH radicals using two different diagnostic methods. Time evolution of the ground-state OH radicals above the liquid surface after the discharge was observed by a laser-induced fluorescence (LIF) technique. In order to observe the ground-state OH, an OH [A 2∑+(v' = 1) <-- X 2Π(v'' = 0)] system at 282 nm was used. As the secondary process, a portion of OH radicals diffused from gas phase to the liquid surface and dissolved in the liquid. These dissolved OH radicals were measured by a chemical probe method. Terephthalic acid was used as an OH radical trap and fluorescence of the resulting 2-hydroxyterephthalic acid was measured. This paper directly presents visualization of OH radicals over the liquid surface by means of LIF, and indirectly describes OH radicals dissolved in water by means of a chemical method.

  18. Formation of an intermediate radical cation in the nanosecond pulse radiolysis of malachite green leucocyanide in organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Grodkowski, J; Bobrowski, K; Mehnert, R; Brede, O

    1989-01-01

    The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl/sub 4/ and acetone with 13 ns electron pulses. Two species with absorption maxima at 620 and 480 nm were observed. The latter was attributed to the malachite green leucocyanide radical cation (MGCN/sup +radical/) and the former to the known carbonium ion of malachite green dye (MG/sup +/). Observation of the consecutive charge transfer via the schemes: DCE/sup +radical/ -> BPh/sup +radical/ -> MGCN/sup +radical/ and DCE/sup +radical/ -> MGCN/sup +radical/ -> TMPD/sup +radical/, allowed to estimate the ionization potential of MGCN molecule in the range 6.9 eV < Ip/sub MGCN/ < 8.27 eV. Presented results and literature data suggest that positive charge in MGCN/sup +radical/ radical cation is located in the ''aniline'' part of the molecule. (author).

  19. Infrared absorption spectroscopy and chemical kinetics of free radicals

    International Nuclear Information System (INIS)

    Curl, R.F.; Glass, G.P.

    1991-01-01

    A new channel producing ketenyl radical (HCCO) was discovered in the flash photolysis of ketene at 193 nm. H 2 CCO + hν(193 nm) → H + HCCO by observation near 2020 cm -1 of the infrared fundamental of ketenyl corresponding to the antisymmetric motion of the heavy atoms. This band has been partially rotationally analyzed and the rate constant for the reaction of ketenyl with NO has been determined. The OH stretching fundamental of hydroxymethyl radical (CH 2 OH) has been observed near 3600 cm -1 producing the radical either by the excimer flash photolysis of acetol (CH 3 COCH 2 OH) or by Cl atom abstraction of a methyl hydrogen from methanol. The assignment of the spectrum to CH 2 OH was confirmed by the agreement of the rate constant for the reaction of the species with O 2 with the literature value. The mechanism of the reaction of C 2 H with O 2 has been explored. There appear to be two channels producing CO product: a fast, direct one producing highly vibrationally excited CO up to v = 6 at the same rate C 2 H disappears and a slow, indirect one producing primarily ground state CO on a much longer timescale than the disappearance of C 2 H. The rate constants for the reactions of C 2 H with CH 4 , C 2 H 6 , C 2 H 4 , D 2 , and CO were determined by following the time decay of a C 2 H infrared transient absorption line originating from the ground vibronic state using diode laser spectroscopy creating the C 2 H by excimer laser flash photolysis (ArF, 193 nm) of CF 3 CCH. The branching ratio into OH of the reaction between NH 2 , and NO, which is the channel thought to propagate the radical chain of the Thermal deNOx process, has been measured up to 925 degree C. The OH yield thus obtained appears to be too small to maintain the process. 5 refs., 3 figs

  20. Retardative chain transfer in free radical free-radical polymerisations of vinyl neo-decanoate in low molecular weight polyisoprene and toluene

    NARCIS (Netherlands)

    Monteiro, M.J.; Subramaniam, N.; Taylor, J.R.; Pham, B.T.T.; Tonge, M.P.; Gilbert, R.G.

    2001-01-01

    The kinetics of free-radical polymerisation of vinyl neo-decanoate (VneoD) and the molecular weight distributions (MWDs) of the polymers formed in the presence and absence of low molecular weight polyisoprene at 50°C under a variety of conditions were investigated. The bulk reaction was successfully