WorldWideScience

Sample records for halogen alkyl alkenyl

  1. 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.

  2. Coordinative saturation and the chemistry of triscyclopentadienyl thorium (IV) alkyls and alkenyls

    International Nuclear Information System (INIS)

    Wachter, W.A.

    1976-01-01

    Air- and moisture-sensitive (C 5 H 5 ) 3 Th(IV)R compounds (R = alkyl, alkenyl) were prepared by reacting (C 5 H 5 ) 3 Th(IV)Cl with the corresponding Grignard or lithium reagent in toluene at -78 0 . They were characterized by elemental analysis, molecular weight, and pmr, infrared, and Raman spectroscopy. The fluxional behavior in the nmr indicates a sigmatropic rearrangement with an activation energy of 8 to 9 kcal/mole. Alcoholysis is faster and more selective for alkane formation than in the analogous uranium system. In aromatic solvents the compounds exhibit first-order decomposition kinetics. Relative thermal stabilities are neopentyl > allyl > n-butyl > 2-cis-2-butenyl > 2-trans-2-butenyl > i-propyl. Respective half-lives of these compounds at 167 0 C are 7500, 566, 96, 39, 21, and 7 hr. Alkanes are the major product for R = alkyl. Retention of configuration is noted for R = cis- and trans-2-butenyl. k/sub H//k/sub D/ is 2.4 for R = n-butyl. The results are consistent with coordinative saturation about the Th center blocking β-elimination. The solid product was also crystallized, and x-ray diffraction results reveal a bridged dimer ((C 5 H 5 ) 2 (C 5 H 4 )Th) 2 . To each Th are bound three rings in a pentahapto fashion and one ring, which is bound in a pentahapto fashion to the other Th center, in a monohapto fashion. These results suggest a short-lived intermediate, possibly an ylid, prior to dimerization. The photochemical decomposition of triscyclopentadienyl Th(IV) isopropyl leads to the formation of propene, propane, and an insoluble green solid. The solid analyzes as (C 15 H 15 Th) 2 , has a temperature-independent paramagnetism of 18.45 x 10 -4 cgs, and exhibits vibrational frequencies characteristic of pentahaptocyclopentadienyl ligands

  3. Synthesis of E-Alkyl Alkenes from Terminal Alkynes via Ni-Catalyzed Cross-Coupling of Alkyl Halides with B-Alkenyl-9-borabicyclo[3.3.1]nonanes.

    Science.gov (United States)

    Di Franco, Thomas; Epenoy, Alexandre; Hu, Xile

    2015-10-02

    The first Ni-catalyzed Suzuki-Miyaura coupling of alkyl halides with alkenyl-(9-BBN) reagents is reported. Both primary and secondary alkyl halides including alkyl chlorides can be coupled. The coupling method can be combined with hydroboration of terminal alkynes, allowing the expedited synthesis of functionalized alkyl alkenes from readily available alkynes with complete (E)-selectivity in one pot. The method was applied to the total synthesis of (±)-Recifeiolide, a natural macrolide.

  4. New Route to Synthesize Surface Organometallic Complexes (SOMC): An Approach by Alkylating Halogenated Surface Organometallic Fragments

    KAUST Repository

    Hamieh, Ali Imad

    2017-02-01

    The aim of this thesis is to explore new simpler and efficient routes for the preparation of surface organometallic complexes (SOMC) for the transformation of small organic molecules to valuable products. The key element in this new route relies on surface alkylation of various halogenated surface coordination complexes or organometallic fragments (SOMF).

  5. New Route to Synthesize Surface Organometallic Complexes (SOMC): An Approach by Alkylating Halogenated Surface Organometallic Fragments

    KAUST Repository

    Hamieh, Ali Imad Ali

    2017-01-01

    The aim of this thesis is to explore new simpler and efficient routes for the preparation of surface organometallic complexes (SOMC) for the transformation of small organic molecules to valuable products. The key element in this new route relies on surface alkylation of various halogenated surface coordination complexes or organometallic fragments (SOMF).

  6. Cytochrome P-450 inactivation by 3-alkylsydnones. Mechanistic implications of N-alkyl and N-alkenyl heme adduct formation

    International Nuclear Information System (INIS)

    Grab, L.A.; Swanson, B.A.; Ortiz de Montellano, P.R.

    1988-01-01

    Incubation of 3-(2-phenylethyl)-4-methylsydnone (PMS) with liver microsomes from phenobarbital-pretreated rats or with reconstituted cytochrome P-450b results in loss of the enzyme chromophore. Chromophore loss is NADPH-dependent even though the sydnone decomposes by an oxygen- but not enzyme-dependent process to give pyruvic acid and, presumably, the (2-phenylethyl)diazonium cation. N-(2-Phenylethyl)protoporphyrin IX and N-(2-phenylethenyl)protoporphyrin IX have been isolated from the livers of rats treated with PMS. Both deuteriums are retained in the N-(2-phenylethyl) adduct derived from 3-(2-phenyl[1,1- 2 H]ethyl)-4-methylsydnone, but one deuterium is lost in the N-(2-phenylethenyl) adduct. The N-(2-phenylethyl) to N-(2-phenylethenyl) adduct ratio is increased by deuterium substitution. Electron paramagnetic resonance (EPR)-spin trapping studies show that carbon radicals are formed in incubations of the sydnones with liver microsomes but by a process that is independent of chromophore destruction. It is proposed that the 2-phenylethyl radical formed by electron transfer to the sydnone-derived (2-phenylethyl)diazonium cation adds to the prosthetic heme group to give the N-(2-phenylethyl) adduct. This alkylation reaction is similar to that observed with (2-phenylethyl)hydrazine. Autoxidation of the Fe-CH(CH 2 Ph)-N bridged species expected from insertion of 2-phenyldiazoethane into one of the heme Fe-N bonds is proposed to explain the unprecedented introduction of a double bond into the N-(2-phenylethenyl)adduct

  7. Alkylation of reticular polymers of ethynyl piperidol by alkyl halogen and investigation of the swelling of the products in water

    International Nuclear Information System (INIS)

    Khakimkhodjaev, S.N.; Khalikov, D.Kh.

    1999-01-01

    In the paper the results of investigation on alkylation of reticular polymer of ethyl piperidol by methyl Iodide and ethyl Iodide are adduced. It have been shown that in the first case the reaction of an alkylation proceeds up to 100% of a degree of completion. In the second case of an alkylation the highest degree of alkylation reaches only 60% which is connected with formation of secondary structures. In both cases the process of an alkylation results in deriving highly swelled system

  8. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    Directory of Open Access Journals (Sweden)

    A. Zuend

    2011-09-01

    Full Text Available We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl, Br, NO3, HSO4, and SO42−. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization

  9. Scope and mechanism in palladium-catalyzed isomerizations of highly substituted allylic, homoallylic, and alkenyl alcohols.

    Science.gov (United States)

    Larionov, Evgeny; Lin, Luqing; Guénée, Laure; Mazet, Clément

    2014-12-03

    Herein we report the palladium-catalyzed isomerization of highly substituted allylic alcohols and alkenyl alcohols by means of a single catalytic system. The operationally simple reaction protocol is applicable to a broad range of substrates and displays a wide functional group tolerance, and the products are usually isolated in high chemical yield. Experimental and computational mechanistic investigations provide complementary and converging evidence for a chain-walking process consisting of repeated migratory insertion/β-H elimination sequences. Interestingly, the catalyst does not dissociate from the substrate in the isomerization of allylic alcohols, whereas it disengages during the isomerization of alkenyl alcohols when additional substituents are present on the alkyl chain.

  10. Alkenylation of Arenes and Heteroarenes with Alkynes.

    Science.gov (United States)

    Boyarskiy, Vadim P; Ryabukhin, Dmitry S; Bokach, Nadezhda A; Vasilyev, Aleksander V

    2016-05-25

    This review is focused on the analysis of current data on new methods of alkenylation of arenes and heteroarenes with alkynes by transition metal catalyzed reactions, Bronsted/Lewis acid promoted transformations, and others. The synthetic potential, scope, limitations, and mechanistic problems of the alkenylation reactions are discussed. The insertion of an alkenyl group into aromatic and heteroaromatic rings by inter- or intramolecular ways provides a synthetic route to derivatives of styrene, stilbene, chalcone, cinnamic acid, various fused carbo- and heterocycles, etc.

  11. In situ generation of N-Boc-protected alkenyl imines: controlling the E/Z geometry of alkenyl moieties in the Mukaiyama-Mannich reaction.

    Science.gov (United States)

    Bai, Jian-Fei; Sasagawa, Hajime; Yurino, Taiga; Kano, Taichi; Maruoka, Keiji

    2017-07-18

    Readily available Boc-protected Z-alkenyl aminals could be used as Z-alkenyl and E-alkenyl imine precursors under acidic conditions. In the Mukaiyama-Mannich reaction of Z-alkenyl Boc-aminals, the E/Z geometry of the products was controlled by the catalyst used. The present method was also applied to asymmetric Mukaiyama-Mannich reactions.

  12. Biogeochemistry of Halogenated Hydrocarbons

    Science.gov (United States)

    Adriaens, P.; Gruden, C.; McCormick, M. L.

    2003-12-01

    Halogenated hydrocarbons originate from both natural and industrial sources. Whereas direct anthropogenic emissions to the atmosphere and biosphere are often easy to assess, particularly when they are tied to major industrial activities, the attribution of emissions to other human activities (e.g., biomass burning), diffuse sources (e.g., atmospheric discharge, run off), and natural production (e.g., soils, fungi, algae, microorganisms) are difficult to quantify. The widespread occurrence of both alkyl and aryl halides in groundwater, surface water, soils, and various trophic food chains, even those not affected by known point sources, suggests a substantial biogeochemical cycling of these compounds (Wania and Mackay, 1996; Adriaens et al., 1999; Gruden et al., 2003). The transport and reactive fate mechanisms controlling their reactivity are compounded by the differences in sources of alkyl-, aryl-, and complex organic halides, and the largely unknown impact of biogenic processes, such as enzymatically mediated halogenation of organic matter, fungal production of halogenated hydrocarbons, and microbial or abiotic transformation reactions (e.g., Asplund and Grimvall, 1991; Gribble, 1996; Watling and Harper, 1998; Oberg, 2002). The largest source may be the natural halogenation processes in the terrestrial environment, as the quantities detected often exceed the amount that can be explained by human activities in the surrounding areas ( Oberg, 1998). Since biogeochemical processes result in the distribution of a wide range of halogenated hydrocarbon profiles, altered chemical structures, and isomer distributions in natural systems, source apportionment (or environmental forensics) can often only be resolved using multivariate statistical methods (e.g., Goovaerts, 1998; Barabas et al., 2003; Murphy and Morrison, 2002).This chapter will describe the widespread occurrence of halogenated hydrocarbons, interpret their distribution and biogeochemical cycling in light of

  13. Halogen effect on structure and 13C NMR chemical shift of 3,6-disubstituted-N-alkyl carbazoles

    DEFF Research Database (Denmark)

    Radula-Janik, Klaudia; Kupka, Teobald; Ejsmont, Krzysztof

    2013-01-01

    Structures of selected 3,6-dihalogeno-N-alkyl carbazole derivatives were calculated at the B3LYP/6-311++G(3df,2pd) level of theory and their 13C NMR isotropic nuclear shieldings were predicted using density functional theory (DFT). The model compounds contained 9H-, N-methyl and N-ethyl derivatives...

  14. Rhenium and Manganese-Catalyzed Selective Alkenylation of Indoles

    KAUST Repository

    Wang, Chengming

    2018-04-06

    An efficient rhenium‐catalyzed regioselective C‐H bond alkenylation of indoles is reported. The protocol operates well for internal as well as terminal alkynes, affording products in good to excellent yields. Furthermore, a manganese catalyzed, acid free, regioselective C2‐alkenylation of indoles with internal alkynes is described. The directing groups can be easily removed after the reaction and the resulting products can be used as valuable building blocks for the synthesis of diverse heterocyclic compounds.

  15. Rhenium and Manganese-Catalyzed Selective Alkenylation of Indoles

    KAUST Repository

    Wang, Chengming; Rueping, Magnus

    2018-01-01

    An efficient rhenium‐catalyzed regioselective C‐H bond alkenylation of indoles is reported. The protocol operates well for internal as well as terminal alkynes, affording products in good to excellent yields. Furthermore, a manganese catalyzed, acid free, regioselective C2‐alkenylation of indoles with internal alkynes is described. The directing groups can be easily removed after the reaction and the resulting products can be used as valuable building blocks for the synthesis of diverse heterocyclic compounds.

  16. Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

    Science.gov (United States)

    Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

    2018-04-01

    Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

  17. Clean and Selective Catalytic C-H alkylation of Alkenes with Environmental friendly Alcohols

    KAUST Repository

    Poater, Albert

    2016-09-14

    Bearing the alkylation of alkene substrates using alcohol as solvent, catalysed by the cationic Ru-based catalyst [(C6H6)(PCy3)(CO)RuH]+, DFT calculations have been carried out to get mechanistic insights of such an environmental friendly reaction. Hard experimental conditions of Yi and coworkers [Science2011, 333, 1613] allow the formation of a C-C bond between indene and ethanol. The predicted mechanism suggests a cationic Ru-alkenyl species once two equivalents of indene interact releasing a molecule of indane subproduct. Then, oxidative addition of the Csingle bondO bond of alcohol to Ru-alkenyl species leads to Ru-alkenyl-alkyl species, followed by the reductive elimination process produces the desired alkylation product and a Ru-hydroxo complex. Finally, vinylic Csingle bondH activation and water elimination regenerates the Ru-alkenyl species. In this paper we present a full description of the complete reaction pathway along with possible alternative pathways, which are predicted to display higher upper barriers. Furthermore, the present study explains the possible reasons for the absence of undesired products such as indene dimer or hydroxylated indene in the experiments.

  18. Visible-Light-Initiated Na2-Eosin Y Catalyzed Highly Regio- and Stereoselective Difunctionalization of Alkynes with Alkyl Bromides.

    Science.gov (United States)

    Wang, Kuai; Meng, Ling-Guo; Wang, Lei

    2016-08-19

    A highly regioselective and stereoselective addition of alkyl bromides (amino-brominated aromatic β,β-dicyanoalkenes) to arylacetylenes by photoredox catalysis was developed. This difunctionalization of arylacetylenes was accomplished under ambient and metal-free conditions to produce alkenyl bromides in high efficiency with a wide range of group tolerance.

  19. Redox shuttle additives for lithium-ion batteries

    Science.gov (United States)

    Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

    2017-03-21

    An electro lye includes a compound of Formula I or IA: where each instance of R.sup.1 is independently H, alkyl, alkoxy, alkenyl, aryl, heteroaryl, or cycloalkyl; each instance of R.sup.2 is independently H, alkyl, alkoxy, alkenyl, aryl, heteroaryl, or cycloalkyl; each instance of R.sup.3 is independently H, alkyl, alkenyl, aryl, or cycloalkyl; each instance of R.sup.4 is independently H, halogen, CN, NO.sub.2, phosphate, alkyl, alkenyl, aryl, heteroaryl, or cycloalkyl; x is 1, 2, 3, 4, or 5; y is 1 or 2; and z is 0, 1, 2, 3, or 4. ##STR00001##

  20. Halogenated fatty acids

    DEFF Research Database (Denmark)

    Mu, Huiling; Sundin, Peter; Wesén, Clas

    1997-01-01

    Halogenated fatty acids are the major contributors to organohalogen compounds in lipids of marine mammals, fish, and bivalves. For the initial characterization of these recently noticed compounds, a determination of the halogen concentration has usually been combined with some lipid isolation......), atomic emission spectrometry, and mass spectrometry. For most environmental samples, chlorinated FAMEs must be enriched prior to GC. ELCD is a useful detection method for indicating halogenated FAMEs in the chromatograms, and tentative identification of the halogenated species can be obtained...

  1. Synthesis of 3-Alkenyl-1-azaanthraquinones via Diels-Alder and Electron Transfer Reactions

    Directory of Open Access Journals (Sweden)

    Patrice Vanelle

    2002-12-01

    Full Text Available A convenient route to 3-alkenyl-1-azaanthraquinones via a hetero Diels-Alder reaction between an azadiene and naphthoquinone, a free radical chlorination and an electron transfer reaction is reported.

  2. [Alkylating agents].

    Science.gov (United States)

    Pourquier, Philippe

    2011-11-01

    With the approval of mechlorethamine by the FDA in 1949 for the treatment of hematologic malignancies, alkylating agents are the oldest class of anticancer agents. Even though their clinical use is far beyond the use of new targeted therapies, they still occupy a major place in specific indications and sometimes represent the unique option for the treatment of refractory diseases. Here, we are reviewing the major classes of alkylating agents and their mechanism of action, with a particular emphasis for the new generations of alkylating agents. As for most of the chemotherapeutic agents used in the clinic, these compounds are derived from natural sources. With a complex but original mechanism of action, they represent new interesting alternatives for the clinicians, especially for tumors that are resistant to conventional DNA damaging agents. We also briefly describe the different strategies that have been or are currently developed to potentiate the use of classical alkylating agents, especially the inhibition of pathways that are involved in the repair of DNA lesions induced by these agents. In this line, the development of PARP inhibitors is a striking example of the recent regain of interest towards the "old" alkylating agents.

  3. Manganese-Catalyzed C−H Functionalizations: Hydroarylations and Alkenylations Involving an Unexpected Heteroaryl Shift

    KAUST Repository

    Wang, Chengming

    2017-06-24

    A manganese-catalyzed regio- and stereoselective hydroarylation of allenes is reported. The C−H functionalization method provides access to various alkenylated indoles in excellent yields. Moreover, a hydroarylation/cyclization cascade involving an unexpected C−N bond cleavage and aryl shift has been developed, which provides a new synthetic approach to substituted pyrroloindolones.

  4. Manganese-Catalyzed C−H Functionalizations: Hydroarylations and Alkenylations Involving an Unexpected Heteroaryl Shift

    KAUST Repository

    Wang, Chengming; Wang, Ai; Rueping, Magnus

    2017-01-01

    A manganese-catalyzed regio- and stereoselective hydroarylation of allenes is reported. The C−H functionalization method provides access to various alkenylated indoles in excellent yields. Moreover, a hydroarylation/cyclization cascade involving an unexpected C−N bond cleavage and aryl shift has been developed, which provides a new synthetic approach to substituted pyrroloindolones.

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

    Science.gov (United States)

    Rissanen, Kari; Haukka, Matti

    2015-01-01

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

  6. Organic halogens in landfill leachates

    DEFF Research Database (Denmark)

    Grøn, C.; Christensen, J. B.; Jensen, Dorthe Lærke

    2000-01-01

    Using a group parameter, total organic halogens (TOX), high TOX concentrations were found in leachates and leachate contaminated groundwaters at two Danish mixed sanitary and hazardous waste sites. With commonly used screening procedures for organic contaminants, the individual halogenated organi...

  7. Apparatus for washing out halogens

    Energy Technology Data Exchange (ETDEWEB)

    Pier, M; Hahn, J; Kroenig, W

    1941-03-26

    An apparatus is described for washing out of halogens and the like or liquid halogen compounds from the products, which are formed on pressure hydrogenation or splitting of carbon-containing material in the presence of halogens or halogen compounds, consisting of a washing apparatus installed between the reaction vessel and the hot separator, which is inclined in relatively small space for steam regulation and contains, with the steam, arranged baffles, especially spirals.

  8. 40 CFR 721.8700 - Halogenated alkyl pyridine.

    Science.gov (United States)

    2010-07-01

    ... tertiary waste treatment will occur, or treatment in a lined, self-contained solar evaporation pond where... evaporation pond where UV light will degrade the substance, the number of kilograms per day per site is...

  9. Tropospheric Halogen Chemistry

    Science.gov (United States)

    von Glasow, R.; Crutzen, P. J.

    2003-12-01

    Halogens are very reactive chemicals that are known to play an important role in anthropogenic stratospheric ozone depletion chemistry, first recognized by Molina and Rowland (1974). However, they also affect the chemistry of the troposphere. They are of special interest because they are involved in many reaction cycles that can affect the oxidation power of the atmosphere indirectly by influencing the main oxidants O3 and its photolysis product OH and directly, e.g., by reactions of the Cl radical with hydrocarbons (e.g., CH4).Already by the middle of the nineteenth century, Marchand (1852) reported the presence of bromine and iodine in rain and other natural waters. He also mentions the benefits of iodine in drinking water through the prevention of goitres and cretinism. In a prophetic monograph "Air and Rain: The Beginnings of a Chemical Climatology," Smith (1872) describes measurements of chloride in rain water, which he states to originate partly from the oceans by a process that he compares with the bursting of "soap bubbles" which produces "small vehicles" that transfer small spray droplets of seawater to the air. From deviations of the sulfate-to-chloride ratio in coastal rain compared to seawater, Smith concluded that chemical processes occur once the particles are airborne.For almost a century thereafter, however, atmospheric halogens received little attention. One exception was the work by Cauer (1939), who reported that iodine pollution has been significant in Western and Central Europe due to the inefficient burning of seaweed, causing mean gas phase atmospheric concentrations as high as or greater than 0.5 μg m-3. In his classical textbook Air Chemistry and Radioactivity, Junge (1963) devoted less than three pages to halogen gas phase chemistry, discussing chlorine and iodine. As reviewed by Eriksson (1959a, b), the main atmospheric source of halogens is sea salt, derived from the bursting of bubbles of air which are produced by ocean waves and other

  10. Cobalt-Catalyzed, Aminoquinoline-Directed sp2 C-H Bond Alkenylation by Alkynes**

    Science.gov (United States)

    Grigorjeva, Liene; Daugulis, Olafs

    2014-01-01

    We have developed a method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed sp2 C-H bond alkenylation by alkynes. Method shows excellent functional group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs Co(OAc)2*4H2O catalyst, Mn(OAc)2 cocatalyst, and oxygen from air as a terminal oxidant. PMID:25060365

  11. Halogen-Mediated Conversion of Hydrocarbons to Commodities.

    Science.gov (United States)

    Lin, Ronghe; Amrute, Amol P; Pérez-Ramírez, Javier

    2017-03-08

    Halogen chemistry plays a central role in the industrial manufacture of various important chemicals, pharmaceuticals, and polymers. It involves the reaction of halogens or halides with hydrocarbons, leading to intermediate compounds which are readily converted to valuable commodities. These transformations, predominantly mediated by heterogeneous catalysts, have long been successfully applied in the production of polymers. Recent discoveries of abundant conventional and unconventional natural gas reserves have revitalized strong interest in these processes as the most cost-effective gas-to-liquid technologies. This review provides an in-depth analysis of the fundamental understanding and applied relevance of halogen chemistry in polymer industries (polyvinyl chloride, polyurethanes, and polycarbonates) and in the activation of light hydrocarbons. The reactions of particular interest include halogenation and oxyhalogenation of alkanes and alkenes, dehydrogenation of alkanes, conversion of alkyl halides, and oxidation of hydrogen halides, with emphasis on the catalyst, reactor, and process design. Perspectives on the challenges and directions for future development in this exciting field are provided.

  12. Halogenated arsenenes as Dirac materials

    International Nuclear Information System (INIS)

    Tang, Wencheng; Sun, Minglei; Ren, Qingqiang; Wang, Sake; Yu, Jin

    2016-01-01

    Highlights: • We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. • All fully-halogenated arsenene except As_2I_2 would spontaneously form and stable in defending the thermal fluctuation in room temperature. - Abstract: Arsenene is the graphene-like arsenic nanosheet, which has been predicted very recently [S. Zhang, Z. Yan, Y. Li, Z. Chen, and H. Zeng, Angewandte Chemie, 127 (2015) 3155–3158]. Using first-principles calculations, we systematically investigate the structures and electronic properties of fully-halogenated arsenenes. Formation energy analysis reveals that all the fully-halogenated arsenenes except iodinated arsenene are energetically favorable and could be synthesized. We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. They may have great potential applications in next generation of high-performance devices.

  13. Cobalt-catalyzed, aminoquinoline-directed C(sp²)-H bond alkenylation by alkynes.

    Science.gov (United States)

    Grigorjeva, Liene; Daugulis, Olafs

    2014-09-15

    A method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed C(sp(2))-H bond alkenylation by alkynes was developed. The method shows excellent functional-group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs a Co(OAc)2⋅4 H2O catalyst, Mn(OAc)2 co-catalyst, and oxygen (from air) as a terminal oxidant. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Direct asymmetric allylic alkenylation of N-itaconimides with Morita-Baylis-Hillman carbonates

    KAUST Repository

    Yang, Wenguo

    2012-08-03

    The asymmetric allylic alkenylation of Morita-Baylis-Hillman (MBH) carbonates with N-itaconimides as nucleophiles has been developed using a commercially available Cinchona alkaloid catalyst. A variety of multifunctional chiral α-methylene-β-maleimide esters were attained in moderate to excellent yields (up to 99%) and good to excellent enantioselectivities (up to 91% ee). The origin of the regio- and stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed regio- and enantioselectivity. © 2012 American Chemical Society.

  15. User-friendly aerobic reductive alkylation of iridium(III) porphyrin chloride with potassium hydroxide: scope and mechanism.

    Science.gov (United States)

    Zuo, Huiping; Liu, Zhipeng; Yang, Wu; Zhou, Zhikuan; Chan, Kin Shing

    2015-12-21

    Alkylation of iridium 5,10,15,20-tetrakistolylporphyrinato carbonyl chloride, Ir(ttp)Cl(CO) (1), with 1°, 2° alkyl halides was achieved to give (ttp)Ir-alkyls in good yields under air and water compatible conditions by utilizing KOH as the cheap reducing agent. The reaction rate followed the order: RCl < RBr < RI (R = alkyl), and suggests an SN2 pathway by [Ir(I)(ttp)](-). Ir(ttp)-adamantyl was obtained under N2 when 1-bromoadamantane was utilized, which could only undergo bromine atom transfer pathway. Mechanistic investigations reveal a substrate dependent pathway of SN2 or halogen atom transfer.

  16. Recent advances in efficient and selective synthesis of di-, tri-, and tetrasubstituted alkenes via Pd-catalyzed alkenylation-carbonyl olefination synergy.

    Science.gov (United States)

    Negishi, Ei-ichi; Huang, Zhihong; Wang, Guangwei; Mohan, Swathi; Wang, Chao; Hattori, Hatsuhiko

    2008-11-18

    Although generally considered competitive, the alkenylation and carbonyl olefination routes to alkenes are also complementary. In this Account, we focus on these approaches for the synthesis of regio- and stereodefined di- and trisubstituted alkenes and a few examples of tetrasubstituted alkenes. We also discuss the subset of regio- and stereodefined dienes and oligoenes that are conjugated. Pd-catalyzed cross-coupling using alkenyl metals containing Zn, Al, Zr, and B (Negishi coupling and Suzuki coupling) or alkenyl halides and related alkenyl electrophiles provides a method of alkenylation with the widest applicability and predictability, with high stereo- and regioselectivity. The requisite alkenyl metals or alkenyl electrophiles are most commonly prepared through highly selective alkyne addition reactions including (i) conventional polar additions, (ii) hydrometalation, (iii) carbometalation, (iv) halometalation, and (v) other heteroatom-metal additions. Although much more limited in applicability, the Heck alkenylation offers an operationally simpler, viable alternative when it is highly selective and satisfactory. A wide variety of carbonyl olefination reactions, especially the Wittig olefination and its modifications represented by the E-selective HWE olefination and the Z-selective Still-Gennari olefination, collectively offer the major alternative to the Pd-catalyzed alkenylation. However, the carbonyl olefination method fundamentally suffers from more limited stereochemical options and generally lower stereoselectivity levels than the Pd-catalyzed alkenylation. In a number of cases, however, very high (>98%) stereoselectivity levels have been attained in the syntheses of both E and Z isomers. The complementarity of the alkenylation and carbonyl olefination routes provide synthetic chemists with valuable options. While the alkenylation involves formation of a C-C single bond to a CC bond, the carbonyl olefination converts a CO bond to a CC bond. When a

  17. Alkylations and hydroxymethylations of pyrazines via green Minisci-type reactions.

    Science.gov (United States)

    Bohman, Bjorn; Berntsson, Benjamin; Dixon, Ruby C M; Stewart, Craig D; Barrow, Russell A

    2014-06-06

    A new general methodology utilizing Minisci-type chemistry has been developed that cleanly and efficiently prepares alkyl- and (hydroxymethyl)pyrazines. The new methods eliminate toxic catalysts and halogenated solvents, providing a greatly improved route to these natural products which are prevalent in many natural systems as bacterial volatiles, plant volatiles, and insect pheromones.

  18. Alkylation and arylation of alkenes by transition metal complexes

    International Nuclear Information System (INIS)

    Volkova, L.G.; Levitin, I.Ya.; Vol'pin, M.E.

    1975-01-01

    In this paper are reviewed methods of alkylation and irylation of unsaturated compounds with complexes of transition metals (Rh, Pd). Analysis of alkylation and arylation of olefines with organic derivatives of transition metals, obtained as a result of exchange reactions between organic compounds of transition metals and salts of metals of the 8th group of the periodic system, allows a conclusion as to the wide possibilities of these reactions in the synthesis of various derivatives of unsaturated compounds. In all the reactions under consideration, intermediate formation of sigma-complexes is assumed. Also considered are alkylation and arylation of olefines with organic derivatives of halogens in the presence of compounds of metals of the 8th group of the periodic system, as well as arylation of olefines with aromatic compounds in the presence of salts of transition metals

  19. Cobalt(III)-catalyzed alkenylation of arenes and 6-arylpurines with terminal alkynes: efficient access to functional dyes.

    Science.gov (United States)

    Wang, Shan; Hou, Ji-Ting; Feng, Mei-Lin; Zhang, Xiao-Zhuan; Chen, Shan-Yong; Yu, Xiao-Qi

    2016-02-14

    Alkenylation of unactivated arenes and 6-arylpurines with terminal alkynes in high yields using Cp*Co(CO)I2 as catalyst under mild conditions is described. This method shows outstanding functional group compatibility and can be applied in the design of a mitochondria-targeted imaging dye.

  20. Pyrroloindolone synthesis via a Cp*Co(III)-catalyzed redox-neutral directed C-H alkenylation/annulation sequence.

    Science.gov (United States)

    Ikemoto, Hideya; Yoshino, Tatsuhiko; Sakata, Ken; Matsunaga, Shigeki; Kanai, Motomu

    2014-04-09

    A unique synthetic utility of a Cp*Co(III) catalyst in comparison with related Cp*Rh(III) catalysts is described. A C2-selective indole alkenylation/annulation sequence proceeded smoothly with catalytic amount of a [Cp*Co(III)(C6H6)](PF6)2 complex and KOAc. Intramolecular addition of an alkenyl-Cp*Co species to a carbamoyl moiety gave pyrroloindolones in 58-89% yield in one pot. Clear difference was observed between the catalytic activity of the Cp*Co(III) complex and those of Cp*Rh(III) complexes, highlighting the unique nucleophilic activity of the organocobalt species. The Cp*Co(III) catalysis was also suitable for simple alkenylation process of N-carbamoyl indoles, and broad range of alkynes, including terminal alkynes, were applicable to give C2-alkenylated indoles in 50-99% yield. Mechanistic studies on C-H activation step under Cp*Co(III) catalysis with the aid of an acetate unit as well as evaluation of the difference between organo-Co(III) species and organo-Rh(III) species are also described.

  1. A straightforward synthesis of alkenyl nonaflates from carbonyl compounds using nonafluorobutane-1-sulfonyl fluoride in combination with phosphazene bases

    Czech Academy of Sciences Publication Activity Database

    Vogel, M. A. K.; Stark, Ch. B.; Lyapkalo, Ilya

    -, č. 18 (2007), s. 2907-2911 ISSN 0936-5214 Institutional research plan: CEZ:AV0Z40550506 Keywords : chemoselectivity * nonafluorobutane-1-sulfonyl fluoride * ketones * regioselectivity * alkenyl nonaflates Subject RIV: CC - Organic Chemistry Impact factor: 2.763, year: 2007

  2. Photoinduced alkylation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dondi, D.; Fagnoni, M.; Albini, A.

    2002-07-01

    Some {alpha}{beta}-unsaturated aldehydes have been alkylated generating alkyl radicals from alcohols and dioxolanes in mixed aqueous-organic solution though photoinduced hydrogen abstraction by disodium benzophenondisulfonate when exposed to solar light (6 to 14 hours for 10 g amounts). (Author) 8 refs.

  3. Interfce alkylation of ethyldiphenylphosphinylacetate

    International Nuclear Information System (INIS)

    Yarkevich, A.N.; Tsvetkov, E.N.

    1994-01-01

    The paper deals with the alkylation of the methyline group of ethyldiphenylphosphinylacetate (1) by different alkylating agents in the presence of Cs 2 CO 3 . In all cases the application of Cs 2 CO 3 results in a significant increase of reaction rate. 10 refs., 3 tabs

  4. Evidence for Interfacial Halogen Bonding.

    Science.gov (United States)

    Swords, Wesley B; Simon, Sarah J C; Parlane, Fraser G L; Dean, Rebecca K; Kellett, Cameron W; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

    2016-05-10

    A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Risk assessment for halogenated solvents

    International Nuclear Information System (INIS)

    Travis, C.C.

    1988-01-01

    A recent development in the cancer risk area is the advent of biologically based pharmacokinetic and pharmacodynamic models. These models allow for the incorporation of biological and mechanistic data into the risk assessment process. These advances will not only improve the risk assessment process for halogenated solvents but will stimulate and guide basic research in the biological area

  6. Halogen bonding in solution: thermodynamics and applications.

    Science.gov (United States)

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

    2013-02-21

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

  7. Dissociative Photoionization of 1-Halogenated Silacyclohexanes: Silicon Traps the Halogen.

    Science.gov (United States)

    Bodi, Andras; Sigurdardottir, Katrin Lilja; Kvaran, Ágúst; Bjornsson, Ragnar; Arnason, Ingvar

    2016-11-23

    The threshold photoelectron spectra and threshold photoionization mass spectra of 1-halogenated-1-silacyclohexanes, for the halogens X = F, Cl, Br, and I, have been obtained using synchrotron vacuum ultraviolet radiation and photoelectron photoion coincidence spectroscopy. As confirmed by a similar ionization onset and density functional theory molecular orbitals, the ionization to the ground state is dominated by electron removal from the silacyclohexane ring for X = F, Cl, and Br, and from the halogen lone pair for X = I. The breakdown diagrams show that the dissociative photoionization mechanism is also different for X = I. Whereas the parent ions decay by ethylene loss for X = F to Br in the low-energy regime, the iodine atom is lost for X = I. The first step is followed by a sequential ethylene loss at higher internal energies in each of the compounds. It is argued that the tendency of silicon to lower bond angles stabilizes the complex cation in which C 2 H 4 is η 2 -coordinated to it, and which precedes ethylene loss. Together with the relatively strong silicon-halogen bonds and the increased inductive effect of the silacyclohexane ring in stabilizing the cation, this explains the main differences observed in the fragmentation of the halogenated silacyclohexane and halogenated cyclohexane ions. The breakdown diagrams have been modeled taking into account slow dissociations at threshold and the resulting kinetic shift. The 0 K appearance energies have been obtained to within 0.08 eV for the ethylene loss for X = F to Br (10.56, 10.51, and 10.51 eV, respectively), the iodine atom loss for X = I (10.11 eV), the sequential ethylene loss for X = F to I (12.29, 12.01, 11.94, and 11.86 eV, respectively), and the minor channels of H loss for X = F (10.56 eV) and propylene loss in X = Cl (also at 10.56 eV). The appearance energies for the major channels likely correspond to the dissociative photoionization reaction energy.

  8. Isobutane/olefin-alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Waitkamp, J.; Maixner, S.

    1983-11-01

    Isobutane/olefin-alkylation - technology and reaction mechanism of a refinery process for production of high octane gasoline components: The alkylation of i-butane with olefins, especially with butenes, is a process for the conversion of light byproducts of a catalytic cracker to high quality gasoline components. Alkylate is a complex mixture of i-paraffins containing 5 to ca. 12 carbon atoms. Due to their octane numbers the four trimethylpentane isomers are the most desirable product components. Indeed, under optimum process conditions these isomers are the main products. Presently, alkylation capacity in the western world amounts to more than 40x10/sup 6/ t/a. Most units are located in the USA. Two liquid-phase processes using sulfuric acid and hydrofluoric acid, respectively, are of commercial importance. At present, there is a definite trend towards HF-alkylation. The reaction mechanism which proceeds via carbocations, is extremely complex. It is composed of a great variety of individual steps. Modern mechanistic concepts are discussed.

  9. 1-alkenyl-2-acyl glycerol is an intermediate in myocardial plasmenylcholine biosynthesis

    International Nuclear Information System (INIS)

    Ford, D.; Gross, R.

    1987-01-01

    The present study was undertaken to identify the metabolic pathway(s) responsible for myocardial plasmenylcholine biosynthesis. Rabbit myocardium contained .46 +/- .09 nmol/g wet wight of 1-alkenyl-2-acyl glycerol (AAG) which predominantly consisted of 16:0 molecular species at the sn-1 position. Incubation of rabbit myocardial microsomes (RMM) with [ 14 C]CDP-choline ( 14 C-CDPC) resulted in the rapid incorporation of radiolabeled choline into the choline glycerophospholipid pool. RP-HPLC separation of molecular species demonstrated that nearly equal amounts of radiolabel were incorporated into plasmenylcholine and phosphatidylcholine subclasses despite the fact that RMM contained 21 times the mass of diacyl glycerol as compared to AAG. RMM incorporation of 14 C-CDPC into choline glycerophospholipids was substantially greater than incorporation of [ 14 C] phosphorylcholine or [ 14 C] choline. RMM incorporation of 14 C-CDPC into plasmalogen molecular species was stimulated two fold by 500 μM CMP. Taken together, these results demonstrate that rabbit myocardium contains substantial quantities of AAG and that endogenous AAG is an efficient precursor of myocardial plasmenylcholine

  10. Identify alkylation hazards

    International Nuclear Information System (INIS)

    Scott, B.

    1992-01-01

    This paper reports that extensive experience shows that alkylation plants regardless of acid catalyst choice, can be operated safely, and with minimum process risk to employees or neighbors. Both types of plants require a comprehensive and fully supported hazard management program that accounts for differing physical properties of the acids involved. Control and mitigation cost to refiners will vary considerably from plant to plant and location to location. In the author's experience, the order of magnitude costs will be about $1 to $2 million for a sulfuric acid (SA) alkylation plant, and about $10 to $15 million for a hydrofluoric acid (HF) plant. These costs include water supply systems and impoundment facilities for contaminated runoff water. The alkylation process, which chemically reacts isobutane and light olefins in the presence of a strong acid catalyst into a premium gasoline component is described

  11. Estrogenicity of halogenated bisphenol A: in vitro and in silico investigations.

    Science.gov (United States)

    Zhang, Jie; Li, Tiezhu; Wang, Tuoyi; Yuan, Cuiping; Zhong, Shuning; Guan, Tianzhu; Li, Zhuolin; Wang, Yongzhi; Yu, Hansong; Luo, Quan; Wang, Yongjun; Zhang, Tiehua

    2018-03-01

    The binding interactions of bisphenol A (BPA) and its halogenated derivatives (halogenated BPAs) to human estrogen receptor α ligand binding domain (hERα-LBD) was investigated using a combined in vitro and in silico approach. First, the recombinant hERα-LBD was prepared as a soluble protein in Escherichia coli BL21(DE3)pLysS. A native fluorescent phytoestrogen, coumestrol, was employed as tracer for the fluorescence polarization assay. The results of the in vitro binding assay showed that bisphenol compounds could bind to hERα-LBD as the affinity ligands. All the tested halogenated BPAs exhibited weaker receptor binding than BPA, which might be explained by the steric effect of substituents. Molecular docking studies elucidated that the halogenated BPAs adopted different conformations in the flexible hydrophobic ligand binding pocket (LBP), which is mainly dependent on their distinct halogenation patterns. The compounds with halogen substituents on the phenolic rings and on the bridging alkyl moiety acted as agonists and antagonists for hERα, respectively. Interestingly, all the compounds in the agonist conformation of hERα formed a hydrogen bond with His524, while the compounds in the antagonist conformation formed a hydrogen bond with Thr347. These docking results suggested a pivotal role of His524/Thr347 in maintaining the hERα structure in the biologically active agonist/antagonist conformation. Comparison of the calculated binding energies vs. experimental binding affinities yielded a good correlation, which might be applicable for the structure-based design of novel bisphenol compounds with reduced toxicities and for environmental risk assessment. In addition, based on hERα-LBD as a recognition element, the proposed fluorescence polarization assay may offer an alternative to chromatographic techniques for the multi-residue determination of bisphenol compounds.

  12. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15-December 31, 1984

    International Nuclear Information System (INIS)

    1985-01-01

    Energetic halogen atoms or ions, activated by various nuclear transformations are studied in gas, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes, and liquid and solid aqueous solutions of biomolecular and organic solutes in order to understand better the mechanisms and dynamics of high energy monovalent species. The experimental program and its goals remain the same, consisting of four interrelated areas: (1) The stereochemistry of energetic 18 F, /sup 34m/Cl, and 38 Cl substitution reactions with chiral molecules in the gas and condensed phase is studied. (2) The gas to condensed state transition in halogen high energy chemistry, involving energetic chlorine, bromine, and iodine reactions in halomethanes, saturated and unsaturated hydrocarbons and aqueous solutions of biomolecules and alkyl halides is being investigated in more detail. Current attention is given to defining the nature of the enhancement yields in the condensed phase. Specifically, energetic halogen reactions in liquid and frozen aqueous solutions or organic and biomolecular solutes are studied. (3) Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular and organic solutes in liquid and frozen aqueous solutions are being studied in an attempt to learn more about the activation events in the condensed phase. (4) The applications of hot chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Current attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as site indicators in liquid and frozen aqueous solutions of halogenated bases and nucleosides are currently being developed. 14 references

  13. Iron Mineral Catalyzed C-H Activation As a Potential Pathway for Halogenation Processes

    Science.gov (United States)

    Tubbesing, C.; Schoeler, H. F.; Benzing, K.; Krause, T.; Lippe, S.; Rudloff, M.

    2014-12-01

    Due to increasing drinking water demand of mankind and an expected climate change the impact of salt lakes and salt deserts will increase within the next decades. Furthermore, a rising sea level influences coastal areas like salt marshes and abets processes which will lead to elevated organohalogen formation. An additional increase of the global warming potential, of particle formation and stratospheric ozone depletion is expected. Understanding these multifaceted processes is essential for mankind to be prepared for these alterations of the atmosphere. For example, Keppler et al. (2000) described the production of volatile halogenated organic compounds via oxidation of organic matter driven by ferric iron. However, the formation of long-chained alkyl halides in salt lakes is yet undisclosed. Despite the relative "inertness" of alkanes a direct halogenation of these compounds might be envisaged. In 2005 Vaillancourt et al. discovered a nonheme iron enzyme which is able to halogenate organic compounds via generating the high valent ferryl cation as reaction center. Based on various publications about C-H activation (Bergman, 2007) we postulate a halogenation process in which an iron containing minerals catalyse the C-H bond cleavage of organic compounds in soils. The generated organic radicals are highly reactive towards halides connected to the iron complex. We suggest that next to diagenetically altered iron containing enzymes, minerals such as oxides, hydroxides and sulfides are involved in abiotic halogenation processes. We applied the amino acid methionine as organic model compound and soluble iron species as reactants. All samples were incubated in aqueous phases containing various NaCl concentrations. As a result various halogenated ethanes and ethenes were identified as reaction products. References Bergman, R. G. (2007) Nature, 446(7134) 391-393 Keppler, F., et al. (2000) Nature, 403(6767) 298-301 Vaillancourt, F. H., et al. (2005) Nature, 436(7054) 1191-1194

  14. METHOD FOR PRODUCING ISOTOPIC METHANES AND PARTIALLY HALOGENATED DERIVATIVES THEROF

    Science.gov (United States)

    Frazer, J.W.

    1959-08-18

    A method is given for producing isotopic methanes and/ or partially halogenated derivatives. Lithium hydride, deuteride, or tritide is reacted with a halogenated methane or with a halogenated methane in combination with free halogen. The process is conveniently carried out by passing a halogenated methane preferably at low pressures or in an admixture with an inert gas through a fixed bed of finely divided lithium hydride heated initially to temperatures of 100 to 200 deg C depending upon the halogenated methane used.

  15. Halogenated hydrocarbons - an environmental problem

    Energy Technology Data Exchange (ETDEWEB)

    Schoeler, H F; Thofern, E

    1984-01-01

    The paper provides a survey of the incidence of highly volatile halogenated hydrocarbons in ground, surface and drinking water as well as in the snows of Western Germany. Almost the entire production of chlorinated solvents is released into the environment. The absorption media are mostly soil, water and atmosphere. Whereas in the atmosphere elimination reactions take place, solvents that have passed the soil get into the ground water owing to their persistence and can cause considerable pollutions of drinking water. Moreover haloforms may occur in drinking water, which are produced during chlorine disinfection of pre-treated water.

  16. Organic halogen compounds in the environment

    International Nuclear Information System (INIS)

    1979-07-01

    There are 20 research reports on selected problems concerning the analysis, the occurence, and the behaviour of a wide spectrum of organic halogen compounds. The work was carried out in the framework of the project 'Organic Halogen Compounds in the Environment', financed by the BMFT, between 1975 and 1978. (orig.) [de

  17. High yield silicon carbide from alkylated or arylated pre-ceramic polymer

    International Nuclear Information System (INIS)

    Baney, R.H.; Gaul, J.H.

    1982-01-01

    Alkylated or arylated methylpolysilanes which exhibit ease of handling and are used to obtain silicon carbide ceramic materials in high yields contain 0 to 60 mole percent (CH 3 ) 2 Si double bond units and 40 to 100 mole percent CH 3 Si triple bond units, wherein there is also bonded to the silicon atoms other silicon atoms and additional alkyl radicals of 1 to 4 carbon atoms or phenyl. They may be prepared by reaction of a Grignard reagent RMgX, where X is halogen and R is Csub(1-4)-alkyl or phenyl, with a starting material which is a solid at 25 0 C, and is identical to the product except that the remaining bonds on the silicon atoms are attached to another silicon atom, or a chlorine or a bromine atom. Ceramics result from heating the polysilane products to 1200 0 C, optionally with fillers. (author)

  18. Halogen bond: a long overlooked interaction.

    Science.gov (United States)

    Cavallo, Gabriella; Metrangolo, Pierangelo; Pilati, Tullio; Resnati, Giuseppe; Terraneo, Giancarlo

    2015-01-01

    Because of their high electronegativity, halogen atoms are typically considered, in most of their derivatives, as sites of high electron density and it is commonly accepted that they can form attractive interactions by functioning as the electron donor site (nucleophilic site). This is the case when they work as hydrogen bond acceptor sites. However, the electron density in covalently bound halogens is anisotropically distributed. There is a region of higher electron density, accounting for the ability of halogens to function as electron donor sites in attractive interactions, and a region of lower electron density where the electrostatic potential is frequently positive (mainly in the heavier halogens). This latter region is responsible for the ability of halogen atoms to function as the electron-acceptor site (electrophilic site) in attractive interactions formed with a variety of lone pair-possessing atoms, anions, and π-systems. This ability is quite general and is shown by a wide diversity of halogenated compounds (e.g., organohalogen derivatives and dihalogens). According to the definition proposed by the International Union of Pure and Applied Chemistry, any attractive interactions wherein the halogen atom is the electrophile is named halogen bond (XB). In this chapter, it is discussed how the practice and the concept of XB developed and a brief history of the interaction is presented. Papers (either from the primary or secondary literature) which have reported major experimental findings in the field or which have given important theoretical contributions for the development of the concept are recollected in order to trace how a unifying and comprehensive categorization emerged encompassing all interactions wherein halogen atoms function as the electrophilic site.

  19. Heterofacial alkylation of alkylenediamines by higher alkyl halides

    International Nuclear Information System (INIS)

    Semenov, V.A.; Kryshko, G.M.; Sokal'skaya, L.I.; Zhukova, N.G.

    1985-01-01

    A study of the physiochemical properties of alkylenediamines substituted by lower alkyls, showed that they possess increased complex-forming ability with respect to salts of different metals as titanium, niobium, zirconium, molybdenum, and zinc. To create a simpler method of synthesis of higher tetraaklyalkylalklyenediamines, based on the use of the accessible domestic raw material, the authors investigated the reaction of alkylenediamines with various alkyl halides. It was established that the best reagents can be obtained using alkyl bromides. It is concluded that the procedure of alkylation of alkylenediamines by higher alkyl halides in the presence of water developed permits the production of terraalkylalkylenediamines in one step with good yield and with purity acceptable for use as extraction reagents

  20. Organic halogens in spruce forest throughfall

    DEFF Research Database (Denmark)

    Öberg, G.; Johansen, C.; Grøn, C.

    1998-01-01

    . No relationship between the position of the collectors and the forest edge or dominating wind-direction was found, suggesting that dry deposition was not a major source. The concentration of organic halogens was related to that of organic carbon and decreased from the tree-trunk and outwards. In addition......, the concentrations were higher during the growing season than during the dormant season. This indicates that the major part of the organic carbon and organic halogens in spruce forest throughfall originates from canopy leachates or other internal sources. (C) 1998 Elsevier Science Ltd.......Deposition of dissolved organic halogens by throughfall was determined in a small spruce forest site in Denmark (56 degrees 28'N, 8 degrees 24'E). The mean annual deposition of dissolved organic halogens was 377 g ha(-1)yr(-1), and larger than the general deposition by precipitation...

  1. The halogen bond: Nature and applications

    Science.gov (United States)

    Costa, Paulo J.

    2017-10-01

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

  2. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

    Energy Technology Data Exchange (ETDEWEB)

    John F. Schabron; Joseph F. Rovani Jr.; Theresa M. Bomstad

    2002-06-01

    Western Research Institute (WRI) initiated exploratory work towards the development of new field screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of carbon-halogen bonds. Commercially available heated diode and corona discharge leak detectors were procured and evaluated for halogenated VOC response. The units were modified to provide a digital readout of signal related to VOC concentration. Sensor response was evaluated with carbon tetrachloride and tetrachloroethylene (perchloroethylene, PCE), which represent halogenated VOCs with and without double bonds. The response characteristics were determined for the VOCs directly in headspace in Tedlar bag containers. Quantitation limits in air were estimated. Potential interferences from volatile hydrocarbons, such as toluene and heptane, were evaluated. The effect of humidity was studied also. The performance of the new devices was evaluated in the laboratory by spiking soil samples and monitoring headspace for halogenated VOCs. A draft concept of the steps for a new analytical method was outlined. The results of the first year effort show that both devices show potential utility for future analytical method development work towards the goal of developing a portable test kit for screening halogenated VOCs in the field.

  3. DNA modification by alkylating compounds

    Energy Technology Data Exchange (ETDEWEB)

    Kruglyakova, E.E.

    1985-09-01

    Results are given for research on the physico-chemical properties of alkylating compounds - nitroso alkyl ureas (NAU) which possess a broad spectrum of biological activity, such as mutagenic, carcinogenic, and anti-tumor action that is due to the alkylation and carbamoylation of DNA as well as other cellular components. Identified chemical products of NAU interaction with DNA and its components are cited. Structural conversions of a DNA macromolecule resulting from its chemical modification are examined. NAU are used to discuss possible biological consequences of DNA modification. 148 references.

  4. Formation of enamines by alkylation of imines

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1966-01-01

    cf. CA 64, 12473c. With ice-cooling, 1 equiv. alkylating agent was added to one equiv. of the imine in 1M soln. in a solvent in the presence of NaH to give both N- and C-alkylated products. The following summarizes the date (imine, solvent, alkylating agent, % unreacted imine, % N-alkylated product,

  5. Poly(alkyl acrylate) nonparticles

    International Nuclear Information System (INIS)

    Kreuter, J.

    1985-01-01

    This study deals with the preparation of poly(alkyl acrylic) and poly(alkyl cyanocrylic) nanoparticles. Nonoparticles are solid colloidal particles, consisting of macromolecular materials in which drugs or biologically active materials are dissolved, entrapped, and encapsulated, and/or to which the active substance is adsorbed or attached. Poly(alkyl acrylic) nanoparticles are much more slowly biodegradable than poly(alkyl cyanoacrylate) nanoparticles, and are thus more suitable for drug delivery purposes. Poly(methyl methacrylate) is the material of choice for the use of nanoparticles as an adjuvant for vaccines and are produced by emulsifier-free polymerization in aqueous media. The polymerization, which can be initiated with gamma rays or with potassium peroxodisulfate, is described

  6. N-oxide as a traceless oxidizing directing group: mild rhodium(III)-catalyzed C-H olefination for the synthesis of ortho-alkenylated tertiary anilines.

    Science.gov (United States)

    Huang, Xiaolei; Huang, Jingsheng; Du, Chenglong; Zhang, Xingyi; Song, Feijie; You, Jingsong

    2013-12-02

    Double role: A traceless directing group also acts as an internal oxidant in a novel Rh(III) -catalyzed protocol developed for the synthesis of ortho-alkenylated tertiary anilines. A five-membered cyclometalated Rh(III) complex is proposed as a plausible intermediate and confirmed by X-ray crystallographic analysis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Studies on halogen quenching through the Stern-Volmer plot

    International Nuclear Information System (INIS)

    Takiue, Makoto; Ishikawa, Hiroaki.

    1978-01-01

    The quenching effect for halogenated benzenes, methanes and ethanes have been investigated. The halogen quenching was accurately measured using the internal conversion electrons emitted from 113 Sn-sup(113m)In. From the quenching constants determined by the Stern-Volmer plots with respect to various halogen quenchers, the following results have been obtained. (1) The quenching constants increase with the number of halogen substituents, so as linearly in halogenated benzenes and exponentially in halogenated methanes and ethanes. Even the isomers of halogenides have different quenching constants. (2) There is a linearity between logarithm of the quenching constant and a polarographic half-wave reduction potential. (3) Electron excitation provides larger quenching constants than UV excitation for halogenated methanes. Based on these results, the mechanism of halogen quenching have been discussed in connection with the exciplex formation. (auth.)

  8. SYNTHESIS AND CHARACTERIZATION OF NEW HALOGENATED CURCUMINOIDS

    Directory of Open Access Journals (Sweden)

    Eugenio Torres

    2013-12-01

    Full Text Available In this work a novel procedure of synthesis of compounds analogues to curcumin with halogens atoms in its structure is described, which can increase its solubility and biological activity. Four halogenated curcuminoids were obtained with great pharmacological interest, none of them reported in literature before. Synthesis was carried out by means of the aldol condensation assisted by microwaves of halogenated aromatic aldehydes and acetylacetona, using morpholine as basic catalyst, in absence of solvent, and the reaction just needed 1 min. The products were purified by treatment of the reaction mixture with methanol under ultrasound irradiation, followed by chromatographic column. All obtained compounds were characterized by infrared spectroscopy, nuclear magnetic resonance, quantitative elementary analysis and high resolution mass spectrometry. The RMN-1H data demonstrate in all structures of synthesized curcuminoids the enol form is the most favored.

  9. Halogens in chondritic meteorites and terrestrial accretion

    Science.gov (United States)

    Clay, Patricia L.; Burgess, Ray; Busemann, Henner; Ruzié-Hamilton, Lorraine; Joachim, Bastian; Day, James M. D.; Ballentine, Christopher J.

    2017-11-01

    Volatile element delivery and retention played a fundamental part in Earth’s formation and subsequent chemical differentiation. The heavy halogens—chlorine (Cl), bromine (Br) and iodine (I)—are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15-37 times lower, respectively, than previously reported and usually accepted estimates. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5 ± 0.2 per cent of Earth’s silicate mass, cannot solely account for present-day terrestrial halogen inventories. It is estimated that 80-90 per cent of heavy halogens are concentrated in Earth’s surface reservoirs and have not undergone the extreme early loss observed in atmosphere-forming elements. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth’s dissolved mantle gases, the efficient extraction of halogen-rich fluids from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track

  10. Thermal behavior of halogenated imidebismaleimide resins

    International Nuclear Information System (INIS)

    Mohammad, A.; Al-Halim, N.Z.

    1995-01-01

    Several new poly-halogenated malecimides, bismaleimides and therir copoly resins were synthessised thermally from their corresponding amic acids. The synthesis was accomplished by two way method (amic acid-polimide) instead of the well-known three way method (amic acid-imide-polyimide). Thermal characterization of monomers and their cured resins was achieved using differential thermal analysis (DTA), dynamic thermogravimetric analysis (TGA) and isothermal gravimetric analysis (IGA). The effect of halogen substituent, especially in the ortho postion, is clear in the imidization proces, while polymerization proceeds almost equally in all systems. Thermal properties of homo and copolymers were correlated with their chemical structures. (author). 15 refs., 4

  11. Is halogen content the most important factor in the removal of halogenated trace organics by MBR treatment?

    Science.gov (United States)

    Hai, Faisal I; Tadkaew, Nichanan; McDonald, James A; Khan, Stuart J; Nghiem, Long D

    2011-05-01

    This study investigated the relationship between physicochemical properties (namely halogen content and hydrophobicity) of halogenated trace organics and their removal efficiencies by a laboratory scale membrane bioreactor (MBR) under stable operating conditions. The reported results demonstrated a combined effect of halogen content and hydrophobicity on the removal. Compounds with high halogen content (>0.3) were well removed (>85%) when they possessed high hydrophobicity (Log D>3.2), while those with lower Log D values were also well removed if they had low halogen content (BIOWIN index (which is based on only biodegradation) or a more specific index such as the halogen content (which captures a chemical aspect) appeared insufficient to predict the removal efficiency of halogenated compounds in MBR. Experimental data confirmed that the ratio of halogen content and Log D, which incorporates two important physico-chemical properties, is comparatively more suitable. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. Passivation of quartz for halogen-containing light sources

    Science.gov (United States)

    Falkenstein, Zoran

    1999-01-01

    Lifetime of halogen containing VUV, UV, visible or IR light sources can be extended by passivating the quartz or glass gas containers with halogens prior to filling the quartz with the halogen and rare gas mixtures used to produce the light.

  13. 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.

  14. Alkyl and aryl phosphorodiiodidites. Pt. 2

    International Nuclear Information System (INIS)

    Feshchenko, N.G.; Kostina, V.G.

    1976-01-01

    Alkyl phosphorodiiodidites are formed in the reactions of alkyl phosphorodichloridites with lithium iodide. They are stable at -60 to -50 0 . When warmed to 20 0 , they disproportionate with conversion into trialkyl phosphites and phosphorus triiodide. The latter also react together and give alkyl iodides, diphosphorus tetraiodide, and a polymer of unestablished structure. Diaryl and dialkyl phosphoriodidites are stable only in solution at low temperatures. They disproportionate in a similar way to aryl and alkyl phosphorodiiodidites. Alkyl phosphorodiiodidites react with iodine with the formation of alkyl iodides and phosphoryl iodide

  15. Literature Survey and Further Studies on the 3-Alkylation of N-Unprotected 3-Monosubstituted Oxindoles. Practical Synthesis of N-Unprotected 3,3-Disubstituted Oxindoles and Subsequent Transformations on the Aromatic Ring.

    Science.gov (United States)

    Kókai, Eszter; Simig, Gyula; Volk, Balázs

    2016-12-26

    The paper provides a comprehensive review of the base-catalysed C3-alkylation of N-unprotected-3-monosubstituted oxindoles. Based on a few, non-systematic studies described in the literature using butyllithium as the deprotonating agent, an optimized method has now been elaborated, via the corresponding lithium salt, for the selective C3-alkylation of this family of compounds. The optimal excess of butyllithium and alkylating agent, and the role of the halogen atom in the latter (alkyl bromides vs. iodides) were also studied. The alkylation protocol has also been extended to some derivatives substituted at the aromatic ring. Finally, various substituents were introduced into the aromatic ring of the N-unprotected 3,3-dialkyloxindoles obtained by this optimized method.

  16. Literature Survey and Further Studies on the 3-Alkylation of N-Unprotected 3-Monosubstituted Oxindoles. Practical Synthesis of N-Unprotected 3,3-Disubstituted Oxindoles and Subsequent Transformations on the Aromatic Ring

    Directory of Open Access Journals (Sweden)

    Eszter Kókai

    2016-12-01

    Full Text Available The paper provides a comprehensive review of the base-catalysed C3-alkylation of N-unprotected-3-monosubstituted oxindoles. Based on a few, non-systematic studies described in the literature using butyllithium as the deprotonating agent, an optimized method has now been elaborated, via the corresponding lithium salt, for the selective C3-alkylation of this family of compounds. The optimal excess of butyllithium and alkylating agent, and the role of the halogen atom in the latter (alkyl bromides vs. iodides were also studied. The alkylation protocol has also been extended to some derivatives substituted at the aromatic ring. Finally, various substituents were introduced into the aromatic ring of the N-unprotected 3,3-dialkyloxindoles obtained by this optimized method.

  17. Syntheses of cytotoxic novel arctigenin derivatives bearing halogen and alkyl groups on aromatic rings.

    Science.gov (United States)

    Yamauchi, Satoshi; Wukirsari, Tuti; Ochi, Yoshiaki; Nishiwaki, Hisashi; Nishi, Kosuke; Sugahara, Takuya; Akiyama, Koichi; Kishida, Taro

    2017-09-01

    The new lignano-9,9'-lactones (α,β-dibenzyl-γ-butyrolactone lignans), which showed the higher cytotoxicity than arctigenin, were synthesized. The well-known cytotoxic arctigenin showed activity against HL-60 cells (EC 50 =12μM), however, it was inactive against HeLa cells (EC 50 >100μM). The synthesized (3,4-dichloro, 2'-butoxy)-derivative 55 and (3,4-dichloro, 4'-butyl)-derivative 66 bearing the lignano-9,9'-lactone structures showed the EC 50 values of 10μM and 9.4μM against HL-60 cells, respectively. Against HeLa cells, the EC 50 value of the derivative 66 was 27μM. By comparing the activities with the corresponding 9,9'-epoxy structure (tetrahydrofuran compounds), the importance of the lactone structure of 55 and 66 for the higher activities was shown. The substituents on the aromatic ring of the lignano-9,9'-lactones affected the cytotoxicity level, observing more than 10-fold difference. Copyright © 2017. Published by Elsevier Ltd.

  18. Retention of Halogens in Waste Glass

    Energy Technology Data Exchange (ETDEWEB)

    Hrma, Pavel R.

    2010-05-01

    In spite of their potential roles as melting rate accelerators and foam breakers, halogens are generally viewed as troublesome components for glass processing. Of five halogens, F, Cl, Br, I, and At, all but At may occur in nuclear waste. A nuclear waste feed may contain up to 10 g of F, 4 g of Cl, and ≤100 mg of Br and I per kg of glass. The main concern is halogen volatility, producing hazardous fumes and particulates, and the radioactive iodine 129 isotope of 1.7x10^7-year half life. Because F and Cl are soluble in oxide glasses and tend to precipitate on cooling, they can be retained in the waste glass in the form of dissolved constituents or as dispersed crystalline inclusions. This report compiles known halogen-retention data in both high-level waste (HLW) and low-activity waste (LAW) glasses. Because of its radioactivity, the main focus is on I. Available data on F and Cl were compiled for comparison. Though Br is present in nuclear wastes, it is usually ignored; no data on Br retention were found.

  19. DNA minor groove alkylating agents.

    Science.gov (United States)

    Denny, W A

    2001-04-01

    Recent work on a number of different classes of anticancer agents that alkylate DNA in the minor groove is reviewed. There has been much work with nitrogen mustards, where attachment of the mustard unit to carrier molecules can change the normal patterns of both regio- and sequence-selectivity, from reaction primarily at most guanine N7 sites in the major groove to a few adenine N3 sites at the 3'-end of poly(A/T) sequences in the minor groove. Carrier molecules discussed for mustards are intercalators, polypyrroles, polyimidazoles, bis(benzimidazoles), polybenzamides and anilinoquinolinium salts. In contrast, similar targeting of pyrrolizidine alkylators by a variety of carriers has little effect of their patterns of alkylation (at the 2-amino group of guanine). Recent work on the pyrrolobenzodiazepine and cyclopropaindolone classes of natural product minor groove binders is also reviewed.

  20. Alkylating agents for Waldenstrom's macroglobulinaemia.

    Science.gov (United States)

    Yang, Kun; Tan, Jianlong; Wu, Taixiang

    2009-01-21

    Waldenstrom's macroglobulinaemia (WM) is an uncommon B-cell lymphoproliferative disorder characterized by bone marrow infiltration and production of monoclonal immunoglobulin. Uncertainty remains if alkylating agents, such as chlorambucil, melphalan or cyclophosphamide, are an effective form of management. To assess the effects and safety of the alkylating agents on Waldenstrom's macroglobulinaemia (WM). We searched the Cochrane Central Register of Controlled Trials (Issue 1, 2008), MEDLINE (1966 to 2008), EMBASE (1980 to 2008), the Chinese Biomedical Base (1982 to 2008) and reference lists of articles.We also handsearched relevant conference proceedings from 1990 to 2008. Randomised controlled trials (RCTs) comparing alkylating agents given concomitantly with radiotherapy, splenectomy, plasmapheresis, stem-cell transplantation in patients with a confirmed diagnosis of WM. Two authors independently assessed trial quality and extracted data. We contacted study authors for additional information. We collected adverse effects information from the trials. One trial involving 92 participants with pretreated/relapsed WM compared the effect of fludarabine versus the combination of cyclophosphamide (the alkylating agent), doxorubicin and prednisone (CAP). Compared to CAP, the Hazard ratio (HR) for deaths of treatment with fludarabine was estimated to be 1.04, with a standard error of 0.30 (95% CI 0.58 to 1.48) and it indicated that the mean difference of median survival time was -4.00 months, and 16.00 months for response duration. The relative risks (RR) of response rate was 2.80 (95% CI 1.10 to 7.12). There were no statistically difference in overall survival rate and median survival months, while on the basis of response rate and response duration, fludarabine seemed to be superior to CAP for pretreated/relapsed patients with macroglobulinaemia. Although alkylating agents have been used for decades they have never actually been tested in a proper randomised trial. This

  1. Thioimidazolium Ionic Liquids as Tunable Alkylating Agents.

    Science.gov (United States)

    Guterman, Ryan; Miao, Han; Antonietti, Markus

    2018-01-19

    Alkylating ionic liquids based on the thioimidazolium structure combine the conventional properties of ionic liquids, including low melting point and nonvolatility, with the alkylating function. Alkyl transfer occurs exclusively from the S-alkyl position, thus allowing for easy derivatization of the structure without compromising specificity. We apply this feature to tune the electrophilicty of the cation to profoundly affect the reactivity of these alkylating ionic liquids, with a caffeine-derived compound possessing the highest reactivity. Anion choice was found to affect reaction rates, with iodide anions assisting in the alkylation reaction through a "shuttling" process. The ability to tune the properties of the alkylating agent using the toolbox of ionic liquid chemistry highlights the modular nature of these compounds as a platform for alkylating agent design and integration in to future systems.

  2. Chichibabin-type direct alkylation of pyridyl alcohols with alkyl lithium reagents.

    Science.gov (United States)

    Jeffrey, Jenna L; Sarpong, Richmond

    2012-11-02

    Direct C(6) alkylation of pyridyl alcohols can be achieved following an initial deprotonation of the hydroxy group. This transformation, which is believed to occur by a Chichibabin-type alkylation, avoids lateral deprotonation prior to pyridine ring alkylation and gives increased regioselectivity for C(6) over C(4) alkylation.

  3. 40 CFR 721.9892 - Alkylated urea.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under this...

  4. Synthesis and evaluation of sequence-specific DNA alkylating agents: effect of alkylation subunits.

    Science.gov (United States)

    Shimizu, Tatsuhiko; Sasaki, Shunta; Minoshima, Masafumi; Shinohara, Ken-ichi; Bando, Toshikazu; Sugiyama, Hiroshi

    2006-01-01

    We have demonstrated that hairpin pyrrole (Py)- imidazole (Im) polyamide-CBI conjugates selectively alkylate predetermined sequences. In this study, we investigated the effect of alkylation subunits, for example conjugates 1-4 with three types of DNA alkylating units, and Py-Im polyamides with indole linker. Conjugate 3 and 4 selectively alkylated the predetermined sequences as described previously, while conjugates 1 and 2 alkylate at mismatched sites.

  5. Boiling points of halogenated ethanes: an explanatory model implicating weak intermolecular hydrogen-halogen bonding.

    Science.gov (United States)

    Beauchamp, Guy

    2008-10-23

    This study explores via structural clues the influence of weak intermolecular hydrogen-halogen bonds on the boiling point of halogenated ethanes. The plot of boiling points of 86 halogenated ethanes versus the molar refraction (linked to polarizability) reveals a series of straight lines, each corresponding to one of nine possible arrangements of hydrogen and halogen atoms on the two-carbon skeleton. A multiple linear regression model of the boiling points could be designed based on molar refraction and subgroup structure as independent variables (R(2) = 0.995, standard error of boiling point 4.2 degrees C). The model is discussed in view of the fact that molar refraction can account for approximately 83.0% of the observed variation in boiling point, while 16.5% could be ascribed to weak C-X...H-C intermolecular interactions. The difference in the observed boiling point of molecules having similar molar refraction values but differing in hydrogen-halogen intermolecular bonds can reach as much as 90 degrees C.

  6. Process for removal of hydrogen halides or halogens from incinerator gas

    Science.gov (United States)

    Huang, H.S.; Sather, N.F.

    1987-08-21

    A process for reducing the amount of halogens and halogen acids in high temperature combustion gas and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

  7. Transition-metal-free synthesis of N-(1-alkenyl)imidazoles by potassium phosphate-promoted addition reaction of alkynes to imidazoles.

    Science.gov (United States)

    Lu, Linhua; Yan, Hong; Liu, Defu; Rong, Guangwei; Mao, Jincheng

    2014-01-01

    The addition reaction of alkynes to N-heterocycles by simply heating in DMSO with potassium phosphate is reported. Good yields with high stereoselectivity could be achieved for a range of substrates. The scope is quite general for both amines and phenylacetylenes. In addition, internal alkynes and α-bromostyrene were also examined in this reaction. This process is efficient and useful for the synthesis of (Z)-N-(1-alkenyl)imidazoles and related Z products. Thus, the reaction is useful because of the importance of the imidazole scaffold. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Excess Substrate is a Spectator Ligand in a Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates with Tolanes

    Science.gov (United States)

    Oinen, Mark Emil; Yu, Robert T.; Rovis, Tomislav

    2009-01-01

    Excess substrate has been identified as an unintended spectator ligand affecting enantioselectivity in the [2+2+2] cycloaddition of alkenyl isocyanates with tolanes. Replacement of excess substrate with an exogenous additive affords products with consistent and higher ee’s. The increase in enantioselectivity is the result of a change in composition of a proposed rhodium(III) intermediate on the catalytic cycle. The net result is a rational probe of a short-lived rhodium(III) intermediate, and gives insight that may have applications in many rhodium catalyzed reactions. PMID:19803471

  9. Molecular activation analysis for organo-halogen contaminants in yogurt

    International Nuclear Information System (INIS)

    Zhang Hong; Chai Zhifang

    2004-01-01

    The concentrations of total halogen (TX), extractable organo-halogen (EOX), extractable persistent organo-halogen (EPOX), organo-chlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in 18 different yogurt specimens of 14 brands from Beijing, Tianjin, Shanghai, Guangzhou and Shijiazhuang were determined by epithermal neutron activation analysis (ENAA), molecular activation analysis (MAA) and GC-Mass Spectrometry (GC-MS), respectively. The results indicated that the halogen in yogurt mainly existed as inorganic species and non-extractable organo-halogen compounds. About 1/3 to 1/4 of EOX was EPOX. Further, EOCl and EPOCl were the main organo-halogen species in yogurt. The average concentration of the unknown organo-chlorine was 96% of the EPOCl. HCHs and DDTs were still the main contaminants of OCPs in the yogurt of interest. Also, PCB202, PCB103 and PCB208 were the main contaminants of PCBs. (authors)

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

    Science.gov (United States)

    Ford, Melissa Coates; Ho, P Shing

    2016-03-10

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

  11. New Type of Halogen Bond: Multivalent Halogen Interacting with π- and σ-Electrons

    Directory of Open Access Journals (Sweden)

    Sławomir J. Grabowski

    2017-12-01

    Full Text Available MP2/aug-cc-pVTZ calculations were performed for complexes of BrF3 and BrF5 acting as Lewis acids through the bromine centre, with species playing a role of Lewis base: dihydrogen, acetylene, ethylene, and benzene. The molecular hydrogen donates electrons by its σ-bond, while in remaining moieties—in complexes of hydrocarbons; such an electron transfer follows from π-electrons. The complexes are linked by a kind of the halogen bond that is analyzed for the first time in this study, i.e., it is the link between the multivalent halogen and π or σ-electrons. The nature of such a halogen bond is discussed, as well as various dependencies and correlations are presented. Different approaches are applied here, the Quantum Theory of Atoms in Molecules, Natural Bond Orbital method, the decomposition of the energy of interaction, the analysis of electrostatic potentials, etc.

  12. The effect of the cation alkyl chain length on density and diffusion in dialkylpyrrolidinium bis(mandelato)borate ionic liquids.

    Science.gov (United States)

    Filippov, Andrei; Taher, Mamoun; Shah, Faiz Ullah; Glavatskih, Sergei; Antzutkin, Oleg N

    2014-12-28

    The physicochemical properties of ionic liquids are strongly affected by the selective combination of the cations and anions comprising the ionic liquid. In particular, the length of the alkyl chains of ions has a clear influence on the ionic liquid's performance. In this paper, we study the self-diffusion of ions in a series of halogen-free boron-based ionic liquids (hf-BILs) containing bis(mandelato)borate anions and dialkylpyrrolidinium cations with long alkyl chains CnH2n+1 with n from 4 to 14 within a temperature range of 293-373 K. It was found that the hf-BILs with n = 4-7 have very similar diffusion coefficients, while hf-BILs with n = 10-14 exhibit two liquid sub-phases in almost the entire temperature range studied (293-353 K). Both liquid sub-phases differ in their diffusion coefficients, while values of the slower diffusion coefficients are close to those of hf-BILs with shorter alkyl chains. To explain the particular dependence of diffusion on the alkyl chain length, we examined the densities of the hf-BILs studied here. It was shown that the dependence of the density on the number of CH2 groups in long alkyl chains of cations can be accurately described using a "mosaic type" model, where regions of long alkyl chains of cations (named 'aliphatic' regions) and the residual chemical moieties in both cations and anions (named 'ionic' regions) give additive contributions. Changes in density due to an increase in temperature and the number of CH2 groups in the long alkyl chains of cations are determined predominantly by changes in the free volume of the 'ionic' regions, while 'aliphatic' regions are already highly compressed by van der Waals forces, which results in only infinitesimal changes in their free volumes with temperature.

  13. Complex responses to alkylating agents

    International Nuclear Information System (INIS)

    Samson, L.D.

    2003-01-01

    Using Affymetrix oligonucleotide GeneChip analysis, we previously found that, upon exposure to the simple alkylating agent methylmethane sulfonate, the transcript levels for about one third of the Saccharomyces cerevisiae genome (∼2,000 transcripts) are induced or repressed during the first hour or two after exposure. In order to determine whether the responsiveness of these genes has any relevance to the protection of cells against alkylating agents we have undertaken several follow-up studies. First, we explored the specificity of this global transcriptional response to MMS by measuring the global response of S. cerevisiae to a broad range of agents that are known to induce DNA damage. We found that each agent produced a very different mRNA transcript profile, even though the exposure doses produced similar levels of toxicity. We also found that the selection of genes that respond to MMS is highly dependent upon what cell cycle phase the cells are in at the time of exposure. Computational clustering analysis of the dataset derived from a large number of exposures identified several promoter motifs that are likely to control some of the regulons that comprise this large set of genes that are responsive to DNA damaging agents. However, it should be noted that these agents damage cellular components other than DNA, and that the responsiveness of each gene need not be in response to DNA damage per se. We have also begun to study the response of other organisms to alkylating agents, and these include E. coli, cultured mouse and human cells, and mice. Finally, we have developed a high throughput phenotypic screening method to interrogate the role of all non-essential S. cerevisiae genes (about 4,800) in protecting S. cerevisiae against the deleterious effects of alkylating agents; we have termed this analysis 'genomic phenotyping'. This study has uncovered a plethora of new pathways that play a role in the recovery of eukaryotic cells after exposure to toxic

  14. Isobutane alkylation over solid catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kozorezov, Y.I.; Lisin, V.I.

    1979-05-01

    Commercial alumina modified with 6Vertical Bar3< by wt boron trifluoride was active in isobutane alkylation with ethylene in a flow reactor at 5:1 isobutane-ethylene and 5-20 min reaction time. The reaction rate was first-order in ethylene and increased with increasing temperature (20/sup 0/-80/sup 0/C) and ethylene pressure (0.2-3 atm). The calculated activation energy was 8.4 kj. Kinetic data and the activity of tert.-butyl chloride, but not ethyl chloride as alkylating agents in place of ethylene suggested a carbonium-ion chain mechanism involving both surface and gas-phase reactions. The ethylene-based yield of the alkylate decreased from 132 to 41Vertical Bar3< by wt after nine hours on stream, and its bromine number increased from 0.2 to 1 g Br/sub 2//100 ml. This inhibition was attributed to adsorption on the active acidic sites of the reaction products, particularly C/sub 10//sup +/ olefins. Catalyst stabilization could probably be achieved by selecting an appropriate solvent that would continuously desorb the inhibiting products from the catalyst surface.

  15. Antimitotic antitumor agents: synthesis, structure-activity relationships, and biological characterization of N-aryl-N'-(2-chloroethyl)ureas as new selective alkylating agents.

    Science.gov (United States)

    Mounetou, E; Legault, J; Lacroix, J; C-Gaudreault, R

    2001-03-01

    A series of N-aryl-N'-(2-chloroethyl)ureas (CEUs) and derivatives were synthesized and evaluated for antiproliferative activity against a wide panel of tumor cell lines. Systematic structure--activity relationship (SAR) studies indicated that: (i) a branched alkyl chain or a halogen at the 4-position of the phenyl ring or a fluorenyl/indanyl group, (ii) an exocyclic urea function, and (iii) a N'-2-chloroethyl moiety were required to ensure significant cytotoxicity. Biological experiments, such as immunofluorescence microscopy, confirmed that these promising compounds alter the cytoskeleton by inducing microtubule depolymerization via selective alkylation of beta-tubulin. Subsequent evaluations demonstrated that potent CEUs were weak alkylators, were non-DNA-damaging agents, and did not interact with the thiol function of either glutathione or glutathione reductase. Therefore, CEUs are part of a new class of antimitotic agents. Finally, among the series of CEUs evaluated, compounds 12, 15, 16, and 27 were selected for further in vivo trials.

  16. Mercury and halogens in coal: Chapter 2

    Science.gov (United States)

    Kolker, Allan; Quick, Jeffrey C.; Granite, Evan J.; Pennline, Henry W.; Senior, Constance L.

    2014-01-01

    Apart from mercury itself, coal rank and halogen content are among the most important factors inherent in coal that determine the proportion of mercury captured by conventional controls during coal combustion. This chapter reviews how mercury in coal occurs, gives available concentration data for mercury in U.S. and international commercial coals, and provides an overview of the natural variation in halogens that influence mercury capture. Three databases, the U.S. Geological Survey coal quality (USGS COALQUAL) database for in-ground coals, and the 1999 and 2010 U.S. Environmental Protection Agency (EPA) Information Collection Request (ICR) databases for coals delivered to power stations, provide extensive results for mercury and other parameters that are compared in this chapter. In addition to the United States, detailed characterization of mercury is available on a nationwide basis for China, whose mean values in recent compilations are very similar to the United States in-ground mean of 0.17 ppm mercury. Available data for the next five largest producers (India, Australia, South Africa, the Russian Federation, and Indonesia) are more limited and with the possible exceptions of Australia and the Russian Federation, do not allow nationwide means for mercury in coal to be calculated. Chlorine in coal varies as a function of rank and correspondingly, depth of burial. As discussed elsewhere in this volume, on a proportional basis, bromine is more effective than chlorine in promoting mercury oxidation in flue gas and capture by conventional controls. The ratio of bromine to chlorine in coal is indicative of the proportion of halogens present in formation waters within a coal basin. This ratio is relatively constant except in coals that have interacted with deep-basin brines that have reached halite saturation, enriching residual fluids in bromine. Results presented here help optimize mercury capture by conventional controls and provide a starting point for

  17. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

    Energy Technology Data Exchange (ETDEWEB)

    John F. Schabron; Joseph F. Rovani, Jr.; Theresa M. Bomstad

    2003-07-01

    Western Research Institute (WRI) is continuing work toward the development of new screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of halogens. In prior work, the devices were tested for response to carbon tetrachloride, heptane, toluene, and water vapors. In the current work, sensor response was evaluated with sixteen halogenated VOCs relative to carbon tetrachloride. The results show that the response of the various chlorinated VOCs is within an order of magnitude of the response to carbon tetrachloride for each of the sensors. Thus, for field screening a single response factor can be used. Both types of leak detectors are being further modified to provide an on-board LCD signal readout, which is related to VOC concentration. The units will be fully portable and will operate with 115-V line or battery power. Signal background, noise level, and response data on the Bacharach heated diode detector and the TIF corona discharge detector show that when the response curves are plotted against the log of concentration, the plot is linear to the upper limit for the particular unit, with some curvature at lower levels. When response is plotted directly against concentration, the response is linear at the low end and is curved at the high end. The dynamic ranges for carbon tetrachloride of the two devices from the lower detection limit (S/N=2) to signal saturation are 4-850 vapor parts per million (vppm) for the corona discharge unit and 0.01-70 vppm for the heated diode unit. Additional circuit modifications are being made to lower the detection limit and increase the dynamic response range of the corona discharge unit. The results indicate that both devices show potential utility for future analytical method development work toward

  18. Laboratory Investigations of Stratospheric Halogen Chemistry

    Science.gov (United States)

    Wine, Paul H.; Nicovich, J. Michael; Stickel, Robert E.; Hynes, Anthony J.

    1997-01-01

    A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

  19. Boiling Heat Transfer to Halogenated Hydrocarbon Refrigerants

    Science.gov (United States)

    Yoshida, Suguru; Fujita, Yasunobu

    The current state of knowledge on heat transfer to boiling refrigerants (halogenated hydrocarbons) in a pool and flowing inside a horizontal tube is reviewed with an emphasis on information relevant to the design of refrigerant evaporators, and some recommendations are made for future research. The review covers two-phase flow pattern, heat transfer characteristics, correlation of heat transfer coefficient, influence of oil, heat transfer augmentation, boiling from tube-bundle, influence of return bend, burnout heat flux, film boiling, dryout and post-dryout heat transfer.

  20. The Scarlet Letter of Alkylation: A Mini Review of Selective Alkylating Agents

    OpenAIRE

    Oronsky, Bryan T; Reid, Tony; Knox, Susan J; Scicinski, Jan J

    2012-01-01

    If there were a stigma scale for chemotherapy, alkylating agents would be ranked at the top of the list. The chemical term alkylation is associated with nonselective toxicity, an association that dates back to the use of nitrogen mustards during World War I as chemical warfare agents. That this stigma persists and extends to compounds that, through selectivity, attempt to “tame” the indiscriminate destructive potential of alkylation is the subject of this review. Selective alkylation, as it i...

  1. Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

    Directory of Open Access Journals (Sweden)

    J. Ofner

    2012-07-01

    Full Text Available Reactive halogen species (RHS, such as X·, X2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA and organic aerosol derived from biomass-burning (BBOA has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols.

    Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy, changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS, or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

  2. Scientific conferences: A big hello to halogen bonding

    Science.gov (United States)

    Erdelyi, Mate

    2014-09-01

    Halogen bonding connects a wide range of subjects -- from materials science to structural biology, from computation to crystal engineering, and from synthesis to spectroscopy. The 1st International Symposium on Halogen Bonding explored the state of the art in this fast-growing field of research.

  3. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Science.gov (United States)

    2010-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject to...

  4. [Near infrared light irradiator using halogen lamp].

    Science.gov (United States)

    Ide, Yasuo

    2012-07-01

    The practical electric light bulb was invented by Thomas Alva Edison in 1879. Halogen lamp is the toughest and brightest electric light bulb. With light filter, it is used as a source of near infrared light. Super Lizer and Alphabeam are made as near infrared light irradiator using halogen lamp. The light emmited by Super Lizer is linear polarized near infrared light. The wave length is from 600 to 1,600 nm and strongest at about 1,000 nm. Concerning Super Lizer, there is evidence of analgesic effects and normalization of the sympathetic nervous system. Super Lizer has four types of probes. SG type is used for stellate ganglion irradiation. B type is used for narrow area irradiation. C and D types are for broad area irradiation. The output of Alphabeam is not polarized. The wave length is from 700 to 1,600 nm and the strongest length is about 1,000nm. Standard attachment is used for spot irradiation. Small attachment is used for stellate ganglion irradiation. Wide attachment is used for broad area irradiation. The effects of Alphabeam are thought to be similar to that of Super Lizer.

  5. S-alkylation of soft scorpionates.

    Science.gov (United States)

    Rajasekharan-Nair, Rajeev; Moore, Dean; Chalmers, Kirsten; Wallace, Dawn; Diamond, Louise M; Darby, Lisa; Armstrong, David R; Reglinski, John; Spicer, Mark D

    2013-02-11

    The alkylation reactions of soft scorpionates are reported. The hydrotris(S-alkyl-methimazolyl)borate dications (alkyl = methyl, allyl, benzyl), which were prepared by the reaction of Tm(Me) anion and primary alkyl halides, have been isolated and structurally characterised. The reaction is, however, not universally successful. DFT analysis of these alkylation reactions (C=S versus B-H alkylation) indicates that the observed outcome is driven by kinetic factors. Extending the study to incorporate alternative imine thiones (mercaptobenzothiazole, bz; thiazoline, tz) led to the structural characterisation of di[aquo-μ-aquohydrotris(mercaptobenzothiazolyl)boratosodium], which contains sodium atoms in the κ(3)-S,S,S coordination mode. Alkylation of Na[Tbz] and Na[tzTtz] leads to decomposition resulting in the formation of the simple S-alkylated heterocycles. The analysis of the species involved in these reactions shows an inherent weakness in the B-N bond in soft scorpionates, which has implications for their use in more advanced chemistry. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Process for production of an alkyl methacrylate

    NARCIS (Netherlands)

    Eastham, Graham Ronald; Johnson, David William; Fraaije, Marco; Winter, Remko

    2015-01-01

    A process for the production of an alkyl methacrylate, particularly methyl methacrylate, is provided, in which a Baeyer-Villiger Monooxygenase enzyme is used to convert an alkylisopropenylketone substrate to the relevant alkyl methacrylate by abnormal asymmetric oxygen insertion. The invention

  7. Isobutane alkylation. Recent developments and future perspectives

    Energy Technology Data Exchange (ETDEWEB)

    Hommeltoft, Sven Ivar [Haldor Topsoe A/S, Nymoellevej 55, DK-2800 Lyngby (Denmark)

    2001-11-30

    In the isobutane alkylation, alkylated gasoline is obtained which is a valuable blending component for the gasoline pool. Thereby the C{sub 3}-C{sub 4} cut from the FCC units can be extensively used. Established technologies and recent developments will be reviewed and future perspectives will be given.

  8. Amino acid nitrosation products as alkylating agents.

    Science.gov (United States)

    García-Santos, M del P; Calle, E; Casado, J

    2001-08-08

    Nitrosation reactions of alpha-, beta-, and gamma-amino acids whose reaction products can act as alkylating agents of DNA were investigated. To approach in vivo conditions for the two-step mechanism (nitrosation and alkylation), nitrosation reactions were carried out in aqueous acid conditions (mimicking the conditions of the stomach lumen) while the alkylating potential of the nitrosation products was investigated at neutral pH, as in the stomach lining cells into which such products can diffuse. These conclusions were drawn: (i) The alkylating species resulting from the nitrosation of amino acids with an -NH(2) group are the corresponding lactones; (ii) the sequence of alkylating power is: alpha-lactones > beta-lactones > gamma-lactones, coming respectively from the nitrosation of alpha-, beta-, and gamma-amino acids; and (iii) the results obtained may be useful in predicting the mutagenic effectiveness of the nitrosation products of amino acids.

  9. Spectrographic determination of traces of halogens; Dosage de traces d'halogenes par la methode spectrographique

    Energy Technology Data Exchange (ETDEWEB)

    Melamed, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    Hollow cathode source is employed for determining traces of halogens (fluorine - chlorine) in the uranium oxide U{sub 3}O{sub 8} qualitatively, detection of at least 40 ppm of fluorine, as alkali fluoride and 125 ppm of chlorine, is possible. (author) [French] Un tube a decharge a cathode creuse a ete utilise pour la determination spectrographique des halogenes (fluor - chlore) presentes a l'etat de traces dans un oxyde d'uranium U{sub 3}O{sub 8}. On a pu deceler qualitativement des teneurs de 40 ppm de fluor sous forme de fluorures alcalins. En ce qui concerne le chlore, la plus faible teneur decelee a ete de 125 ppm. (auteur)

  10. Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse.

    Science.gov (United States)

    Agarwal, Vinayak; Miles, Zachary D; Winter, Jaclyn M; Eustáquio, Alessandra S; El Gamal, Abrahim A; Moore, Bradley S

    2017-04-26

    Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

  11. Independent Evolution of Six Families of Halogenating Enzymes.

    Science.gov (United States)

    Xu, Gangming; Wang, Bin-Gui

    2016-01-01

    Halogenated natural products are widespread in the environment, and the halogen atoms are typically vital to their bioactivities. Thus far, six families of halogenating enzymes have been identified: cofactor-free haloperoxidases (HPO), vanadium-dependent haloperoxidases (V-HPO), heme iron-dependent haloperoxidases (HI-HPO), non-heme iron-dependent halogenases (NI-HG), flavin-dependent halogenases (F-HG), and S-adenosyl-L-methionine (SAM)-dependent halogenases (S-HG). However, these halogenating enzymes with similar biological functions but distinct structures might have evolved independently. Phylogenetic and structural analyses suggest that the HPO, V-HPO, HI-HPO, NI-HG, F-HG, and S-HG enzyme families may have evolutionary relationships to the α/β hydrolases, acid phosphatases, peroxidases, chemotaxis phosphatases, oxidoreductases, and SAM hydroxide adenosyltransferases, respectively. These halogenating enzymes have established sequence homology, structural conservation, and mechanistic features within each family. Understanding the distinct evolutionary history of these halogenating enzymes will provide further insights into the study of their catalytic mechanisms and halogenation specificity.

  12. Experimental and computational evidence of halogen bonds involving astatine

    Science.gov (United States)

    Guo, Ning; Maurice, Rémi; Teze, David; Graton, Jérôme; Champion, Julie; Montavon, Gilles; Galland, Nicolas

    2018-03-01

    The importance of halogen bonds—highly directional interactions between an electron-deficient σ-hole moiety in a halogenated compound and an acceptor such as a Lewis base—is being increasingly recognized in a wide variety of fields from biomedicinal chemistry to materials science. The heaviest halogens are known to form stronger halogen bonds, implying that if this trend continues down the periodic table, astatine should exhibit the highest halogen-bond donating ability. This may be mitigated, however, by the relativistic effects undergone by heavy elements, as illustrated by the metallic character of astatine. Here, the occurrence of halogen-bonding interactions involving astatine is experimentally evidenced. The complexation constants of astatine monoiodide with a series of organic ligands in cyclohexane solution were derived from distribution coefficient measurements and supported by relativistic quantum mechanical calculations. Taken together, the results show that astatine indeed behaves as a halogen-bond donor—a stronger one than iodine—owing to its much more electrophilic σ-hole.

  13. Ozone Depletion in Tropospheric Volcanic Plumes: From Halogen-Poor to Halogen-Rich Emissions

    Directory of Open Access Journals (Sweden)

    Tjarda J. Roberts

    2018-02-01

    Full Text Available Volcanic halogen emissions to the troposphere undergo a rapid plume chemistry that destroys ozone. Quantifying the impact of volcanic halogens on tropospheric ozone is challenging, only a few observations exist. This study presents measurements of ozone in volcanic plumes from Kīlauea (HI, USA, a low halogen emitter. The results are combined with published data from high halogen emitters (Mt Etna, Italy; Mt Redoubt, AK, USA to identify controls on plume processes. Ozone was measured during periods of relatively sustained Kīlauea plume exposure, using an Aeroqual instrument deployed alongside Multi-Gas SO2 and H2S sensors. Interferences were accounted for in data post-processing. The volcanic H2S/SO2 molar ratio was quantified as 0.03. At Halema‘uma‘u crater-rim, ozone was close to ambient in the emission plume (at 10 ppmv SO2. Measurements in grounding plume (at 5 ppmv SO2 about 10 km downwind of Pu‘u ‘Ō‘ō showed just slight ozone depletion. These Kīlauea observations contrast with substantial ozone depletion reported at Mt Etna and Mt Redoubt. Analysis of the combined data from these three volcanoes identifies the emitted Br/S as a strong but non-linear control on the rate of ozone depletion. Model simulations of the volcanic plume chemistry highlight that the proportion of HBr converted into reactive bromine is a key control on the efficiency of ozone depletion. This underlines the importance of chemistry in the very near-source plume on the fate and atmospheric impacts of volcanic emissions to the troposphere.

  14. Structural study of some halogen oxyfluorides

    International Nuclear Information System (INIS)

    Tantot, Georges.

    1976-12-01

    Some halogen oxyfluorides are studied from a structural point of view by vibrational spectroscopy and nuclear magnetic resonance. Force constant and molecular orbital calculations are added to the experimental data. The pyramidal shape of ClO 2 F under its three physical states is confirmed. In the gas and liquid phases an intermolecular association is observed. A similar interaction takes place in ClOF 3 . ClO 3 F has only a solid state transition above 10K. The structures of ClO 2 F and KBrO 2 F 2 are partly determined. The theoretical calculations are well correlated with the experimental data. They suggest a major influence of the ligands [fr

  15. Alkylation of organic aromatic compounds

    Science.gov (United States)

    Smith, Jr., Lawrence A.

    1989-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  16. Alkylation of organic aromatic compounds

    Science.gov (United States)

    Smith, L.A. Jr.

    1989-07-18

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  17. UARS Halogen Occultation Experiment (HALOE) Level 2 V001

    Data.gov (United States)

    National Aeronautics and Space Administration — The HALOE home page on the WWW is http://haloe.gats-inc.com/home/index.php The Halogen Occultation Experiment (HALOE) on NASA's Upper Atmosphere Research Satellite...

  18. Investigating the nature of palladium chain-walking in the enantioselective redox-relay Heck reaction of alkenyl alcohols.

    Science.gov (United States)

    Hilton, Margaret J; Xu, Li-Ping; Norrby, Per-Ola; Wu, Yun-Dong; Wiest, Olaf; Sigman, Matthew S

    2014-12-19

    The mechanism of the redox-relay Heck reaction was investigated using deuterium-labeled substrates. Results support a pathway through a low energy palladium-alkyl intermediate that immediately precedes product formation, ruling out a tautomerization mechanism. DFT calculations of the relevant transition structures at the M06/LAN2DZ+f/6-31+G* level of theory show that the former pathway is favored by 5.8 kcal/mol. Palladium chain-walking toward the alcohol, following successive β-hydride eliminations and migratory insertions, is also supported in this study. The stereochemistry of deuterium labels is determined, lending support that the catalyst remains bound to the substrate during the relay process and that both cis- and trans-alkenes form from β-hydride elimination.

  19. Alkylation of N-substituted 2-phenylacetamides

    Directory of Open Access Journals (Sweden)

    SLOBODAN D. PETROVIC

    2004-10-01

    Full Text Available Various N-substituted phenylacetamides were alkylated using different alkylating agents under neutral and basic conditions. Reactions were performed at different reaction temperatures and in various solvents. Also, a number of various catalysts were used including phase-transfer catalysts. Reactions were followed using GC or GC-MS technique and the presence as well as the yields of the alkylation products were established. Generally, the best yield and high selectivity in the studied reactions were achieved under basic conditions where in the certain cases some products, mostly N-product, were obtained solely in quantitative yields.

  20. The alkylation of imine anions formation of enamines

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The ambident anions derived from imines were alkylated using a variety of solvents and alkylating agents. Under reactive conditions enamines (N-alkylation) are formed as the main products instead of the usually obsd. homologous imines (C-alkylation). The influence of the type of imine, solvent, and

  1. Alkylation of enolate anions formation of enol ethers

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The alkylation of ambident enolate anions-obtained from aliphatic ketones (and one particular type of aldehyde)-was studied using various solvents, bases, alkylating agents and substrates. Alkylation with a reactive alkylating agent (dialkyl sulfates, triethyloxonium fluoroborate) in an aprotic

  2. Halogenation dictates the architecture of amyloid peptide nanostructures.

    Science.gov (United States)

    Pizzi, Andrea; Pigliacelli, Claudia; Gori, Alessandro; Nonappa; Ikkala, Olli; Demitri, Nicola; Terraneo, Giancarlo; Castelletto, Valeria; Hamley, Ian W; Baldelli Bombelli, Francesca; Metrangolo, Pierangelo

    2017-07-20

    Amyloid peptides yield a plethora of interesting nanostructures though difficult to control. Here we report that depending on the number, position, and nature of the halogen atoms introduced into either one or both phenylalanine benzene rings of the amyloid β peptide-derived core-sequence KLVFF, four different architectures were obtained in a controlled manner. Our findings demonstrate that halogenation may develop as a general strategy to engineer amyloidal peptide self-assembly and obtain new amyloidal nanostructures.

  3. N-Alkylation Using Sodium Triacetoxyborohydride with Carboxylic Acids as Alkyl Sources.

    Science.gov (United States)

    Tamura, Satoru; Sato, Keigo; Kawano, Tomikazu

    2018-01-01

    A versatile N-alkylation was performed using sodium triacetoxyborohydride and carboxylic acid as an alkyl source. The combination of these reagents furnished products different from those given previously by a similar reaction. Moreover, the mild conditions of our method allowed some functional groups to remain through the reaction, whereas they would react and be converted into other moieties in the similar reductive N-alkylation reported previously. Herein, we provide a new procedure for the preparation of various compounds containing nitrogen atoms.

  4. Alkylation of Zwitterionic Thiooxalic Acid Derivatives

    Directory of Open Access Journals (Sweden)

    Manfred Michalik

    2001-05-01

    Full Text Available The new S-alkyl thiooxal-1-hydrazono-2-amidrazonium halides 2-4 were synthesized by reaction of the corresponding zwitterionic thiooxalic acid derivatives 1 with alkyl halides in methanol. The structures of compounds 4b and 4d were proven by X-ray structural analysis. Both compounds form an interesting intermolecular network of hydrogen bonds in the solid state.

  5. Mechanochemical N-alkylation of imides

    Directory of Open Access Journals (Sweden)

    Anamarija Briš

    2017-08-01

    Full Text Available The mechanochemical N-alkylation of imide derivatives was studied. Reactions under solvent-free conditions in a ball mill gave good yields and could be put in place of the classical solution conditions. The method is general and can be applied to various imides and alkyl halides. Phthalimides prepared under ball milling conditions were used in a mechanochemical Gabriel synthesis of amines by their reaction with 1,2-diaminoethane.

  6. N-Alkylation by Hydrogen Autotransfer Reactions.

    Science.gov (United States)

    Ma, Xiantao; Su, Chenliang; Xu, Qing

    2016-06-01

    Owing to the importance of amine/amide derivatives in all fields of chemistry, and also the green and environmentally benign features of using alcohols as alkylating reagents, the relatively high atom economic dehydrative N-alkylation reactions of amines/amides with alcohols through hydrogen autotransfer processes have received much attention and have developed rapidly in recent decades. Various efficient homogeneous and heterogeneous transition metal catalysts, nano materials, electrochemical methods, biomimetic methods, asymmetric N-alkylation reactions, aerobic oxidative methods, and even certain transition metal-free, catalyst-free, or autocatalyzed methods, have also been developed in recent years. With a brief introduction to the background and developments in this area of research, this chapter focuses mainly on recent progress and technical and conceptual advances contributing to the development of this research in the last decade. In addition to mainstream research on homogeneous and heterogeneous transition metal-catalyzed reactions, possible mechanistic routes for hydrogen transfer and alcohol activation, which are key processes in N-alkylation reactions but seldom discussed in the past, the recent reports on computational mechanistic studies of the N-alkylation reactions, and the newly emerged N-alkylation methods based on novel alcohol activation protocols such as air-promoted reactions and transition metal-free methods, are also reviewed in this chapter. Problems and bottlenecks that remained to be solved in the field, and promising new research that deserves greater future attention and effort, are also reviewed and discussed.

  7. Negative Halogen Ions for Fusion Applications

    International Nuclear Information System (INIS)

    Grisham, L.R.; Kwan, J.W.; Hahto, S.K.; Hahto, S.T.; Leung, K.N.; Westenskow, G.

    2006-01-01

    Over the past quarter century, advances in hydrogen negative ion sources have extended the usable range of hydrogen isotope neutral beams to energies suitable for large magnetically confined fusion devices. Recently, drawing upon this experience, negative halogen ions have been proposed as an alternative to positive ions for heavy ion fusion drivers in inertial confinement fusion, because electron accumulation would be prevented in negative ion beams, and if desired, the beams could be photo-detached to neutrals. This paper reports the results of an experiment comparing the current density and beam emittance of Cl+ and Cl- extracted from substantially ion-ion plasmas with that of Ar+ extracted from an ordinary electron-ion plasma, all using the same source, extractor, and emittance scanner. At similar discharge conditions, the Cl- current was typically 85-90% of the positive chlorine current, with an e-/ Cl- ratio as low as seven without grid magnets. The Cl- was as much as 76% of the Ar+ current from a discharge with the same RF drive. The minimum normalized beam emittance and inferred ion temperatures of Cl+, Cl-, and Ar+ were all similar, so the current density and optical quality of Cl- appear as suitable for heavy ion fusion driver applications as a positive noble gas ion of similar mass. Since F, I, and Br should all behave similarly in an ion source, they should also be suitable as driver beams

  8. The interaction of mercury with halogenated graphene

    Science.gov (United States)

    Kirchofer, Abigail; Sasmaz, Erdem; Wilcox, Jennifer

    2011-03-01

    The interaction of mercury with halogenated graphene was studied using plane-wave density functional theory. Various configurations of H, Hg, O and Br or Cl on the zigzag edge sites of graphene were investigated. Although Hg-Br (or -Cl) complexes were found to be stable on the surface, the most stable configurations found were those with Hg adjacent to O. The surface atoms Hg, O, and Br tend to repel each other during geometric optimization, moving towards an H atom nearest-neighbor where possible. The strength of the Hg-graphene interaction is very sensitive to the local environment. The Hg-graphene binding energy is strongest when the Hg is located next to a surface O but not immediately next to a bound Br. DOS analysis revealed that Hg adsorption involves a gain in Hg 6 p-states and a loss in Hg 5 s electron density, resulting in an oxidized surface-bound Hg complex. DOS analysis suggests that Br strengthens the Hg-graphene interaction by modifying the surface carbon electron density; however, when Br is adjacent to Hg, a direct Hg-Br interaction weakens the Hg-C bond. These investigations provide insight into the mechanism associated with enhanced Hg adsorption on Br-functionalized carbon materials for Hg emissions reductions from coal-fired power plant applications. The authors acknowledge the financial support by Electric Power Research Institute (EPRI).

  9. Molecular design of sequence specific DNA alkylating agents.

    Science.gov (United States)

    Minoshima, Masafumi; Bando, Toshikazu; Shinohara, Ken-ichi; Sugiyama, Hiroshi

    2009-01-01

    Sequence-specific DNA alkylating agents have great interest for novel approach to cancer chemotherapy. We designed the conjugates between pyrrole (Py)-imidazole (Im) polyamides and DNA alkylating chlorambucil moiety possessing at different positions. The sequence-specific DNA alkylation by conjugates was investigated by using high-resolution denaturing polyacrylamide gel electrophoresis (PAGE). The results showed that polyamide chlorambucil conjugates alkylate DNA at flanking adenines in recognition sequences of Py-Im polyamides, however, the reactivities and alkylation sites were influenced by the positions of conjugation. In addition, we synthesized conjugate between Py-Im polyamide and another alkylating agent, 1-(chloromethyl)-5-hydroxy-1,2-dihydro-3H-benz[e]indole (seco-CBI). DNA alkylation reactivies by both alkylating polyamides were almost comparable. In contrast, cytotoxicities against cell lines differed greatly. These comparative studies would promote development of appropriate sequence-specific DNA alkylating polyamides against specific cancer cells.

  10. The scarlet letter of alkylation: a mini review of selective alkylating agents.

    Science.gov (United States)

    Oronsky, Bryan T; Reid, Tony; Knox, Susan J; Scicinski, Jan J

    2012-08-01

    If there were a stigma scale for chemotherapy, alkylating agents would be ranked at the top of the list. The chemical term alkylation is associated with nonselective toxicity, an association that dates back to the use of nitrogen mustards during World War I as chemical warfare agents. That this stigma persists and extends to compounds that, through selectivity, attempt to "tame" the indiscriminate destructive potential of alkylation is the subject of this review. Selective alkylation, as it is referred to herein, constitutes an extremely nascent and dynamic field in oncology. The pharmacodynamic response to this selective strategy depends on a delicate kinetic balance between specificity and the rate and extent of binding. Three representative compounds are presented: RRx-001, 3-bromopyruvate, and TH-302. The main impetus for the development of these compounds has been the avoidance of the serious complications of traditional alkylating agents; therefore, it is the thesis of this review that they should not experience stigma by association.

  11. Alkylation of isobutane with light olefins: Yields of alkylates for different olefins

    Energy Technology Data Exchange (ETDEWEB)

    Albright, L.F. [Purdue Univ., West Lafayette, IN (United States); Kranz, K.E.; Masters, K.R. [STRATCO, Inc., Leawood, KS (United States)

    1993-12-01

    For alkylation of isobutane with C{sub 3}-C{sub 5} olefins using sulfuric acid as the catalyst, the yields of alkylates with different olefins are compared as the operating conditions are changed. The results of recent pilot plant experiments with propylene, C{sub 4} olefins, and C{sub 5} olefins permit such comparisons. The yields expressed as weight of alkylate produced per 100 wt of olefin consumed varied from about 201:100 to 220:100. Weight ratios of the isobutane consumed per olefin consumed vary from about 101:100 to 120:100. differences of yield values are explained by the changes in the overall chemistry. The procedure employed to calculate yields with good accuracy is based on the analysis of the alkylate and the amount of conjunct polymers produced. Based on literature data, yields are also reported for alkylations using HF as the catalyst.

  12. Alkyl phosphonic acids and sulfonic acids in the Murchison meteorite

    Science.gov (United States)

    Cooper, George W.; Onwo, Wilfred M.; Cronin, John R.

    1992-01-01

    Homologous series of alkyl phosphonic acids and alkyl sulfonic acids, along with inorganic orthophosphate and sulfate, are identified in water extracts of the Murchison meteorite after conversion to their t-butyl dimethylsilyl derivatives. The methyl, ethyl, propyl, and butyl compounds are observed in both series. Five of the eight possible alkyl phosphonic acids and seven of the eight possible alkyl sulfonic acids through C4 are identified. Abundances decrease with increasing carbon number as observed of other homologous series indigenous to Murchison. Concentrations range downward from approximately 380 nmol/gram in the alkyl sulfonic acid series, and from 9 nmol/gram in the alkyl phosphonic acid series.

  13. The light activated alkylation of glycine

    International Nuclear Information System (INIS)

    Knowles, H.S.

    2001-04-01

    The work contained in this thesis focuses on the light-initiated alkylation of the α-centre of glycine compounds. The elaboration of the glycines in this manner represents a versatile, clean and cost effective alternative to ionic routes to higher α-amino acids. Preliminary investigations demonstrated that a range of nitrogen protecting groups were compatible with the radical alkylation. A variety of solvents could also be used although solvents with easily removable hydrogen atoms were found to interfere with the alkylation. Furthermore, a number of photo-initiators were investigated and the use of di-tert-butyl peroxide was found to afford the desired phenylalanine products in up to 27% yield (54% based on recovered starting material) when toluene was used as the alkylating agent. A range of different precursor concentrations was investigated and it was found that the optimum concentration of the glycine precursor was 0.13 mol dm -3 ; the phenylalanine yields were reduced when the concentration was less than this value. Owing to the poor UV absorption by di-tert-butyl peroxide, benzophenone (an effective photosensitiser) was added to the reaction mixture and this was shown to increase the alkylation yields. The ratio of reagents which produced the highest yield of phenylalanine products was found to be 1 : 5 : 5 : 10 for glycine : di-tert-butyl peroxide : benzophenone : toluene. This produced the phenylalanine product in up to 37% yield (57% based on recovered starting material). A number of substituents. (e.g. F, Cl etc.) could be attached to the aromatic ring of the toluene alkylating agent, affording substituted phenylalanines in 5 - 36% under these conditions. The formation of chiral phenylalanine products was probed by reacting glycine precursors bearing chiral auxiliaries. However, low diastereoselectivities were observed; the d.r. ranged from 1 : 1.1 to 1 : 1.5 only when chiral ester and amide protecting groups were used. In the final chapter, the α-alkylation

  14. Aryl sulfonate based anticancer alkylating agents.

    Science.gov (United States)

    Sheikh, Hamdullah Khadim; Arshad, Tanzila; Kanwal, Ghazala

    2018-05-01

    This research work revolves around synthesis of antineoplastic alkylating sulfonate esters with dual alkylating sites for crosslinking of the DNA strands. These molecules were evaluated as potential antineoplastic cross linking alkylating agents by reaction with the nucleoside of Guanine DNA nucleobase at both ends of the synthesized molecule. Synthesis of the alkylating molecules and the crosslinking with the guanosine nucleoside was monitored by MALDITOF mass spectroscopy. The synthesized molecule's crosslinking or adduct forming rate with the nucleoside was compared with that of 1,4 butane disulfonate (busulfan), in form of time taken for the appearance of [M+H] + . It was found that aryl sulfonate leaving group was causing higher rate of nucleophilic attack by the Lewis basic site of the nucleobase. Furthermore, the rate was also found to be a function of electron withdrawing or donating nature of the substituent on the aryl ring. Compound with strong electron withdrawing substituent on the para position of the ring reacted fastest. Hence, new alkylating agents were synthesized with optimized or desired reactivity.

  15. Rational design of organic semiconductors for texture control and self-patterning on halogenated surfaces

    KAUST Repository

    Ward, Jeremy W.; Li, Ruipeng; Obaid, Abdulmalik; Payne, Marcia M.; Smilgies, Detlef Matthias; Anthony, John Edward; Amassian, Aram; Jurchescu, Oana D.

    2014-01-01

    new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self-assembled monolayer on the formation of the crystalline texture directly affecting

  16. Determination of halogens by flame emission of metal halogenides

    International Nuclear Information System (INIS)

    Henrion, G.; Marquardt, D.; Stoecker, B.

    1979-01-01

    The A-B systems InF, InCl, InBr, and InI have been excited by laminar H 2 -N 2 flames in order to dermine individual halogens or their mixtures qualitatively or quantitatively. In optimizing the fuel gas composition two different behavior patterns have been found for band intensities, which are correlated with binding energies of InX (X = halogen). The low temperature of the flame leads to complicated matrix effects which first of all result from effects on excitation and from competitive reactions. In general, cations cause a decreased intensity. Therefore, salts have to be converted into hydrohalide acids by ion exchange. Qualitative determinations of individual halogens are possible at a 500 to 50,000fold excess of the others, whereas quantitative determinations can be performed at a 100 to 5,000fold excess in 10 -4 molar solutions with errors of 2 to 10 per cent. (author)

  17. Enantioselective Rhodium-Catalyzed [2+2+2] Cycloadditions of Terminal Alkynes and Alkenyl Isocyanates: Mechanistic Insights Lead to a Unified Model that Rationalizes Product Selectivity

    Science.gov (United States)

    Dalton, Derek M.; Oberg, Kevin M.; Yu, Robert T.; Lee, Ernest E.; Perreault, Stéphane; Oinen, Mark Emil; Pease, Melissa L.; Malik, Guillaume; Rovis, Tomislav

    2009-01-01

    This manuscript describes the development and scope of the asymmetric rhodium-catalyzed [2+2+2] cycloaddition of terminal alkynes and alkenyl isocyanates leading to the formation of indolizidine and quinolizidine scaffolds. The use of phosphoramidite ligands proved crucial for avoiding competitive terminal alkyne dimerization. Both aliphatic and aromatic terminal alkynes participate well, with product selectivity a function of both the steric and electronic character of the alkyne. Manipulation of the phosphoramidite ligand leads to tuning of enantio- and product selectivity, with a complete turnover in product selectivity seen with aliphatic alkynes when moving from Taddol-based to biphenol-based phosphoramidites. Terminal and 1,1-disubstituted olefins are tolerated with nearly equal efficacy. Examination of a series of competition experiments in combination with analysis of reaction outcome shed considerable light on the operative catalytic cycle. Through a detailed study of a series of X-ray structures of rhodium(cod)chloride/phosphoramidite complexes, we have formulated a mechanistic hypothesis that rationalizes the observed product selectivity. PMID:19817441

  18. Synthesis of o-Alkenylated 2-Arylbenzoxazoles via Rh-Catalyzed Oxidative Olefination of 2-Arylbenzoxazoles: Scope Investigation, Structural Features, and Mechanism Studies.

    Science.gov (United States)

    Zhou, Quan; Zhang, Jing-Fan; Cao, Hui; Zhong, Rui; Hou, Xiu-Feng

    2016-12-16

    2-Arylbenzazoles are promising molecules for potential applications in medicine and material areas. Efficient protocols for direct regioselective functionalization of 2-arylbenzoxazoles are in high demand. Herein, we disclose a general method for selective ortho-olefination of 2-arylbenzo[d]oxazoles with alkenes enabled by versatile Cp*Rh(III) in high yields. This protocol features broad functional group tolerance and high regioselectivity. Intermolecular competition studies and kinetic isotope effect experiments imply that the oxidative olefination process occurs via an electrophilic C-H activation pathway. The molecular structure of the m-fluoro-substituted olefination product confirms regioselective C-H activation/olefination at the more hindered site in cases where the meta F atom or heteroatom substituent existed. Apparent torsion angles were observed in the structures of mono- and bis-olefination products, which resulted in distinct different chemical shifts of olefinic protons. Additionally, two gram-scale reactions and further transformation experiments demonstrate that this method is practical for synthesis of ortho-alkenylated 2-arylbenzoxazole derivatives.

  19. Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration.

    Science.gov (United States)

    Grigg, R David; Van Hoveln, Ryan; Schomaker, Jennifer M

    2012-10-03

    A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markovnikov hydrocupration of the o-halostyrene, oxidative addition of the resulting Cu(I) complex into the Ar-X bond, reductive elimination of the new sp(3) C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.

  20. Symmetric and asymmetric halogen-containing metallocarboranylporphyrins and uses thereof

    Science.gov (United States)

    Miura, Michiko; Wu, Haitao

    2013-05-21

    The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity halogenated, carborane-containing 5,10,15,20-tetraphenylporphyrin compounds and methods for their use particularly in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) for the treatment of tumors of the brain, head and neck, and surrounding tissue. The invention is also directed to using these halogenated, carborane-containing tetraphenylporphyrin compounds in methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

  1. Halogens determination in vegetable NBS standard reference materials

    International Nuclear Information System (INIS)

    Stella, R.; Genova, N.; Di Casa, M.

    1977-01-01

    Levels of all four halogens in Orchard Leaves, Pine Needles and Tomato Leaves NBS reference standards were determined. For fluorine a spiking isotope dilution method was used followed by HF absorption on glass beads. Instrumental nuclear activation analysis was adopted for chlorine and bromine determination. Radiochemical separation by a distillation procedure was necessary for iodine nuclear activation analysis after irradiation. Activation parameters of Cl, Br and I are reported. Results of five determinations for each halogen in Orchard Leaves, Pine Needles and Tomato Leaves NBS Standard Materials and Standard deviations of the mean are reported. (T.I.)

  2. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting under...

  3. Outlook for the U.S. alkylation industry

    International Nuclear Information System (INIS)

    Felten, J.R.; Bradshaw, T.; McCarthy, K.

    1994-01-01

    Alkylation has long been recognized in the refining industry as one of the best options to convert refinery olefins into valuable, clean, high octane blending components. In fact, refinery alkylation is a preferred source of blending stocks for reformulated gasoline. However, the hydrofluoric acid (HF) alkylation process and, to a lesser extent, the sulfuric acid (SA) process have come under increasing pressure in the US due to safety and environmental concerns. This paper examines the current outlook for the US alkylation industry including: key trends and driving forces in the industry, the impact of environmental issues on both HF and SA alkylation, US alkylation supply/demand forecast including the outlook for oxygenates, how US refines will respond to the increased demand and restricted supply for alkylates, and the outlook for new solid acid alkylation (SAC) technology

  4. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    Science.gov (United States)

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  5. Orientational diffusion of n-alkyl cyanides

    International Nuclear Information System (INIS)

    Zhu Xiang; Farrer, Richard A; Zhong Qin; Fourkas, John T

    2005-01-01

    Ultrafast optical Kerr effect spectroscopy has been used to study the temperature-dependent orientational dynamics of a series of nitriles with n-alkyl chains ranging from one to 11 carbons in length. In all cases the orientational diffusion is found to be described by a single-exponential decay. Analysis of the orientational correlation times using the Debye-Stokes-Einstein equation suggests that the molecules adopt extended configurations and reorient as rigid rods. The liquids with shorter alkyl chains undergo an apparent ordering transition as they are cooled

  6. Mechanisms of resistance to alkylating agents

    OpenAIRE

    Damia, G.; D‘Incalci, M.

    1998-01-01

    Alkylating agents are the most widely used anticancer drugs whose main target is the DNA, although how exactly the DNA lesions cause cell death is still not clear. The emergence of resistance to this class of drugs as well as to other antitumor agents is one of the major causes of failure of cancer treatment. This paper reviews some of the best characterized mechanisms of resistance to alkylating agents. Pre- and post-target mechanisms are recognized, the former able to limit the formation of...

  7. Graft copolymerization of a series of alkyl acrylates and alkyl methacrylates onto polyethylene

    International Nuclear Information System (INIS)

    Zurakowska-Orszagh, J.; Soerjosoeharto, K.; Busz, W.; Oldziejewski, J.

    1977-01-01

    Graft copolymerization of a series of alkyl acrylates and alkyl methacrylates into polyethylene of Polish production was investigated, using benzoyl peroxide as the initiator as well as preirradiation technique, namely ionizing radiation from a 60 Co γ-source. The effect of α-carbon methyl substituent of methacrylates as well as the influence of the length of alkyl chains in the ester groups of both series of monomers into the grafting process was observed. The ungrafted and some of the grafted polyethylene film obtained was studied by infrared spectrophotometry. (author)

  8. IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

    Science.gov (United States)

    A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

  9. 40 CFR 721.555 - Alkyl amino nitriles (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl amino nitriles (generic). 721... Substances § 721.555 Alkyl amino nitriles (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96...

  10. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for the...

  11. Transition from metal-ligand bonding to halogen bonding involving a metal as halogen acceptor a study of Cu, Ag, Au, Pt, and Hg complexes

    Science.gov (United States)

    Oliveira, Vytor; Cremer, Dieter

    2017-08-01

    Utilizing all-electron Dirac-exact relativistic calculations with the Normalized Elimination of the Small Component (NESC) method and the local vibrational mode approach, the transition from metal-halide to metal halogen bonding is determined for Au-complexes interacting with halogen-donors. The local stretching force constants of the metal-halogen interactions reveal a smooth transition from weak non-covalent halogen bonding to non-classical 3-center-4-electron bonding and finally covalent metal-halide bonding. The strongest halogen bonds are found for dialkylaurates interacting with Cl2 or FCl. Differing trends in the intrinsic halogen-metal bond strength, the binding energy, and the electrostatic potential are explained.

  12. Quantitative estimation of the extent of alkylation of DNA following treatment of mammalian cells with non-radioactive alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Snyder, R.D. (Univ. of Tennessee, Oak Ridge); Regan, J.D.

    1981-01-01

    Alkaline sucrose sedimentation has been used to quantitate phosphotriester formation following treatment of human cells with the monofunctional alkylating agents methyl and ethyl methanesulfonate. These persistent alkaline-labile lesions are not repaired during short-term culture conditions and thus serve as a useful and precise index of the total alkylation of the DNA.Estimates of alkylation by this procedure compare favorably with direct estimates by use of labeled alkylating agents.

  13. Williamson alkylation approach to the synthesis of poly(alkyl vinyl ether) copolymers

    International Nuclear Information System (INIS)

    Markova, D.; Christova, D.; Velichkova, R.

    2008-01-01

    A method for synthesis of poly(alkyl vinyl ether-co-vinyl alcohol) copolymers was developed based on the Williamson's alkylation of poly(vinyl acetate) (PVAc) with alkyl iodides. The influence of the alkylating agent and the reaction conditions on the efficiency of the modification reaction was investigated. The copolymers obtained were characterized by means of 1 H NMR and GPC. It was proved that by applying the proposed method copolymers of different composition and properties containing methyl vinyl ether, ethyl vinyl ether as well as n-butyl vinyl ether units could be prepared. Poly(methyl vinyl ether-co-vinyl alcohol)s of high degree of methylation exhibit sharp temperature response at 38-39 deg C in aqueous solution typical of the so-called smart polymers. (authors)

  14. Development of halogen-free cables for nuclear power plants

    International Nuclear Information System (INIS)

    Yamamoto, Mitsuo; Ito, Kazumi; Yaji, Takeo; Yoshida, Shin; Sakurai, Takako; Matsushita, Shigetoshi.

    1990-01-01

    On the occasion where serious fire accidents were experienced in the past, the need for making flame-retardant wire and cable incombustible took place and has since been generalizing. Various sorts of flame-retardant cables have already been developed and been actually used. From the viewpoint of avoiding the interference with the evacuation and fire-fighting activity in case of fire or the secondary accidents such as corrosion of the distributing panel, etc., the demand for non-halogen flame-retardant cable has rapidly been increasing in recent years in some fields of general industries, because this specific cable would generate the least amount of toxic smoke or corrosive gas even when it should burn. Similar demand has been increasing also for the cable used for nuclear power plants. In this field, earnest desire has been made for the development of non-halogen flame-retardant cable having specific environmental resistance specially required at nuclear power plants in addition to the properties and capacities required in general industries. The authors have continued examinations on the anti-environmental properties of the materials for cable such as long heat resistance, radiation resistance, steam resistance and succeeded in completing various sorts of non-halogen flame-retardant cable for nuclear power plants. In this report, we will introduce various features of the cable we have developed this time as well as the long-term reliability of non-halogen flame-retardant materials. (author)

  15. Development of non-halogen cables for nuclear power stations

    Energy Technology Data Exchange (ETDEWEB)

    Yagyu, Hideki; Yamamoto, Yasuaki; Onishi, Takao (Hitachi Cable, Ltd., Tokyo (Japan))

    1983-12-01

    The non-halogen fire-resistant cables for nuclear power stations which never generate halogen gas, have been developed. The cables comprise the insulator of EP rubber and the sheath of polyolefine containing non-halogen inorganic fire-retardant. The results of the environmental test and fire-resistance test are described. In the environmental test, the cables were subjected to the heating, gamma-irradiation and steam exposure successively, according to IEEE specification 323,383, and subsequently the change in the appearance, tensile strength and electrical performance of the cables was measured. In the fire-resistance test, the vertical tray fire test according to the IEEE specification 383 was adopted, and other tests including the vertical fire test on insulator cores, oxygen index, the generation of corrosive gas, copper mirror corrosion test, gas toxicity test and optical smoke density test were carried out. It became clear that the cables did not generate halogen gas on burning, and brought about reduced toxicity, corrosion and smoke, and that the safety against fire is greatly improved by using the cables.

  16. Polar Flattening and the Strength of Halogen Bonding

    Czech Academy of Sciences Publication Activity Database

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

    2015-01-01

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

  17. Is there theoretical evidence for mutual influence between halogen

    Indian Academy of Sciences (India)

    Based on many-body analysis, two and three-body terms of interaction energies have a positive contribution to the total interaction energy. It was found that the amount of charge transfer in the triads is higher than that in the corresponding dyads. AIM analyses showed that the halogen and pnicogen-hydride bonds in the ...

  18. Benchmark Calculations of Noncovalent Interactions of Halogenated Molecules

    Czech Academy of Sciences Publication Activity Database

    Řezáč, Jan; Riley, Kevin Eugene; Hobza, Pavel

    2012-01-01

    Roč. 8, č. 11 (2012), s. 4285-4292 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : halogenated molecules * noncovalent interactions * benchmark calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.389, year: 2012

  19. Development of non-halogen cables for nuclear power stations

    International Nuclear Information System (INIS)

    Yagyu, Hideki; Yamamoto, Yasuaki; Onishi, Takao

    1983-01-01

    The non-halogen fire-resistant cables for nuclear power stations which never generate halogen gas, have been developed. The cables comprise the insulator of EP rubber and the sheath of polyolefine containing non-halogen inorganic fire-retardant. The results of the environmental test and fire-resistance test are described. In the environmental test, the cables were subjected to the heating, gamma-irradiation and steam exposure successively, according to IEEE specification 323,383, and subsequently the change in the appearance, tensile strength and electrical performance of the cables was measured. In the fire-resistance test, the vertical tray fire test according to the IEEE specification 383 was adopted, and other tests including the vertical fire test on insulator cores, oxygen index, the generation of corrosive gas, copper mirror corrosion test, gas toxicity test and optical smoke density test were carried out. It became clear that the cables did not generate halogen gas on burning, and brought about reduced toxicity, corrosion and smoke, and that the safety against fire is greatly improved by using the cables. (Yoshitake, I.)

  20. Stereoselective Alkylation of Thiacalix[4]arenes

    Czech Academy of Sciences Publication Activity Database

    Himl, M.; Pojarová, M.; Stibor, I.; Sýkora, Jan; Lhoták, P.

    2005-01-01

    Roč. 46, č. 3 (2005), s. 461-464 ISSN 0040-4039 R&D Projects: GA ČR(CZ) GA104/00/1722 Institutional research plan: CEZ:AV0Z40720504 Keywords : calixarene * alkylation * conformations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.477, year: 2005

  1. Polypyrrole Doped with Alkyl Benzene Sulphonates

    DEFF Research Database (Denmark)

    Bay, Lasse; Mogensen, Naja; Skaarup, Steen

    2002-01-01

    The properties of polypyrrole (PPy) are to a large extent determined by the condition of synthesis and especially by the counterion incorporated as dopant during synthesis. In this work, PPy doped with different alkyl benzenesulfonates are compared. The polymer films are prepared by constant curr...

  2. Biodesulfurization of dibenzothiophene and its alkylated derivatives ...

    African Journals Online (AJOL)

    RIPI-S81 is a new dibenzothiophene (DBT)-desulfurizing bacterium, which was isolated by Research Institute of Petroleum Industry in Iran. Resting cells and growing cells of RIPI-S81 was able to convert alkylated dibenzothiophenes (Cx DBTs) to hydroxybiphenyls such that they were almost stoichiometrically accumulated ...

  3. Poly(ethyleneoxide) functionalization through alkylation

    Science.gov (United States)

    Sivanandan, Kulandaivelu; Eitouni, Hany Basam; Li, Yan; Pratt, Russell Clayton

    2015-04-21

    A new and efficient method of functionalizing high molecular weight polymers through alkylation using a metal amide base is described. This novel procedure can also be used to synthesize polymer-based macro-initiators containing radical initiating groups at the chain-ends for synthesis of block copolymers.

  4. Spurious cooperativity in alkylated succinic acids

    Science.gov (United States)

    Ben-Naim, A.

    1998-03-01

    The proton-proton correlation, as measured by the ratio between the second and the first dissociation constants of dibasic acid, is sometimes very large and far beyond what could be explained by electrostatic theories. We propose a novel interpretation of this phenomenon based on the idea of spurious cooperativity. The general theoretical framework underlying the onset of spurious cooperativity is developed first. The basic result is that whenever a binding (or dissociating) two-site (or more) system splits into a mixture of noninterconverting isomers the binding isotherm (or the titration curve) behaves as if it is more negatively cooperative compared with the genuine cooperativities of the individual isomer. The theory is applied to a specific system of α-α' dialkyl succinic acid. It is known that the Meso form of these alkylated derivatives show a normal correlation of the same order of magnitude as in succinic acid. On the other hand, the Racemic form of these alkylated derivatives shows anomalous strong negative correlations when the alkyl groups become large (e.g., isopropyl and tert butyl). It is shown that the theory of spurious cooperativity can explain the different behavior of the Racemic and the Meso forms, as well as the onset of anomalous strong negative correlations when the alkyl groups become large.

  5. Recent developments in isobutane/olefin alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Lercher, J.A.; Feller, A. [Inst. fuer Technische Chemie, Technische Univ. Muenchen (Germany)

    2002-07-01

    The isobutane/alkene alkylation is reviewed with respect to recent process developments based on liquid and solid acid catalysts. A brief overview about the established processes is given followed by the description of new processes based on solid acids under development. (orig.)

  6. Catalytic Asymmetric Alkylation of Aryl Heteroaryl Ketones

    NARCIS (Netherlands)

    Ortiz, Pablo; Harutyunyan, Syuzanna; del Hoyo, Ana

    Tertiary diarylmethanols are highly bioactive structural motifs. A new strategy to access chiral tertiary diarylmethanols through copper-catalyzed direct alkylation of (di)(hetero)aryl ketones by using Grignard reagents was developed. The low reactivity and the similarity of the enantiotopic faces

  7. Mechanisms of action of quinone-containing alkylating agents: DNA alkylation by aziridinylquinones.

    Science.gov (United States)

    Hargreaves, R H; Hartley, J A; Butler, J

    2000-11-01

    Aziridinyl quinones can be activated by cellular reductases eg. DT-diaphorase and cytochrome P450 reductase to form highly reactive DNA alkylating agents. The mechanisms by which this activation and alkylation take place are many and varied. Using clinically relevant and experimental agents this review will describe many of these mechanisms. The agents discussed are Mitomycin C, EO9 and analogues, diaziridinylbenzoquinones and the pyrrolo[1, 2-alpha]benzimidazolequinones.

  8. Bis(trialkylsilyl) peroxides as alkylating agents in the copper-catalyzed selective mono-N-alkylation of primary amides.

    Science.gov (United States)

    Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

    2017-06-13

    The copper-catalyzed selective mono-N-alkylation of primary amides with bis(trialkylsilyl) peroxides as alkylating agents was reported. The results of a mechanistic study suggest that this reaction should proceed via a free radical process that includes the generation of alkyl radicals from bis(trialkylsilyl) peroxides.

  9. Sulfonium Salts as Alkylating Agents for Palladium-Catalyzed Direct Ortho Alkylation of Anilides and Aromatic Ureas.

    Science.gov (United States)

    Simkó, Dániel Cs; Elekes, Péter; Pázmándi, Vivien; Novák, Zoltán

    2018-02-02

    A novel method for the ortho alkylation of acetanilide and aromatic urea derivatives via C-H activation was developed. Alkyl dibenzothiophenium salts are considered to be new reagents for the palladium-catalyzed C-H activation reaction, which enables the transfer of methyl and other alkyl groups from the sulfonium salt to the aniline derivatives under mild catalytic conditions.

  10. Manganese Catalyzed C–H Halogenation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Wei; Groves, John T.

    2015-06-16

    The remarkable aliphatic C–H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon–halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C–H bonds to C–Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L–MnV$=$O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn–F fluorine source, effecting carbon–fluorine bond

  11. Process for reducing halogen impurities in oil products

    Energy Technology Data Exchange (ETDEWEB)

    Basler, F.

    1990-08-14

    Oil products, in particular waste oils, may be efficiently reprocessed according to an economic and technically simple method for removing impurities, notably halogens. In this method, the oil product is treated at temperatures up to about 150{degree}C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof. The oil product obtained in this step is treated at increased temperatures with at least one halogen binding agent. The water and/or solids from the product so treated are separated out. The process of the invention can be carried out in a conventional stripping apparatus. The strong acid used in the first step is preferably selected from sulfurous acid, phosphoric acid, phosphorous acid, and phosphonic acid. The salt of the weak base and strong acid is preferably ammonium sulfate, ammonium bisulfate, ammonium sulfite, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphite, and ammonium phosphonic acid. The second step of the method is preferably a coagulation step in which organic halogen compounds break down into hydrogen halides which are neutralized by the added halogen binding agents. The preferred halogen binding agents are ammonia and/or an organic base. The coagulation is preferably carried out in heat exchangers so that the oil is heated in 3 stages and the oil from each stage is passed through a cascade tower. In the third step, additives may be used to enhance separation of the oil. Experiments are described to illustrate the method of the invention. 1 tab.

  12. E. S. R. studies of halogenated pyrimidines in. gamma. -irradiated alkaline glasses. [Halogenated uracil bases; bromouridine; bromodeoxyuridine

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, L D; Zimbrick, J D [Kansas Univ., Lawrence (USA)

    1975-11-01

    The reactions of mobile electrons (e/sup -//sub m/) and oxygen radical anions (O./sup -/) with halogenated bases and nucleosides have been studied in ..gamma..-irradiated alkaline glasses by e.s.r. and specific halogen-ion electrode techniques. It was shown that electrons react with halogenated uracil bases (XUr where X = Cl, Br, I but not F) by dissociative electron attachment to form uracil-5-yl radicals (U.) and halogen anions. The relative rates of reaction of e/sup -//sub m/ with XUr decreased in the sequence BrUr > ClUr > FUr > IUr. Thermal annealing studies carried out on U. in H/sub 2/O and D/sub 2/O matrices supported the hypothesis that U. in H/sub 2/O hydrates across the 5-6 double bond in the temperature region 135/sup 0/ to 155/sup 0/ K, and deuterates to a much smaller extent in D/sub 2/O at temperatures above 155/sup 0/ K. Studies on bromouridine and bromodeoxyuridine suggested that e/sup -/sub(m) reacts with the base moieties to form U. type radicals which abstract H. from the sugar moieties of adjacent nucleosides.

  13. BF3·Et2O-promoted cleavage of the Csp-Csp2 bond of 2-propynolphenols/anilines: route to C2-alkenylated benzoxazoles and benzimidazoles.

    Science.gov (United States)

    Song, Xian-Rong; Qiu, Yi-Feng; Song, Bo; Hao, Xin-Hua; Han, Ya-Ping; Gao, Pin; Liu, Xue-Yuan; Liang, Yong-Min

    2015-02-20

    A novel BF3·Et2O-promoted tandem reaction of easily prepared 2-propynolphenols/anilines and trimethylsilyl azide is developed to give C2-alkenylated benzoxazoles and benzimidazoles in moderate to good yields. Most reactions could be accomplished in 30 min at room temperature. This tandem process involves a Csp-Csp2 bond cleavage and a C-N bond formation. Moreover, both tertiary and secondary propargylic alcohols with diverse functional groups were tolerated under the mild conditions.

  14. Embryotoxicity induced by alkylating agents. Some methodological aspects of DNA alkylation studies in murine embryos using ethylmethanesulfonate.

    Science.gov (United States)

    Platzek, T; Bochert, G; Rahm, U; Neubert, D

    1987-05-01

    Synthesis and spectroscopic analysis of some alkylated DNA purine bases are described. HPLC separation methods are developed for the determination of DNA alkylation rates in mammalian embryonic tissues. Following treatment of pregnant mice with the ethylating agent ethylmethanesulfonate (EMS), an appreciable amount of alkylation (ethylation and methylation) was found in the nuclear DNA of the embryos during organogenesis. The results are discussed in context of our thesis that a certain amount of DNA alkylation in the embryos is correlated to the teratogenic potential of alkylating agents.

  15. Radioiodination of proteins by reductive alkylation

    International Nuclear Information System (INIS)

    Panuska, J.R.; Parker, C.W.

    1987-01-01

    The use of the aliphatic aldehyde, para-hydroxyphenylacetaldehyde as the reactive moiety in the radioiodination of proteins by reductive alkylation is described. The para-hydroxyphenyl group is radiolabeled with 125 I, reacted through its aliphatic aldehyde group with primary amino groups on proteins to form a reversible Schiff base linkage which can then be stabilized with the mild reducing agent NaCNBH 3 . The introduction of the methylene group between the benzene ring and the aldehyde group increases its reactivity with protein amino groups permitting efficient labeling at low aldehyde concentrations. Using this method, radioiodinated proteins with high specific activity can be produced. The reductive alkylation procedure is advantageous in that the labeling conditions are mild, the reaction is specific for lysyl residues, and the modification of the epsilon-ammonium group of lysine results in ionizable secondary amino groups avoiding major changes in protein charge

  16. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter

    2011-01-01

    are highlighted with emphasis on those leading to C-C bond formation, but where it was deemed necessary for the general understanding of the process closely related C-H oxidations and aminations are also included. It is found that C-H cleavage is most likely achieved by ligand participation which could involve......-H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation...... an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence...

  17. The Scarlet Letter of Alkylation: A Mini Review of Selective Alkylating Agents

    Science.gov (United States)

    Oronsky, Bryan T; Reid, Tony; Knox, Susan J; Scicinski, Jan J

    2012-01-01

    If there were a stigma scale for chemotherapy, alkylating agents would be ranked at the top of the list. The chemical term alkylation is associated with nonselective toxicity, an association that dates back to the use of nitrogen mustards during World War I as chemical warfare agents. That this stigma persists and extends to compounds that, through selectivity, attempt to “tame” the indiscriminate destructive potential of alkylation is the subject of this review. Selective alkylation, as it is referred to herein, constitutes an extremely nascent and dynamic field in oncology. The pharmacodynamic response to this selective strategy depends on a delicate kinetic balance between specificity and the rate and extent of binding. Three representative compounds are presented: RRx-001, 3-bromopyruvate, and TH-302. The main impetus for the development of these compounds has been the avoidance of the serious complications of traditional alkylating agents; therefore, it is the thesis of this review that they should not experience stigma by association. PMID:22937173

  18. Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

    Science.gov (United States)

    Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

    2014-02-05

    The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.

  19. Flue gas corrosion through halogen compounds in fuel gas

    Energy Technology Data Exchange (ETDEWEB)

    Eisenmann, R

    1987-04-01

    The halogens of chlorine and fluorine greatly influence the corrosion speed of metal materials. If small quantities of chlorinated and/or fluorinated hydrocarbons are present in fuel gas like in landfill gas, they must not result in enhanced corrosion of gas appliances. Data from literature and the initial results of tests run by the author indicate that quantities at about 10 mg/cbm (in terms of chlorine) can be assumed not to cause any noticeable acceleration of corrosion speed.

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

    Czech Academy of Sciences Publication Activity Database

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

    2016-01-01

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

  1. Natural elimination of volatile halogenated hydrocarbons from the environment

    Energy Technology Data Exchange (ETDEWEB)

    Harress, H.M.; Grathwohl, P.; Torunski, H.

    1987-01-01

    Recently carried out field investigations of groundwater contaminations with volatile halogenated hydrocarbons have shown evidence of natural elimination of these hazardous substances. This elimination effects is rare and observed in connection with special geological conditions. With regard to some contaminated sites, the following mechanisms for this behaviour are discussed: 1. Stripping by naturally ascending gases. 2. Sorption on soil organic matter. 3. Biodegradation. The so far compiled knowledge allowed to develop further research programmes, which are pursued in various projects.

  2. Allergic contact dermatitis due to highly reactive halogenated compounds

    Energy Technology Data Exchange (ETDEWEB)

    Pickering, F C; Ive, F A

    1983-11-01

    Ten cases of dermatitis in a fine organic chemicals plant are reported. These cases were all due to exposure to chemical compounds with reactive bromine or chlorine atoms. This type of chemical is always extremely irritant, but evidence is put forward to suggest that these cases were the result of allergic sensitization. Chemicals with reactive halogen atoms should always be handled with extreme care and patch testing should be approached with caution.

  3. Structure-Energy Relationships of Halogen Bonds in Proteins.

    Science.gov (United States)

    Scholfield, Matthew R; Ford, Melissa Coates; Carlsson, Anna-Carin C; Butta, Hawera; Mehl, Ryan A; Ho, P Shing

    2017-06-06

    The structures and stabilities of proteins are defined by a series of weak noncovalent electrostatic, van der Waals, and hydrogen bond (HB) interactions. In this study, we have designed and engineered halogen bonds (XBs) site-specifically to study their structure-energy relationship in a model protein, T4 lysozyme. The evidence for XBs is the displacement of the aromatic side chain toward an oxygen acceptor, at distances that are equal to or less than the sums of their respective van der Waals radii, when the hydroxyl substituent of the wild-type tyrosine is replaced by a halogen. In addition, thermal melting studies show that the iodine XB rescues the stabilization energy from an otherwise destabilizing substitution (at an equivalent noninteracting site), indicating that the interaction is also present in solution. Quantum chemical calculations show that the XB complements an HB at this site and that solvent structure must also be considered in trying to design molecular interactions such as XBs into biological systems. A bromine substitution also shows displacement of the side chain, but the distances and geometries do not indicate formation of an XB. Thus, we have dissected the contributions from various noncovalent interactions of halogens introduced into proteins, to drive the application of XBs, particularly in biomolecular design.

  4. First principles study of halogens adsorption on intermetallic surfaces

    International Nuclear Information System (INIS)

    Zhu, Quanxi; Wang, Shao-qing

    2016-01-01

    Graphical abstract: - Highlights: • The linear relation between adsorbates induced work function change and dipole moment change also exists for intermetallic surfaces. • It is just a common linear relationship rather than a directly proportion. • A new weight parameter β is proposed to describe different factors effect on work function shift. - Abstract: Halides are often present at electrochemical environment, they can directly influence the electrode potential or zero charge potential through the induced work-function change. In this work, we focused in particular on the halogen-induced work function change as a function of the coverage of fluorine, chlorine, bromine and iodine on Al_2Au and Al_2Pt (110) surfaces. Results show that the real relation between work function change and dipole moment change for halogens adsorption on intermetallic surfaces is just a common linear relationship rather than a directly proportion. Besides, the different slopes between fitted lines and the theoretical slope employed in pure metal surfaces demonstrating that the halogens adsorption on intermetallic surfaces are more complicated. We also present a weight parameter β to describe different factors effect on work function shift and finally qualify which factor dominates the shift direction.

  5. Development of no halogen incombustible cables for atomic energy

    International Nuclear Information System (INIS)

    Ishii, Nobumasa; Kimura, Hitoshi; Fujimura, Shun-ichi

    1990-01-01

    In upgrading light water reactor technology, it is important to improve the reliability of machinery and equipment, to make regular inspection efficient, to extend the period of continuous operation, to optimize operation cycle and to improve the maintainability of plant facilities. For the cables for nuclear power stations, high incombustibility is required, and at present halogen system incombustible materials are used. Recently the development of no halogen incombustible cables has been advanced, with which the generation of corrosive gas and smoke at the time of fires is slight. In this study, the application of such no halogen incombustible cables to nuclear power stations and the improvement of reliability of the cables were investigated. The cables to be developed are those for electric power, control and instrumentation in BWR plants and insulated electric wires. The required characteristics are incombustibility, no generation of smoke and corrosive gas at the time of fires, radiation resistance and steam resistance in LOCA. The selection of base polymers, metal hydrates and radiation protectors, the evaluation of radiation resistance and steam resistance, the examination of the corrosive and poisonous properties of generated gas and smoke generation and so on are reported. The development was successful. (K.I.)

  6. DNA-directed alkylating ligands as potential antitumor agents: sequence specificity of alkylation by intercalating aniline mustards.

    Science.gov (United States)

    Prakash, A S; Denny, W A; Gourdie, T A; Valu, K K; Woodgate, P D; Wakelin, L P

    1990-10-23

    The sequence preferences for alkylation of a series of novel parasubstituted aniline mustards linked to the DNA-intercalating chromophore 9-aminoacridine by an alkyl chain of variable length were studied by using procedures analogous to Maxam-Gilbert reactions. The compounds alkylate DNA at both guanine and adenine sites. For mustards linked to the acridine by a short alkyl chain through a para O- or S-link group, 5'-GT sequences are the most preferred sites at which N7-guanine alkylation occurs. For analogues with longer chain lengths, the preference of 5'-GT sequences diminishes in favor of N7-adenine alkylation at the complementary 5'-AC sequence. Magnesium ions are shown to selectively inhibit alkylation at the N7 of adenine (in the major groove) by these compounds but not the alkylation at the N3 of adenine (in the minor groove) by the antitumor antibiotic CC-1065. Effects of chromophore variation were also studied by using aniline mustards linked to quinazoline and sterically hindered tert-butyl-9-aminoacridine chromophores. The results demonstrate that in this series of DNA-directed mustards the noncovalent interactions of the carrier chromophores with DNA significantly modify the sequence selectivity of alkylation by the mustard. Relationships between the DNA alkylation patterns of these compounds and their biological activities are discussed.

  7. Distribution of methyl and ethyl adducts following alkylation with monofunctional alkylating agents.

    Science.gov (United States)

    Beranek, D T

    1990-07-01

    Alkylating agents, because of their ability to react directly with DNA either in vitro or in vivo, or following metabolic activation as in the case of the dialkylnitrosamines, have been used extensively in studying the mechanisms of mutagenicity and carcinogenicity. Their occurrence is widespread in the environment and human exposure from natural and pollutant sources is universal. Since most of these chemicals show varying degrees of both carcinogenicity and mutagenicity, and exhibit compound-specific binding patterns, they provide an excellent model for studying molecular dosimetry. Molecular dosimetry defines dose as the number of adducts bound per macromolecule and relates the binding of these adducts to the human mutagenic or carcinogenic response. This review complies DNA alkylation data for both methylating and ethylating agents in a variety of systems and discusses the role these alkylation products plays in molecular mutagenesis.

  8. Manganese-catalyzed Dehydrogenative Alkylation or α-Olefination of Alkyl-N-Heteroaromatics by Alcohols.

    Science.gov (United States)

    Kempe, Rhett; Zhang, Guoying; Irrgang, Torsten; Dietel, Thomas; Kallmeier, Fabian

    2018-05-02

    Catalysis involving earth-abundant transition metals is an option to help save our rare noble metal resources and is especially interesting if novel reactivity or selectivity patterns are observed. We report here on a novel reaction: the dehydrogenative alkylation or α-olefination of alkyl-N-heteroaromatics by alcohols. Manganese complexes developed in our laboratory catalyze the reaction efficiently. Fe and Co complexes stabilized by such ligands are essentially inactive. Hydrogen is liberated during the reaction and bromo or iodo functional groups and olefins can be tolerated. A variety of alkyl-N-heteroaromatics can be functionalized, and benzyl and aliphatic alcohols undergo the reaction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Visible light- and radiation-induced alkylation of pyridine ring with alkanoic acid

    International Nuclear Information System (INIS)

    Sugimori, Akira; Yamada, Tetsuo

    1986-01-01

    Quinoline and 4-methylquinoline are efficiently alkylated with alkanoic acid in the presence of iron(III) sulfate upon visible light-irradiation. Iron(III) sulfate not only accelerates the photoreaction but also increases the yield of alkylation. Gamma-irradiation also brings about the alkylation. In the photo- and radiation-induced alkylation with alkanoic acid, alkyl radicals play important roles. (author)

  10. Halogens are key cofactors in building of collagen IV scaffolds outside the cell.

    Science.gov (United States)

    Brown, Kyle L; Hudson, Billy G; Voziyan, Paul A

    2018-05-01

    The purpose of this review is to highlight recent advances in understanding the molecular assembly of basement membranes, as exemplified by the glomerular basement membrane (GBM) of the kidney filtration apparatus. In particular, an essential role of halogens in the basement membrane formation has been discovered. Extracellular chloride triggers a molecular switch within non collagenous domains of collagen IV that induces protomer oligomerization and scaffold assembly outside the cell. Moreover, bromide is an essential cofactor in enzymatic cross-linking that reinforces the stability of scaffolds. Halogenation and halogen-induced oxidation of the collagen IV scaffold in disease states damage scaffold function. Halogens play an essential role in the formation of collagen IV scaffolds of basement membranes. Pathogenic damage of these scaffolds by halogenation and halogen-induced oxidation is a potential target for therapeutic interventions.

  11. Alkylation damage by lipid electrophiles targets functional protein systems.

    Science.gov (United States)

    Codreanu, Simona G; Ullery, Jody C; Zhu, Jing; Tallman, Keri A; Beavers, William N; Porter, Ned A; Marnett, Lawrence J; Zhang, Bing; Liebler, Daniel C

    2014-03-01

    Protein alkylation by reactive electrophiles contributes to chemical toxicities and oxidative stress, but the functional impact of alkylation damage across proteomes is poorly understood. We used Click chemistry and shotgun proteomics to profile the accumulation of proteome damage in human cells treated with lipid electrophile probes. Protein target profiles revealed three damage susceptibility classes, as well as proteins that were highly resistant to alkylation. Damage occurred selectively across functional protein interaction networks, with the most highly alkylation-susceptible proteins mapping to networks involved in cytoskeletal regulation. Proteins with lower damage susceptibility mapped to networks involved in protein synthesis and turnover and were alkylated only at electrophile concentrations that caused significant toxicity. Hierarchical susceptibility of proteome systems to alkylation may allow cells to survive sublethal damage while protecting critical cell functions.

  12. Alkylation Damage by Lipid Electrophiles Targets Functional Protein Systems*

    Science.gov (United States)

    Codreanu, Simona G.; Ullery, Jody C.; Zhu, Jing; Tallman, Keri A.; Beavers, William N.; Porter, Ned A.; Marnett, Lawrence J.; Zhang, Bing; Liebler, Daniel C.

    2014-01-01

    Protein alkylation by reactive electrophiles contributes to chemical toxicities and oxidative stress, but the functional impact of alkylation damage across proteomes is poorly understood. We used Click chemistry and shotgun proteomics to profile the accumulation of proteome damage in human cells treated with lipid electrophile probes. Protein target profiles revealed three damage susceptibility classes, as well as proteins that were highly resistant to alkylation. Damage occurred selectively across functional protein interaction networks, with the most highly alkylation-susceptible proteins mapping to networks involved in cytoskeletal regulation. Proteins with lower damage susceptibility mapped to networks involved in protein synthesis and turnover and were alkylated only at electrophile concentrations that caused significant toxicity. Hierarchical susceptibility of proteome systems to alkylation may allow cells to survive sublethal damage while protecting critical cell functions. PMID:24429493

  13. A Survey of Electron Impact Cross-Sections for Halogens and Halogen Compounds of Interest to Plasma Processing

    Science.gov (United States)

    Sharma, S. P.; Rao, M. V. V. S.; Arnold, James O. (Technical Monitor)

    1998-01-01

    Published electron impact cross section data on halogens Cl2, F2, and halogen containing compounds such as Cx Fy, HCl, Cx Cly Fz are reviewed and critically evaluated based on the information provided by various researchers. The present work reports data on electron impact excitation, ionization, dissociation, electron attachment, electron detachment, and photo detachment. Elastic scattering cross sections and data on bulk properties such as diffusion coefficients in various background gases are also evaluated. Since some of the cross sectional data is derived from indirect measurements such as drift velocity, care has been taken to reconcile the differences among the reported data with due attention to the measurement technique. In conclusion, the processes with no or very limited amount of data and questionable set of data are identified and recommendation for further research direction is made.

  14. Halogen bond tunability II: the varying roles of electrostatic and dispersion contributions to attraction in halogen bonds

    Czech Academy of Sciences Publication Activity Database

    Riley, Kevin Eugene; Murray, J. S.; Fanfrlík, Jindřich; Řezáč, Jan; Solá, R. J.; Concha, M. C.; Ramos, F. M.; Politzer, P.

    2013-01-01

    Roč. 19, č. 11 (2013), s. 4651-4659 ISSN 1610-2940 R&D Projects: GA ČR GBP208/12/G016 Grant - others:Operational Program Research and Development for Innovations(XE) CZ.1.05/2.1.00/03.0058 Institutional support: RVO:61388963 Keywords : dispersion * electrostatics * halogen bonding * noncovalent interactions Subject RIV: CE - Biochemistry Impact factor: 1.867, year: 2013

  15. Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

    Science.gov (United States)

    Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

    2015-01-01

    A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. A new strategy for aromatic ring alkylation in cylindrocyclophane biosynthesis.

    Science.gov (United States)

    Nakamura, Hitomi; Schultz, Erica E; Balskus, Emily P

    2017-08-01

    Alkylation of aromatic rings with alkyl halides is an important transformation in organic synthesis, yet an enzymatic equivalent is unknown. Here, we report that cylindrocyclophane biosynthesis in Cylindrospermum licheniforme ATCC 29412 involves chlorination of an unactivated carbon center by a novel halogenase, followed by a previously uncharacterized enzymatic dimerization reaction featuring sequential, stereospecific alkylations of resorcinol aromatic rings. Discovery of the enzymatic machinery underlying this unique biosynthetic carbon-carbon bond formation has implications for biocatalysis and metabolic engineering.

  17. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter

    2009-01-01

    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...... for the development of allylic C-H alkylation into a widely applicable methodology, thus providing a means to enhance synthetic efficiency in these reactions....

  18. Possible targets for the aneugenic activity of alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Pellerano, P. [IST-National Institute for Research on Cancer, Genova (Italy); Abbondandolo, A. [Univ. of Genova (Italy); Bonatti, S.; Simili, M. [CNR Institute of Mutagenesis and Differentiation, Pisa (Italy)

    1993-12-31

    Alkylating agents have been of invaluable help in mutation research for half a century. In all tested organisms, they have proved able to induce a large variety of genetic effects, including aneuploidy. Credible molecular models exist to explain the ability of alkylating agents to induce gene mutation and to act as initiators in carcinogenesis as a consequence of DNA alkylation at specific sites. On the contrary, neither the mechanism of aneuploidy induction nor the relevant cellular targets are known.

  19. Development of novel alkylating drugs as anticancer agents.

    Science.gov (United States)

    Izbicka, Elzbieta; Tolcher, Anthony W

    2004-06-01

    Although conventional alkylating drugs have proven efficacy in the treatment of malignancies, the agents themselves are not selective. Therefore, non-specific alkylation of cellular nucleophilic targets may contribute to many of the observed toxic effects. Novel approaches to drug discovery have resulted in candidate agents that are focused on 'soft alkylation'--alkylators with greater target selectivity. This review highlights the discovery of small molecule drugs that bind to DNA with higher selectivity, act in a unique hypoxic tumor environment, or covalently bind specific protein targets overexpressed in cancer, such as topoisomerase II, glutathione transferase pi1, beta-tubulin and histone deacetylase.

  20. Removal of Intermediate Aromatic Halogenated DBPs by Activated Carbon Adsorption: A New Approach to Controlling Halogenated DBPs in Chlorinated Drinking Water.

    Science.gov (United States)

    Jiang, Jingyi; Zhang, Xiangru; Zhu, Xiaohu; Li, Yu

    2017-03-21

    During chlorine disinfection of drinking water, chlorine may react with natural organic matter (NOM) and bromide ion in raw water to generate halogenated disinfection byproducts (DBPs). To mitigate adverse effects from DBP exposure, granular activated carbon (GAC) adsorption has been considered as one of the best available technologies for removing NOM (DBP precursor) in drinking water treatment. Recently, we have found that many aromatic halogenated DBPs form in chlorination, and they act as intermediate DBPs to decompose and form commonly known DBPs including trihalomethanes and haloacetic acids. In this work, we proposed a new approach to controlling drinking water halogenated DBPs by GAC adsorption of intermediate aromatic halogenated DBPs during chlorination, rather than by GAC adsorption of NOM prior to chlorination (i.e., traditional approach). Rapid small-scale column tests were used to simulate GAC adsorption in the new and traditional approaches. Significant reductions of aromatic halogenated DBPs were observed in the effluents with the new approach; the removals of total organic halogen, trihalomethanes, and haloacetic acids by the new approach always exceeded those by the traditional approach; and the effluents with the new approach were considerably less developmentally toxic than those with the traditional approach. Our findings indicate that the new approach is substantially more effective in controlling halogenated DBPs than the traditional approach.

  1. Determination of reaction rate constants for alkylation of 4-(p-nitrobenzyl) pyridine by different alkylating agents.

    Science.gov (United States)

    Walles, S A

    1980-02-01

    The rate constants have been determined for the reaction between some different alkylating agents and 4-(p-nitrobenzyl) pyridine (NBP) in methanol. These constants have been compared with those for alkylation of aniline in water. All the constants were lower in methanol than in water but in different degrees. The rate constants of the different alkylating agents have been calculated at a nucleophilic strength n=2. The genetic risk defined as the degree of alkylation of a nucleophile (n=2) is equivalent to the rate constant kn=2 and the target dose. The dependence of the genetic risk on the rate constant (kn=2) is discussed.

  2. Thermogravimetric studies on alkyl methacrylate polymers and poly(alkyl methacrylate)-grafted polypropylene fibers

    International Nuclear Information System (INIS)

    Hayakawa, Kiyoshi; Taoda, Hiroshi; Kawase, Kaoru; Tazawa, Masato; Yamakita, Hiromi

    1986-01-01

    Thermal behavior of several kinds of poly (alkyl methacrylate) and polypropylene-g-poly (alkyl methacrylate) fibers prepared by γ-irradiation was investigated by thermogravimetric measurements with the intermittent analysis of the gaseous products. The degradation of poly (methyl methacrylate) proceeded according to the deploymerization mechanism reproducing the pristine monomer exclusively. The thermogram in inert atmosphere showed the features of a two-step depolymerization, while in air it showed no such a stepwise decrease with the elevating temperature. The dissolution-precipitation treatment of polymer seemed to affect the decomposition behavior. On other alkyl methacrylate polymers, the thermal decomposition generally proceeded also according to the depolymerization mechanism. But, for instance, at least two kinds of products besides its own monomer were formed from poly (isobutyl methacrylate), and their relative fractions differed with the temperature. Polypropylene-g-poly (alkyl methacrylate) fibers showed lowering of initiation temperature of decomposition with the increase in extent of the grafting, and their initiation temperatures of decomposition in air were lower than those in inert atmosphere. (author)

  3. Hydration of urea and alkylated urea derivatives

    Science.gov (United States)

    Kaatze, Udo

    2018-01-01

    Compressibility data and broadband dielectric spectra of aqueous solutions of urea and some of its alkylated derivatives have been evaluated to yield their numbers Nh of hydration water molecules per molecule of solute. Nh values in a broad range of solute concentrations are discussed and are compared to hydration numbers of other relevant molecules and organic ions. Consistent with previous results, it is found that urea differs from other solutes in its unusually small hydration number, corresponding to just one third of the estimated number of nearest neighbor molecules. This remarkable hydration behavior is explained by the large density φH of hydrogen bonding abilities offered by the urea molecule. In terms of currently discussed models of reorientational motions and allied dynamics in water and related associating liquids, the large density φH causes a relaxation time close to that of undisturbed water with most parts of water encircling the solute. Therefore only a small part of disturbed ("hydration") water is left around each urea molecule. Adding alkyl groups to the basic molecule leads to Nh values which, within the series of n-alkylurea derivatives, progressively increase with the number of methyl groups per solute. With n-butylurea, Nh from dielectric spectra, in conformity with many other organic solutes, slightly exceeds the number of nearest neighbors. Compared to such Nh values, hydration numbers from compressibility data are substantially smaller, disclosing incorrect assumptions in the formula commonly used to interpret the experimental compressibilities. Similar to other series of organic solutes, effects of isomerization have been found with alkylated urea derivatives, indicating that factors other than the predominating density φH of hydrogen bond abilities contribute also to the hydration properties.

  4. New di:thiophosphite, di:thiophosphate, thio:phosphoramidite and thio:phosphonite compounds - are intermediates for synthesis of oligo- and poly-nucleotide(s) having phosphorothioate linkages

    DEFF Research Database (Denmark)

    1997-01-01

    , halogen, SH, amino, azido or WR2; B = a nucleoside or deoxynucleoside base; W = O, S or N; X = NR6R7; R2, R4 = blocking groups; and R5-R9 = alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, cycloalkenyl, aralkenyl, aralkynyl or cycloalkynyl (all containing up to 20C and optionally being...... agents; for treatment of tumours, viral and bacterial infections; for targeting to deliver drugs, metal ions, toxins or intercalating agents to specific cell and tissue sites; and, by attachment to a label (e.g. a fluorophore, antigen, antibody, protein or metal ion), for the diagnosis of diseases...

  5. Sorbate-nitrite interactions: acetonitrile oxide as an alkylating agent.

    Science.gov (United States)

    Pérez-Prior, M Teresa; Gómez-Bombarelli, Rafael; González-Pérez, Marina; Manso, José A; García-Santos, M Pilar; Calle, Emilio; Casado, Julio

    2009-07-01

    Because chemical species with DNA-damaging and mutagenic activity are formed in sorbate-nitrite mixtures and because sorbic acid sometimes coexists with nitrite occurring naturally or incorporated as a food additive, the study of sorbate-nitrite interactions is important. Here, the alkylating potential of the products resulting from such interactions was investigated. Drawn were the following conclusions: (i) Acetonitrile oxide (ACNO) is the compound responsible for the alkylating capacity of sorbate-nitrite mixtures; (ii) ACNO alkylates 4-(p-nitrobenzyl)pyridine (NBP), a trap for alkylating agents with nucleophilic characteristics similar to those of DNA bases, forming an adduct (AD; epsilon = 1.4 x 10(4) M(-1) cm(-1); lambda = 519 nm); (iii) the NBP alkylation reaction complies with the rate equation, r = d[AD]/dt = k(alk)(ACNO)[ACNO][NBP]-k(hyd)(AD)[AD], k(alk)(ACNO) being the NBP alkylation rate constant for ACNO and k(hyd)(AD) the rate constant for the adduct hydrolysis reaction; (iv) the small fraction of ACNO forming the adduct with NBP, as well as the small magnitude of the quotient (k(alk) (ACNO)/k(hyd)(ACNO)) as compared with those reported for other alkylating agents, such as some lactones and N-alkyl-N-nitrosoureas, reveals the ACNO effective alkylating capacity to be less significant; (v) the low value of the NBP-ACNO adduct life (defined as the total amount of adduct present along the progression of the NBP alkylation per unit of alkylating agent concentration) points to the high instability of this adduct; and (vi) the obtained results are in accordance with the low carcinogenicity of ACNO.

  6. Direct, Regioselective N-Alkylation of 1,3-Azoles.

    Science.gov (United States)

    Chen, Shuai; Graceffa, Russell F; Boezio, Alessandro A

    2016-01-04

    Regioselective N-alkylation of 1,3-azoles is a valuable transformation. Organomagnesium reagents were discovered to be competent bases to affect regioselective alkylation of various 1,3-azoles. Counterintuitively, substitution selectively occurred at the more sterically hindered nitrogen atom. Numerous examples are provided, on varying 1,3-azole scaffolds, with yields ranging from 25 to 95%.

  7. Alkylation of hydrothiophosphoryl compounds in conditions of interphase catalysis

    International Nuclear Information System (INIS)

    Aladzheva, I.M.; Odinets, I.L.; Petrovskij, P.V.; Mastryukova, T.A.; Kabachkin, M.I.

    1993-01-01

    A method of interphase catalysis permitted to develop a common method for synthesis of compounds with thiophosphoryl group. The effect of nature of hydrothiophosphoryl compound, alkylating agent, two-phase system and reaction conditions on alkylation product yields was investigated in detail

  8. Oxidative Umpolung α‐Alkylation of Ketones

    DEFF Research Database (Denmark)

    Shneider, O. Svetlana; Pisarevsky, Evgeni; Fristrup, Peter

    2015-01-01

    We disclose a hypervalent iodine mediated α-alkylative umpolung reaction of carbonyl compounds with dialkylzinc as the alkyl source. The reaction is applicable to all common classes of ketones including 1,3-dicarbonyl compounds and regular ketones via their lithium enolates. The α...

  9. Cellular effects of halogen blue light from dental curing unit

    International Nuclear Information System (INIS)

    Trosic, I.; Pavicic, I.; Jukic, S.

    2008-01-01

    Full text: Halogen curing lights are the most frequently used polymerization source in dental offices. Light-cured bonding systems have become increasingly popular among clinicians because they offer a number of advantages over self-cured adhesives. The effort to increase polymerization quality releases the commercially available high power light density dental curing units. Emitted visible blue light belongs to the range of nonionizing radiation. Common concern in both, patients and dentist grows with regard to the unfavorable effects on the pulp tissue. The aim of study was to evaluate the time and dose dependence effect of halogen light curing unit (Elipar TriLight, ESPE Dental AG, Germany) at the disposed condition modes in vitro. A quartz-tungsten-halogen light source emits radiation of the wavelengths between 400 and 515 nm. This halogen blue light source operates in the three illumination modes, medium (M), exponential (E) and standard (S), and five illumination times. The total irradiance or the light intensity was measured by the light intensity control area on the control panel of device and mean light intensity given by manufacturer was 800 m W/cm 2 . Continuous culture of V79 cells was illuminated in triplicate. The influence of medium mode (M), exponential (E) and standard (S) illumination during 20, 40 and 80 sec on the cell viability, colony forming ability and proliferation of V79 cell culture was investigated. Trypan blue exclusion test was used to determine cell viability, both, in the treated and control cell samples. Colony forming ability was assessed for each exposure time and mode by colony count on post-exposure day 7. Cell proliferation was determined by cell counts for each time and mode of exposure during five post-exposure days. Statistical difference were determined at p<0.05 (Statistica 7.0, StatSoft Inc., USA). Viability of cells was not affected by blue light in view of exposure time and modes. Regardless to exposure or illumination

  10. Preparation of trialkylindium by alkylation of metallic indium

    International Nuclear Information System (INIS)

    Eremeev, I.V.; Danov, S.M.; Sakhipov, V.R.

    1995-01-01

    The investigation results on production of trialkyl indium by alkylation of metallic indium are presented. In contradistinction to the known techniques for the production of trialkyls on indium by alkylation it is suggested to separate the synthesis into two steps. At the first step indium is alkylated by alkylhalide to alkyl indium halide, and at the second alkylation is carried out using. Grignard reagent. The techniques for preparation of trimethyl- and triethylindium, developed on the bases of this scheme, are noted for good reproducibility, allow to preclude, agglomeration of indium during the synthesis, as well as to reduce the consumption coefficients, and amounts, of the introduced starting reagents, i.e. magnesium and alkylhalide. Refs. 16

  11. Nanostructured poly(benzimidazole membranes by N-alkylation

    Directory of Open Access Journals (Sweden)

    J. Weber

    2014-01-01

    Full Text Available Modification of poly(benzimidazole (PBI by N-alkylation leads to polymers capable of undergoing microphase separation. Polymers with different amounts of C18 alkyl chains have been prepared. The polymers were analyzed by spectroscopy, thermal analysis, electron microscopy and X-ray scattering. The impact of the amount of alkyl chains on the observed microphase separation was analyzed. Membranes prepared from the polymers do show microphase separation, as evidenced by scattering experiments. While no clear morphology could be derived for the domains in the native state, evidence for the formation of lamellar morphologies upon doping with phosphoric acid is provided. Finally, the proton conductivity of alkyl-modified PBI is compared with that of pure PBI, showing that the introduction of alkyl side chains does not result in significant conductivity changes.

  12. Tuning the viscosity of halogen free bulk heterojunction inks for inkjet printed organic solar cells

    NARCIS (Netherlands)

    Lamont, C.A.; Eggenhuisen, T.M.; Coenen, M.J.J.; Slaats, T.W.L.; Andriessen, R.; Groen, P.

    2015-01-01

    For the solution processing of organic photovoltaics on an industrial scale, the exclusion of halogenated solvents is a necessity. However, the limited solubility of most semiconducting polymer/fullerene blends in non-halogenated solvents results in ink formulations with low viscosities which poses

  13. Impact of enhanced ozone deposition and halogen chemistry on tropospheric ozone over the Northern Hemisphere

    Science.gov (United States)

    Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen ch...

  14. UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Sehested, J.

    1994-01-01

    Alkyl and alkyl peroxy radicals from 1-butyl alcohol (TBA), HOC (CH3)2CH2. and HOC(CH3)2CH2O2. have been studied in the ps phase at 298 K. Two techniques were used: pulse radiolysis UV absorption to measure the spectra and kinetics, and long path-length Fourier transform infrared spectroscopy (FTIR...

  15. Alkylation of terminal alkynes with transient σ-alkylpalladium(II) complexes: a carboalkynylation route to alkyl-substituted alkynes.

    Science.gov (United States)

    Zhou, Ming-Bo; Huang, Xiao-Cheng; Liu, Yan-Yun; Song, Ren-Jie; Li, Jin-Heng

    2014-02-10

    A mild and general alkylation of terminal alkynes with transient σ-alkylpalladium(II) complexes for assembling alkyl-substituted alkynes is described. This method represents a new way to the use of transient σ-alkylpalladium(II) complexes in organic synthesis through 1,2-carboalkynylation of alkenes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Cu(I)-Catalyzed Enantioselective Friedel-Crafts Alkylation of Indoles with 2-Aryl-N-sulfonylaziridines as Alkylating Agents.

    Science.gov (United States)

    Ge, Chen; Liu, Ren-Rong; Gao, Jian-Rong; Jia, Yi-Xia

    2016-07-01

    A highly enantioselective Friedel-Crafts alkylation of indoles with N-sulfonylaziridines as alkylating agents has been developed by utilizing the complex of Cu(CH3CN)4BF4/(S)-Segphos as a catalyst. A range of optically active tryptamine derivatives are obtained in good to excellent yields and enantioselectivities (up to >99% ee) via a kinetic resolution process.

  17. Selective C-H Halogenation with a Highly Fluorinated Manganese Porphyrin.

    Science.gov (United States)

    Li, Gang; Dilger, Andrew K; Cheng, Peter T; Ewing, William R; Groves, John T

    2018-01-26

    The selective C-H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C-H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-Mn V species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Special features of self-compensation of halogen donor action in lead telluride

    International Nuclear Information System (INIS)

    Kajdanov, V.I.; Nemov, S.A.; Ravich, Yu.I.; Dereza, A.Yu.

    1985-01-01

    Specific features of self-compensation of halogen donor action in lead telluride are investigasted. Lead telluride samples with chlorine additions (with tellurium excess) and, besides, with bromine- and iodine additions were studied in order to reveal general regularities in alloyind with all halogen donor impurities. Experimental dependences of the difference between the electron and hole concentrations (n-p) in PbTe as a function of an amount of introduced halogen impurities (Ni) are presented for samples with a maximum compensation at 295 K. General features of the n-p=f(Ni) dependence are presented for all halogens. The hypothesis on the kinetic mechanism of increasing the efficiency of self-compensation of halogen donor action in lead telluride is suggested

  19. Retention efficiencies of halogenated and non-halogenated hydrocarbons in selected wetland ecosystem in Lake Victoria Basin

    Directory of Open Access Journals (Sweden)

    Shadrack Mule

    2015-06-01

    Full Text Available The determination of retention efficiencies of halogenated and non-halogenated hydrocarbon in selected wetland ecosystems in Lake Victoria basin was carried out. Qualitative and quantitative determination of the presence of residual hydrocarbons in Kigwal/Kimondi, Nyando and Nzoia wetland ecosystems using Gas Chromatography - Mass Spectrometer (GC-MS instrument indicated the presence of residual organochlorines, organophosphorus, carbamates and synthetic pyrethroid hydrocarbons in water, sediment and plant materials. In order to compare the retention efficiencies of the wetlands, the wetland ecosystems were divided into three different sections, namely: inlet, mid and outlet. Calculations of mass balances of residual halogenated and non-halogenated hydrocarbons at the respective sections was done taking into account the partition of the studied compounds in samples of water, sediments and papyrus reed plant materials and analyzed using validated Gas Chromatography - Mass Spectrometer (GC-MS method. From the analysis, several residual hydrocarbons namely: bendiocarb, benzene hexachloride (BHC, carbaryl, cypermethrin, decis, deltamethrin, diazinon, dieldrin, DDT, DDD, DDE, malathion, propoxur, sumithion, 5-phenylrhodanine, 1,3,5-trichlorobenzene, 1-(2-phenoxybenzylhydrazine were detected and quantified. The levels of the selected residual hydrocarbons in water samples were used to calculate the retention efficiencies of a specific hydrocarbon and the values recorded. Generally, River Nyando wetland recorded mean percentage retention efficiencies of 76 and 94% for dry and rainy seasons respectively; Kigwal/Kimondi wetland had seasonal mean percentage retention efficiencies of 63 to 78%. River Nzoia also had calculated seasonal mean percentage retention efficiencies of between 56 to 88%. Dry season had lower mean percentages retention efficiencies as compared to rainy season in the three wetlands of interest during the period of study. The study

  20. Long-term Studies of Marine Halogen Release

    Science.gov (United States)

    Tschritter, J.; Holla, R.; Frieß, U.; Platt, U.

    2009-04-01

    Institute of Enviromental Physics, Heidelberg, Germany. Long term measurements of atmospheric trace gases using multi-axis DOAS instruments are pursued at the new SOLAS observatory on the island of Sao Vicente, (Cape Verde). This research is part of the SOPRAN (Surface Ocean Processes in the ANthropocene) project (Fördernummer:03F0462F). Reactive halogen species (RHS) such as bromine- and iodine- containing species play major roles in the chemistry of ozone in both the troposphere and lower stratosphere and thus possibly influence the ozone budget on a global scale. In addition iodine-species emitted from the ocean surface have been shown to be responsible for the production of new atmospheric particles in the marine boundary layer. This may have an effect on cloud formation and radiation transfer on local and global scales. Long term measurements of RHS abundances will help to identify their key regions and processes for formation. A new long term Multi-MAX-DOAS instrument has been installed at the SOLAS observatory on the island of Sao Vicente, (Cape Verde). The main focus of these unique measurements is the investigation of reactive halogen chemistry in the subtropical marine boundary layer based on measurements of BrO, IO, and possibly OIO. Because of its wide spectral range also the use for O4-retrievals to gain aerosol profiles is possible. IO has been detected with mixing ratios up to 1.3 ppt. For BrO an upper limit of 2 ppt could be determined.

  1. Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts

    DEFF Research Database (Denmark)

    Khokarale, Santosh Govind; He, Jian; Schill, Leonhard

    2018-01-01

    Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) was performed with various base-metal supported catalysts. A high yield of 77 % MP was obtained with bimetallic Fe-Ni/ZrO2 in methanol at 220 °C and 50 bar H2 . A synergistic effect of Ni increased the yield of MP...... of the material. Interestingly, it was observed that Fe-Ni/ZrO2 also effectively catalyzed methanol reforming to produce H2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N2 instead of H2. Fe-Ni/ZrO2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl...

  2. Cytotoxicity of Poly(Alkyl Cyanoacrylate Nanoparticles

    Directory of Open Access Journals (Sweden)

    Einar Sulheim

    2017-11-01

    Full Text Available Although nanotoxicology has become a large research field, assessment of cytotoxicity is often reduced to analysis of one cell line only. Cytotoxicity of nanoparticles is complex and should, preferentially, be evaluated in several cell lines with different methods and on multiple nanoparticle batches. Here we report the toxicity of poly(alkyl cyanoacrylate nanoparticles in 12 different cell lines after synthesizing and analyzing 19 different nanoparticle batches and report that large variations were obtained when using different cell lines or various toxicity assays. Surprisingly, we found that nanoparticles with intermediate degradation rates were less toxic than particles that were degraded faster or more slowly in a cell-free system. The toxicity did not vary significantly with either the three different combinations of polyethylene glycol surfactants or with particle size (range 100–200 nm. No acute pro- or anti-inflammatory activity on cells in whole blood was observed.

  3. Optimization of the alkyl side chain length of fluorine-18-labeled 7α-alkyl-fluoroestradiol

    International Nuclear Information System (INIS)

    Okamoto, Mayumi; Shibayama, Hiromitsu; Naka, Kyosuke; Kitagawa, Yuya; Ishiwata, Kiichi; Shimizu, Isao; Toyohara, Jun

    2016-01-01

    Introduction: Several lines of evidence suggest that 7α-substituted estradiol derivatives bind to the estrogen receptor (ER). In line with this hypothesis, we designed and synthesized 18 F-labeled 7α-fluoroalkylestradiol (Cn-7α-[ 18 F]FES) derivatives as molecular probes for visualizing ERs. Previously, we successfully synthesized 7α-(3-[ 18 F]fluoropropyl)estradiol (C3-7α-[ 18 F]FES) and showed promising results for quantification of ER density in vivo, although extensive metabolism was observed in rodents. Therefore, optimization of the alkyl side chain length is needed to obtain suitable radioligands based on Cn-7α-substituted estradiol pharmacophores. Methods: We synthesized fluoromethyl (23; C1-7α-[ 18 F]FES) to fluorohexyl (26; C6-7α-[ 18 F]FES) derivatives, except fluoropropyl (C3-7α-[ 18 F]FES) and fluoropentyl derivatives (C5-7α-[ 18 F]FES), which have been previously synthesized. In vitro binding to the α-subtype (ERα) isoform of ERs and in vivo biodistribution studies in mature female mice were carried out. Results: The in vitro IC 50 value of Cn-7α-FES tended to gradually decrease depending on the alkyl side chain length. C1-7α-[ 18 F]FES (23) showed the highest uptake in ER-rich tissues such as the uterus. Uterus uptake also gradually decreased depending on the alkyl side chain length. As a result, in vivo uterus uptake reflected the in vitro ERα affinity of each compound. Bone uptake, which indicates de-fluorination, was marked in 7α-(2-[ 18 F]fluoroethyl)estradiol (C2-7α-[ 18 F]FES) (24) and 7α-(4-[ 18 F]fluorobutyl)estradiol (C4-7α-[ 18 F]FES) (25) derivatives. However, C1-7α-[ 18 F]FES (23) and C6-7α-[ 18 F]FES (26) showed limited uptake in bone. As a result, in vivo bone uptake (de-fluorination) showed a bell-shaped pattern, depending on the alkyl side chain length. C1-7α-[ 18 F]FES (23) showed the same levels of uptake in uterus and bone compared with those of 16α-[ 18 F]fluoro-17β-estradiol. Conclusions: The optimal alkyl

  4. An adaptive response to alkylating agents in Aspergillus nidulans.

    Science.gov (United States)

    Hooley, P; Shawcross, S G; Strike, P

    1988-11-01

    A simple method is described for demonstrating adaptation to alkylation damage in Aspergillus nidulans. One wild type, two MNNG-sensitive, and one MNNG-resistant strain all showed improvement in colony growth when challenged with MNNG following appropriate inducing pretreatments. Other alkylating agents (MMS, EMS) could also adapt mycelium to later MNNG challenge, while 4NQO and UV could not. The inducible effect was not transmissible through conidia. A standard reversion assay based upon methG proved impractical for studying mutation frequencies during alkylation treatments owing to variations in MNNG resistance amongst revertants.

  5. A yeast mutant specifically sensitive to bifunctional alkylation

    International Nuclear Information System (INIS)

    Ruhland, A.; Kircher, M.; Wilborn, F.; Brendel, M.

    1981-01-01

    A mutation that specifically confers sensitivity to bi- and tri-functional alkylating agents is presented. No or little cross-sensitivity to radiation or monofunctional agents could be detected. Sensitivity does not seem to be due to preferential alkylation of mutant DNA as parent and mutant strain exhibit the same amount of DNA alkylation and the same pattern of DNA lesions including interstrand crosslinks. The mutation is due to a defect in a nuclear gene which has been designated SNM1 (sensitive to nitrogen mustard); it may control an important step in the repair of DNA interstrand crosslinks (orig.(AJ)

  6. Participation of the Halogens in Photochemical Reactions in Natural and Treated Waters

    Directory of Open Access Journals (Sweden)

    Yi Yang

    2017-10-01

    Full Text Available Halide ions are ubiquitous in natural waters and wastewaters. Halogens play an important and complex role in environmental photochemical processes and in reactions taking place during photochemical water treatment. While inert to solar wavelengths, halides can be converted into radical and non-radical reactive halogen species (RHS by sensitized photolysis and by reactions with secondary reactive oxygen species (ROS produced through sunlight-initiated reactions in water and atmospheric aerosols, such as hydroxyl radical, ozone, and nitrate radical. In photochemical advanced oxidation processes for water treatment, RHS can be generated by UV photolysis and by reactions of halides with hydroxyl radicals, sulfate radicals, ozone, and other ROS. RHS are reactive toward organic compounds, and some reactions lead to incorporation of halogen into byproducts. Recent studies indicate that halides, or the RHS derived from them, affect the concentrations of photogenerated reactive oxygen species (ROS and other reactive species; influence the photobleaching of dissolved natural organic matter (DOM; alter the rates and products of pollutant transformations; lead to covalent incorporation of halogen into small natural molecules, DOM, and pollutants; and give rise to certain halogen oxides of concern as water contaminants. The complex and colorful chemistry of halogen in waters will be summarized in detail and the implications of this chemistry for global biogeochemical cycling of halogen, contaminant fate in natural waters, and water purification technologies will be discussed.

  7. Influence of Halogen Substituents on the Catalytic Oxidation of 2,4,6-Halogenated Phenols by Fe(III-Tetrakis(p-hydroxyphenyl porphyrins and Potassium Monopersulfate

    Directory of Open Access Journals (Sweden)

    Seiya Nagao

    2011-12-01

    Full Text Available The influence of halogen substituents on the catalytic oxidation of 2,4,6-trihalogenated phenols (TrXPs by iron(III-porphyrin/KHSO5 catalytic systems was investigated. Iron(III-5,10,15,20-tetrakis(p-hydroxyphenylporphyrin (FeTHP and its supported variants were employed, where the supported catalysts were synthesized by introducing FeTHP into hydroquinone-derived humic acids via formaldehyde poly-condensation. F (TrFP, Cl (TrCP, Br (TrBP and I (TrIP were examined as halogen substituents for TrXPs. Although the supported catalysts significantly enhanced the degradation and dehalogenation of TrFP and TrCP, the oxidation of TrBP and TrIP was not enhanced, compared to the FeTHP catalytic system. These results indicate that the degree of oxidation of TrXPs is strongly dependent on the types of halogen substituent. The order of dehalogenation levels for halogen substituents in TrXPs was F > Cl > Br > I, consistent with their order of electronegativity. The electronegativity of a halogen substituent affects the nucleophilicity of the carbon to which it is attached. The levels of oxidation products in the reaction mixtures were analyzed by GC/MS after extraction with n-hexane. The most abundant dimer product from TrFP via 2,6-difluoroquinone is consistent with a scenario where TrXP, with a more electronegative halogen substituent, is readily oxidized, while less electronegative halogen substituents are oxidized less readily by iron(III-porphyrin/KHSO5 catalytic systems.

  8. The unique role of halogen substituents in the design of modern agrochemicals.

    Science.gov (United States)

    Jeschke, Peter

    2010-01-01

    The past 30 years have witnessed a period of significant expansion in the use of halogenated compounds in the field of agrochemical research and development. The introduction of halogens into active ingredients has become an important concept in the quest for a modern agrochemical with optimal efficacy, environmental safety, user friendliness and economic viability. Outstanding progress has been made, especially in synthetic methods for particular halogen-substituted key intermediates that were previously prohibitively expensive. Interestingly, there has been a rise in the number of commercial products containing 'mixed' halogens, e.g. one or more fluorine, chlorine, bromine or iodine atoms in addition to one or more further halogen atoms. Extrapolation of the current trend indicates that a definite growth is to be expected in fluorine-substituted agrochemicals throughout the twenty-first century. A number of these recently developed agrochemical candidates containing halogen substituents represent novel classes of chemical compounds with new modes of action. However, the complex structure-activity relationships associated with biologically active molecules mean that the introduction of halogens can lead to either an increase or a decrease in the efficacy of a compound, depending on its changed mode of action, physicochemical properties, target interaction or metabolic susceptibility and transformation. In spite of modern design concepts, it is still difficult to predict the sites in a molecule at which halogen substitution will result in optimal desired effects. This review describes comprehensively the successful utilisation of halogens and their unique role in the design of modern agrochemicals, exemplified by various commercial products from Bayer CropScience coming from different agrochemical areas.

  9. Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines.

    Science.gov (United States)

    Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

    2017-07-06

    The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Digital solar edge tracker for the Halogen Occultation Experiment

    Science.gov (United States)

    Mauldin, L. E., III; Moore, A. S.; Stump, C. W.; Mayo, L. S.

    1987-01-01

    The optical and electronic design of the Halogen Occultation Experiment (Haloe) elevation sun sensor is described. The Haloe instrument is a gas-correlation radiometer now being developed at NASA Langley for the Upper Atmosphere Research Satellite. The system uses a Galilean telescope to form a solar image on a linear silicon photodiode array. The array is a self-scanned monolithic CCD. The addresses of both solar edges imaged on the array are used by the control/pointing system to scan the Haloe science instantaneous field of view (IFOV) across the vertical solar diameter during instrument calibration and then to maintain the science IFOV 4 arcmin below the top edge during the science data occultation event. Vertical resolution of 16 arcsec and a radiometric dynamic range of 100 are achieved at the 700-nm operating wavelength. The design provides for loss of individual photodiode elements without loss of angular tracking capability.

  11. Microwave assisted pyrolysis of halogenated plastics recovered from waste computers.

    Science.gov (United States)

    Rosi, Luca; Bartoli, Mattia; Frediani, Marco

    2018-03-01

    Microwave Assisted Pyrolysis (MAP) of the plastic fraction of Waste from Electric and Electronic Equipment (WEEE) from end-life computers was run with different absorbers and set-ups in a multimode batch reactor. A large amount of various different liquid fractions (up to 76.6wt%) were formed together with a remarkable reduction of the solid residue (up to 14.2wt%). The liquid fractions were characterized using the following different techniques: FT-IR ATR, 1 H NMR and a quantitative GC-MS analysis. The liquid fractions showed low density and viscosity, together with a high concentration of useful chemicals such as styrene (up to 117.7mg/mL), xylenes (up to 25.6mg/mL for p-xylene) whereas halogenated compounds were absent or present in a very low amounts. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Use of pyrrole black in zinc-halogen batteries

    Energy Technology Data Exchange (ETDEWEB)

    Mengoli, G.; Musiani, M.M.; Tomat, R.; Valcher, S.; Pletcher, D.

    1985-09-01

    The storage of Br/sub 2//Br/sup -/ and I/sub 2//I/sup -/ couples in a conducting polymer matrix, polypyrrole coated on a reticulated vitreous carbon disc, is described and the application of these positive electrodes in zinc-halogen model batteries is discussed. The cell based on the polypyrrole bromine adduct shows the higher open circuit voltage which, however, depends on the state of charge. Such cells self discharge thus limiting their usefulness. In the case of the iodine cell the self discharge is due to loss of iodine from the polymer to the bulk solution, but with the bromine cell the cause is oxidative bromination and depolymerization of the polypyrrole. 22 references, 6 figures, 2 tables.

  13. Retention of Halogenated Solutes on Stationary Phases Containing Heavy Atoms

    Directory of Open Access Journals (Sweden)

    Toshio Miwa

    2013-05-01

    Full Text Available To examine the effects of weak intermolecular interactions on solid-phase extraction (SPE and chromatographic separation, we synthesized some novel stationary phases with a heavy atom effect layer by immobilizing halogenated aromatic rings and hydroxyl groups onto the surface of a hydrophilic base polymer. Using SPE cartridges packed with the functionalized materials, we found that the heavy atom stationary phases could selectively retain halophenols in organic solvents, such as 1-propanol which blocks the hydrogen bonding, or acetonitrile which blocks the p-p interaction. The extraction efficiency of the materials toward the halophenols depended on the dipole moments of phenoxy groups present as functional groups. On the other hand, the extraction efficiency of solutes toward the functional group depended on their molar refractions, i.e., induced dipole moments. The retention of the solutes to the stationary phase ultimately depended on not only strong intermolecular interactions, but also the effects of weak interactions such as the dispersion force.

  14. Iron Coordination and Halogen-Bonding Assisted Iodosylbenzene Activation

    DEFF Research Database (Denmark)

    Wegeberg, Christina; Poulsen de Sousa, David; McKenzie, Christine

    catalytic mixtures using soluble terminal oxygen transfer agents. Isolation of a reactive iron-terminal oxidant adduct, an unique Fe(III)-OIPh complex, is facilitated by strong stabilizing supramolecular halogen-bonding. L3-edge XANES suggests +1.6 for the average oxidation state for the iodine atom3......The iron complex of the hexadentate ligand N,N,N'-tris(2-pyridylmethyl)ethylendiamine-N'-acetate (tpena) efficiently catalyzes selective oxidations of electron-rich olefins and sulfides by insoluble iodosylbenzene (PhIO). Surprisingly, these reactions are faster and more selective than homogenous...... in the iron(III)-coordinated PhIO. This represents a reduction of iodine relative to the original “hypervalent” (+3) PhIO. The equivalent of electron density must be removed from the {(tpena)Fe(III)O} moiety, however Mössbauer spectroscopy shows that the iron atom is not high valent....

  15. Fluorescence cell imaging and manipulation using conventional halogen lamp microscopy.

    Directory of Open Access Journals (Sweden)

    Kazuo Yamagata

    Full Text Available Technologies for vitally labeling cells with fluorescent dyes have advanced remarkably. However, to excite fluorescent dyes currently requires powerful illumination, which can cause phototoxic damage to the cells and increases the cost of microscopy. We have developed a filter system to excite fluorescent dyes using a conventional transmission microscope equipped with a halogen lamp. This method allows us to observe previously invisible cell organelles, such as the metaphase spindle of oocytes, without causing phototoxicity. Cells remain healthy even after intensive manipulation under fluorescence observation, such as during bovine, porcine and mouse somatic cell cloning using nuclear transfer. This method does not require expensive epifluorescence equipment and so could help to reduce the science gap between developed and developing countries.

  16. Halogenated furanones inhibit quorum sensing through accelerated LuxR turnover

    DEFF Research Database (Denmark)

    Manefield, M.; Rasmussen, Thomas Bovbjerg; Henzter, M.

    2002-01-01

    fischeri overproduced in Escherichia coli. Whilst a stable interaction between the algal metabolite and the bacterial protein was not found, it was noted by Western analysis that the half-life of the protein is reduced up to 100-fold in the presence of halogenated furanones. This suggests that halogenated...... that the reduction in LuxR concentration is the mechanism by which furanones control expression of AHL-dependent phenotypes. The mode of action by which halogenated furanones reduce cellular concentrations of the LuxR protein remains to be characterized....

  17. Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases.

    Science.gov (United States)

    Alkorta, Ibon; Blanco, Fernando; Solimannejad, Mohammad; Elguero, Jose

    2008-10-30

    A theoretical study of the complexes formed by hypohalous acids (HOX, X = F, Cl, Br, I, and At) with three nitrogenated bases (NH 3, N 2, and NCH) has been carried out by means of ab initio methods, up to MP2/aug-cc-pVTZ computational method. In general, two minima complexes are found, one with an OH...N hydrogen bond and the other one with a X...N halogen bond. While the first one is more stable for the smallest halogen derivatives, the two complexes present similar stabilities for the iodine case and the halogen-bonded structure is the most stable one for the hypoastatous acid complexes.

  18. Structures and anti-inflammatory properties of 4-halogenated -mofebutazones

    Science.gov (United States)

    Reichelt, Hendrik; Paradies, Henrich H.

    2018-02-01

    The crystal structures of the 4-halogenated (hal: F, Cl, Br)-4-butyl-1-phenyl-1,3-pyrolidine-dione (mofebutazone) are determined, and compared with their solution structures. The racemic 4-halogenated mofebutazone approximants crystallize in a monoclinic space group with four molecules in the unit cell. The 4-hal-mofebutazone molecules reveal strong hydrogen bonding between the hydrogen atom located at the N-2 nitrogen atom and a carbonyl oxygen atom of an adjacent 4-hal-mofebutazone molecule. The hydrogen bond angle for 4-Br-mifebutazone N (2)sbnd H (1)⋯O (1) is 173(3) °, so that the hydrogen bond is essentially linear indicating an infinite chain hydrogen bond network. The 3d and 2d structures are stabilized by π-π and σ-π interactions, short intermolecular distances, and apolar forces between adjacently stacked phenyl rings. Small-angle-X-ray scattering (SAXS) experiments and osmometric measurements reveal the presence of dimers for the 4-hal-mofebutazone molecules. Molecular simulations indicate similar solution structure factors for the 4-hal-mofebutazones solutions, S(Q), and in the solid state. There is a strong indication that the [1,1,0], [1,0,0], and [1,0,0] periodicities of the 4-Brsbnd , 4-Clsbnd and 4-F-mofebutazone in the crystalline solid state were also present in the solution phase. The biochemical and cellular activities of the different 4-hal-mofebutazones were monitored by the magnitude of their inhibition of the PGE2 biosynthesis through the cyclo-oxygenase (COX-1) in macrophages, and on the inhibition of LTD4 (5-lipoxygenase) in polymorphonuclear leukocytes.

  19. Detection of Alkylating Agents using Electrical and Mechanical Means

    Science.gov (United States)

    Gerchikov, Yulia; Borzin, Elena; Gannot, Yair; Shemesh, Ariel; Meltzman, Shai; Hertzog-Ronen, Carmit; Tal, Shay; Stolyarova, Sara; Nemirovsky, Yael; Tessler, Nir; Eichen, Yoav

    2011-08-01

    Alkylating agents are reactive molecules having at least one polar bond between a carbon atom and a good leaving group. These often simple molecules are frequently used in organic synthesis, as sterilizing agents in agriculture and even as anticancer agents in medicine. Unfortunately, for over a century, some of the highly reactive alkylating agents are also being used as blister chemical warfare agents. Being relatively simple to make, the risk is that these will be applied by terrorists as poor people warfare agents. The detection and identification of such alkylating agents is not a simple task because of their high reactivity and simple structure of the reactive site. Here we report on new approaches to the detection and identification of such alkylating agents using electrical (organic field effect transistors) and mechanical (microcantilevers) means.

  20. Detection of Alkylating Agents using Electrical and Mechanical Means

    International Nuclear Information System (INIS)

    Gerchikov, Yulia; Borzin, Elena; Gannot, Yair; Shemesh, Ariel; Meltzman, Shai; Hertzog-Ronen, Carmit; Eichen, Yoav; Tal, Shay; Stolyarova, Sara; Nemirovsky, Yael; Tessler, Nir

    2011-01-01

    Alkylating agents are reactive molecules having at least one polar bond between a carbon atom and a good leaving group. These often simple molecules are frequently used in organic synthesis, as sterilizing agents in agriculture and even as anticancer agents in medicine. Unfortunately, for over a century, some of the highly reactive alkylating agents are also being used as blister chemical warfare agents. Being relatively simple to make, the risk is that these will be applied by terrorists as poor people warfare agents. The detection and identification of such alkylating agents is not a simple task because of their high reactivity and simple structure of the reactive site. Here we report on new approaches to the detection and identification of such alkylating agents using electrical (organic field effect transistors) and mechanical (microcantilevers) means.

  1. Regulation of DNA Alkylation Damage Repair: Lessons and Therapeutic Opportunities.

    Science.gov (United States)

    Soll, Jennifer M; Sobol, Robert W; Mosammaparast, Nima

    2017-03-01

    Alkylation chemotherapy is one of the most widely used systemic therapies for cancer. While somewhat effective, clinical responses and toxicities of these agents are highly variable. A major contributing factor for this variability is the numerous distinct lesions that are created upon alkylation damage. These adducts activate multiple repair pathways. There is mounting evidence that the individual pathways function cooperatively, suggesting that coordinated regulation of alkylation repair is critical to prevent toxicity. Furthermore, some alkylating agents produce adducts that overlap with newly discovered methylation marks, making it difficult to distinguish between bona fide damaged bases and so-called 'epigenetic' adducts. Here, we discuss new efforts aimed at deciphering the mechanisms that regulate these repair pathways, emphasizing their implications for cancer chemotherapy. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. 21 CFR 176.120 - Alkyl ketene dimers.

    Science.gov (United States)

    2010-04-01

    ..., processing, preparing, treating, packaging, transporting, or holding food, subject to the provisions of this... paperboard. (c) The alkyl ketene dimers may be used in the form of an aqueous emulsion which may contain...

  3. Detection of Alkylating Agents using Electrical and Mechanical Means

    Energy Technology Data Exchange (ETDEWEB)

    Gerchikov, Yulia; Borzin, Elena; Gannot, Yair; Shemesh, Ariel; Meltzman, Shai; Hertzog-Ronen, Carmit; Eichen, Yoav [Schulich Department of Chemistry, Technion-Israel Institute of Technology, Technion City, 32000, Haifa (Israel) (Israel); Tal, Shay [Present address: Systems Biology Department, Harvard Medical School, Boston, MA 02115 (United States); Stolyarova, Sara; Nemirovsky, Yael; Tessler, Nir, E-mail: chryoav@tx.technion.ac.il [Department of Electrical Engineering, Technion-Israel Institute of Technology, Technion City, 32000, Haifa (Israel)

    2011-08-17

    Alkylating agents are reactive molecules having at least one polar bond between a carbon atom and a good leaving group. These often simple molecules are frequently used in organic synthesis, as sterilizing agents in agriculture and even as anticancer agents in medicine. Unfortunately, for over a century, some of the highly reactive alkylating agents are also being used as blister chemical warfare agents. Being relatively simple to make, the risk is that these will be applied by terrorists as poor people warfare agents. The detection and identification of such alkylating agents is not a simple task because of their high reactivity and simple structure of the reactive site. Here we report on new approaches to the detection and identification of such alkylating agents using electrical (organic field effect transistors) and mechanical (microcantilevers) means.

  4. Regeneration of a deactivated USY alkylation catalyst using supercritical isobutane

    Energy Technology Data Exchange (ETDEWEB)

    Daniel M. Ginosar; David N. Ghompson; Kyle C. Burch

    2005-01-01

    Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical isobutane. A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical isobutane over the catalyst bed at different reactivation conditions. Temperature, pressure and regeneration time were found to play important roles in the supercritical isobutane regeneration process when applied to a completely deactivated USY zeolite alkylation catalyst. Manipulation of the variables that influence solvent strength, diffusivity, surface desorption, hydride transfer rates, and coke aging, strongly influence regeneration effectiveness.

  5. Construction of Tungsten Halogen, Pulsed LED, and Combined Tungsten Halogen-LED Solar Simulators for Solar Cell I-V Characterization and Electrical Parameters Determination

    Directory of Open Access Journals (Sweden)

    Anon Namin

    2012-01-01

    Full Text Available I-V characterization of solar cells is generally done under natural sunlight or solar simulators operating in either a continuous mode or a pulse mode. Simulators are classified on three features of irradiance, namely, spectral match with respect to air mass 1.5, spatial uniformity, and temporal stability. Commercial solar simulators use Xenon lamps and halogen lamps, whereas LED-based solar simulators are being developed. In this work, we build and test seven simulators for solar cell characterization, namely, one tungsten halogen simulator, four monochromatic (red, green, blue, and white LED simulators, one multicolor LED simulator, and one tungsten halogen-blue LED simulator. The seven simulators provide testing at nonstandard test condition. High irradiance from simulators is obtained by employing elevated supply voltage to tungsten halogen lamps and high pulsing voltages to LEDs. This new approach leads to higher irradiance not previously obtained from tungsten halogen lamps and LEDs. From I-V curves, electrical parameters of solar cell are made and corrected based on methods recommended in the IEC 60891 Standards. Corrected values obtained from non-STC measurements are in good agreement with those obtained from Class AAA solar simulator.

  6. Iminium Salts by Meerwein Alkylation of Ehrlich’s Aldehyde

    Directory of Open Access Journals (Sweden)

    Gerhard Laus

    2013-03-01

    Full Text Available 4-(Dimethylaminobenzaldehyde is alkylated at the N atom by dialkyl sulfates, MeI, or Me3O BF4. In contrast, ethylation by Et3O BF4 occurs selectively at the O atom yielding a quinoid iminium ion. 4-(Diethylaminobenzaldehyde is alkylated only at O by either Et or Me oxonium reagent. The iminium salts are prone to hydrolysis giving the corresponding hydrotetrafluoroborates. Five crystal structures were determined.

  7. Solid acid zeolite catalysts for benzene/ ethylene alkylation reactions

    OpenAIRE

    2011-01-01

    Alkylation of benzene with ethylene to ethylbenzene is widely used in the petrochemical industry. Ethylbenzene is an important raw material in the petrochemical industry. It is used as feedstock for the production of styrene, an important material for plastic and rubber production.The conventional catalyst for this alkylation process is AlCl₃, which accounted for 24% of the worldwide ethylbenzene production in 2009.As utilization of this catalyst involves problems with separation, handling, s...

  8. Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement

    OpenAIRE

    Liu, Wen-Bo; Okamoto, Noriko; Alexy, Eric J.; Hong, Allen Y.; Tran, Kristy; Stoltz, Brian M.

    2016-01-01

    A catalytic, enantioselective ? -alkylation of ?,?-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- and enantioselective iridium-catalyzed ?-alkylation of an extended enolate, and a subsequent translocation of chirality to the ?-position via a Cope rearrangement.

  9. Mechanisms of chemoresistance to alkylating agents in malignant glioma.

    Science.gov (United States)

    Sarkaria, Jann N; Kitange, Gaspar J; James, C David; Plummer, Ruth; Calvert, Hilary; Weller, Michael; Wick, Wolfgang

    2008-05-15

    Intrinsic or acquired chemoresistance to alkylating agents is a major cause of treatment failure in patients with malignant brain tumors. Alkylating agents, the mainstay of treatment for brain tumors, damage the DNA and induce apoptosis, but the cytotoxic activity of these agents is dependent on DNA repair pathways. For example, O6-methylguanine DNA adducts can cause double-strand breaks, but this is dependent on a functional mismatch repair pathway. Thus, tumor cell lines deficient in mismatch repair are resistant to alkylating agents. Perhaps the most important mechanism of resistance to alkylating agents is the DNA repair enzyme O6-methylguanine methyltransferase, which can eliminate the cytotoxic O6-methylguanine DNA adduct before it causes harm. Another mechanism of resistance to alkylating agents is the base excision repair (BER) pathway. Consequently, efforts are ongoing to develop effective inhibitors of BER. Poly(ADP-ribose)polymerase plays a pivotal role in BER and is an important therapeutic target. Developing effective strategies to overcome chemoresistance requires the identification of reliable preclinical models that recapitulate human disease and which can be used to facilitate drug development. This article describes the diverse mechanisms of chemoresistance operating in malignant glioma and efforts to develop reliable preclinical models and novel pharmacologic approaches to overcome resistance to alkylating agents.

  10. Alcohols as alkylating agents in heteroarene C-H functionalization

    Science.gov (United States)

    Jin, Jian; MacMillan, David W. C.

    2015-09-01

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of `spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

  11. Salvage of failed protein targets by reductive alkylation.

    Science.gov (United States)

    Tan, Kemin; Kim, Youngchang; Hatzos-Skintges, Catherine; Chang, Changsoo; Cuff, Marianne; Chhor, Gekleng; Osipiuk, Jerzy; Michalska, Karolina; Nocek, Boguslaw; An, Hao; Babnigg, Gyorgy; Bigelow, Lance; Joachimiak, Grazyna; Li, Hui; Mack, Jamey; Makowska-Grzyska, Magdalena; Maltseva, Natalia; Mulligan, Rory; Tesar, Christine; Zhou, Min; Joachimiak, Andrzej

    2014-01-01

    The growth of diffraction-quality single crystals is of primary importance in protein X-ray crystallography. Chemical modification of proteins can alter their surface properties and crystallization behavior. The Midwest Center for Structural Genomics (MCSG) has previously reported how reductive methylation of lysine residues in proteins can improve crystallization of unique proteins that initially failed to produce diffraction-quality crystals. Recently, this approach has been expanded to include ethylation and isopropylation in the MCSG protein crystallization pipeline. Applying standard methods, 180 unique proteins were alkylated and screened using standard crystallization procedures. Crystal structures of 12 new proteins were determined, including the first ethylated and the first isopropylated protein structures. In a few cases, the structures of native and methylated or ethylated states were obtained and the impact of reductive alkylation of lysine residues was assessed. Reductive methylation tends to be more efficient and produces the most alkylated protein structures. Structures of methylated proteins typically have higher resolution limits. A number of well-ordered alkylated lysine residues have been identified, which make both intermolecular and intramolecular contacts. The previous report is updated and complemented with the following new data; a description of a detailed alkylation protocol with results, structural features, and roles of alkylated lysine residues in protein crystals. These contribute to improved crystallization properties of some proteins.

  12. Salvage of Failed Protein Targets by Reductive Alkylation

    Science.gov (United States)

    Tan, Kemin; Kim, Youngchang; Hatzos-Skintges, Catherine; Chang, Changsoo; Cuff, Marianne; Chhor, Gekleng; Osipiuk, Jerzy; Michalska, Karolina; Nocek, Boguslaw; An, Hao; Babnigg, Gyorgy; Bigelow, Lance; Joachimiak, Grazyna; Li, Hui; Mack, Jamey; Makowska-Grzyska, Magdalena; Maltseva, Natalia; Mulligan, Rory; Tesar, Christine; Zhou, Min; Joachimiak, Andrzej

    2014-01-01

    The growth of diffraction-quality single crystals is of primary importance in protein X-ray crystallography. Chemical modification of proteins can alter their surface properties and crystallization behavior. The Midwest Center for Structural Genomics (MCSG) has previously reported how reductive methylation of lysine residues in proteins can improve crystallization of unique proteins that initially failed to produce diffraction-quality crystals. Recently, this approach has been expanded to include ethylation and isopropylation in the MCSG protein crystallization pipeline. Applying standard methods, 180 unique proteins were alkylated and screened using standard crystallization procedures. Crystal structures of 12 new proteins were determined, including the first ethylated and the first isopropylated protein structures. In a few cases, the structures of native and methylated or ethylated states were obtained and the impact of reductive alkylation of lysine residues was assessed. Reductive methylation tends to be more efficient and produces the most alkylated protein structures. Structures of methylated proteins typically have higher resolution limits. A number of well-ordered alkylated lysine residues have been identified, which make both intermolecular and intramolecular contacts. The previous report is updated and complemented with the following new data; a description of a detailed alkylation protocol with results, structural features, and roles of alkylated lysine residues in protein crystals. These contribute to improved crystallization properties of some proteins. PMID:24590719

  13. Regioselective 1-N-Alkylation and Rearrangement of Adenosine Derivatives.

    Science.gov (United States)

    Oslovsky, Vladimir E; Drenichev, Mikhail S; Mikhailov, Sergey N

    2015-01-01

    Several methods for the preparation of some N(6)-substituted adenosines based on selective 1-N-alkylation with subsequent Dimroth rearrangement were developed. The proposed methods seem to be effective for the preparation of natural N(6)-isopentenyl- and N(6)-benzyladenosines, which are known to possess pronounced biological activities. Direct 1-N-alkylation of 2',3',5'-tri-O-acetyladenosine and 3',5'-di-O-acetyl-2'-deoxyadenosine with alkyl halides in N,N-dimethylformamide (DMF) in the presence of BaCO3 and KI gave 1-N-substituted derivatives with quantitative yields, whereas 1-N-alkylation of adenosine was accompanied by significant O-alkylation. Moreover, the reaction of trimethylsilyl derivatives of N(6)-acetyl-2',3',5'-tri-O-acetyladenosine and N(6)-acetyl-3',5'-di-O-acetyl-2'-deoxyadenosine with alkyl halides leads to the formation of the stable 1-N-substituted adenosines. Dimroth rearrangement of 1-N-substituted adenosines in aqueous ammonia yields pure N(6)-substituted adenosines.

  14. Alcohols as alkylating agents in heteroarene C–H functionalization

    Science.gov (United States)

    Jin, Jian; MacMillan, David W. C.

    2015-01-01

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage1. One of the core principles that underlies DNA biosynthesis is the radical-mediated elimnation of H2O to deoxygenate ribonucleotides, an example of ‘spin-center shift’ (SCS)2, during which an alcohol C–O bond is cleaved, resulting in a carbon-centered radical intermediate. While SCS is a well-understood biochemical process, it is underutilized by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylations using alcohols as radical precursors. Considering traditional radical-based alkylation methods require the use of stoichiometric oxidants, elevated temperatures, or peroxides3–7, the development of a mild protocol using simple and abundant alkylating agents would have significant utility in the synthesis of diversely functionalized pharmacophores. In this manuscript, we describe the successful execution of this idea via the development of a dual catalytic alkylation of heteroarenes using alcohols as mild alkylating reagents. This method represents the first broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer (HAT) catalysis. The utility of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone. PMID:26308895

  15. Final Technical Report [Development of Catalytic Alkylation and Fluoroalkylation Methods

    Energy Technology Data Exchange (ETDEWEB)

    Vicic, David A.

    2014-05-01

    In the early stages of this DOE-funded research project, we sought to prepare and study a well-defined nickel-alkyl complex containing tridentate nitrogen donor ligands. We found that reaction of (TMEDA)NiMe2 (1) with terpyridine ligand cleanly led to the formation of (terpyridyl)NiMe (2), which we also determined to be an active alkylation catalyst. The thermal stability of 2 was unlike that seen for any of the active pybox ligands, and enabled a number of key studies on alkyl transfer reactions to be performed, providing new insights into the mechanism of nickel-mediated alkyl-alkyl cross-coupling reactions. In addition to the mechanistic studies, we showed that the terpyridyl nickel compounds can catalytically cross-couple alkyl iodides in yields up to 98% and bromides in yields up to 46 %. The yields for the bromides can be increased up to 67 % when the new palladium catalyst [(tpy’)Pd-Ph]I is used. The best route to the targeted [(tpy)NiBr] (1) was found to involve the comproportionation reaction of [(dme)NiBr{sub 2}] and [Ni(COD){sub 2}] in the presence of two equivalents of terpyridine. This reaction was driven to high yields of product formation (72 % isolated) by the precipitation of 1 from THF solvent.

  16. Alcohols as alkylating agents in heteroarene C-H functionalization.

    Science.gov (United States)

    Jin, Jian; MacMillan, David W C

    2015-09-03

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of 'spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

  17. Alkyl-halogenide promoted ionic liquid catalysis of isobutane/butene-alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Schilder, L.; Korth, W.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering

    2011-07-01

    The effect of two different types of promoters on the performance of Lewis-acidic chloroaluminate ionic liquid catalysts was studied for liquid liquid biphasic isobutane/2-butene alkylation. In particular, the activity and selectivity of such catalytic systems was investigated. Experimental results obtained from a batch reactor show, that tert-butyl halides increase the reaction rate significantly and shift the C8-selectivity towards the desired high-octane trimethylpentanes (TMPs). But, secondary reactions like oligomerization and cracking are not affected by the use of these promoters. (orig.)

  18. DNA minor groove targeted alkylating agents based on bisbenzimidazole carriers: synthesis, cytotoxicity and sequence-specificity of DNA alkylation.

    Science.gov (United States)

    Smaill, J B; Fan, J Y; Denny, W A

    1998-12-01

    A series of bisbenzimidazoles bearing a variety of alkylating agents [ortho- and meta-mustards, imidazolebis(hydroxymethyl), imidazolebis(methylcarbamate) and pyrrolebis(hydroxymethyl)], appended by a propyl linker chain, were prepared and investigated for sequence-specificity of DNA alkylation and their cytotoxicity. Previous work has shown that, for para-aniline mustards, a propyl linker is optimal for cytotoxicity. Alkaline cleavage assays using a variety of different labelled oligonucleotides showed that the preferred sequences for adenine alkylation were 5'-TTTANANAANN and 5'-ATTANANAANN (underlined bases show the drug alkylation sites), with AT-rich sequences required on both the 5' and 3' sides of the alkylated adenine. The different aniline mustards showed little variation in alkylation pattern and similar efficiencies of DNA cross-link formation despite the changes in orientation and positioning of the mustard, suggesting that the propyl linker has some flexibility. The imidazole- and pyrrolebis(hydroxymethyl) alkylators showed no DNA strand cleavage following base treatment, indicating that no guanine or adenine N3 or N7 adducts were formed. Using the PCR-based polymerase stop assay, these alkylators showed PCR blocks at 5'-C*G sites (the * nucleotide indicates the blocked site), particularly at 5'-TAC*GA 5'-AGC*GGA, and 5'-AGCC*GGT sequences, caused by guanine 2-NH2 lesions on the opposite strand. Only the (more reactive) imidazolebis(methylcarbamoyl) and pyrrolebis(hydroxymethyl) alkylators demonstrated interstrand cross-linking ability. All of the bifunctional mustards showed large (approximately 100-fold) increases in cytotoxicity over chlorambucil, with the corresponding monofunctional mustards being 20- to 60-fold less cytotoxic. These results suggest that in the mustards the propyl linker provides sufficient flexibility to achieve delivery of the alkylator to favoured (adenine N3) sites in the minor groove, regardless of its exact geometry with

  19. UV absorption spectra and kinetics for alkyl and alkyl peroxy radicals originating from di-tert-butyl ether

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.; Langer, S.

    1995-01-01

    Alkyl, (CH3)(3)COC(CH3)(2)CH2, and alkyl peroxy, (CH3)(3)COC(CH3)(2)CH2O2, radicals from di-tert-butyl ether (DTBE), have been studied in the gas phase at 296 K. A pulse radiolysis UV absorption technique was used to measure the spectra and kinetics. Absorption cross sections were quantified over...

  20. Propargyl organometallic compounds. II. Alkylation of sodium derivatives of 1-alkyl-1-aryl-2-alkynes in liquid ammonia

    International Nuclear Information System (INIS)

    Libman, N.M.; Sevryukov, Yu.P.

    1987-01-01

    In most cases the alkylation of the sodium derivatives of 1-phenyl-1-alkyl-2-alkynes by methyl, ethyl, isopropyl, and tert-butyl bromides in liquid ammonia takes place preferentially at the sp 2 -hybridized carbon atom, and this leads to the formation of the corresponding acetylenes, The regioselectivity of the reaction is explained by the greater softness of the trigonal atom of the ambient propargyl anion and its smaller screening by the solvate shell compared with the diagonal atom

  1. Beyond Alkylating Agents for Gliomas: Quo Vadimus?

    Science.gov (United States)

    Puduvalli, Vinay K; Chaudhary, Rekha; McClugage, Samuel G; Markert, James

    2017-01-01

    Recent advances in therapies have yielded notable success in terms of improved survival in several cancers. However, such treatments have failed to improve outcome in patients with gliomas for whom surgery followed by radiation therapy and chemotherapy with alkylating agents remain the standard of care. Genetic and epigenetic studies have helped identify several alterations specific to gliomas. Attempts to target these altered pathways have been unsuccessful due to various factors, including tumor heterogeneity, adaptive resistance of tumor cells, and limitations of access across the blood-brain barrier. Novel therapies that circumvent such limitations have been the focus of intense study and include approaches such as immunotherapy, targeting of signaling hubs and metabolic pathways, and use of biologic agents. Immunotherapeutic approaches including tumor-targeted vaccines, immune checkpoint blockade, antibody-drug conjugates, and chimeric antigen receptor-expressing cell therapies are in various stages of clinical trials. Similarly, identification of key metabolic pathways or converging hubs of signaling pathways that are tumor specific have yielded novel targets for therapy of gliomas. In addition, the failure of conventional therapies against gliomas has led to a growing interest among patients in the use of alternative therapies, which in turn has necessitated developing evidence-based approaches to the application of such therapies in clinical studies. The development of these novel approaches bears potential for providing breakthroughs in treatment of more meaningful and improved outcomes for patients with gliomas.

  2. Halogenated organic compounds in archived whale oil: A pre-industrial record

    International Nuclear Information System (INIS)

    Teuten, Emma L.; Reddy, Christopher M.

    2007-01-01

    To provide additional evidence that several halogenated organic compounds (HOCs) found in environmental samples are natural and not industrially produced, we analyzed an archived whale oil sample collected in 1921 from the last voyage of the whaling ship Charles W. Morgan. This sample, which pre-dates large-scale industrial manufacture of HOCs, contained two methoxylated polybrominated diphenyl ethers (MeO-PBDEs), five halogenated methyl bipyrroles (MBPs), one halogenated dimethyl bipyrrole (DMBP), and tentatively one dimethoxylated polybrominated biphenyl (diMeO-PBB). This result indicates, at least in part, a natural source of the latter compounds. - Nine halogenated organic compounds have been detected in archived whale oil from the early 1920s

  3. Halogenated organic compounds in archived whale oil: A pre-industrial record

    Energy Technology Data Exchange (ETDEWEB)

    Teuten, Emma L. [Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, 360 Woods Hole Road, Woods Hole, MA 02543 (United States)]. E-mail: emma.teuten@plymouth.ac.uk; Reddy, Christopher M. [Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, 360 Woods Hole Road, Woods Hole, MA 02543 (United States)]. E-mail: creddy@whoi.edu

    2007-02-15

    To provide additional evidence that several halogenated organic compounds (HOCs) found in environmental samples are natural and not industrially produced, we analyzed an archived whale oil sample collected in 1921 from the last voyage of the whaling ship Charles W. Morgan. This sample, which pre-dates large-scale industrial manufacture of HOCs, contained two methoxylated polybrominated diphenyl ethers (MeO-PBDEs), five halogenated methyl bipyrroles (MBPs), one halogenated dimethyl bipyrrole (DMBP), and tentatively one dimethoxylated polybrominated biphenyl (diMeO-PBB). This result indicates, at least in part, a natural source of the latter compounds. - Nine halogenated organic compounds have been detected in archived whale oil from the early 1920s.

  4. PATTERN RECOGNITION STUDIES OF HALOGENATED ORGANIC COMPOUNDS USING CONDUCTING POLYMER SENSOR ARRAYS. (R825323)

    Science.gov (United States)

    Direct measurement of volatile and semivolatile halogenated organic compounds of environmental interest was carried out using arrays of conducting polymer sensors. Mathematical expressions of the sensor arrays using microscopic polymer network model is described. A classical, non...

  5. Ultraviolet radiation and blue-light emissions from spotlights incorporating tungsten halogen lamps

    CERN Document Server

    MacKinlay, Alistair F; Whillock, M J

    1989-01-01

    This report summarises measurements of the ultraviolet radiation and blue-light emissions from eleven 'desk-top' tungsten halogen (quartz) lamps and one 'floor-standing' tungsten halogen (quartz) lamp available in the UK. Values of occupational hazard weighted and erythemally weighted ultraviolet radiation irradiance and measurements and relevant calculations of blue-light hazards are presented. It is concluded that the safety design of some desk-top tungsten halogen lamps is inadequate to prevent unnecessary exposure of the skin to potentially harmful ultraviolet radiation. It is recommended that all tungsten halogen lamps should have sufficient filtration to reduce their ultraviolet emissions to an acceptably low level. As long as the comfort aversion responses of the eye are respected, direct viewing of the lamps examined should not constitute a retinal hazard.

  6. Ultraviolet radiation and blue-light emissions from spotlights incorporating tungsten halogen lamps

    International Nuclear Information System (INIS)

    McKinlay, A.F.; Whillock, M.J.; Meulemans, C.C.E.

    1989-07-01

    This report summarises measurements of the ultraviolet radiation and blue-light emissions from eleven 'desk-top' tungsten halogen (quartz) lamps and one 'floor-standing' tungsten halogen (quartz) lamp available in the UK. Values of occupational hazard weighted and erythemally weighted ultraviolet radiation irradiance and measurements and relevant calculations of blue-light hazards are presented. It is concluded that the safety design of some desk-top tungsten halogen lamps is inadequate to prevent unnecessary exposure of the skin to potentially harmful ultraviolet radiation. It is recommended that all tungsten halogen lamps should have sufficient filtration to reduce their ultraviolet emissions to an acceptably low level. As long as the comfort aversion responses of the eye are respected, direct viewing of the lamps examined should not constitute a retinal hazard. (author)

  7. First-principles studies on the effects of halogen adsorption on monolayer antimony.

    Science.gov (United States)

    Yeoh, Keat Hoe; Yoon, Tiem Leong; Ong, Duu Sheng; Lim, Thong Leng; Zuntu Abdullahi, Yusuf

    2017-09-27

    Using first-principles calculations, we carry out systematic studies on the electronic, magnetic and structural properties of halogenated β-phase antimonene. We consider two different levels of halogen adatom coverage i.e. Θ = 1/8 and Θ = 1/18. It is found that F, Cl and Br adatoms act as acceptors whereas the I adatom acts as a donor. For a high coverage of Θ = 1/8, halogenated β-phase antimonene exhibits metallic characteristics. With a lower coverage of Θ = 1/18, through the adsorption of F, Cl and Br the semiconducting unstrained antimonene becomes metallic. In contrast, I-adsorbed antimonene remains semiconducting but exhibits magnetic behavior. We further investigate the effects of bi-axial strain on the halogenated β-phase antimonene. It is found that bi-axial strain can only induce ferromagnetism on the halogenated antimonene at Θ = 1/18. However, the ferromagnetism is suppressed when the applied strain is high. We uncover that the emergence of strain-dependent magnetism is attributed to the presence of localized states in the bandgap resulting from collective effects of bi-axial strain and the adsorption of halogen atoms.

  8. Induction of bacterial antibiotic resistance by mutagenic halogenated nitrogenous disinfection byproducts

    International Nuclear Information System (INIS)

    Lv, Lu; Yu, Xin; Xu, Qian; Ye, Chengsong

    2015-01-01

    Halogenated nitrogenous disinfection byproducts (N-DBPs) raise concerns regarding their mutagenicity and carcinogenicity threatening public health. However, environmental consequence of their mutagenicity has received less attention. In this study, the effect of halogenated N-DBPs on bacterial antibiotic resistance (BAR) was investigated. After exposure to bromoacetamide (BAcAm), trichloroacetonitrile (TCAN) or tribromonitromethane (TBNM), the resistance of Pseudomonas aeruginosa PAO1 to both individual and multiple antibiotics (ciprofloxacin, gentamicin, polymyxin B, rifampin, tetracycline, ciprofloxacin + gentamicin and ciprofloxacin + tetracycline) was increased, which was predominantly ascribed to the overexpression of efflux pumps. The mechanism of this effect was demonstrated to be mutagenesis through sequencing and analyzing antibiotic resistance genes. The same induction phenomena also appeared in Escherichia coli, suggesting this effect may be universal to waterborne pathogens. Therefore, more attention should be given to halogenated N-DBPs, as they could increase not only genotoxicological risks but also epidemiological risks of drinking water. - Highlights: • The halogenated N-DBPs could induce bacterial antibiotic resistance. • Both individual and multiple resistances could be induced. • Efflux mechanism played an important role in the induced antibiotic resistance. • The halogenated N-DBPs induced bacterial antibiotic resistance via mutagenesis. • Effects of N-DBPs on antibiotic resistance may be universal to waterborne pathogens. - Halogenated N-DBPs could increase antibiotic resistance, even multidrug resistance via mutagenesis, contributing to the enrichment of antibiotic resistant bacteria in drinking water

  9. Evaluation of remaining behavior of halogen on the fabrication of MOX pellet containing Am

    International Nuclear Information System (INIS)

    Ozaki, Yoko; Osaka, Masahiko; Obayashi, Hiroshi; Tanaka, Kenya

    2004-11-01

    It is important to limit the content of halogen elements, namely fluorine and chlorine that are sources of making cladding material corrode, in nuclear fuel from the viewpoint of quality assurance. The halogen content should be more carefully limited in the MOX fuel containing Americium (Am-MOX), which is fabricated in the Alpha-Gamma Facility (AGF) for irradiation testing to be conducted in the experimental fast reactor JOYO, because fluorine may remain in the sintered pellets owing to a formation of AmF 3 known to have a low vapor pressure and may exceeds the limit of 25 ppm. In this study, a series of experimental determination of halogen element in Am-MOX were performed by a combination method of pyrolysis and ion-chromatography for the purpose of an evaluation of behavior of remaining halogen through the sintering process. Oxygen potential, temperature and time were changed as experimental parameters and their effects on the remaining behavior of halogen were examined. It was confirmed that good pellets, which contained small amount of halogen, could be obtained by the sintering for 3 hour at 1700degC in the oxygen potential range from -520 to -390 kJ/mol. In order to analysis of fluorine chemical form in green pellet, thermal analysis was performed. AmF 3 and PuF 3 have been confirmed to remain in the green pellet. (author)

  10. Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts.

    Science.gov (United States)

    Khokarale, Santosh Govind; He, Jian; Schill, Leonhard; Yang, Song; Riisager, Anders; Saravanamurugan, Shunmugavel

    2018-02-22

    Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) was performed with various base-metal supported catalysts. A high yield of 77 % MP was obtained with bimetallic Fe-Ni/ZrO 2 in methanol at 220 °C and 50 bar H 2 . A synergistic effect of Ni increased the yield of MP significantly when using Fe-Ni/ZrO 2 instead of Fe/ZrO 2 alone. Moreover, the ZrO 2 support contributed to improve the yield as a phase transition of ZrO 2 from tetragonal to monoclinic occurred after metal doping giving rise to fine dispersion of the Fe and Ni on the ZrO 2 , resulting in a higher catalytic activity of the material. Interestingly, it was observed that Fe-Ni/ZrO 2 also effectively catalyzed methanol reforming to produce H 2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N 2 instead of H 2 . Fe-Ni/ZrO 2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl propionates in high yields around 70 %. No loss of activity of Fe-Ni/ZrO 2 occurred in five consecutive reaction runs demonstrating the high durability of the catalyst system. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Depolymerization of coal by oxidation and alkylation; Sanka bunkai to alkyl ka ni yoru sekitan kaijugo

    Energy Technology Data Exchange (ETDEWEB)

    Tomita, H.; Isoda, T.; Kusakabe, K.; Morooka, S. [Kyushu University, Fukuoka (Japan). Faculty of Engineering; Hayashi, J. [Hokkaido University, Sapporo (Japan). Center for Advanced Research of Energy Technology

    1996-10-28

    Change in depolymerization degree and coal structure was studied for depolymerization treatment of coal in various alcohol containing aqueous hydrogen peroxide. In experiment, the mixture of Yallourn coal, alcohol and aqueous hydrogen peroxide was agitated in nitrogen atmosphere of normal pressure at 70{degree}C for 12 hours. As the experimental result, the methanol solubility of only 5% of raw coal increased up to 35.2% by hydrogen peroxide treatment, while the yield of insoluble matters also decreased from 94% to 62%. Most of the gas produced during treatment was composed of inorganic gases such as CO and CO2, and its carbon loss was extremely decreased by adding alcohol. From the analytical result of carbon loss in hydrogen peroxide treatment, it was clarified that alkylation advances with introduction of alkyl group derived from alcohol into coal by hydrogen peroxide treatment under a coexistence of alcohol, and depolymerization reaction of coal itself is thus promoted by alcohol. 4 refs., 7 figs., 1 tab.

  12. Aryl- and alkyl-phosphorus-containing flame retardants induced mitochondrial impairment and cell death in Chinese hamster ovary (CHO-k1) cells

    International Nuclear Information System (INIS)

    Huang, Chao; Li, Na; Yuan, Shengwu; Ji, Xiaoya; Ma, Mei; Rao, Kaifeng; Wang, Zijian

    2017-01-01

    Phosphorus-containing flame retardants (PFRs) are increasingly in demand worldwide as replacements for brominated flame retardants (BFRs), but insufficient available toxicological information on PFRs makes assessing their health risks challenging. Mitochondria are important targets of various environmental pollutants, and mitochondrial dysfunction may lead to many common diseases. In the present study, mitochondria impairment-related endpoints were measured by a high content screening (HCS) assay for 11 selected non-halogen PFRs in Chinese hamster ovary (CHO-k1) cells. A cluster analysis was used to categorize these PFRs into three groups according to their structural characteristics and results from the HCS assay. Two groups, containing long-chain alkyl-PFRs and all aryl-PFRs, were found to cause mitochondrial impairment but showed different mechanisms of toxicity. Due to the high correlation between cell death and mitochondrial impairment, two PFRs with different structures, trihexyl phosphate (THP) and cresyl diphenyl phosphate (CDP), were selected and compared with chlorpyrifos (CPF) to elucidate their mechanism of inducing cell death. THP (an alkyl-PFR) was found to utilize a similar pathway as CPF to induce apoptosis. However, cell death induced by CDP (an aryl-PFR) was different from classical necrosis based on experiments to discriminate among the different modes of cell death. These results confirm that mitochondria might be important targets for some PFRs and that differently structured PFRs could function via distinct mechanisms of toxicity. - Highlights: • Mitochondrial impairment induced by PFRs was observed in CHO-k1 cells. • THP (an alkyl-PFR) induced a caspase-mediated apoptosis in CHO-k1 cells. • The cell death induced by CDP (an aryl-PFR) was not traditional apoptosis or necrosis.

  13. SERIES: Genomic instability in cancer Balancing repair and tolerance of DNA damage caused by alkylating agents

    Science.gov (United States)

    Fu, Dragony; Calvo, Jennifer A.; Samson, Leona D

    2013-01-01

    Alkylating agents comprise a major class of frontline chemotherapeutic drugs that inflict cytotoxic DNA damage as their main mode of action, in addition to collateral mutagenic damage. Numerous cellular pathways, including direct DNA damage reversal, base excision repair (BER), and mismatch repair (MMR) respond to alkylation damage to defend against alkylation-induced cell death or mutation. However, maintaining a proper balance of activity both within and between these pathways is crucial for an organism's favorable response to alkylating agents. Furthermore, an individual's response to alkylating agents can vary considerably from tissue to tissue and from person to person, pointing to genetic and epigenetic mechanisms that modulate alkylating agent toxicity. PMID:22237395

  14. When alcohol is the answer: Trapping, identifying and quantifying simple alkylating species in aqueous environments.

    Science.gov (United States)

    Penketh, Philip G; Shyam, Krishnamurthy; Baumann, Raymond P; Zhu, Rui; Ishiguro, Kimiko; Sartorelli, Alan C; Ratner, Elena S

    2016-09-01

    Alkylating agents are a significant class of environmental carcinogens as well as commonly used anticancer therapeutics. Traditional alkylating activity assays have utilized the colorimetric reagent 4-(4-nitrobenzyl)pyridine (4NBP). However, 4NBP based assays have a relatively low sensitivity towards harder, more oxophilic alkylating species and are not well suited for the identification of the trapped alkyl moiety due to adduct instability. Herein we describe a method using water as the trapping agent which permits the trapping of simple alkylating electrophiles with a comparatively wide range of softness/hardness and permits the identification of donated simple alkyl moieties. Copyright © 2016 Elsevier Inc. All rights reserved.

  15. Halogen bonding: A new retention mechanism for the solid phase extraction of perfluorinated iodoalkanes

    International Nuclear Information System (INIS)

    Yan Xiaoqing; Shen Qianjin; Zhao Xiaoran; Gao Haiyue; Pang Xue; Jin Weijun

    2012-01-01

    Highlights: ► Halogen bonding (XB) is firstly utilised in solid phase extraction. ► The perfluorinated iodine alkanes can be extracted by C-I⋯Cl − halogen bonding. ► The C-I⋯Cl − halogen bond is well characterised by spectroscopy methods. ► The analytes with strong halogen-bonding abilities can be selectively extracted. - Abstract: For the first time, halogen-bonding interaction is utilised in the solid phase extraction of perfluorinated iodoalkane (PFI). Nine PFIs, as model analytes, were tested, and analyses by UV, 19 F NMR and Raman spectroscopies demonstrate that the PFIs are extracted by a strong anion exchange (SAX) sorbent from n-hexane due to the C-I⋯Cl − halogen-bonding interactions. The results also show that the adsorptivities of SAX for the diiodoperfluoro-alkanes (diiodo-PFIs) were much stronger than those for the perfluoroalkyl iodides (monoiodo-PFIs). Specifically, the recoveries for 1,6-diiodoperfluorohexane and 1,8-diiodoperfluorooctane were higher than 80% when 100 mL of sample spiked with a 5 ng mL −1 analyte mixture was extracted. Interestingly, SAX had no adsorption for hexafluorobenzene at all, which is known to be unable to form a halogen bond with Cl − . The analytical performance of the halogen bond-based SPE-GC–MS method for the diiodo-PFIs was also examined in soil samples. The sorbent SAX enabled the selective extraction of four diiodo-PFIs successfully from soil samples. The recoveries of the diiodo-PFIs extracted from 5 g soil sample at the 100 ng g −1 spike level were in the range of 73.2–93.8% except 26.8% for 1,2-diiodoperfluoroethane. The limit of detection varied from 0.02 to 0.04 ng g −1 in soil samples. Overall, this work reveals the great application potential of halogen bonding in the field of solid phase extraction to selectively extract compounds with strong halogen-bonding abilities.

  16. Extended exposure to alkylator chemotherapy: delayed appearance of myelodysplasia.

    Science.gov (United States)

    Chamberlain, Marc C; Raizer, Jeffrey

    2009-06-01

    A case series of gliomas treated with alkylator-based chemotherapy who subsequently developed myelodysplastic syndrome (tMDS) or acute myelocytic leukemia (AML). Alkylator-based chemotherapy is recognized to be leukemogenic; however, it is infrequently described as a delayed consequence of anti-glioma treatment. Seven patients (4 men; 3 women) ages 34-69 years (median 44), with gliomas (3 Grade 2; 4 Grade 3) were treated with surgery, all but one with involved-field radiotherapy and all with alkylator-based chemotherapy (temozolomide; 6 patients, nitrosoureas; 5 patients, both agents; 5 patients). Exposure to alkylator-based chemotherapy ranged from 8 to 30 months (median 24). The diagnosis of tMDS was determined by bone marrow biopsy in 7 patients. Seven patients showed chromosomal abnormalities consistent with chemotherapy induced MDS. Three patients were diagnosed with AML as well (in two determined by bone marrow and one at autopsy). Interval from last chemotherapy exposure to diagnosis of tMDS/AML ranged from 3 to 31 months (median 24 months). Two patients were treated with bone marrow transplantation and 5 received supportive care only. Five patients have died, 2 as a consequence of recurrent brain tumor, 1 as a complication of transplantation, and 2 due to AML. Although rare, induction of tMDS/AML following extended use of alkylator-based chemotherapy may become more relevant with the evolving practice to treat gliomas for protracted periods. Future work to determine at risk patients would be important.

  17. Effect of Amphiphilic Alkyl Chain Length Upon Purified LATEX Stability

    International Nuclear Information System (INIS)

    Amira Amir Hassan; Amir Hashim Mohd Yatim

    2015-01-01

    Rubber particles in purified latex (PL) are stabilized by a film of protein and fatty acid soap (surfactant). Saturated straight-chain fatty acid soaps can assist an enhancement of latex stability. However, whether the alkyl chain length plays an important role in increasing the stability is still an issue. The aim of this study is to investigate the effect of alkyl chain length of anionic surfactant on the stability of purified latex. The fatty acid soap of decanoate (9), laurate (11), sodium dodecyl sulphate (SDS) (12) and palmitate (15) were used. The numbers in parentheses indicating the number of carbon present in alkyl chain of the soap. The results showed that the impact of alkyl chain length on the stability of latex is in the order of laurate > decanoate > SDS > palmitate > purified latex accordingly. The alkyl chain length does giving a significant effect on latex stability after longer stirring time. The particle size of latex with the presence of surfactant is greater compare to a single particle itself due to extension of particles diameter. Thus suitable interaction of the nonpolar tail of surfactant with the hydrophobic regions of latex surface played a major role in maintaining a stable latex system. (author)

  18. General Allylic C–H Alkylation with Tertiary Nucleophiles

    Science.gov (United States)

    2015-01-01

    A general method for intermolecular allylic C–H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C–H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C–H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C–H reactivity are illustrated in an allylic C–H alkylation/Diels–Alder reaction cascade: a reactive diene is generated via intermolecular allylic C–H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids. PMID:24641574

  19. General allylic C-H alkylation with tertiary nucleophiles.

    Science.gov (United States)

    Howell, Jennifer M; Liu, Wei; Young, Andrew J; White, M Christina

    2014-04-16

    A general method for intermolecular allylic C-H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C-H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C-H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C-H reactivity are illustrated in an allylic C-H alkylation/Diels-Alder reaction cascade: a reactive diene is generated via intermolecular allylic C-H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.

  20. Identification and quantification of the halogenated natural product BC-3

    Energy Technology Data Exchange (ETDEWEB)

    Melcher, J.; Olbrich, D.; Vetter, W. [Hohenheim Univ., Stuttgart (Germany). Inst. fuer Lebensmittelchemie; Marsh, G. [Stockholm Univ. (Sweden). Dept. of Environmental Chemistry; Gaus, C.; Mueller, J.F. [National Research Centre for Environmental Toxicology, Coopers Plains (Australia)

    2004-09-15

    Halogenated natural products (HNPs) of marine origin are increasingly recognized as critical residues in foodstuff (e. g. fish) and environmental samples (e. g. marine mammals and birds). Some of these HNPs (Q1, MHC-1, BC-2, and HDBPs including BC-10) were detected in diverse fish and marine mammal samples at concentrations sometimes exceeding those of PCBs, DDT, and other anthropogenic pollutants. Recent studies with marine mammal samples from Australia led to the detection of six abundant HNPs (Q1, BC-1, BC-2, BC-3, BC-10, and BC-11). In the meantime, Q1 was identified as heptachloro-1{sup '}-methyl-1,2{sup '}-bipyrrole, BC-2 as 4,6-dibromo-2-(2{sup '},4{sup '}-dibromo)phenoxyanisole, BC- 10 as 1,1{sup '}-dimethyl-3,3{sup '},4,4{sup '}-tetrabromo-5,5{sup '}-dichloro-2,2{sup '}-bipyrrole, and BC-11 as 3,5-dibromo- 2-(3{sup '},5{sup '}-dibromo,2{sup '}-methoxy)phenoxyanisole. However the identity of BC-1 and BC-3 remained unclear. The goal of the present study was the identification of BC-3. The tetrabromo compound BC-3 has previously been detected in marine mammals from four continents. Furthermore, we attempted establishing quantitative concentrations in diverse marine biota samples.

  1. Sea ice dynamics influence halogen deposition to Svalbard

    Directory of Open Access Journals (Sweden)

    A. Spolaor

    2013-10-01

    Full Text Available Sea ice is an important parameter in the climate system and its changes impact upon the polar albedo and atmospheric and oceanic circulation. Iodine (I and bromine (Br have been measured in a shallow firn core drilled at the summit of the Holtedahlfonna glacier (Northwest Spitsbergen, Svalbard. Changing I concentrations can be linked to the March–May maximum sea ice extension. Bromine enrichment, indexed to the Br / Na sea water mass ratio, appears to be influenced by changes in the seasonal sea ice area. I is emitted from marine biota and so the retreat of March–May sea ice coincides with enlargement of the open-ocean surface which enhances marine primary production and consequent I emission. The observed Br enrichment could be explained by greater Br emissions during the Br explosions that have been observed to occur mainly above first year sea ice during the early springtime. In this work we present the first comparison between halogens in surface snow and Arctic sea ice extension. Although further investigation is required to characterize potential depositional and post-depositional processes, these preliminary findings suggest that I and Br can be linked to variability in the spring maximum sea ice extension and seasonal sea ice surface area.

  2. Solubility of gases in 1-alkyl-3methylimidazolium alkyl sulfate ionic liquids: Experimental determination and modeling

    International Nuclear Information System (INIS)

    Bermejo, María Dolores; Fieback, Tobias M.; Martín, Ángel

    2013-01-01

    Highlights: ► The solubility of CO 2 , CH 4 and C 2 H 6 in [emim][EtSO 4 ] is measured with a magnetic suspension balance. ► New data and literature results have been modeled with a Group Contribution equation of state. ► A specific group definition is required to model data of ionic liquids with a [MeSO 4 ] anion. ► Deviations between model and experiments are lower than 10% in most cases. ► Deviations of 34% are observed in the case of the solubility of ethane in the ionic liquid. -- Abstract: The solubility of different gases (carbon dioxide, methane, ethane, carbon monoxide and hydrogen) in ionic liquids with an alkyl sulfate anion has been modeled with the Group Contribution equation of state developed by Skjold-Jørgensen. New gas solubility measurements have been carried out with a high pressure magnetic suspension balance in order to cover pressure and temperature ranges not considered in previous studies and to obtain more experimental information for the correlation of parameters of the equation of state. New solubility measurements include the solubility of carbon dioxide in 1-ethyl 3-methyl imidazolium ethyl sulfate [emim][EtSO 4 ] at temperatures of 298 K and 348 K and pressures ranging from 0.3 MPa to 6.5 MPa, the solubility of methane in [emim][EtSO 4 ] at a temperature of 293 K and pressures ranging from 0.2 MPa to 10.2 MPa, and the solubility of ethane in [emim][EtSO 4 ] at temperatures of 323 K and 350 K and pressures ranging from 0.2 MPa to 4 MPa. Results show that the Group Contribution equation of state can be used to describe the solubility of gases in alkyl sulfate ionic liquids as well as infinite dilution coefficients of alkanes in the ionic liquids, with average deviations between experiments and calculations ranging from 1% to 10% in the case of mixtures with CO 2 , CO, CH 4 and H 2 with the alkyl sulfate ionic liquids to up to 34% in the case of the solubility of ethane in [emim][EtSO 4

  3. Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions

    Directory of Open Access Journals (Sweden)

    Naoya Usuki

    2017-12-01

    Full Text Available Isotactic (it- and syndiotactic (st- poly(methyl methacrylates (PMMAs form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st- PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl4 as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN3. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH3CN and was affected by the block lengths and ratios.

  4. Isostructurality and non-isostructurality in the series of halogenated organic crystal substances. The structure of Hal-aggregates

    International Nuclear Information System (INIS)

    Grineva, O.V.; Zorkij, P.M.

    2001-01-01

    Local characteristics and the type of intermolecular Hal-aggregates (ensembles of contacting halogen atoms of adjacent molecules) present in chemically similar halogenated crystal substances, differing only in the nature of Hal atoms, are compared. 23 series of halogenated hydrocarbons, including 57 crystal structures were considered. A clearly pronounced specificity of Hal-aggregates for compounds with a low and intermediate content of halogen was revealed. It was found that, as a rule, coordination number of Hal atom by Hal adjacent atoms increases in the series F-Cl-Br-I [ru

  5. Singlet oxygen production by combining erythrosine and halogen light for photodynamic inactivation of Streptococcus mutans.

    Science.gov (United States)

    Fracalossi, Camila; Nagata, Juliana Yuri; Pellosi, Diogo Silva; Terada, Raquel Sano Suga; Hioka, Noboru; Baesso, Mauro Luciano; Sato, Francielle; Rosalen, Pedro Luiz; Caetano, Wilker; Fujimaki, Mitsue

    2016-09-01

    Photodynamic inactivation of microorganisms is based on a photosensitizing substance which, in the presence of light and molecular oxygen, produces singlet oxygen, a toxic agent to microorganisms and tumor cells. This study aimed to evaluate singlet oxygen quantum yield of erythrosine solutions illuminated with a halogen light source in comparison to a LED array (control), and the photodynamic effect of erythrosine dye in association with the halogen light source on Streptococcus mutans. Singlet oxygen quantum yield of erythrosine solutions was quantified using uric acid as a chemical-probe in an aqueous solution. The in vitro effect of the photodynamic antimicrobial activity of erythrosine in association with the halogen photopolimerizing light on Streptococcus mutans (UA 159) was assessed during one minute. Bacterial cultures treated with erythrosine alone served as negative control. Singlet oxygen with 24% and 2.8% degradation of uric acid in one minute and a quantum yield of 0.59 and 0.63 was obtained for the erythrosine samples illuminated with the halogen light and the LED array, respectively. The bacterial cultures with erythrosine illuminated with the halogen light presented a decreased number of CFU mL(-1) in comparison with the negative control, with minimal inhibitory concentrations between 0.312 and 0.156mgmL(-1). The photodynamic response of erythrosine induced by the halogen light was capable of killing S. mutans. Clinical trials should be conducted to better ascertain the use of erythrosine in association with halogen light source for the treatment of dental caries. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Alkylation of imidazole under ultrasound irradiation over alkaline carbons

    International Nuclear Information System (INIS)

    Costarrosa, L.; Calvino-Casilda, V.; Ferrera-Escudero, S.; Duran-Valle, C.J.; Martin-Aranda, R.M.

    2006-01-01

    N-Alkyl-imidazole has been synthesized by sonochemical irradiation of imidazole and 1-bromobutane using alkaline-promoted carbons (exchanged with the binary combinations of Na, K and Cs). The catalysts were characterized by X-ray photoelectron spectroscopy, thermal analysis and N 2 adsorption isotherms. Under the experimental conditions, N-alkyl-imidazoles can be prepared with a high activity and selectivity. It is observed that imidazole conversion increases in parallel with increasing the basicity of the catalyst. The influence of the alkaline promoter, the reaction temperature, and the amount of catalyst on the catalytic activity has been studied. For comparison, the alkylation of imidazole has also been performed in a batch reactor system under thermal activation

  7. From old alkylating agents to new minor groove binders.

    Science.gov (United States)

    Puyo, Stéphane; Montaudon, Danièle; Pourquier, Philippe

    2014-01-01

    Alkylating agents represent the oldest class of anticancer agents with the approval of mechloretamine by the FDA in 1949. Even though their clinical use is far beyond the use of new targeted therapies, they still occupy a major place in the treatment of specific malignancies, sometimes representing the unique option for the treatment of refractory tumors. Here, we are reviewing the major classes of alkylating agents, with a particular focus on the latest generations of compounds that specifically target the minor groove of the DNA. These naturally occurring derivatives have a unique mechanism of action that explains the recent regain of interest in developing new classes of alkylating agents that could be used in combination with other anticancer drugs to enhance tumor response in the clinic. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  8. Alkyl Radicals as Hydrogen Bond Acceptors: Computational Evidence

    DEFF Research Database (Denmark)

    Hammerum, Steen

    2009-01-01

    Spectroscopic, energetic and structural information obtained by DFT and G3-type computational studies demonstrates that charged proton donors can form moderately strong hydrogen bonds to simple alkyl radicals. The presence of these bonds stabilizes the adducts and modifies their structure......, and gives rise to pronounced shifts of IR stretching frequencies and to increased absorption intensities. The hydrogen bond acceptor properties of alkyl radicals equal those of many conventional acceptors, e.g., the bond length changes and IR red-shifts suggest that tert-butyl radicals are slightly better...... acceptors than formaldehyde molecules, while propyl radicals are as good as H2O. The hydrogen bond strength appears to depend on the proton affinity of the proton donor and on the ionization energy of the acceptor alkyl radical, not on the donor-acceptor proton affinity difference, reflecting...

  9. Highly Effective Gene Transfection In Vivo by Alkylated Polyethylenimine

    Directory of Open Access Journals (Sweden)

    Jennifer A. Fortune

    2011-01-01

    Full Text Available We mechanistically explored the effect of increased hydrophobicity of the polycation on the efficacy and specificity of gene delivery in mice. N-Alkylated linear PEIs with varying alkyl chain lengths and extent of substitution were synthesized and characterized by biophysical methods. Their in vivo transfection efficiency, specificity, and biodistribution were investigated. N-Ethylation improves the in vivo efficacy of gene expression in the mouse lung 26-fold relative to the parent polycation and more than quadruples the ratio of expression in the lung to that in all other organs. N-Propyl-PEI was the best performer in the liver and heart (581- and 3.5-fold enhancements, resp. while N-octyl-PEI improved expression in the kidneys over the parent polymer 221-fold. As these enhancements in gene expression occur without changing the plasmid biodistribution, alkylation does not alter the cellular uptake but rather enhances transfection subsequent to cellular uptake.

  10. Radiation-chemical alkylation of olefines with adamantane

    International Nuclear Information System (INIS)

    Podkhalyuzin, A.T.; Vikulin, V.V.; Morozov, V.A.; Nazarova, M.P.; Vereshchinskii, I.V.

    1977-01-01

    Radiation-chemical alkylation of C 2 to C 4 olefines with adamantane was studied in gas phase at temperatures 270 to 430 0 C. The main reaction product is monoalkyladamantane. The reaction proceeds by a free radical chain mechanism. The effective activation energy is of the order of 8 to 10 kcal/mole. Thermal alkylation was carried out for comparison and the contribution of the thermal component to the radiation-thermal process was estimated. Liquid phase alkylation of hexafluoropropylene with adamantane was studied in the presence of solvents. Under various conditions mono- and di-substituted adamantanes are produced containing fluorine in end groups. These compounds were converted to corresponding fluoroalkenyladamantanes by dehydrofluorination. The kinetic parameters were calculated and physical-chemical data concerning some of the resulting products were determined. (author)

  11. Alkylation sensitivity screens reveal a conserved cross-species functionome

    Science.gov (United States)

    Svilar, David; Dyavaiah, Madhu; Brown, Ashley R.; Tang, Jiang-bo; Li, Jianfeng; McDonald, Peter R.; Shun, Tong Ying; Braganza, Andrea; Wang, Xiao-hong; Maniar, Salony; St Croix, Claudette M.; Lazo, John S.; Pollack, Ian F.; Begley, Thomas J.; Sobol, Robert W.

    2013-01-01

    To identify genes that contribute to chemotherapy resistance in glioblastoma, we conducted a synthetic lethal screen in a chemotherapy-resistant glioblastoma derived cell line with the clinical alkylator temozolomide (TMZ) and an siRNA library tailored towards “druggable” targets. Select DNA repair genes in the screen were validated independently, confirming the DNA glycosylases UNG and MYH as well as MPG to be involved in the response to high dose TMZ. The involvement of UNG and MYH is likely the result of a TMZ-induced burst of reactive oxygen species. We then compared the human TMZ sensitizing genes identified in our screen with those previously identified from alkylator screens conducted in E. coli and S. cerevisiae. The conserved biological processes across all three species composes an Alkylation Functionome that includes many novel proteins not previously thought to impact alkylator resistance. This high-throughput screen, validation and cross-species analysis was then followed by a mechanistic analysis of two essential nodes: base excision repair (BER) DNA glycosylases (UNG, human and mag1, S. cerevisiae) and protein modification systems, including UBE3B and ICMT in human cells or pby1, lip22, stp22 and aim22 in S. cerevisiae. The conserved processes of BER and protein modification were dual targeted and yielded additive sensitization to alkylators in S. cerevisiae. In contrast, dual targeting of BER and protein modification genes in human cells did not increase sensitivity, suggesting an epistatic relationship. Importantly, these studies provide potential new targets to overcome alkylating agent resistance. PMID:23038810

  12. Solid-Phase S-Alkylation Promoted by Molecular Sieves.

    Science.gov (United States)

    Calce, Enrica; Leone, Marilisa; Mercurio, Flavia Anna; Monfregola, Luca; De Luca, Stefania

    2015-11-20

    A solid-phase S-alkylation procedure to introduce chemical modification on the cysteine sulfhydryl group of a peptidyl resin is reported. The reaction is promoted by activated molecular sieves and consists of a solid-solid process, since both the catalyst and the substrate are in a solid state. The procedure was revealed to be efficient and versatile, particularly when used in combination with the solution S-alkylation approach, allowing for the introduction of different molecular diversities on the same peptide molecule.

  13. The effect of alkylating agents on model supported metal clusters

    Energy Technology Data Exchange (ETDEWEB)

    Erdem-Senatalar, A.; Blackmond, D.G.; Wender, I. (Pittsburgh Univ., PA (USA). Dept. of Chemical and Petroleum Engineering); Oukaci, R. (CERHYD, Algiers (Algeria))

    1988-01-01

    Interactions between model supported metal clusters and alkylating agents were studied in an effort to understand a novel chemical trapping technique developed for identifying species adsorbed on catalyst surfaces. It was found that these interactions are more complex than had previously been suggested. Studies were completed using deuterium-labeled dimethyl sulfate (DMS), (CH{sub 3}){sub 2}SO{sub 4}, as a trapping agent to interact with the supported metal cluster ethylidyne tricobalt enneacarbonyl. Results showed that oxygenated products formed during the trapping reaction contained {minus}OCD{sub 3} groups from the DMS, indicating that the interaction was not a simple alkylation. 18 refs., 1 fig., 3 tabs.

  14. Direct α-alkylation of ketones with alcohols in water.

    Science.gov (United States)

    Xu, Guoqiang; Li, Qiong; Feng, Jiange; Liu, Qiang; Zhang, Zuojun; Wang, Xicheng; Zhang, Xiaoyun; Mu, Xindong

    2014-01-01

    The direct α-alkylation of ketones with alcohols has emerged as a new green protocol to construct C-C bonds with H2 O as the sole byproduct. In this work, a very simple and convenient Pd/C catalytic system for the direct α-alkylation of ketones with primary alcohols in pure water is developed. Based on this catalytic system, aqueous mixtures of dilute acetone, 1-butanol, and ethanol (mimicking ABE fermentation products) can be directly transformed into C5 -C11 or longer-chain ketones and alcohols, which are precursors to fuels. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Regeneration of zeolite catalysts of isobutane alkylation with butenes

    Energy Technology Data Exchange (ETDEWEB)

    Manza, I.A.; Tsupryk, I.N.; Bartyshevskii, V.A.; Gaponenko, O.I.; Petrilyak, K.I.

    1986-12-10

    The industrial adoption of alkylation of isoalkanes with alkenes is held back by the rapid and irreversible deactivation of the zeolite catalysts appropriate to the process. This paper is aimed specifically at the restoration of the catalytic activity and increase in the service life of zeolite alkylation catalysts. The catalyst chosen for the investigation was HLaCaNaX zeolite both unmodified and modified with various multivalence cations. The thermochemical and oxidative regeneration process as well as the equipment utilized are described. Both the advantages and the drawbacks of the method are given; explanations for the possibly irreversible losses of the catalytic properties in the regenerated zeolites are also put forward.

  16. A Theoretical Study of the Mechanism of the Alkylation of Guanine by N- Nitroso Compounds.

    Science.gov (United States)

    1992-01-01

    these chemical agents alkylate DNA, but, as yet, the precise mechanism is unknown. What is known is that the result is a DNA-mutagen adduct with an alkyl ... nitrosoureas , Singer et. al. found that about 25% of the alkylation caused by MNU was on the DNA phospate backbone while, for ENU, phosphate...sites. 1.3 Mutagenicity of N-Nitroso Compounds In early experimental work with agents which alkylate DNA, comparisons of ultraviolet absorption

  17. Analysis of Halogen-Mercury Reactions in Flue Gas

    Energy Technology Data Exchange (ETDEWEB)

    Paula Buitrago; Geoffrey Silcox; Constance Senior; Brydger Van Otten

    2010-01-01

    Oxidized mercury species may be formed in combustion systems through gas-phase reactions between elemental mercury and halogens, such as chorine or bromine. This study examines how bromine species affect mercury oxidation in the gas phase and examines the effects of mixtures of bromine and chlorine on extents of oxidation. Experiments were conducted in a bench-scale, laminar flow, methane-fired (300 W), quartz-lined reactor in which gas composition (HCl, HBr, NO{sub x}, SO{sub 2}) and temperature profile were varied. In the experiments, the post-combustion gases were quenched from flame temperatures to about 350 C, and then speciated mercury was measured using a wet conditioning system and continuous emissions monitor (CEM). Supporting kinetic calculations were performed and compared with measured levels of oxidation. A significant portion of this report is devoted to sample conditioning as part of the mercury analysis system. In combustion systems with significant amounts of Br{sub 2} in the flue gas, the impinger solutions used to speciate mercury may be biased and care must be taken in interpreting mercury oxidation results. The stannous chloride solution used in the CEM conditioning system to convert all mercury to total mercury did not provide complete conversion of oxidized mercury to elemental, when bromine was added to the combustion system, resulting in a low bias for the total mercury measurement. The use of a hydroxylamine hydrochloride and sodium hydroxide solution instead of stannous chloride showed a significant improvement in the measurement of total mercury. Bromine was shown to be much more effective in the post-flame, homogeneous oxidation of mercury than chlorine, on an equivalent molar basis. Addition of NO to the flame (up to 400 ppmv) had no impact on mercury oxidation by chlorine or bromine. Addition of SO{sub 2} had no effect on mercury oxidation by chlorine at SO{sub 2} concentrations below about 400 ppmv; some increase in mercury oxidation

  18. Process for removing halogenated aliphatic and aromatic compounds from petroleum products

    Science.gov (United States)

    Googin, J.M.; Napier, J.M.; Travaglini, M.A.

    1983-09-20

    A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

  19. Simultaneous determination of radioactive halogen isotopes and 99Tc

    International Nuclear Information System (INIS)

    Kabai, E.; Vajda, N.; Gaca, P.

    2003-01-01

    The purpose of this study was to develop a simplified method for simultaneous determination of radiologically important halogen isotopes and 99 Tc from different types of samples like environmental, biological and waste samples. Due to their long half-lives (longer than 10 5 years) they play important role in the nuclear cycle, especially in environmental monitoring and protection. For a rapid response in the evaluation of 129 I, 36 Cl and 99 Tc contamination levels of these samples it is advantageous to combine the existing individual methods. According to the present procedure, iodine, chlorine and technetium are separated selectively from the same sample aliquot followed by the β spectrometry of the purified fractions. Increased sensitivities can be achieved by neutron activation (NA) especially in the case of 129 I. Our work intends to solve the problem by combining the well-known hot acidic distillation method for iodine separation with the organic extraction process characteristic for technetium separation. The major objective of the work was to separate the disturbing halides from iodine. For this purpose a selective oxidant was applied. For the sample destruction and fractionated distillation an air flow-through installation was used with hot concentrated sulphuric and nitric acids. The trap for iodine contained 3 M NaOH solution. After iodine separation the trap was exchanged for a new one containing the same solution for trapping chlorine or bromine with an addition of 0.01 M KMnO 4 solution as an oxidative agent. As expected, the main part of technetium was contained in the acidic residue after distillation. Tc purification was performed by organic extraction with TBP and TEVA column. (author)

  20. 13C separation by IRMPD of halogenated difluoromethanes

    International Nuclear Information System (INIS)

    Ma Peihua; Chen Guancheng; Wu Bin; Liu Julin; Jing Yan; Chu Minxiong; Arai, Shigeyoshi.

    1995-01-01

    Isotopically-selective consecutive two-stage infrared multiphoton dissociation (IRMPD) of halogenated difluoromethanes in the presence of scavengers produces carbon-13 over 95 %. The reaction mechanism for the IRMPD of mixture of CHClF 2 and HI can be explained by a series of first-order dissociation reactions and followed radical-scavenger reactions occurred in a continuous irradiation procedure. Furthermore, 13 C enrichment at laboratory scaling-up level by the 13 C selective IRMPD of CHClF 2 /Br 2 mixture has been investigated in a flow reactor. The 13 C production rates, 13 C atomic fractions in the CBr 2 F 2 products and 13 C depletions in the CHClF 2 reactants at different flow rates and laser repetition frequencies were examined to optimize the parameters suitable for large-scale production of carbon isotope. The data obtained from the flow tests demonstrated a 40 mg h -1 production rate for CB 2 F 2 at 65 % carbon-13 by using a 40 W (4J, 10 Hz) laser beam focused with a lens of focal length 120 cm. If a reliable TEA CO 2 laser can be operated with 100 W (10 J, 10 Hz) output, the production rate of CBr 2 F 2 for carbon-13 at 60 % can attain 200 mg h -1 . The measurements of spatial profile of focused laser beam imply a 2 g h -1 production rate for the 60 % carbon-13 product for an incident power of 200 W (20 J, 10 Hz). (author)

  1. Immobilization of lipases on alkyl silane modified magnetic nanoparticles: effect of alkyl chain length on enzyme activity.

    Directory of Open Access Journals (Sweden)

    Jiqian Wang

    Full Text Available BACKGROUND: Biocatalytic processes often require a full recycling of biocatalysts to optimize economic benefits and minimize waste disposal. Immobilization of biocatalysts onto particulate carriers has been widely explored as an option to meet these requirements. However, surface properties often affect the amount of biocatalysts immobilized, their bioactivity and stability, hampering their wide applications. The aim of this work is to explore how immobilization of lipases onto magnetite nanoparticles affects their biocatalytic performance under carefully controlled surface modification. METHODOLOGY/PRINCIPAL FINDINGS: Magnetite nanoparticles, prepared through a co-precipitation method, were coated with alkyl silanes of different alkyl chain lengths to modulate their surface hydrophobicity. Candida rugosa lipase was then directly immobilized onto the modified nanoparticles through hydrophobic interaction. Enzyme activity was assessed by catalytic hydrolysis of p-nitrophenyl acetate. The activity of immobilized lipases was found to increase with increasing chain length of the alkyl silane. Furthermore, the catalytic activities of lipases immobilized on trimethoxyl octadecyl silane (C18 modified Fe(3O(4 were a factor of 2 or more than the values reported from other surface immobilized systems. After 7 recycles, the activities of the lipases immobilized on C18 modified nanoparticles retained 65%, indicating significant enhancement of stability as well through hydrophobic interaction. Lipase immobilized magnetic nanoparticles facilitated easy separation and recycling with high activity retaining. CONCLUSIONS/SIGNIFICANCE: The activity of immobilized lipases increased with increasing alkyl chain length of the alkyl trimethoxy silanes used in the surface modification of magnetite nanoparticles. Lipase stability was also improved through hydrophobic interaction. Alkyl silane modified magnetite nanoparticles are thus highly attractive carriers for

  2. Immobilization of lipases on alkyl silane modified magnetic nanoparticles: effect of alkyl chain length on enzyme activity.

    Science.gov (United States)

    Wang, Jiqian; Meng, Gang; Tao, Kai; Feng, Min; Zhao, Xiubo; Li, Zhen; Xu, Hai; Xia, Daohong; Lu, Jian R

    2012-01-01

    Biocatalytic processes often require a full recycling of biocatalysts to optimize economic benefits and minimize waste disposal. Immobilization of biocatalysts onto particulate carriers has been widely explored as an option to meet these requirements. However, surface properties often affect the amount of biocatalysts immobilized, their bioactivity and stability, hampering their wide applications. The aim of this work is to explore how immobilization of lipases onto magnetite nanoparticles affects their biocatalytic performance under carefully controlled surface modification. Magnetite nanoparticles, prepared through a co-precipitation method, were coated with alkyl silanes of different alkyl chain lengths to modulate their surface hydrophobicity. Candida rugosa lipase was then directly immobilized onto the modified nanoparticles through hydrophobic interaction. Enzyme activity was assessed by catalytic hydrolysis of p-nitrophenyl acetate. The activity of immobilized lipases was found to increase with increasing chain length of the alkyl silane. Furthermore, the catalytic activities of lipases immobilized on trimethoxyl octadecyl silane (C18) modified Fe(3)O(4) were a factor of 2 or more than the values reported from other surface immobilized systems. After 7 recycles, the activities of the lipases immobilized on C18 modified nanoparticles retained 65%, indicating significant enhancement of stability as well through hydrophobic interaction. Lipase immobilized magnetic nanoparticles facilitated easy separation and recycling with high activity retaining. The activity of immobilized lipases increased with increasing alkyl chain length of the alkyl trimethoxy silanes used in the surface modification of magnetite nanoparticles. Lipase stability was also improved through hydrophobic interaction. Alkyl silane modified magnetite nanoparticles are thus highly attractive carriers for enzyme immobilization enabling efficient enzyme recovery and recycling.

  3. The formation of [M-H]+ ions in N-alkyl-substituted thieno[3,4-c]-pyrrole-4,6-dione derivatives during atmospheric pressure photoionization mass spectrometry

    KAUST Repository

    Sioud, Salim

    2014-10-09

    RESULTS [M-H]+ ions were observed under APPI conditions. The type of dopant and the length of the alkyl chain affected the formation of these ions. MS/MS fragmentation of [M-H]+ and [M + H]+ ions exhibited completely different patterns. Theoretical calculations revealed that the loss of hydrogen molecules from the [M + H]+ ions is the most favourable condition under which to form [M-H]+ ions.CONCLUSIONS [M-H]+ ions were detected in all the TPD derivatives studied here under the special experimental conditions during APPI, using a halogenated benzene dopant, and TPD containing substituted N-alkyl side chains with a minimum of four carbon atoms. Density functional theory calculations showed that for [M-H]+ ions to be formed under these conditions, the loss of hydrogen molecules from the [M + H]+ ions is proposed to be necessary.RATIONALE The formation of ions during atmospheric pressure photoionization (APPI) mass spectrometry in the positive mode usually provides radical cations and/or protonated species. Intriguingly, during the analysis of some N-alkyl-substituted thieno[3,4-c]pyrrole-4,6-dione (TPD) derivatives synthesized in our laboratory, unusual [M-H]+ ion peaks were observed. In this work we investigate the formation of [M-H]+ ions observed under APPI conditions.METHODS Multiple experimental parameters, including the type of ionization source, the composition of the solvent, the type of dopant, the infusion flow rate, and the length of the alkyl side chain were investigated to determine their effects on the formation of [M-H]+ ions. In addition, a comparison study of the gas-phase tandem mass spectrometric (MS/MS) fragmentation of [M + H]+ vs [M-H]+ ions and computational approaches were used.

  4. 40 CFR 721.10143 - Amines, bis (C11-14-branched and linear alkyl).

    Science.gov (United States)

    2010-07-01

    ... linear alkyl). 721.10143 Section 721.10143 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10143 Amines, bis (C11-14-branched and linear alkyl). (a) Chemical..., bis (C11-14-branched and linear alkyl) (PMN P-06-733; CAS No. 900169-60-0) is subject to reporting...

  5. 40 CFR 721.520 - Alanine, N-(2-carboxyethyl)-N-alkyl-, salt.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alanine, N-(2-carboxyethyl)-N-alkyl... Specific Chemical Substances § 721.520 Alanine, N-(2-carboxyethyl)-N-alkyl-, salt. (a) Chemical substance... alanine, N-(2-carboxyethyl)-N- alkyl-, salt (P-89-336) is subject to reporting under this section for the...

  6. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under this...

  7. 40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

    Science.gov (United States)

    2010-07-01

    ..., alkali and amine salts. 721.2565 Section 721.2565 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.2565 Alkylated sulfonated diphenyl oxide, alkali and... substances identified as alkylated sulfonated diphenyl oxide, alkali salt (PMN P-93-352) and alkylated...

  8. Synthesis and Performance of a Biomimetic Indicator for Alkylating Agents.

    Science.gov (United States)

    Provencher, Philip A; Love, Jennifer A

    2015-10-02

    4-(4-Nitrobenzyl)pyridine (NBP) is a colorimetric indicator compound for many types of carcinogenic alkylating agents. Because of the similar reactivity of NBP and guanine in DNA, NBP serves as a DNA model. NBP assays are used in the toxicological screening of pharmaceutical compounds, detection of chemical warfare agents, environmental hygiene technology, preliminary toxicology tests, mutagenicity of medicinal compounds, and other chemical analyses. Nevertheless, the use of NBP as a DNA model suffers from the compound's low water solubility, its lack of reactive oxygen sites, and dissimilar steric encumbrance compared to DNA. We report herein the design and synthesis of NBP derivatives that address some of these issues. These derivatives have been tested in solution and found to be superior in the colorimetric assay of the alkylating anticancer drug cyclophosphamide. The derivatives have also been integrated into a polymeric silica material which changes color upon the exposure to dangerous alkylating agents, such as iodomethane vapor, without the need for an exogenous base. This material modernizes the NBP assay from a time-consuming laboratory analysis to a real-time solid state sensor, which requires neither solvent nor additional reagents and can detect both gas- and solution-phase alkylating agents.

  9. Synthesis and Antiangiogenic Activity of N-Alkylated Levamisole Derivatives

    DEFF Research Database (Denmark)

    Hansen, Anders N.; Bendiksen, Christine D.; Sylvest, Lene

    2012-01-01

    profile, was recently shown to be an inhibitor of angiogenesis in vitro and exhibited tumor growth inhibition in mice. Here we describe the synthesis and in vitro evaluation of a series of N-alkylated analogues of levamisole with the aim of characterizing structure-activity relationships with regard...

  10. Leukemia after therapy with alkylating agents for childhood cancer

    International Nuclear Information System (INIS)

    Tucker, M.A.; Meadows, A.T.; Boice, J.D. Jr.

    1987-01-01

    The risk of leukemia was evaluated in 9,170 2-or-more-year survivors of childhood cancer in the 13 institutions of the Late Effects Study Group. Secondary leukemia occurred in 22 nonreferred individuals compared to 1.52 expected, based on general population rates [relative risk (RR) = 14; 95% confidence interval (CI), 9-22]. The influence of therapy for the first cancer on subsequent leukemia risk was determined by a case-control study conducted on 25 cases and 90 matched controls. Treatment with alkylating agents was associated with a significantly elevated risk of leukemia (RR = 4.8; 95% CI, 1.2-18.9). A strong dose-response relationship was also observed between leukemia risk and total dose of alkylating agents, estimated by an alkylator score. The RR of leukemia reached 23 in the highest dose category. Radiation therapy, however, did not increase risk. Although doxorubicin was also identified as a possible risk factor, the excess risk of leukemia following treatment for childhood cancer appears almost entirely due to alkylating agents

  11. Ionic liquid containing hydroxamate and N-alkyl sulfamate ions

    Science.gov (United States)

    Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

    2016-03-15

    Embodiments of the invention are related to ionic liquids and more specifically to ionic liquids used in electrochemical metal-air cells in which the ionic liquid includes a cation and an anion selected from hydroxamate and/or N-alkyl sulfamate anions.

  12. Alkyl chitosan film-high strength, functional biomaterials.

    Science.gov (United States)

    Lu, Li; Xing, Cao; Xin, Shen; Shitao, Yu; Feng, Su; Shiwei, Liu; Fusheng, Liu; Congxia, Xie

    2017-11-01

    Biofilm with strong tensile strength is a topic item in the area of tissue engineering, medicine engineering, and so forth. Here we introduced an alkyl chitosan film with strong tensile strength and its possibility for an absorbable anticoagulation material in vivo was tested in the series of blood test, such as dynamic coagulation time, plasma recalcification time and hemolysis. Alkyl chitosan film was a better biomaterial than traditional chitosan film in the anticoagulation, tissue compatibility and cell compatibility. The unique trait of alkyl chitosan film may be for its greater contact angle and hydrophobicity ability to reduce the adsorption capacity for the blood component and the activity of fibrinolytic enzymes, enhance the antibacterial capacity than chitosan film. Moreover, none of chitosan film or butyl chitosan film exhibited quick inflammation or other disadvantage and degraded quickly by implanted test. Therefore, Alkyl chitosan film is of prospective properties as an implantable, absorbable agent for tissue heals, and this material need further research. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 3034-3041, 2017. © 2017 Wiley Periodicals, Inc.

  13. A Green Alternative to Aluminum Chloride Alkylation of Xylene

    Science.gov (United States)

    Sereda, Grigoriy A.; Rajpara, Vikul B.

    2007-01-01

    An acutely less toxic 2-bromobutane is used to develop a simple graphite-promoted procedure of alkylation of p-xylene. It is further demonstrated that aluminum chloride is not required, the need for aqueous workup is eliminated, waste solutions are not produced and the multiple use of the catalyst is allowed.

  14. An efficient, heterogeneous and reusable catalyst for -alkylation of ...

    Indian Academy of Sciences (India)

    Fe(HSO4)3(FHS) was used as an efficient catalyst for the heterogeneous addition of a series of benzylic and allylic alcohols to various -dicarbonyl compounds, which afforded moderate to excellent yields of -alkylated products in 1,2-dichloroethane. In comparison with the previous methods, the present research ...

  15. Alkoxy(alkyl)silylalkyl derivatives of nitrogen-containing heterocycles

    International Nuclear Information System (INIS)

    Trofimova, Ol'ga M; Voronkov, Mikhail G; Chernov, Nikolai F

    1999-01-01

    The published data on the synthesis, properties and transformations of alkoxy(alkyl)silylalkyl derivatives of nitrogen-containing heterocycles of the general formula Het(CH 2 ) n SiX 3 are surveyed and systematised. Data on the biological activities and applications of these compounds are presented. The bibliography includes 255 references.

  16. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic).

    Science.gov (United States)

    2010-07-01

    ... are: (i) Industrial, commercial, and consumer activities. Requirements as specified in § 721.80(s... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl phosphine oxide (generic). 721.10087 Section 721.10087 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED...

  17. Manganese Catalyzed Regioselective C–H Alkylation: Experiment and Computation

    KAUST Repository

    Wang, Chengming

    2018-05-08

    A new efficient manganese-catalyzed selective C2-alkylation of indoles via carbenoid insertion has been achieved. The newly developed C-H functionalization protocol provides access to diverse products and shows good functional group tolerance. Mechanistic and computational studies support the formation of a Mn(CO)3 acetate complex as the catalytically active species.

  18. Alkylation of isobutane with light olefins catalyzed by zeolite beta

    NARCIS (Netherlands)

    Nivarthy, G.S.; Feller, A.P.; Seshan, Kulathuiyer; Lercher, J.A.

    2000-01-01

    Alkylation of isobutane with ethene and propene was studied over an H-BEA catalyst in a well-stirred reactor. Under similar conditions of space velocity and paraffin-to-olefin feed ratio, lower initial olefin conversions were observed with ethene or propene than those reported earlier for butene.

  19. Isobutane/olefin alkylation - present state and recent developments

    Energy Technology Data Exchange (ETDEWEB)

    Feller, A.; Lercher, J.A. [Inst. fuer Technische Chemie, Technische Univ. Muenchen (Germany)

    2002-12-01

    Isobutane/alkene alkylation is reviewed with respect to recent process developments based on liquid and solid acid catalysts. The reaction mechanism and its consequences for both liquid and solid acid based processes is briefly discussed. Established liquid acid catalyzed processes are introduced followed by the description of new processes based on solid acids, which are currently under development. (orig.)

  20. Copper-Catalyzed Synthesis of Mixed Alkyl Aryl Phosphonates

    NARCIS (Netherlands)

    Fañanás-Mastral, Martín; Feringa, Ben L

    2014-01-01

    Copper-catalysis allows the direct oxygenarylation of dialkyl phosphonates with diaryliodonium salts. This novel methodology proceeds with a wide range of phosphonates and phosphoramidates under mild conditions and gives straightforward access to valuable mixed alkyl aryl phosphonates in very good

  1. A new route alpha-alkyl-alpha-fluoromethylenebisphosphonates

    Czech Academy of Sciences Publication Activity Database

    Beier, Petr; Opekar, Stanislav; Zibinsky, M.; Bychinskaya, I.; Prakash, G. K. S.

    2011-01-01

    Roč. 9, č. 11 (2011), s. 4035-4038 ISSN 1477-0520 R&D Projects: GA ČR GP203/08/P310 Institutional research plan: CEZ:AV0Z40550506 Keywords : fluorine * phosphonate * alkylation Subject RIV: CC - Organic Chemistry Impact factor: 3.696, year: 2011

  2. On the Boiling Points of the Alkyl Halides.

    Science.gov (United States)

    Correia, John

    1988-01-01

    Discusses the variety of explanations in organic chemistry textbooks of a physical property of organic compounds. Focuses on those concepts explaining attractive forces between molecules. Concludes that induction interactions play a major role in alkyl halides and other polar organic molecules and should be given wider exposure in chemistry texts.…

  3. Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

    Science.gov (United States)

    Cruz-Ramirez de Arellano, Daniel

    2013-01-01

    Organic chemistry is an essential subject for many undergraduate students completing degrees in science, engineering, and pre-professional programs. However, students often struggle with the concepts and skills required to successfully solve organic chemistry exercises. Since alkyl halides are traditionally the first functional group that is…

  4. Alkyltransferase-like proteins: brokers dealing with alkylated DNA bases.

    Science.gov (United States)

    Schärer, Orlando D

    2012-07-13

    A new pathway for the repair of DNA alkylation damage is described in this issue of Molecular Cell (Latypov et al., 2012). Alkyltransferase-like enzymes mark O(6)-alkylguanine lesions and, depending on adduct size, channel them into global genome or transcription-coupled nucleotide excision repair pathways. Copyright © 2012 Elsevier Inc. All rights reserved.

  5. Manganese Catalyzed Regioselective C–H Alkylation: Experiment and Computation

    KAUST Repository

    Wang, Chengming; Maity, Bholanath; Cavallo, Luigi; Rueping, Magnus

    2018-01-01

    A new efficient manganese-catalyzed selective C2-alkylation of indoles via carbenoid insertion has been achieved. The newly developed C-H functionalization protocol provides access to diverse products and shows good functional group tolerance. Mechanistic and computational studies support the formation of a Mn(CO)3 acetate complex as the catalytically active species.

  6. Detection of halogenated flame retardants in polyurethane foam by particle induced X-ray emission

    International Nuclear Information System (INIS)

    Maley, Adam M.; Falk, Kyle A.; Hoover, Luke; Earlywine, Elly B.; Seymour, Michael D.; DeYoung, Paul A.; Blum, Arlene; Stapleton, Heather M.; Peaslee, Graham F.

    2015-01-01

    A novel application of particle-induced X-ray emission (PIXE) has been developed to detect the presence of chlorinated and brominated flame retardant chemicals in polyurethane foams. Traditional Gas Chromatography–Mass Spectrometry (GC–MS) methods for the detection and identification of halogenated flame retardants in foams require extensive sample preparation and data acquisition time. The elemental analysis of the halogens in polyurethane foam performed by PIXE offers the opportunity to identify the presence of halogenated flame retardants in a fraction of the time and sample preparation cost. Through comparative GC–MS and PIXE analysis of 215 foam samples, excellent agreement between the two methods was obtained. These results suggest that PIXE could be an ideal rapid screening method for the presence of chlorinated and brominated flame retardants in polyurethane foams

  7. SYNTHESIS AND STUDY OF HALOGENATED BENZYLAMIDES OF SOME ISOCYCLIC AND HETEROCYCLIC ACIDS AS POTENTIAL ANTICONVULSANTS.

    Science.gov (United States)

    Strupińska, Marzanna; Rostafińska-Suchar, Grażyna; Pirianowicz-Chaber, Elżbieta; Grabczuk, Mateusz; Józwenko, Magdalena; Kowalczyk, Hubert; Szuba, Joanna; Wójcicka, Monika; Chen, Tracy; Mazurek, Aleksander P

    2015-01-01

    A series of potential anticonvulsants have been synthesized. There are eight fluorobenzylamides and three chlorobenzylamides of isocyclic or heterocyclic acids. Two not halogenated benzylamides were also synthesized to compare the effect of halogenation. The aim of the research performed was to evaluate whether halogenation of the mother structure is able to improve its anticonvulsant activity. The compounds were tested in Anticonvulsant Screening Project (ASP) of Antiepileptic Drug Development Program (ADDP) of NIH. Compound 1 showed MES ED50 = 80.32 mg/kg, PI = 3.16. Compound 7 showed CKM ED50 = 56.72 mg/kg. Compound 8 showed MES ED50 = 34.23 mg/kg and scPTZ ED50 > 300 mg/kg, PI = 8.53.Compound 13 showed 6Hz ED50 = 78.96, PI = 3.37. The results indicate that fluorination does not improve activity, whereas chlorination in our experiment even reduces it.

  8. Selenium-Mediated Dehalogenation of Halogenated Nucleosides and its Relevance to the DNA Repair Pathway.

    Science.gov (United States)

    Mondal, Santanu; Manna, Debasish; Mugesh, Govindasamy

    2015-08-03

    Halogenated nucleosides can be incorporated into the newly synthesized DNA of replicating cells and therefore are commonly used in the detection of proliferating cells in living tissues. Dehalogenation of these modified nucleosides is one of the key pathways involved in DNA repair mediated by the uracil-DNA glycosylase. Herein, we report the first example of a selenium-mediated dehalogenation of halogenated nucleosides. We also show that the mechanism for the debromination is remarkably different from that of deiodination and that the presence of a ribose or deoxyribose moiety in the nucleosides facilitates the deiodination. The results described herein should help in understanding the metabolism of halogenated nucleosides in DNA and RNA. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Ab Initio Calculations on Halogen Bond Between N-Br and Electron-donating Groups

    Institute of Scientific and Technical Information of China (English)

    WANG Yan-hua; CHEN Xue-song; ZOU Jian-wei; YU Qing-sen

    2007-01-01

    Ab initio calculations of complexes formed between N-bromosuccinimide and a series of electron-donating groups were performed at the level of MP2/Lanl2DZ* to gain a deeper insight into the nature of the N-Br halogen stronger halogen-bonding complex than the C-Br. A comparison of neutral hydrogen bond complex series reveals that the electron-donating capacities of the atoms decrease in the order, N>O>S; O(sp3)>O(sp2), which is adequate for the C-Br halogen bonding. Interaction energies, in conjunction with the geometrical parameters show that the affinitive capacity of trihalide anions X-3 with N-bromosuccinimide are markedly lower than that of the corresponding X- with N-bromosuccinimide, even lower than those of neutral molecules with N-bromosuccinimide. AIM analyses further confirmed the above results.

  10. Development of halogen-free, heat-resistant, low-voltage wire for automotive use

    International Nuclear Information System (INIS)

    Ueno, Keiji; Suzuki, Sizuo; Takahagi, Masatoshi; Uda, Ikujiro

    1995-01-01

    The environmental load of our motorized society is of major concern, and includes considerations of recycling of automotive parts as the industrial wastes. The total average length of AV, AVX (electrical wire insulated with PVC, cross-linked PVC), and AEX (electrical wire insulated with cross-linked polyolefin) wires required for the harnesses in modern automobiles is approximately 2,000-3,000 meters per unit. However these electrical wires contain a large amount of halogen, which can generate the smoke and corrosive gas. In response to this problem the authors have developed the electron beam irradiated halogen-free, heat-resistant, low-voltage electrical wire which does not contain any halogen based polymer or flame retardants. The developed wire features the reliability equivalent to AEX wire with minimum environmental load. (Author)

  11. Development of Halogen-free flame-retardant cable for nuclear power plant

    International Nuclear Information System (INIS)

    Ishii, Nobuhisa; Morii, Akira; Fujimura, Shunichi

    1992-01-01

    Conventional flame-retardant cables release a large volume of corrosive and toxic gases as well as smoke while combusted. Cables covered with halogen-free flame-retardant material, containing no halogen in it, have been developed to reduce generation of such gases and smoke, and have already been used in telecommunication service, subway and shipboard applications. However, for cables for nuclear power plant, covering materials should also have radiation resistance and other properties, including long-term physical stability. We have developed halogen-free flame-retardant cables for BWR nuclear power plant with sufficient flame retardancy radiation resistance and environmental resistance including steam-exposure resistance all of which are in accordance with Japanese specifications for BWR nuclear cables and have such characteristics as low corrosiveness, low toxicity and low smoke emission. (author)

  12. Development of halogen-free flame-retardant cable for nuclear power plant

    International Nuclear Information System (INIS)

    Ishii, Nobuhisa; Morii, Akira; Fujimura, Shunichi

    1991-01-01

    Conventional flame-retardant cables release a large amount of corrosive and toxic gases and also smoke during combustion on fire. Cables covered with halogen-free flame-retardant material, containing no halogen in it, have been developed to reduce generation of such gases and smoke, and already used in telecommunication plant, subway and shipboard applications. In the case of nuclear power plant application, cable covering materials should also have radiation resistance and other properties including long-term physical stability. We have developed halogen-free flame-retardant cables for nuclear power plant with sufficient flame retardancy, radiation resistance, and environmental resistance including steam-exposure resistance, all of which are in accordance with Japanese specifications for nuclear cables, and with characteristics as low corrosiveness, low toxicity, and low smoke evolution. (author)

  13. Recoil halogen reactions in liquid and frozen aqueous solutions of biomolecules

    International Nuclear Information System (INIS)

    Arsenault, L.J.; Blotcky, A.J.; Firouzbakht, M.L.; Rack, E.P.; Nebraska Univ., Omaha

    1982-01-01

    Reactions of recoil 38 Cl, 80 Br and 128 I have been studied in crystalline systems of 5-halouracil, 5-halo-2'-deoxyuridine and 5-halouridine as well as liquid and frozen aqueous solutions of these halogenated biomolecules. In all systems expect crystalline 5-iuodouracil the major product was the radio-labelled halide ion. There was no evidence for other halogen inorganic species. The major labelled organic product was the parent molecule. A recoil atom tracer technique was developed to acquire site information of the biomolecule solutes in the liquid and frozen aqueous systems. For all liquid and frozen aqueous systems, the halogenated biomolecules tended to aggregate. For liquid systems, the tendency for aggregation diminished as the solute concentration approached zero, where the probable state of the solute approached a monomolecular dispersion. Unlike the liquid state, the frozen ice lattice demonstated a ''caging effect'' for the solute aggregates which resulted in constant product yields over the whole concentration range. (orig.)

  14. Detection of halogenated flame retardants in polyurethane foam by particle induced X-ray emission

    Energy Technology Data Exchange (ETDEWEB)

    Maley, Adam M.; Falk, Kyle A.; Hoover, Luke; Earlywine, Elly B.; Seymour, Michael D. [Department of Chemistry, Hope College, 35 E. 12th Street, Holland, MI 49423 (United States); DeYoung, Paul A. [Department of Physics, Hope College, 27 Graves Place, Holland, MI 49423 (United States); Blum, Arlene [Green Science Policy Institute, Box 5455, Berkeley, CA 94705 (United States); Stapleton, Heather M. [Nicholas School of the Environment, Duke University, LSRC Box 90328, Durham, NC 27708 (United States); Peaslee, Graham F., E-mail: peaslee@hope.edu [Department of Chemistry, Hope College, 35 E. 12th Street, Holland, MI 49423 (United States)

    2015-09-01

    A novel application of particle-induced X-ray emission (PIXE) has been developed to detect the presence of chlorinated and brominated flame retardant chemicals in polyurethane foams. Traditional Gas Chromatography–Mass Spectrometry (GC–MS) methods for the detection and identification of halogenated flame retardants in foams require extensive sample preparation and data acquisition time. The elemental analysis of the halogens in polyurethane foam performed by PIXE offers the opportunity to identify the presence of halogenated flame retardants in a fraction of the time and sample preparation cost. Through comparative GC–MS and PIXE analysis of 215 foam samples, excellent agreement between the two methods was obtained. These results suggest that PIXE could be an ideal rapid screening method for the presence of chlorinated and brominated flame retardants in polyurethane foams.

  15. Halogen bond preferences of thiocyanate ligand coordinated to Ru(II) via sulphur atom

    Science.gov (United States)

    Ding, Xin; Tuikka, Matti; Hirva, Pipsa; Haukka, Matti

    2017-09-01

    Halogen bonding between [Ru(bpy)(CO)2(S-SCN)2] (bpy = 2,2'-bipyridine), I2 was studied by co-crystallising the metal compound and diiodine from dichloromethane. The only observed crystalline product was found to be [Ru(bpy)(CO)2(S-SCN)2]ṡI2 with only one NCSṡṡṡI2 halogen bond between I2 and the metal coordinated S atom of one of the thiocyanate ligand. The dangling nitrogen atoms were not involved in halogen bonding. However, computational analysis suggests that there are no major energetic differences between the NCSṡṡṡI2 and SCNṡṡṡI2 bonding modes. The reason for the observed NCSṡṡṡI2 mode lies most probably in the more favourable packing effects rather than energetic preferences between NCSṡṡṡI2 and SCNṡṡṡI2 contacts.

  16. Flame retardant synergism between molybdenum and halogen-containing compounds in unsaturated polyesters. [Smoke suppression

    Energy Technology Data Exchange (ETDEWEB)

    Skinner, G.A.; Parker, L.E.; Marshall, P.J.

    1978-01-01

    Oxygen index results for a series of unsaturated polyesters, containing molybdenum oxide and various halogenated compounds, have provided definite evidence for some form of flame retardant synergistic effect between molybdenum and halogen. With the halogenated compounds used, the magnitude of the effect was greater in the presence of bromine but was dependent on the type of compound. When dibromoneopentyl glycol was used as the bromine source, the synergistic effect exhibited by molybdenum oxide was comparable to that shown by antimony oxide. Since molybdenum oxide also acts as a smoke suppressant, it could offer a useful alternative to antimony oxide particularly in the light of probable changes in standards and regulatory control regarding smoke emission. 4 figures, 2 tables.

  17. Bifunctional Molybdenum Polyoxometalates for the Combined Hydrodeoxygenation and Alkylation of Lignin-Derived Model Phenolics.

    Science.gov (United States)

    Anderson, Eric; Crisci, Anthony; Murugappan, Karthick; Román-Leshkov, Yuriy

    2017-05-22

    Reductive catalytic fractionation of biomass has recently emerged as a powerful lignin extraction and depolymerization method to produce monomeric aromatic oxygenates in high yields. Here, bifunctional molybdenum-based polyoxometalates supported on titania (POM/TiO 2 ) are shown to promote tandem hydrodeoxygenation (HDO) and alkylation reactions, converting lignin-derived oxygenated aromatics into alkylated benzenes and alkylated phenols in high yields. In particular, anisole and 4-propylguaiacol were used as model compounds for this gas-phase study using a packed-bed flow reactor. For anisole, 30 % selectivity for alkylated aromatic compounds (54 % C-alkylation of the methoxy groups by methyl balance) with an overall 72 % selectivity for HDO at 82 % anisole conversion was observed over H 3 PMo 12 O 40 /TiO 2 at 7 h on stream. Under similar conditions, 4-propylguaiacol was mainly converted into 4-propylphenol and alkylated 4-propylphenols with a selectivity to alkylated 4-propylphenols of 42 % (77 % C-alkylation) with a total HDO selectivity to 4-propylbenzene and alkylated 4-propylbenzenes of 4 % at 92 % conversion (7 h on stream). Higher catalyst loadings pushed the 4-propylguaiacol conversion to 100 % and resulted in a higher selectivity to propylbenzene of 41 %, alkylated aromatics of 21 % and alkylated phenols of 17 % (51 % C-alkylation). The reactivity studies coupled with catalyst characterization revealed that Lewis acid sites act synergistically with neighboring Brønsted acid sites to simultaneously promote alkylation and hydrodeoxygenation activity. A reaction mechanism is proposed involving activation of the ether bond on a Lewis acid site, followed by methyl transfer and C-alkylation. Mo-based POMs represent a versatile catalytic platform to simultaneously upgrade lignin-derived oxygenated aromatics into alkylated arenes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Halogen degassing during ascent and eruption of water-poor basaltic magma

    Science.gov (United States)

    Edmonds, M.; Gerlach, T.M.; Herd, Richard A.

    2009-01-01

    A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO2/HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO2/HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of < 1??MPa, equivalent to < ~ 35??m in the conduit. Fluid-melt partition coefficients for Cl and F are low (< 1.5); F only degasses appreciably at < 0.1??MPa above atmospheric pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

  19. Chalcogen- and halogen-bonds involving SX2 (X = F, Cl, and Br) with formaldehyde.

    Science.gov (United States)

    Mo, Lixin; Zeng, Yanli; Li, Xiaoyan; Zhang, Xueying; Meng, Lingpeng

    2016-07-01

    The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)-S bonds, and two σ-holes upon extension of S-Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F-S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX'2 (X = F, Cl, Br, and X' = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds. Graphical Abstract Molecular electrostatic potential and contour map of the Laplacian of the electron density in Cl2S···H2CO···SCl2 complex.

  20. Halogen Bonding from Dispersion-Corrected Density-Functional Theory: The Role of Delocalization Error.

    Science.gov (United States)

    Otero-de-la-Roza, A; Johnson, Erin R; DiLabio, Gino A

    2014-12-09

    Halogen bonds are formed when a Lewis base interacts with a halogen atom in a different molecule, which acts as an electron acceptor. Due to its charge transfer component, halogen bonding is difficult to model using many common density-functional approximations because they spuriously overstabilize halogen-bonded dimers. It has been suggested that dispersion-corrected density functionals are inadequate to describe halogen bonding. In this work, we show that the exchange-hole dipole moment (XDM) dispersion correction coupled with functionals that minimize delocalization error (for instance, BH&HLYP, but also other half-and-half functionals) accurately model halogen-bonded interactions, with average errors similar to other noncovalent dimers with less charge-transfer effects. The performance of XDM is evaluated for three previously proposed benchmarks (XB18 and XB51 by Kozuch and Martin, and the set proposed by Bauzá et al.) spanning a range of binding energies up to ∼50 kcal/mol. The good performance of BH&HLYP-XDM is comparable to M06-2X, and extends to the "extreme" cases in the Bauzá set. This set contains anionic electron donors where charge transfer occurs even at infinite separation, as well as other charge transfer dimers belonging to the pnictogen and chalcogen bonding classes. We also show that functional delocalization error results in an overly delocalized electron density and exact-exchange hole. We propose intermolecular Bader delocalization indices as an indicator of both the donor-acceptor character of an intermolecular interaction and the delocalization error coming from the underlying functional.

  1. Rational design of organic semiconductors for texture control and self-patterning on halogenated surfaces

    KAUST Repository

    Ward, Jeremy W.

    2014-05-15

    Understanding the interactions at interfaces between the materials constituting consecutive layers within organic thin-film transistors (OTFTs) is vital for optimizing charge injection and transport, tuning thin-film microstructure, and designing new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self-assembled monolayer on the formation of the crystalline texture directly affecting the performance of OTFTs is explored. By correlating the results from microbeam grazing incidence wide angle X-ray scattering (μGIWAXS) measurements of structure and texture with OTFT characteristics, two or more interaction paths between the terminating atoms of the semiconductor and the halogenated surface are found to be vital to templating a highly ordered morphology in the first layer. These interactions are effective when the separating distance is lower than 2.5 dw, where dw represents the van der Waals distance. The ability to modulate charge carrier transport by several orders of magnitude by promoting "edge-on" versus "face-on" molecular orientation and crystallographic textures in OSCs is demonstrated. It is found that the "edge-on" self-assembly of molecules forms uniform, (001) lamellar-textured crystallites which promote high charge carrier mobility, and that charge transport suffers as the fraction of the "face-on" oriented crystallites increases. The role of interfacial halogenation in mediating texture formation and the self-patterning of organic semiconductor films, as well as the resulting effects on charge transport in organic thin-film transistors, are explored. The presence of two or more anchoring sites between a halogenated semiconductor and a halogenated self-assembled monolayer, closer than about twice the corresponding van der Waals distance, alter the microstructure and improve electrical properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Global impacts of tropospheric halogens (Cl, Br, I on oxidants and composition in GEOS-Chem

    Directory of Open Access Journals (Sweden)

    T. Sherwen

    2016-09-01

    Full Text Available We present a simulation of the global present-day composition of the troposphere which includes the chemistry of halogens (Cl, Br, I. Building on previous work within the GEOS-Chem model we include emissions of inorganic iodine from the oceans, anthropogenic and biogenic sources of halogenated gases, gas phase chemistry, and a parameterised approach to heterogeneous halogen chemistry. Consistent with Schmidt et al. (2016 we do not include sea-salt debromination. Observations of halogen radicals (BrO, IO are sparse but the model has some skill in reproducing these. Modelled IO shows both high and low biases when compared to different datasets, but BrO concentrations appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggest the model represents a lower limit of the impacts of these species, likely due to underestimates in emissions and therefore burdens. Inclusion of Cl, Br, and I results in a general improvement in simulation of ozone (O3 concentrations, except in polar regions where the model now underestimates O3 concentrations. Halogen chemistry reduces the global tropospheric O3 burden by 18.6 %, with the O3 lifetime reducing from 26 to 22 days. Global mean OH concentrations of 1.28  ×  106 molecules cm−3 are 8.2 % lower than in a simulation without halogens, leading to an increase in the CH4 lifetime (10.8 % due to OH oxidation from 7.47 to 8.28 years. Oxidation of CH4 by Cl is small (∼  2 % but Cl oxidation of other VOCs (ethane, acetone, and propane can be significant (∼  15–27 %. Oxidation of VOCs by Br is smaller, representing 3.9 % of the loss of acetaldehyde and 0.9 % of the loss of formaldehyde.

  3. Thermodynamics parameters for binding of halogenated benzotriazole inhibitors of human protein kinase CK2α.

    Science.gov (United States)

    Winiewska, Maria; Kucińska, Katarzyna; Makowska, Małgorzata; Poznański, Jarosław; Shugar, David

    2015-10-01

    The interaction of human CK2α (hCK2α) with nine halogenated benzotriazoles, TBBt and its analogues representing all possible patterns of halogenation on the benzene ring of benzotriazole, was studied by biophysical methods. Thermal stability of protein-ligand complexes, monitored by calorimetric (DSC) and optical (DSF) methods, showed that the increase in the mid-point temperature for unfolding of protein-ligand complexes (i.e. potency of ligand binding to hCK2α) follow the inhibitory activities determined by biochemical assays. The dissociation constant for the ATP-hCK2α complex was estimated with the aid of microscale thermophoresis (MST) as 4.3±1.8 μM, and MST-derived dissociation constants determined for halogenated benzotriazoles, when converted according to known ATP concentrations, perfectly reconstruct IC50 values determined by the biochemical assays. Ligand-dependent quenching of tyrosine fluorescence, together with molecular modeling and DSC-derived heats of unfolding, support the hypothesis that halogenated benzotriazoles bind in at least two alternative orientations, and those that are efficient hCK2α inhibitors bind in the orientation which TBBt adopts in its complex with maize CK2α. DSC-derived apparent heat for ligand binding (ΔΔHbind) is driven by intermolecular electrostatic interactions between Lys68 and the triazole ring of the ligand, as indicated by a good correlation between ΔΔHbind and ligand pKa. Overall results, additionally supported by molecular modeling, confirm that a balance of hydrophobic and electrostatic interactions contribute predominantly (~40 kJ/mol), relative to possible intermolecular halogen/hydrogen bonding (less than 10 kJ/mol), in binding of halogenated benzotriazoles to the ATP-binding site of hCK2α. This article is part of a Special Issue entitled: Inhibitors of Protein Kinases. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Predicting Alkylate Yield and its Hydrocarbon Composition for Sulfuric Acid Catalyzed Isobutane Alkylation with Olefins Using the Method of Mathematical Modeling

    OpenAIRE

    Nurmakanova, А. Е.; Ivashkina, Elena Nikolaevna; Ivanchina, Emilia Dmitrievna; Dolganov, I. A.; Boychenko, S. S.

    2015-01-01

    The article provides the results of applied mathematical model of isobutane alkylation with olefins catalyzed by sulfuric acid to predict yield and hydrocarbon composition of alkylate caused by the changes in the feedstock composition and process parameters. It is shown that the alkylate produced from feedstock with less mass fraction of isobutane has lower octane value. Wherein the difference in composition of the feedstock contributes to antiknock index by the amount of 1.0-2.0 points.

  5. Design of novel antitumor DNA alkylating agents: the benzacronycine series.

    Science.gov (United States)

    David-Cordonnier, Marie-Hélène; Laine, William; Gaslonde, Thomas; Michel, Sylvie; Tillequin, Francois; Koch, Michel; Léonce, Stéphane; Pierré, Alain; Bailly, Christian

    2004-03-01

    Acronycine, a natural alkaloid originally extracted from the bark of the Australian ash scrub Acronychia baueri, has shown a significant antitumor activity in animal models. Acronycine has been tested against human cancers in the early 1980s, but the clinical trials showed modest therapeutic effects and its development was rapidly discontinued. In order to optimize the antineoplastic effect, different benzoacronycine derivatives were synthesized. Among those, the di-acetate compound S23906-1 was recently identified as a promising anticancer drug candidate and a novel alkylating agent specifically reacting with the exocylic 2-NH2 group of guanines in DNA. The study of DNA bonding capacity of acronycine derivatives leads to the identification of the structural requirements for DNA alkylation. In nearly all cases, the potent alkylating agents, such as S23906-1, were found to be much more cytotoxic than the unreactive analogs such as acronycine itself or diol derivatives. Alkylation of DNA by the monoacetate derivative S28687-1, which is a highly reactive hydrolysis metabolite of S23906-1, occurs with a marked preference for the N2 position of guanine. Other bionucleophiles can react with S23906-1. The benzacronycine derivatives, which efficiently alkylate DNA, also covalently bind to the tripeptide glutathione (GSH) but not to the oxidized product glutathione disulfide. Here we review the reactivity of S23906-1 and some derivatives toward DNA and GSH. The structure-activity relationships in the benzacronycine series validate the reaction mechanism implicating DNA as the main molecular target. S23906-1 stands as the most promising lead of a medicinal chemistry program aimed at discovering novel antitumor drugs based on the acronycine skeleton.

  6. C2-Selective Branched Alkylation of Benzimidazoles by Rhodium(I)-Catalyzed C-H Activation.

    Science.gov (United States)

    Tran, Gaël; Confair, Danielle; Hesp, Kevin D; Mascitti, Vincent; Ellman, Jonathan A

    2017-09-01

    Herein, we report a Rh(I)/bisphosphine/K 3 PO 4 catalytic system allowing for the first time the selective branched C-H alkylation of benzimidazoles with Michael acceptors. Branched alkylation with N,N-dimethyl acrylamide was successfully applied to the alkylation of a broad range of benzimidazoles incorporating a variety of N-substituents and with both electron-rich and -poor functionality displayed at different sites of the arene. Moreover, the introduction of a quaternary carbon was achieved by alkylation with ethyl methacrylate. The method was also shown to be applicable to the C2-selective branched alkylation of azabenzimidazoles.

  7. Neutron activation analysis for study of distribution patterns of organo-halogen pollutants in apple

    International Nuclear Information System (INIS)

    Zhang Hong; Luo Jialing; Sun Huibin; Chai Zhifang; Chinese Academy of Sciences, Beijing

    2007-01-01

    The distribution characteristics of organo-halogens in apple and their sources were studied by neutron activation analysis combined with statistical analysis. The results indicated that concentrations of organo-halogens in apple were in the order of organo-chlorine >> organo-bromine > organo-iodine, and concentrations of the organo-chlorine in four parts of apple were in the order of seed >> peel >> endocarp ≥ pulp. Also, the organo-chlorine, -bromine and-iodine in apple were found to have different sources. The latter two were mainly from naturally synthetic products by plant itself, while the former was mainly from anthropogenic pollutants. (authors)

  8. A 19F NMR study of C-I....pi- halogen bonding

    DEFF Research Database (Denmark)

    Hauchecorne, Dieter; vand er Veken, Benjamin J.; Herrebout, Wouter A.

    2011-01-01

    The formation of halogen bonded complexes between toluene-d8 and the perfluoroiodopropanes 1-C3F7I and 2-C3F7I has been investigated using 19F NMR spectroscopy. For both Lewis acids, evidence was found for the formation of a C–I⋯π halogen bonded complex. The complex formed is a 1:1 type. Using sp...... results are supported by ab initio calculations at the B3LYP-PCM/6-311++G(d,p) + LanL2DZ∗ level....

  9. Organic halogen compounds and surface water pollution; Composti organoalogenati alifatici e contaminazione delle acque superficiali

    Energy Technology Data Exchange (ETDEWEB)

    Cocchioni, M.; Pellegrini, M. G.; Grappasonni, I.; Nacciarriti, L.; Bernacchia, G. [Camerino, Univ. (Italy). Dipt. di Scienze Igienistiche e Sanitarie-Ambientali

    1997-03-01

    A brief review of the effects of halogenated organic compounds on the fluvial ecosystem is followed by results from a detailed monitoring of these substances in all the Marches Region rivers. The results show generally modest concentrations, except for sporadic peaks for chloroform. Sites revealing significant concentrations of halogenated organic compounds also manifested a worsening of the biological quality of the waters with lessening of E.B.I. Attention is drawn to the negative effects of indiscriminate chlorination of purification plant outputs, as this practice often fails to resolve infective problems and in itself adds toxicity to the watercourse.

  10. Halogen effect for improving high temperature oxidation resistance of Ti-50Al by anodization

    Science.gov (United States)

    Mo, Min-Hua; Wu, Lian-Kui; Cao, Hua-Zhen; Lin, Jun-Pin; Zheng, Guo-Qu

    2017-06-01

    The high temperature oxidation resistance of Ti-50Al was significantly improved via halogen effect which was achieved by anodizing in an ethylene glycol solution containing with fluorine ion. The anodized Ti-50Al with holes and micro-cracks could be self-repaired during oxidation at 1000 °C. The thickness of the oxide scale increases with the prolonging of oxidation time. On the basis of halogen effect for improving the high temperature oxidation resistance of Ti-50Al by anodization, only fluorine addition into the electrolyte can effectively improve the high temperature oxidation resistance of Ti-50Al.

  11. Halogen Bonding Involving CO and CS with Carbon as the Electron Donor

    Directory of Open Access Journals (Sweden)

    Janet E. Del Bene

    2017-11-01

    Full Text Available MP2/aug’-cc-pVTZ calculations have been carried out to investigate the halogen-bonded complexes formed when CO and CS act as electron-pair donors through C to ClF, ClNC, ClCl, ClOH, ClCN, ClCCH, and ClNH2. CO forms only complexes stabilized by traditional halogen bonds, and all ClY molecules form traditional halogen-bonded complexes with SC, except ClF which forms only an ion-pair complex. Ion-pair complexes are also found on the SC:ClNC and SC:ClCl surfaces. SC:ClY complexes stabilized by traditional halogen bonds have greater binding energies than the corresponding OC:ClY complexes. The largest binding energies are found for the ion-pair SC–Cl+:−Y complexes. The transition structures which connect the complex and the ion pair on SC:ClNC and SC:ClCl potential surfaces provide the barriers for inter-converting these structures. Charge-transfer from the lone pair on C to the σ-hole on Cl is the primary charge-transfer interaction stabilizing OC:ClY and SC:ClY complexes with traditional halogen bonds. A secondary charge-transfer occurs from the lone pairs on Cl to the in-plane and out-of-plane π antibonding orbitals of ClY. This secondary interaction assumes increased importance in the SC:ClNH2 complex, and is a factor leading to its unusual structure. C–O and C–S stretching frequencies and 13C chemical shieldings increase upon complex formation with ClY molecules. These two spectroscopic properties clearly differentiate between SC:ClY complexes and SC–Cl+:−Y ion pairs. Spin–spin coupling constants 1xJ(C–Cl for OC:ClY complexes increase with decreasing distance. As a function of the C–Cl distance, 1xJ(C–Cl and 1J(C–Cl provide a fingerprint of the evolution of the halogen bond from a traditional halogen bond in the complexes, to a chlorine-shared halogen bond in the transition structures, to a covalent bond in the ion pairs.

  12. Tuning the electronic structure of graphene through alkali metal and halogen atom intercalation

    Science.gov (United States)

    Ahmad, Sohail; Miró, Pere; Audiffred, Martha; Heine, Thomas

    2018-04-01

    The deposition, intercalation and co-intercalation of heavy alkali metals and light halogens atoms in graphene mono- and bilayers have been studied using first principles density-functional calculations. Both the deposition and the intercalation of alkali metals gives rise to n-type doping due to the formation of M+-C- pairs. The co-intercalation of a 1:1 ratio of alkali metals and halogens derives into the formation of ionic pairs among the intercalated species, unaltering the electronic structure of the layered material.

  13. Chlorine dioxide as phenol and H2S scavenger - formation of halogenated phenols and subsequent environmental risk

    Energy Technology Data Exchange (ETDEWEB)

    Melbye, Alf G.; Faksness, Liv-Guri; Knudsen, Boerre Leif

    2006-03-15

    Formation of halogenated phenols as side products from treatment of produced water with aqueous chlorine dioxide has been investigated. The literature describes formation of halogenated hydrocarbons in effluent treatment using chlorine, hypochlorite and chlorine dioxide. A new chlorine dioxide product, originally intended as a H2S scavenger in the oil and gas industry, has been tested both as a phenol scavenger and H2S-scavenger for produced water applications. The concern about the possible formation of halogenated by-products initiated laboratory testing of chlorine dioxide as phenol and H2S scavenger for produced water applications. The tests also included synthetic matrixes containing phenols, and the tests show that halogenated phenols, mainly brominated species, are found in produced water after treatment with chlorine dioxide. Due to potential environmental risk from halogenated organic contaminants, the use of chlorine dioxide as phenol and H2S scavenger is not recommended. (Author)

  14. Determination of N-containing halogenated natural products using gas chromatography in combination of a nitrogen-phosphorus-detector

    Energy Technology Data Exchange (ETDEWEB)

    Melcher, J.; Vetter, W. [Hohenheim Univ., Stuttgart (Germany). Inst. fuer Lebensmittelchemie

    2004-09-15

    In the last few years several nonpolar halogenated natural products (HNPs) such as Q1, MHC-1, BC-2, BC-3, BC-10 were detected at elevated concentrations in marine biota samples. In addition, there are still some abundant peaks of halogenated compounds frequently found in the gas chromatograms of many marine samples which have not yet been identified. Some of the known halogenated natural products (Q1, HDBPs including BC-10, bromoindoles) contain N-heterocyclic backbones. Since nitrogen is scarcely found in anthropogenic halogenated compounds, the detection of N-containing halogenated substances may be used as a first indicator for the presence of HNPs in a sample extract. In the presented method we studied the suitability of a nitrogen phosphorous detector (NPD) for quantification of Q1 and the detection of Ncontaining compounds in marine biota. Analyses were accompanied with GC/ECD analyses.

  15. 40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

    Science.gov (United States)

    2010-07-01

    ... Halogen HAP Emissions or HAP Metals Emissions From Process Vents 3 Table 3 to Subpart FFFF of Part 63... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions or...

  16. 40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

    Science.gov (United States)

    2010-07-01

    ... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this subpart that... section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you must...

  17. Study of hydrogen mobility by hydrogen-deuterium exchange. II. Theoretical kinetic study in alkyl and amino-alkyl pyrimidines

    International Nuclear Information System (INIS)

    Pompon, Alain

    1975-01-01

    Alkyl groups bound to the pyrimidine ring can be deuterium substituted on the carbon adjacent to the ring, in acidic D 2 O; kinetic equations corresponding to various exchange mechanism hypothesis are established. It is shown that theoretical and experimental results can be compared in order to precise the mechanism and to measure the characteristic parameters of the exchange reaction [fr

  18. 4-Alkyl radical extrusion in the cytochrome P-450-catalyzed oxidation of 4-alkyl-1,4-dihydropyridines

    International Nuclear Information System (INIS)

    Lee, J.S.; Jacobsen, N.E.; Ortiz de Montellano, P.R.

    1988-01-01

    Rat liver microsomal cytochrome P-450 oxidizes the 4-methyl, 4-ethyl (DDEP), and 4-isopropyl derivatives of 3,5-bis(carbethoxy)-2,6-dimethyl-1,4,-dihydropyridine to mixtures of the corresponding 4-alkyl and 4-dealkyl pyridines. A fraction of the total microsomal enzyme is destroyed in the process. The 4-dealkyl to 4-alkyl pyridine metabolite ratio, the extent of cytochrome P-450 destruction, and the rate of spin-trapped radical accumulation are correlated in a linear inverse manner with the homolytic or heterolytic bond energies of the 4-alkyl groups of the 4-alkyl-1,4-dihydropyridines. No isotope effects are observed on the pyridine matabolite ratio, the destruction of cytochrome P-450, or the formation of ethyl radicals when [4- 2 H]DDEP is used instead of DDEP. N-Methyl- and N-ethyl-DDEP undergo N-dealkylation rather than aromatization but N-phenyl-DDEP is oxidized to a mixture of the 4-ethyl and 4-deethyl N-phenylpyridinium metabolites. In contrast to the absence of an isotope effect in the oxidation of DDEP, the 4-deethyl to 4-ethyl N-phenylpyridinium metabolite ratio increases 6-fold when N-phenyl[4- 2 H]DDEP is used. The results support the hypothesis that cytochrome P-450 catalyzes the oxidation of dihydropyridines to radical cations and show that the radical cations decay to nonradical products by multiple, substituent-dependent, mechanisms

  19. Determination of alkylation of bacterial DNA as a rapid test for toxicological evaluation of alkylating xenobiotic agents

    Energy Technology Data Exchange (ETDEWEB)

    Botzenhart, K.; Waldner-Sander, S.; Schweinsberg, F.

    1986-05-01

    Alkylated purine bases from hydrolized DNA can be separated by HPLC and quantified with a fluorescence detector. We applied this method to bacterial DNA. 7-methylguanine was detected after treatment of Serratia marcescens with iodoacetamide, dimethyl sulfate and with polluted air.

  20. Halogenated organic species over the tropical South American rainforest

    Directory of Open Access Journals (Sweden)

    S. Gebhardt

    2008-06-01

    Full Text Available Airborne measurements of the halogenated trace gases methyl chloride, methyl bromide and chloroform were conducted over the Atlantic Ocean and about 1000 km of pristine tropical rainforest in Suriname and French Guyana (3–6° N, 51–59° W in October 2005. In the boundary layer (0–1.4 km, maritime air masses, advected over the forest by southeasterly trade winds, were measured at various distances from the coast. Since the organohalogens presented here have relatively long atmospheric lifetimes (0.4–1.0 years in comparison to the advection times from the coast (1–2 days, emissions will accumulate in air traversing the rainforest. The distributions of methyl chloride, methyl bromide and chloroform were analyzed as a function of time the air spent over land and the respective relationship used to determine net fluxes from the rainforest for one week within the long dry season.

    Net fluxes from the rainforest ecosystem have been calculated for methyl chloride and chloroform as 9.5 (±3.8 2σ and 0.35 (±0.15 2σμg m-2 h−1, respectively. No significant flux was observed for methyl bromide within the limits of these measurements.

    The global budget of methyl chloride contains large uncertainties, in particular with regard to a possible source from tropical vegetation. Our measurements are used in a large-scale approach to determine the net flux from a tropical ecosystem to the planetary boundary layer. The obtained global net flux of 1.5 (±0.6 2σ Tg yr-1 for methyl chloride is at the lower end of current estimates for tropical vegetation sources, which helps to constrain the range of tropical sources and sinks (0.82 to 8.2 Tg yr-1 from tropical plants, 0.03 to 2.5 Tg yr-1 from senescent/dead leaves and a sink of 0.1 to 1.6 Tg yr-1 by soil uptake. Nevertheless, these results show that the contribution of the rainforest ecosystem is the major source in the

  1. Halogenated flame retardants in the Great Lakes environment.

    Science.gov (United States)

    Venier, Marta; Salamova, Amina; Hites, Ronald A

    2015-07-21

    Flame retardants are widely used industrial chemicals that are added to polymers, such as polyurethane foam, to prevent them from rapidly burning if exposed to a small flame or a smoldering cigarette. Flame retardants, especially brominated flame retardants, are added to many polymeric products at percent levels and are present in most upholstered furniture and mattresses. Most of these chemicals are so-called "additive" flame retardants and are not chemically bound to the polymer; thus, they migrate from the polymeric materials into the environment and into people. As a result, some of these chemicals have become widespread pollutants, which is a concern given their possible adverse health effects. Perhaps because of their environmental ubiquity, the most heavily used group of brominated flame retardants, the polybrominated diphenyl ethers (PBDEs), was withdrawn from production and use during the 2004-2013 period. This led to an increasing demand for other flame retardants, including other brominated aromatics and organophosphate esters. Although little is known about the use or production volumes of these newer flame retardants, it is evident that some of these chemicals are also becoming pervasive in the environment and in humans. In this Account, we describe our research on the occurrence of halogenated and organophosphate flame retardants in the environment, with a specific focus on the Great Lakes region. This Account starts with a short introduction to the first generation of brominated flame retardants, the polybrominated biphenyls, and then presents our measurements of their replacement, the PBDEs. We summarize our data on PBDE levels in babies, bald eagles, and in air. Once these compounds came off the market, we began to measure several of the newer flame retardants in air collected on the shores of the Great Lakes once every 12 days. These new measurements focus on a tetrabrominated benzoate, a tetrabrominated phthalate, a hexabrominated diphenoxyethane

  2. Halogens in pore water of peat bogs – the role of peat decomposition and dissolved organic matter

    Directory of Open Access Journals (Sweden)

    H. Biester

    2006-01-01

    Full Text Available Halogens are strongly enriched in peat and peatlands and such they are one of their largest active terrestrial reservoir. The enrichment of halogens in peat is mainly attributed to the formation of organohalogens and climatically controlled humification processes. However, little is known about release of halogens from the peat substrate and the distribution of halogens in the peat pore water. In this study we have investigated the distribution of chlorine, bromine and iodine in pore water of three pristine peat bogs located in the Magellanic Moorlands, southern Chile. Peat pore waters were collected using a sipping technique, which allows in situ sampling down to a depth greater than 6m. Halogens and halogen species in pore water were determined by ion-chromatography (IC (chlorine and IC-ICP-MS (bromine and iodine. Results show that halogen concentrations in pore water are 15–30 times higher than in rainwater. Mean concentrations of chlorine, bromine and iodine in pore water were 7–15 mg l−1, 56–123 μg l−1, and 10–20 μg l−1, which correspond to mean proportions of 10–15%, 1–2.3% and 0.5–2.2% of total concentrations in peat, respectively. Organobromine and organoiodine were the predominant species in pore waters, whereas chlorine in pore water was mostly chloride. Advection and diffusion of halogens were found to be generally low and halogen concentrations appear to reflect release from the peat substrate. Release of bromine and iodine from peat depend on the degree of peat degradation, whereas this relationship is weak for chlorine. Relatively higher release of bromine and iodine was observed in less degraded peat sections, where the release of dissolved organic carbon (DOC was also the most intensive. It has been concluded that the release of halogenated dissolved organic matter (DOM is the predominant mechanism of iodine and bromine release from peat.

  3. Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

    International Nuclear Information System (INIS)

    Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao; Li, Jian-Li; Yin, Bing; Bai, Hongcun

    2015-01-01

    The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M 2 (CN) 5 ] −1 (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca 2 (CN) 5 ] −1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties

  4. Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

    Science.gov (United States)

    Li, Jin-Feng; Sun, Yin-Yin; Bai, Hongcun; Li, Miao-Miao; Li, Jian-Li; Yin, Bing

    2015-06-01

    The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M2(CN)5]-1 (M = Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca2(CN)5]-1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green's function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

  5. Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao; Li, Jian-Li; Yin, Bing, E-mail: rayinyin@nwu.edu.cn [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Bai, Hongcun [Key Laboratory of Energy Source and Chemical Engineering, Ningxia University, Yinchuan, Ningxia 750021 (China)

    2015-06-15

    The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M{sub 2}(CN){sub 5}]{sup −1} (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca{sub 2}(CN){sub 5}]{sup −1} which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

  6. Production of high-octane, unleaded motor fuel by alkylation of isobutane with isoamylenes obtained by dehydrogenation of isopentane

    Energy Technology Data Exchange (ETDEWEB)

    Hutson, T. Jr.; Hann, P.D.

    1981-01-31

    A process combination, with inter-cooperation, for producing high-octane alkylates comprising (a) dehydrogenating isopentane to isopentenes (amylenes), (b) introducing the mixture of said amylenes and unconverted isopentane into an HF alkylation unit for reaction with fresh or recycled isobutane, (c) separating the alkylation products into high octane alkylates, isopentane (for recycling to the dehydrogenation reactor) and isobutane (for recycling to the alkylation reactor).

  7. Degradation of halogenated aliphatic compounds by the ammonia- oxidizing bacterium Nitrosomonas europaea.

    OpenAIRE

    Vannelli, T; Logan, M; Arciero, D M; Hooper, A B

    1990-01-01

    Suspensions of Nitrosomonas europaea catalyzed the ammonia-stimulated aerobic transformation of the halogenated aliphatic compounds dichloromethane, dibromomethane, trichloromethane (chloroform), bromoethane, 1,2-dibromoethane (ethylene dibromide), 1,1,2-trichloroethane, 1,1,1-trichloroethane, monochloroethylene (vinyl chloride), gem-dichloroethylene, cis- and trans-dichloroethylene, cis-dibromoethylene, trichloroethylene, and 1,2,3-trichloropropane, Tetrachloromethane (carbon tetrachloride),...

  8. Evaluation of 10 aliphatic halogenated hydrocarbons in the mouse bone marrow micronucleus test.

    Science.gov (United States)

    Crebelli, R; Carere, A; Leopardi, P; Conti, L; Fassio, F; Raiteri, F; Barone, D; Ciliutti, P; Cinelli, S; Vericat, J A

    1999-03-01

    Ten halogenated aliphatic hydrocarbons (carbon tetrachloride, 1-chlorohexane, 2,3-dichlorobutane, 1,2-dichloroethane, 1,2-dichloroethylene, 1,3-dichloropropane, hexachloroethane, 1,1,2-trichloroethane, 1,2,3-trichloropropane and 1,1,3-trichloropropene), previously assayed in genetic assays in fungi, were evaluated in the mouse bone marrow micronucleus test in order to assess their genotoxicity in vivo. All chemicals were administered once i.p. at 40 and 70-80% of their respective LD50 to male and female CD-1 mice, 24 and 48 h before killing. All treatments produced evident clinical symptoms, but no marked depression of bone marrow proliferation. No statistically significant increases in the incidence of micronucleated polychromatic erythrocytes over the control values were observed at any sampling time with any of the 10 halogenated hydrocarbons assayed. The comparison of the results obtained in this study with the findings provided by in vitro micronucleus assays on the same chemicals, reported by other authors, indicate that mouse bone marrow is weakly sensitive to the genotoxic effects induced by halogenated hydrocarbons in other test systems. This suggests that the role of such an assay in carcinogen screening may be questionable for this chemical class. An examination of mouse bone marrow micronucleus test results with the halogenated aliphatic hydrocarbons classified as carcinogens by IARC supports this conclusion.

  9. Molecular recognition of halogen-tagged aromatic VOCs at the air-silicon interface.

    Science.gov (United States)

    Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Gurrieri, Ettore; Betti, Paolo; Dalcanale, Enrico

    2010-01-14

    Selective and reversible complexation of halogen-tagged aromatic VOCs by a quinoxaline cavitand-decorated Si surface is demonstrated. The specific host-guest interactions of the Si-bonded receptors are proved to be responsible of the surface recognition properties, while extracavity non specific adsorptions are totally suppressed compared to the bulk material.

  10. Noncovalent Halogen Bonding as a Mechanism for Gas-Phase Clustering

    DEFF Research Database (Denmark)

    Wegeberg, Christina; Donald, William A.; McKenzie, Christine

    2017-01-01

    in the crystalline phases of PhIO2 and its derivatives serve as models for the structures of larger gas-phase clusters, and calculations on simple model gas-phase dimer and trimer clusters result in similar motifs. This is the first account of halogen bonding playing an extensive role in gas-phase associations....

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

    Science.gov (United States)

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

    2016-09-05

    The synthesis of the first halogen bonding [3]rotaxane host system containing a bis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo-triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the (1) H NMR anion binding results. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  12. Solution and solid-phase halogen and C-H hydrogen bonding to perrhenate.

    Science.gov (United States)

    Massena, Casey J; Riel, Asia Marie S; Neuhaus, George F; Decato, Daniel A; Berryman, Orion B

    2015-01-28

    (1)H NMR spectroscopic and X-ray crystallographic investigations of a 1,3-bis(4-ethynyl-3-iodopyridinium)benzene scaffold with perrhenate reveal strong halogen bonding in solution, and bidentate association in the solid state. A nearly isostructural host molecule demonstrates significant C-H hydrogen bonding to perrhenate in the same phases.

  13. Halogen bonded complexes between volatile anaeshetics (chloroform, halothane, enflurane, isoflurane) and formaldehyde: a theoretical study

    Czech Academy of Sciences Publication Activity Database

    Zierkiewicz, W.; Wieczorek, R.; Hobza, Pavel; Michalska, D.

    2011-01-01

    Roč. 13, č. 11 (2011), s. 5105-5113 ISSN 1463-9076 R&D Projects: GA MŠk LC512 Institutional research plan: CEZ:AV0Z40550506 Keywords : halogen bond * anaesthetics * ab initio calculation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.573, year: 2011

  14. High-temperature peaks of thermostimulated luminescence in the ammonium halogens

    International Nuclear Information System (INIS)

    Kim, L.M.; Musenova, Eh.K.; Mukhamedrakhimov, K.U.

    2003-01-01

    The ammonium halogen crystals (AHC) are the close analogs of the alkali halogen crystals by the type of chemical bonds and crystal lattice structure. The ammonium halogen after irradiation by X-rays within 80-300 K range have two peaks of thermo-stimulation luminescence. Its maximums in dependence of anions type are in the 110-120 K and 170-180 K ranges. The first range is related with activation of auto-localized holes migration, and the second one - with the NH 3 + defects decay. Experimentally is established, that the pure ammonium halogens have memory about the previous irradiation at heating up to 300 K. After repeat irradiation the recombination luminescence high-temperature peak's shoulder is appearing. The second luminescence peak's shoulder revealing does not depend on the impurity center nature. It is known, that in the AHC there is the next thermo-stimulation luminescence peak within 340-360 K. The thermal annealing of this peak leads to the memory effect disappearance. So, the observing phenomenon is related with own defect of the matrix in the cation sublattice. Experimentally is established, that at a room temperature the AHC memorizing about previous irradiation during 20 h

  15. Impact of enhanced ozone deposition and halogen chemistry on model performance

    Science.gov (United States)

    In this study, an enhanced ozone deposition scheme due to the interaction of iodide in sea-water and atmospheric ozone and the detailed chemical reactions of organic and inorganic halogen species are incorporated into the hemispheric Community Multiscale Air Quality model. Prelim...

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

    Czech Academy of Sciences Publication Activity Database

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

    2012-01-01

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

  17. Rearrangements in the halogenation of tetraalkylethylenes with N-halosuccinimides and tert-butyl hypochlorite

    NARCIS (Netherlands)

    Meijer, E.W.; Kellogg, R.M.; Wynberg, H.

    1982-01-01

    The reaction of N-halosuccinimides and Me3COCl with tetraalkylethylenes involves halo-cation addn. to the double bond in a fast reaction, followed by abstraction of an allylic proton, resulting in a double bond shift. Homoallylic halogenation occurs in tetraalkylethylenes which can not undergo a

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

    Directory of Open Access Journals (Sweden)

    Christer B. Aakeröy

    2015-09-01

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

  19. Phosphorylated lignin as a halogen-free flame retardant additive for epoxy composites

    Science.gov (United States)

    Gamini P. Mendis; Sydney G. Weiss; Matthew Korey; Charles R. Boardman; Mark Dietenberger; Jeffrey P. Youngblood; John A. Howarter

    2016-01-01

    Sustainable, non-halogenated flame retardants are desired for a variety of industry applications. Lignin, as an industrially processed wood derivative, has been examined as a potential sustainable flame retardant additive to polymer systems. Here, the lignin is phosphorylated using a pyridine-catalysed esterification reaction with diphenyl phosphoryl chloride to...

  20. Performance analysis of photoresistor and phototransistor for automotive’s halogen and xenon bulbs light output

    Science.gov (United States)

    Rammohan, A.; Kumar, C. Ramesh

    2017-11-01

    Illumination of any light is measured using a different kind of calibrated equipment’s available in the market such as a goniometer, spectral radiometer, photometer, Lux meter and camera based systems which directly display the illumination of automotive headlights light distribution in the unit of lux, foot-candles, lumens/sq. ft. and Lambert etc., In this research, we dealt with evaluating the photo resistor or Light Dependent Resistor (LDR) and phototransistor whether it is useful for sensing light patterns of Automotive Halogen and Xenon bulbs. The experiments are conducted during night hours under complete dark space. We have used the headlamp setup available in TATA SUMO VICTA vehicle in the Indian market and conducted the experiments separately for Halogen and Xenon bulbs under low and high beam operations at various degrees and test points within ten meters of distance. Also, we have compared the light intensity of halogen and xenon bulbs to prove the highest light intensity between halogen and Xenon bulbs. After doing a rigorous test with these two sensors it is understood both are good to sensing beam pattern of automotive bulbs and even it is good if we use an array of sensors or a mixed combination of sensors for measuring illumination purposes under perfect calibrations.

  1. Low molecular weight halogenated hydrocarbons (LMHHs) in Mediterranean sea water: Preliminary observations

    International Nuclear Information System (INIS)

    Elder, D.L.; Villeneuve, J.P.; Harvey, G.R.

    1976-01-01

    Halogenated organic compounds containing 1-3 carbon atoms are among the most extensively produced synthetic chemicals. Within this group of compounds are solvents such as chloroform, carbon tetrachloride, trichloroethane and the chlorofluoro carbons or freons which are used as refrigerants and aerosol sprays. Once produced many of these compounds are eventually released to the environment

  2. 21 CFR 700.15 - Use of certain halogenated salicylanilides as ingredients in cosmetic products.

    Science.gov (United States)

    2010-04-01

    ... ingredients in cosmetic products. 700.15 Section 700.15 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.15 Use of certain halogenated salicylanilides as ingredients in cosmetic products. (a...

  3. Tumour radiosensitization with the halogenated pyrimidines 5'-bromo-and 5'-iododeoxyuridine

    International Nuclear Information System (INIS)

    Epstein, A.H.; Cook, J.A.; Goffman, T.; Glatstein, E.

    1993-01-01

    The authors review studies of the use of iododeoxyuridine (IdUrd) and bromodeoxyuridine as radiosensitizers and attempt to correlate the clinical outcome for patients treated with radiation and IdUrd with the extent of halogenated pyrimidine cellular uptake and incorporation. (U.K.)

  4. Tumour radiosensitization with the halogenated pyrimidines 5'-bromo-and 5'-iododeoxyuridine

    Energy Technology Data Exchange (ETDEWEB)

    Epstein, A.H.; Cook, J.A.; Goffman, T. (National Cancer Inst., Bethesda, MD (United States)); Glatstein, E. (Texas Univ., Dallas, TX (United States). Southwestern Medical Center)

    1993-02-01

    The authors review studies of the use of iododeoxyuridine (IdUrd) and bromodeoxyuridine as radiosensitizers and attempt to correlate the clinical outcome for patients treated with radiation and IdUrd with the extent of halogenated pyrimidine cellular uptake and incorporation. (U.K.).

  5. Actinic-radiation curable polymers prepared from a reactive polymer, halogenated cyclic anhydride and glycidyl ester

    International Nuclear Information System (INIS)

    Pastor, S.D.

    1979-01-01

    A novel class of photosensitive polymers are disclosed which are prepared by the reaction, preferably in the presence of a catalyst, of a reactive polymer, a halogenated cyclic anhydride and glycidyl ester of an alpha, beta-unsaturated carboxylic acid. These polymers are capable of undergoing vinyl-type polymerization when exposed to actinic radiation

  6. Halogenation of Hydraulic Fracturing Additives in the Shale Well Parameter Space

    Science.gov (United States)

    Sumner, A. J.; Plata, D.

    2017-12-01

    Horizontal Drilling and Hydraulic fracturing (HDHF) involves the deep-well injection of a `fracking fluid' composed of diverse and numerous chemical additives designed to facilitate the release and collection of natural gas from shale plays. The potential impacts of HDHF operations on water resources and ecosystems are numerous, and analyses of flowback samples revealed organic compounds from both geogenic and anthropogenic sources. Furthermore, halogenated chemicals were also detected, and these compounds are rarely disclosed, suggesting the in situ halogenation of reactive additives. To test this transformation hypothesis, we designed and operated a novel high pressure and temperature reactor system to simulate the shale well parameter space and investigate the chemical reactivity of twelve commonly disclosed and functionally diverse HDHF additives. Early results revealed an unanticipated halogenation pathway of α-β unsaturated aldehyde, Cinnamaldehyde, in the presence of oxidant and concentrated brine. Ongoing experiments over a range of parameters informed a proposed mechanism, demonstrating the role of various shale-well specific parameters in enabling the demonstrated halogenation pathway. Ultimately, these results will inform a host of potentially unintended interactions of HDHF additives during the extreme conditions down-bore of a shale well during HDHF activities.

  7. Changes in patterns of persistent halogenated compounds through a pelagic food web in the Baltic Sea

    DEFF Research Database (Denmark)

    Stephansen, Diana Agnete; Svendsen, Tore Christian; Vorkamp, Katrin

    2012-01-01

    The concentrations and patterns of persistent halogenated compounds (PHCs), including polychlorinated biphenyls (PCBs), DDT, hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB) and polybrominated diphenyl ethers (PBDEs) were examined in a pelagic food web from the southern Baltic Sea consisting...... for the assessment of PHC patterns, e.g. for tracing migratory fish....

  8. Can Halogen Enrichment in Reduced Enstatite Chondrites Provide Clues to Volatile Accretion in the Early Earth?

    Science.gov (United States)

    Clay, P. L.; Burgess, R.; Busemann, H.; Ruzié, L.; Joachim, B.; Ballentine, C.

    2013-12-01

    Understanding how the Earth obtained and ultimately retained its volatiles is important for our overall understanding of large scale planetary evolution. Numerous models exist for the heterogeneous accretion of volatiles to early Earth, but accounting for all elements through accretion of typical planetary building blocks (e.g., CI chondrites) is difficult. Proto-planetary collisions resulting in the accretion of volatile-poor material under reducing conditions followed by accretion of volatile-rich material under oxidizing conditions has been suggested in such models [e.g., 1]. The heavy halogens (Cl, Br and I), a group of moderately volatile elements, are excellent tracers of planetary processing due to their low abundance and incompatible nature. Therefore characterizing halogen abundance and distribution in materials that accreted to form the planets, e.g., primitive meteorites, is crucial. One group of primitive meteorites, the enstatite chondrites (EC's), are amongst the most reduced materials in the solar system as evidenced by their unique mineral assemblage. Yet despite forming under ultra-reducing conditions, they are enriched in the moderately volatile elements, such as the halogens. The ECs are of particular interest owing to their oxygen isotopic composition which plots along the terrestrial fractionation line, linking them isotopically to the Earth-Moon system. These samples can thus potentially provide clues on the accretion of moderately volatile element rich material under reducing conditions, such as it may have existed during the early stages of Earth's accretion. Chlorine, Br and I concentrations in ECs were determined through step-heating small neutron-irradiated samples (0.3 to 3.3 mg) and measured by mass spectrometry using the noble gas proxy isotopes 38ArCl/Cl, 80KrBr/Br and 128XeI/I. The EH chondrites are consistently enriched in the heavy halogens (up to 330 ppm Cl, 2290 ppb Br and 180 ppb I), compared to other ordinary and carbonaceous

  9. Alkylating agent (MNU)-induced mutation in space environment

    Science.gov (United States)

    Ohnishi, T.; Takahashi, A.; Ohnishi, K.; Takahashi, S.; Masukawa, M.; Sekikawa, K.; Amano, T.; Nakano, T.; Nagaoka, S.

    2001-01-01

    In recent years, some contradictory data about the effects of microgravity on radiation-induced biological responses in space experiments have been reported. We prepared a damaged template DNA produced with an alkylating agent (N-methyl-N-nitroso urea; MNU) to measure incorrect base-incorporation during DNA replication in microgravity. We examined whether mutation frequency is affected by microgravity during DNA replication for a DNA template damaged by an alkylating agent. Using an in vitro enzymatic reaction system, DNA synthesis by Taq polymerase or polymerase III was done during a US space shuttle mission (Discovery, STS-91). After the flight, DNA replication and mutation frequencies were measured. We found that there was almost no effect of microgravity on DNA replication and mutation frequency. It is suggested that microgravity might not affect at the stage of substrate incorporation in induced-mutation frequency.

  10. Conformational Restriction of Peptides Using Dithiol Bis-Alkylation.

    Science.gov (United States)

    Peraro, L; Siegert, T R; Kritzer, J A

    2016-01-01

    Macrocyclic peptides are highly promising as inhibitors of protein-protein interactions. While many bond-forming reactions can be used to make cyclic peptides, most have limitations that make this chemical space challenging to access. Recently, a variety of cysteine alkylation reactions have been used in rational design and library approaches for cyclic peptide discovery and development. We and others have found that this chemistry is versatile and robust enough to produce a large variety of conformationally constrained cyclic peptides. In this chapter, we describe applications, methods, mechanistic insights, and troubleshooting for dithiol bis-alkylation reactions for the production of cyclic peptides. This method for efficient solution-phase macrocyclization is highly useful for the rapid production and screening of loop-based inhibitors of protein-protein interactions. © 2016 Elsevier Inc. All rights reserved.

  11. Method for reactivating solid catalysts used in alkylation reactions

    Science.gov (United States)

    Ginosar, Daniel M.; Thompson, David N.; Coates, Kyle; Zalewski, David J.; Fox, Robert V.

    2003-06-17

    A method for reactivating a solid alkylation catalyst is provided which can be performed within a reactor that contains the alkylation catalyst or outside the reactor. Effective catalyst reactivation is achieved whether the catalyst is completely deactivated or partially deactivated. A fluid reactivating agent is employed to dissolve catalyst fouling agents and also to react with such agents and carry away the reaction products. The deactivated catalyst is contacted with the fluid reactivating agent under pressure and temperature conditions such that the fluid reactivating agent is dense enough to effectively dissolve the fouling agents and any reaction products of the fouling agents and the reactivating agent. Useful pressures and temperatures for reactivation include near-critical, critical, and supercritical pressures and temperatures for the reactivating agent. The fluid reactivating agent can include, for example, a branched paraffin containing at least one tertiary carbon atom, or a compound that can be isomerized to a molecule containing at least one tertiary carbon atom.

  12. Rapid NIR determination of alkyl esters in virgin olive oil

    International Nuclear Information System (INIS)

    Cayuela, J.A.

    2017-01-01

    The regulation of The European Union for olive oil and olive pomace established the limit of 35 mg·kg-1 for fatty acids ethyl ester contents in extra virgin olive oils, from grinding seasons after 2016. In this work, predictive models have been established for measuring fatty acid ethyl and methyl esters and to measure the total fatty acid alkyl esters based on near infrared spectroscopy (NIRS), and used successfully for this purpose. The correlation coefficients from the external validation exercises carried out with these predictive models ranged from 0.84 to 0.91. Different classification tests using the same models for the thresholds 35 mg·kg-1 for fatty acid ethyl esters and 75 mg·kg-1 for fatty acid alkyl esters provided success percentages from 75.0% to 95.2%. [es

  13. Synthesis and Antioxidant Activity of Alkyl Nitroderivatives of Hydroxytyrosol

    Directory of Open Access Journals (Sweden)

    Elena Gallardo

    2016-05-01

    Full Text Available A series of alkyl nitrohydroxytyrosyl ether derivatives has been synthesized from free hydroxytyrosol (HT, the natural olive oil phenol, in order to increase the assortment of compounds with potential neuroprotective activity in Parkinson’s disease. In this work, the antioxidant activity of these novel compounds has been evaluated using Ferric Reducing Antioxidant Power (FRAP, 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid diammonium salt (ABTS, and Oxygen Radical Scavenging Capacity (ORAC assays compared to that of nitrohydroxytyrosol (NO2HT and free HT. New compounds showed variable antioxidant activity depending on the alkyl side chain length; compounds with short chains (2–4 carbon atoms maintained or even improved the antioxidant activity compared to NO2HT and/or HT, whereas those with longer side chains (6–8 carbon atoms showed lower activity than NO2HT but higher than HT.

  14. New unit for sulfuric acid alkylation of isobutane by olefins

    Energy Technology Data Exchange (ETDEWEB)

    Khadzhiev, S.N.; Baiburskii, V.L.; Deineko, P.S.; Gruzdev, A.S.; Tagavov, I.T.

    1987-01-01

    The authors describe and illustrate a sulfuric acid alkylation unit with a horizontal contact. As a result of the use of this design solution, the isobutane/olefin ratio is 10/1 in comparison with 4/1 to 5/1 in the other types of units, namely vertical reactors and cascade tank reactors. The unit was designed to process the butane-butylene cut (BBC) and part of the propane-propylene cut (PPC) from the G-43-107 cat cracker. The unit design includes provisions for controlled caustic washing of the feed and dehydration in an electric field. The authors present the basic data obtained in the three months of unit operation after startup, in comparison with the operating indexes of a sulfuric acid alkylation unit.

  15. Alkylation of isobutane by ethylene: A thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Goupil, J.M.; Poirier, J.L.; Cornet, D. (Univ. of Caen (France). Lab. Catalyse et Spectrochimie)

    1994-03-01

    Alkylation of isobutane by ethylene produces mainly hexanes, but a variety of other compounds, alkanes or alkenes, may be formed by secondary reactions such as successive alkylations, isomerization, and ethylene polymerization. The equilibrium distribution of products is evaluated in the temperature range 280--680 K and at various initial compositions and pressures. Isomer groups are treated using Alberty's formulation. Calculations show that alkenes are thermodynamically unstable under usual reaction conditions. The equilibrium amounts of alkanes are such that C[sub 6] [much gt] C[sub 8] [much gt] C[sub 10] and heavy alkanes also appear unstable. The selective formation of particular isomers (dimethylbutanes, trimethylpentanes) is also integrated in the equilibrium equations. The calculated compositions (C[sub 6]:C[sub 8]:C[sub 10]) are compared with experimental data.

  16. Antioxidant activity of alkyl gallates and glycosyl alkyl gallates in fish oil in water emulsions: relevance of their surface active properties and of the type of emulsifier.

    Science.gov (United States)

    González, María J; Medina, Isabel; Maldonado, Olivia S; Lucas, Ricardo; Morales, Juan C

    2015-09-15

    The antioxidant activity of gallic acid and a series of alkyl gallates (C4-C18) and glycosylated alkyl gallates (C4-C18) on fish oil-in-water emulsions was studied. Three types of emulsifiers, lecithin, Tween-20 and sodium dodecyl sulphate (SDS) were tested. A nonlinear behavior of the antioxidant activity of alkyl gallates when increasing alkyl chain length was observed for emulsions prepared with lecithin. Medium-size alkyl gallates (C6-C12) were the best antioxidants. In contrast, for emulsions prepared with Tween-20, the antioxidants seem to follow the polar paradox. Glucosyl alkyl gallates were shown previously to be better surfactants than alkyl gallates. Nevertheless, they exhibited a worse antioxidant capacity than their corresponding alkyl gallates, in emulsions prepared with lecithin or Tween-20, indicating the greater relevance of having three OH groups at the polar head in comparison with having improved surfactant properties but just a di-ortho phenolic structure in the antioxidant. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. The formation of quasi-alicyclic rings in alkyl-aromatic compounds

    Science.gov (United States)

    Straka, Pavel; Buryan, Petr; Bičáková, Olga

    2018-02-01

    The alkyl side chains of n-alkyl phenols, n-alkyl benzenes and n-alkyl naphthalenes are cyclised, as demonstrated by GC measurements, FTIR spectroscopy and molecular mechanics calculations. Cyclisation occurs due to the intramolecular interaction between an aromatic ring (-δ) and a hydrogen of the terminal methyl group (+δ) of an alkyl chain. In fact, conventional molecules are not aliphatic-aromatic, but quasi-alicyclic-aromatic. With the aromatic molecules formed with a quasi-alicyclic ring, the effect of van der Waals attractive forces increases not only intramolecularly but also intermolecularly. This effect is strong in molecules with propyl and higher alkyl substituents. The increase of intermolecular van der Waals attractive forces results in bi-linearity in the GC retention time of the compounds in question, observed in the dependence of the logarithm of the relative retention time on the number of carbons in a molecule in both polar and nonpolar stationary phases with both capillary and packed columns. The role of van der Waals forces has been demonstrated using the potential energies of covalent and noncovalent interactions for 2-n-alkyl phenols, n-alkyl benzenes and 1-n-alkyl- and 2-n-alkyl naphthalenes.

  18. A Convenient Approach to Synthesizing Peptide C-Terminal N-Alkyl Amides

    Science.gov (United States)

    Fang, Wei-Jie; Yakovleva, Tatyana; Aldrich, Jane V.

    2014-01-01

    Peptide C-terminal N-alkyl amides have gained more attention over the past decade due to their biological properties, including improved pharmacokinetic and pharmacodynamic profiles. However, the synthesis of this type of peptide on solid phase by current available methods can be challenging. Here we report a convenient method to synthesize peptide C-terminal N-alkyl amides using the well-known Fukuyama N-alkylation reaction on a standard resin commonly used for the synthesis of peptide C-terminal primary amides, the PAL-PEG-PS (Peptide Amide Linker-polyethylene glycol-polystyrene) resin. The alkylation and oNBS deprotection were conducted under basic conditions and were therefore compatible with this acid labile resin. The alkylation reaction was very efficient on this resin with a number of different alkyl iodides or bromides, and the synthesis of model enkephalin N-alkyl amide analogs using this method gave consistently high yields and purities, demonstrating the applicability of this methodology. The synthesis of N-alkyl amides was more difficult on a Rink amide resin, especially the coupling of the first amino acid to the N-alkyl amine, resulting in lower yields for loading the first amino acid onto the resin. This method can be widely applied in the synthesis of peptide N-alkyl amides. PMID:22252422

  19. Mutagenic activity of halogenated propanes and propenes: effect of bromine and chlorine positioning.

    Science.gov (United States)

    Låg, M; Omichinski, J G; Dybing, E; Nelson, S D; Søderlund, E J

    1994-10-01

    A series of halogenated propanes and propenes were studied for mutagenic effects in Salmonella typhimurium TA100 in the absence or presence of NADPH plus liver microsomes from phenobarbital-induced rats as an exogenous metabolism system. The cytotoxic and mutagenic effects of the halogenated propane 1,2-dibromo-3-chloropropane (DBCP) has previously been studied in our laboratories. These studies showed that metabolic activation of DBCP was required to exert its detrimental effects. All of the trihalogenated propane analogues were mutagenic when the microsomal activation system was included. The highest mutagenic activity was obtained with 1,2,3-tribromopropane, with approximately 50-fold higher activity than the least mutagenic trihalogenated propane, 1,2,3-trichloropropane. The order of mutagenicity was as follows: 1,2,3-tribromopropane > or = 1,2-dibromo- 3-chloropropane > 1,3-dibromo-2-chloropropane > or = 1,3-dichloro-2-bromopropane > 1-bromo-2,3-dichloropropane > 1,2,3-trichloropropane. Compared to DBCP, the dihalogenated propanes were substantially less mutagenic. Only 1,2-dibromopropane was mutagenic and its mutagenic potential was approximately 1/30 of that of DBCP. In contrast to DBCP, 1,2-dibromopropane showed similar mutagenic activity with and without the addition of an activation system. The halogenated propenes 2,3-dibromopropene and 2-bromo-3-chloropropene were mutagenic to the bacteria both in the absence and presence of the activation system, whereas 2,3-dichloropropene did not show any mutagenic effect. The large differences in mutagenic potential between the various halogenated propanes and propenes are proposed to be due to the formation of different possible proximate and ultimate mutagenic metabolites resulting from the microsomal metabolism of the various halogenated propanes and propenes, and to differences in the rate of formation of the metabolites. Pathways are proposed for the formation of genotoxic metabolites of di- and trihalogenated

  20. Reconciliation of Halogen-Induced Ozone Loss with the Total-Column Ozone Record

    Science.gov (United States)

    Shepherd, T. G.; Plummer, D. A.; Scinocca, J. F.; Hegglin, M. I.; Fioletov, V. E.; Reader, M. C.; Remsberg, E.; von Clarmann, T.; Wang, H. J.

    2014-01-01

    The observed depletion of the ozone layer from the 1980s onwards is attributed to halogen source gases emitted by human activities. However, the precision of this attribution is complicated by year-to-year variations in meteorology, that is, dynamical variability, and by changes in tropospheric ozone concentrations. As such, key aspects of the total-column ozone record, which combines changes in both tropospheric and stratospheric ozone, remain unexplained, such as the apparent absence of a decline in total-column ozone levels before 1980, and of any long-term decline in total-column ozone levels in the tropics. Here we use a chemistry-climate model to estimate changes in halogen-induced ozone loss between 1960 and 2010; the model is constrained by observed meteorology to remove the eects of dynamical variability, and driven by emissions of tropospheric ozone precursors to separate out changes in tropospheric ozone. We show that halogen-induced ozone loss closely followed stratospheric halogen loading over the studied period. Pronounced enhancements in ozone loss were apparent in both hemispheres following the volcanic eruptions of El Chichon and, in particular, Mount Pinatubo, which significantly enhanced stratospheric aerosol loads. We further show that approximately 40% of the long-term non-volcanic ozone loss occurred before 1980, and that long-term ozone loss also occurred in the tropical stratosphere. Finally, we show that halogeninduced ozone loss has declined by over 10% since stratospheric halogen loading peaked in the late 1990s, indicating that the recovery of the ozone layer is well underway.

  1. Extending Halogen-based Medicinal Chemistry to Proteins: IODO-INSULIN AS A CASE STUDY.

    Science.gov (United States)

    El Hage, Krystel; Pandyarajan, Vijay; Phillips, Nelson B; Smith, Brian J; Menting, John G; Whittaker, Jonathan; Lawrence, Michael C; Meuwly, Markus; Weiss, Michael A

    2016-12-30

    Insulin, a protein critical for metabolic homeostasis, provides a classical model for protein design with application to human health. Recent efforts to improve its pharmaceutical formulation demonstrated that iodination of a conserved tyrosine (Tyr B26 ) enhances key properties of a rapid-acting clinical analog. Moreover, the broad utility of halogens in medicinal chemistry has motivated the use of hybrid quantum- and molecular-mechanical methods to study proteins. Here, we (i) undertook quantitative atomistic simulations of 3-[iodo-Tyr B26 ]insulin to predict its structural features, and (ii) tested these predictions by X-ray crystallography. Using an electrostatic model of the modified aromatic ring based on quantum chemistry, the calculations suggested that the analog, as a dimer and hexamer, exhibits subtle differences in aromatic-aromatic interactions at the dimer interface. Aromatic rings (Tyr B16 , Phe B24 , Phe B25 , 3-I-Tyr B26 , and their symmetry-related mates) at this interface adjust to enable packing of the hydrophobic iodine atoms within the core of each monomer. Strikingly, these features were observed in the crystal structure of a 3-[iodo-Tyr B26 ]insulin analog (determined as an R 6 zinc hexamer). Given that residues B24-B30 detach from the core on receptor binding, the environment of 3-I-Tyr B26 in a receptor complex must differ from that in the free hormone. Based on the recent structure of a "micro-receptor" complex, we predict that 3-I-Tyr B26 engages the receptor via directional halogen bonding and halogen-directed hydrogen bonding as follows: favorable electrostatic interactions exploiting, respectively, the halogen's electron-deficient σ-hole and electronegative equatorial band. Inspired by quantum chemistry and molecular dynamics, such "halogen engineering" promises to extend principles of medicinal chemistry to proteins. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  2. Chromatographic resolution of closely related species in pharmaceutical chemistry: dehalogenation impurities and mixtures of halogen isomers.

    Science.gov (United States)

    Regalado, Erik L; Zhuang, Ping; Chen, Yadan; Makarov, Alexey A; Schafer, Wes A; McGachy, Neil; Welch, Christopher J

    2014-01-07

    In recent years, the use of halogen-containing molecules has proliferated in the pharmaceutical industry, where the incorporation of halogens, especially fluorine, has become vitally important for blocking metabolism and enhancing the biological activity of pharmaceuticals. The chromatographic separation of halogen-containing pharmaceuticals from associated isomers or dehalogenation impurities can sometimes be quite difficult. In an attempt to identify the best current tools available for addressing this important problem, a survey of the suitability of four chromatographic method development platforms (ultra high-performance liquid chromatography (UHPLC), core shell HPLC, achiral supercritical fluid chromatography (SFC) and chiral SFC) for separating closely related mixtures of halogen-containing pharmaceuticals and their dehalogenated isosteres is described. Of the 132 column and mobile phase combinations examined for each mixture, a small subset of conditions were found to afford the best overall performance, with a single UHPLC method (2.1 × 50 mm, 1.9 μm Hypersil Gold PFP, acetonitrile/methanol based aqueous eluents containing either phosphoric or perchloric acid with 150 mM sodium perchlorate) affording excellent separation for all samples. Similarly, a survey of several families of closely related halogen-containing small molecules representing the diversity of impurities that can sometimes be found in purchased starting materials for synthesis revealed chiral SFC (Chiralcel OJ-3 and Chiralpak IB, isopropanol or ethanol with 25 mM isobutylamine/carbon dioxide) as well as the UHPLC (2.1 × 50 mm, 1.8 μm ZORBAX RRHD Eclipse Plus C18 and the Gold PFP, acetonitrile/methanol based aqueous eluents containing phosphoric acid) as preferred methods.

  3. Computational insights into the photocyclization of diclofenac in solution: effects of halogen and hydrogen bonding.

    Science.gov (United States)

    Bani-Yaseen, Abdulilah Dawoud

    2016-08-21

    The effects of noncovalent interactions, namely halogen and hydrogen bonding, on the photochemical conversion of the photosensitizing drug diclofenac (DCF) in solution were investigated computationally. Both explicit and implicit solvent effects were qualitatively and quantitatively assessed employing the DFT/6-31+G(d) and SQM(PM7) levels of theory. Full geometry optimizations were performed in solution for the reactant DCF, hypothesized radical-based intermediates, and the main product at both levels of theories. Notably, in good agreement with previous experimental results concerning the intermolecular halogen bonding of DCF, the SQM(PM7) method revealed different values for d(ClO, Å) and ∠(C-ClO, °) for the two chlorine-substituents of DCF, with values of 2.63 Å/162° and 3.13 Å/142° for the trans and cis orientations, respectively. Employing the DFT/6-31+G(d) method with implicit solvent effects was not conclusive; however, explicit solvent effects confirmed the key contribution of hydrogen and halogen bonding in stabilizing/destabilizing the reactant and hypothesized intermediates. Interestingly, the obtained results revealed that a protic solvent such as water can increase the rate of photocyclization of DCF not only through hydrogen bonding effects, but also through halogen bonding. Furthermore, the atomic charges of atoms majorly involved in the photocyclization of DCF were calculated using different methods, namely Mulliken, Hirshfeld, and natural bond orbital (NBO). The obtained results revealed that in all cases there is a notable nonequivalency in the noncovalent intermolecular interactions of the two chlorine substituents of DCF and the radical intermediates with the solvent, which in turn may account for the discrepancy of their reactivity in different media. These computational results provide insight into the importance of halogen and hydrogen bonding throughout the progression of the photochemical conversion of DCF in solution.

  4. The anomalous halogen bonding interactions between chlorine and bromine with water in clathrate hydrates.

    Science.gov (United States)

    Dureckova, Hana; Woo, Tom K; Udachin, Konstantin A; Ripmeester, John A; Alavi, Saman

    2017-10-13

    Clathrate hydrate phases of Cl 2 and Br 2 guest molecules have been known for about 200 years. The crystal structure of these phases was recently re-determined with high accuracy by single crystal X-ray diffraction. In these structures, the water oxygen-halogen atom distances are determined to be shorter than the sum of the van der Waals radii, which indicates the action of some type of non-covalent interaction between the dihalogens and water molecules. Given that in the hydrate phases both lone pairs of each water oxygen atom are engaged in hydrogen bonding with other water molecules of the lattice, the nature of the oxygen-halogen interactions may not be the standard halogen bonds characterized recently in the solid state materials and enzyme-substrate compounds. The nature of the halogen-water interactions for the Cl 2 and Br 2 molecules in two isolated clathrate hydrate cages has recently been studied with ab initio calculations and Natural Bond Order analysis (Ochoa-Resendiz et al. J. Chem. Phys. 2016, 145, 161104). Here we present the results of ab initio calculations and natural localized molecular orbital analysis for Cl 2 and Br 2 guests in all cage types observed in the cubic structure I and tetragonal structure I clathrate hydrates to characterize the orbital interactions between the dihalogen guests and water. Calculations with isolated cages and cages with one shell of coordinating molecules are considered. The computational analysis is used to understand the nature of the halogen bonding in these materials and to interpret the guest positions in the hydrate cages obtained from the X-ray crystal structures.

  5. Chiral halogenated Schiff base compounds: green synthesis, anticancer activity and DNA-binding study

    Science.gov (United States)

    Ariyaeifar, Mahnaz; Amiri Rudbari, Hadi; Sahihi, Mehdi; Kazemi, Zahra; Kajani, Abolghasem Abbasi; Zali-Boeini, Hassan; Kordestani, Nazanin; Bruno, Giuseppe; Gharaghani, Sajjad

    2018-06-01

    Eight enantiomerically pure halogenated Schiff base compounds were synthesized by reaction of halogenated salicylaldehydes with 3-Amino-1,2-propanediol (R or S) in water as green solvent at ambient temperature. All compounds were characterized by elemental analyses, NMR (1H and 13C), circular dichroism (CD) and FT-IR spectroscopy. FS-DNA binding studies of these compounds carried out by fluorescence quenching and UV-vis spectroscopy. The obtained results revealed that the ligands bind to DNA as: (Rsbnd ClBr) > (Rsbnd Cl2) > (Rsbnd Br2) > (Rsbnd I2) and (Ssbnd ClBr) > (Ssbnd Cl2) > (Ssbnd Br2) > (Ssbnd I2), indicating the effect of halogen on binding constant. In addition, DNA-binding constant of the Ssbnd and R-enantiomers are different from each other. The ligands can form halogen bonds with DNA that were confirmed by molecular docking. This method was also measured the bond distances and bond angles. The study of obtained data can have concluded that binding affinity of the ligands to DNA depends on strength of halogen bonds. The potential anticancer activity of ligands were also evaluated on MCF-7 and HeLa cancer cell lines by using MTT assay. The results showed that the anticancer activity and FS-DNA interaction is significantly dependent on the stereoisomers of Schiff base compounds as R-enantiomers displayed significantly higher activity than S-enantiomers. The molecular docking was also used to illustrate the specific DNA-binding of synthesized compounds and groove binding mode of DNA interaction was proposed for them. In addition, molecular docking results indicated that there are three types of bonds (Hsbnd and X-bond and hX-bond) between synthesized compounds and base pairs of DNA.

  6. DNA Damage Induced by Alkylating Agents and Repair Pathways

    OpenAIRE

    Natsuko Kondo; Akihisa Takahashi; Koji Ono; Takeo Ohnishi

    2010-01-01

    The cytotoxic effects of alkylating agents are strongly attenuated by cellular DNA repair processes, necessitating a clear understanding of the repair mechanisms. Simple methylating agents form adducts at N- and O-atoms. N-methylations are removed by base excision repair, AlkB homologues, or nucleotide excision repair (NER). O 6-methylguanine (MeG), which can eventually become cytotoxic and mutagenic, is repaired by O 6-methylguanine-DNA methyltransferase, and O 6MeG:T mispairs are recognized...

  7. Optimizing the use of alkylators in neuro-oncology

    OpenAIRE

    Perry, J R; Wick, W; Weller, M

    2011-01-01

    For more than three decades, alkylating agents have been the most widely used class of chemotherapeutic agents for the treatment of glial brain tumors. Today, concomitant and adjuvant temozolomide is the standard of care for newly diagnosed glioblastoma. Temozolomide alone or in combination with radiotherapy is being explored in ongoing trials in newly diagnosed patients with low-grade and anaplastic glioma. Rechallenge with alternative dosing schedules of temozolomide is a valid treatment op...

  8. 3-alkyl fentanyl analogues: Structure-activity-relationship study

    OpenAIRE

    Vučković, Sonja; Savić-Vujović, Katarina; Srebro, Dragana; Ivanović, Milovan; Došen-Mićović, Ljiljana; Stojanović, Radan; Prostran, Milica

    2012-01-01

    Introduction. Fentanyl belongs to 4-anilidopiperidine class of synthetic opioid analgesics. It is characterized by high potency, rapid onset and short duration of action. A large number of fentanyl analogues have been synthesized so far, both to establish the structure-activity-relationship (SAR) and to find novel, clinically useful analgesic drugs. Objective. In this study, newly synthesized 3-alkyl fentanyl analogues were examined for analgesic activity and compared with fentanyl. Methods. ...

  9. New potential of the reductive alkylation of amines

    International Nuclear Information System (INIS)

    Gusak, K N; Ignatovich, Zh V; Koroleva, E V

    2015-01-01

    Available data on the reductive alkylation of amines with carbonyl compounds — a key method for the preparation of secondary and tertiary amines — are described systematically. The review provides information on the relevant reducing agents and catalysts and on the use of chiral catalysts in stereo- and enantiocontrolled reactions of amine synthesis. The effect of the reactant and catalyst structures on the reaction rates and chemo- and stereo(enantio)selectivity is considered. The bibliography includes 156 references

  10. Ruthenium-Catalyzed Alkylation of Oxindole with Alcohols

    DEFF Research Database (Denmark)

    Jensen, Thomas; Madsen, Robert

    2009-01-01

    An atom-economical and solvent-free catalytic procedure for the mono-3-alkylation of oxindole with alcohols is described. The reaction is mediated by the in situ generated catalyst from RuCl3 center dot xH(2)O and PPh3 in the presence of sodium hydroxide, The reactions proceed in good to excellent...... yields with a wide range of aromatic, heteroaromatic, and aliphatic alcohols....

  11. Alkylation of isobutane by butenes on zirconium sulfate catalysts

    International Nuclear Information System (INIS)

    Lavrenov, A.V.; Perelevskij, E.V.; Finevich, V.P.; Zajkovskij, V.I.; Paukshtis, E.A.; Duplyakiv, V.K.; Bal'zhinimaev, B.S.

    2003-01-01

    Preparation of applied zirconium sulfate catalysts obtained by the method of impregnation is investigated. Results of comparative study of structural, acid-base and catalytic properties of sulfated zirconium dioxide applied on silica gel and aluminium oxide are represented. Intervals of values of synthesis basic parameters and characteristics of catalysts properties providing achievement of high activity and selectivity in isobutane alkylation by butenes in liquid phase are determined [ru

  12. A new phenylethyl alkyl amide from the Ambrostoma quadriimpressum Motschulsky

    Directory of Open Access Journals (Sweden)

    Guolei Zhao

    2011-09-01

    Full Text Available A new phenylethyl alkyl amide, (10R-10-hydroxy-N-phenethyloctadecanamide (1, was isolated from the beetle Ambrostoma quadriimpressum Motschulsky. The structure of the amide was determined by NMR and MS. The absolute configuration of compound 1 was confirmed by an asymmetric total synthesis, which was started from L-glutamic acid. The construction of the aliphatic chain was accomplished by the selective protection of the hydroxy groups and two-time implementation of the Wittig olefination reaction.

  13. Halogen poisoning effect of Pt-TiO{sub 2} for formaldehyde catalytic oxidation performance at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Xiaofeng; Cheng, Bei [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Yu, Jiaguo, E-mail: jiaguoyu@yahoo.com [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia); Ho, Wingkei, E-mail: keithho@ied.edu.hk [Department of Science and Environmental Studies and Centre for Education in Environmental Sustainability, The Hong Kong Institute of Education, Tai Po, N.T. Hong Kong (China)

    2016-02-28

    Graphical abstract: - Highlights: • The Pt-TiO{sub 2} catalyst is deactivated by adsorption of halogen ions. • The halogen poison is mainly attributed to the active site blocking of the Pt surface. • Halogen ions and Pt form Pt−X coordination bonds. • Large halogen diameter exhibits severe poisoning effect. - Abstract: Catalytic decomposition of formaldehyde (HCHO) at room temperature is an important method for HCHO removal. Pt-based catalysts are the optimal catalyst for HCHO decomposition at room temperature. However, the stability of this catalyst remains unexplored. In this study, Pt-TiO{sub 2} (Pt-P25) catalysts with and without adsorbed halogen ions (including F{sup −}, Cl{sup −}, Br{sup −}, and I{sup −}) were prepared through impregnation and ion modification. Pt-TiO{sub 2} samples with adsorbed halogen ions exhibited reduced catalytic activity for formaldehyde decomposition at room temperature compared with the Pt-TiO{sub 2} sample; the catalytic activity followed the order of F-Pt-P25, Cl-Pt-P25, Br-Pt-P25, and I-Pt-P25. Characterization results (including XRD, TEM, HRTEM, BET, XPS, and metal dispersion) showed that the adsorbed halogen ions can poison Pt nanoparticles (NPs), thereby reducing the HCHO oxidation activity of Pt-TiO{sub 2}. The poison mechanism is due to the strong adsorption of halogen ions on the surface of Pt NPs. The adsorbed ions form coordination bonds with surface Pt atoms by transferring surplus electrons into the unoccupied 5d orbit of the Pt atom, thereby inhibiting oxygen adsorption and activation of the Pt NP surface. Moreover, deactivation rate increases with increasing diameter of halogen ions. This study provides new insights into the fabrication of high-performance Pt-based catalysts for indoor air purification.

  14. Concentration-dependent multiple chirality transition in halogen-bond-driven 2D self-assembly process

    Science.gov (United States)

    Miao, Xinrui; Li, Jinxing; Zha, Bao; Miao, Kai; Dong, Meiqiu; Wu, Juntian; Deng, Wenli

    2018-03-01

    The concentration-dependent self-assembly of iodine substituted thienophenanthrene derivative (5,10-DITD) is investigated at the 1-octanic acid/graphite interface using scanning tunneling microscopy. Three kinds of chiral arrangement and transition of 2D molecular assembly mainly driven by halogen bonding is clearly revealed. At high concentration the molecules self-assembled into a honeycomb-like chiral network. Except for the interchain van der Waals forces, this pattern is stabilized by intermolecular continuous Cdbnd O⋯I⋯S halogen bonds in each zigzag line. At moderate concentration, a chiral kite-like nanoarchitecture are observed, in which the Cdbnd O⋯I⋯S and I⋯Odbnd C halogen bonds, along with the molecule-solvent Cdbnd O⋯I⋯H halogen bonds are the dominated forces to determine the structural formation. At low concentration, the molecules form a chiral cyclic network resulting from the solvent coadsorption mainly by molecule-molecule Cdbnd O⋯I⋯S halogen bonds and molecule-solvent Cdbnd O⋯I⋯H halogen bonds. The density of molecular packing becomes lower with the decreasing of the solution concentration. The solution-concentration dependent self-assembly of thienophenanthrene derivative with iodine and ester chain moieties reveals that the type of intermolecular halogen bond and the number of the co-adsorbing 1-octanic acids by molecule-solvent Cdbnd O⋯I⋯H halogen bonds determine the formation and transformation of chirality. This research emphasizes the role of different types of halogen (I) bonds in the controllable supramolecular structures and provides an approach for the fabrication of chirality.

  15. Chemotherapy-induced pulmonary hypertension: role of alkylating agents.

    Science.gov (United States)

    Ranchoux, Benoît; Günther, Sven; Quarck, Rozenn; Chaumais, Marie-Camille; Dorfmüller, Peter; Antigny, Fabrice; Dumas, Sébastien J; Raymond, Nicolas; Lau, Edmund; Savale, Laurent; Jaïs, Xavier; Sitbon, Olivier; Simonneau, Gérald; Stenmark, Kurt; Cohen-Kaminsky, Sylvia; Humbert, Marc; Montani, David; Perros, Frédéric

    2015-02-01

    Pulmonary veno-occlusive disease (PVOD) is an uncommon form of pulmonary hypertension (PH) characterized by progressive obstruction of small pulmonary veins and a dismal prognosis. Limited case series have reported a possible association between different chemotherapeutic agents and PVOD. We evaluated the relationship between chemotherapeutic agents and PVOD. Cases of chemotherapy-induced PVOD from the French PH network and literature were reviewed. Consequences of chemotherapy exposure on the pulmonary vasculature and hemodynamics were investigated in three different animal models (mouse, rat, and rabbit). Thirty-seven cases of chemotherapy-associated PVOD were identified in the French PH network and systematic literature analysis. Exposure to alkylating agents was observed in 83.8% of cases, mostly represented by cyclophosphamide (43.2%). In three different animal models, cyclophosphamide was able to induce PH on the basis of hemodynamic, morphological, and biological parameters. In these models, histopathological assessment confirmed significant pulmonary venous involvement highly suggestive of PVOD. Together, clinical data and animal models demonstrated a plausible cause-effect relationship between alkylating agents and PVOD. Clinicians should be aware of this uncommon, but severe, pulmonary vascular complication of alkylating agents. Copyright © 2015 American Society for Investigative Pathology. Published by Elsevier Inc. All rights reserved.

  16. Effects of alkylating carcinogens on human tumor cells in culture

    International Nuclear Information System (INIS)

    Goth-Goldstein, R.; Hughes, M.

    1987-01-01

    In Escherichia coli 3-methyladenine and 3-methylguanine have been identified as lethal lesions, since two types of alkylating agent-sensitive mutants were deficient in repair of either of these lesions. Similar alkylation-sensitive human cell lines exist. These are the tumor cell lines of the complex Mer - phenotype. All Mer - cells examined were hypersensitive to killing by MNNG and other alkylating agents, and failed to repair O 6 -methylguanine. The widely studied HeLa S3 cell line has the Mer + phenotype, but a Mer - variant (HeLa MR) has arisen. This offers the possibility to study Mer - and Mer + cells of otherwise similar genetic background. We are using these two variants to analyze the Mer - phenotype further. When HeLa S3 and HeLa MR were treated with a highly dose of MNNG, and the surviving population exposed to a second dose of MNNG 2-3 weeks later, HeLa S3 (Mer + ) cells were equally or even slightly more sensitive to a second exposure of MNNG, whereas the surviving HeLa MR (Mer - ) population was much more resistant to MNNG. 1 fig., 1 tab

  17. DNA Damage Induced by Alkylating Agents and Repair Pathways

    Science.gov (United States)

    Kondo, Natsuko; Takahashi, Akihisa; Ono, Koji; Ohnishi, Takeo

    2010-01-01

    The cytotoxic effects of alkylating agents are strongly attenuated by cellular DNA repair processes, necessitating a clear understanding of the repair mechanisms. Simple methylating agents form adducts at N- and O-atoms. N-methylations are removed by base excision repair, AlkB homologues, or nucleotide excision repair (NER). O6-methylguanine (MeG), which can eventually become cytotoxic and mutagenic, is repaired by O6-methylguanine-DNA methyltransferase, and O6MeG:T mispairs are recognized by the mismatch repair system (MMR). MMR cannot repair the O6MeG/T mispairs, which eventually lead to double-strand breaks. Bifunctional alkylating agents form interstrand cross-links (ICLs) which are more complex and highly cytotoxic. ICLs are repaired by complex of NER factors (e.g., endnuclease xeroderma pigmentosum complementation group F-excision repair cross-complementing rodent repair deficiency complementation group 1), Fanconi anemia repair, and homologous recombination. A detailed understanding of how cells cope with DNA damage caused by alkylating agents is therefore potentially useful in clinical medicine. PMID:21113301

  18. Decreased stability of DNA in cells treated with alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Frankfurt, O.S. (Cedars Medical Center, Miami, FL (United States))

    1990-12-01

    A modified highly sensitive procedure for the evaluation of DNA damage in individual cells treated with alkylating agents is reported. The new methodology is based on the amplification of single-strandedness in alkylated DNA by heating in the presence of Mg{sup 2+}. Human ovarian carcinoma cells A2780 were treated with nitrogen mustard (HN2), fixed in methanol, and stained with monoclonal antibody (MOAB) F7-26 generated against HN2-treated DNA. Binding of MOAB was measured by flow cytometry with indirect immunofluorescence. Intensive binding of MOAB to control and drug-treated cells was observed after heating in Tris buffer supplemented with MgCl{sub 2}. Thus, the presence of phosphates and MgCl{sub 2} during heating was necessary for the detection of HN2-induced changes in DNA stability. Fluorescence of HN2-treated cells decreased to background levels after treatment with single-strand-specific S{sub 1} nuclease. MOAB F7-26 interacted with single-stranded regions in DNA and did not bind to dsDNA or other cellular antigens. It is suggested that alkylation of guanines decreased the stability of the DNA molecule and increased the access of MOAB F7-26 to deoxycytidines on the opposite DNA strand.

  19. Synthesis of alkyl phenols by means of radiofrequency plasmas

    International Nuclear Information System (INIS)

    Ropero, M.; Armas, F.; Iacocca, D.; Patino, P.

    1992-01-01

    New and promising possibilities in chemical synthesis have been opened through the interactions of oxygen plasmas with liquid alkyl benzene compounds. The alkyl phenols are the main products of the reaction mixtures (> 80%) oxygen, excited by radio-frequency (R.F.) is allowed to reach the surface of the liquid organic compound. The R.F. power supply is a Branson/IPC-PM 118. The substrate we have chosen are: methyl, ethyl, propyl, n-butyl, t-butyl, dimethyl and trimethyl benzenes. Under the same O 2 pressure and a power of 60 W, m-xylene and mesethylene behaved similarly. For all these substrates, values for the temperature of the liquid surface seem to indicate that oxidation tends to an optimum when P O 2 /vapor pressure (substrate) is higher than 20. In our experiments oxygen pressure in the reactor was about 0.2 Torr. Oxidation is basically attributed to O 3 P and the addition to alkyl benzenes selectively takes place on the aromatic rings, at low reactor pressure. The oxygen atom impinges on the liquid surface and epoxy intermediates could be formed. These intermediates then progress to the corresponding phenols. (author)

  20. Separation of products of alkylation of isobutane by olefins

    Energy Technology Data Exchange (ETDEWEB)

    Ward, J.

    1979-03-15

    The alkylation (A1) of isobutane (I) by propylene, butylene and amylenes is carried out at 24-52 degrees, pressure sufficient to maintain the liquid phase, and a molar ratio of I to olefins (O1) 10:1-15:1. The bulk ratio of catalysts to hydrocarbons in the reaction zone was 0.5:1-10:1; when using HF-K-T as the catalysts, it should contain less than 5 percent water and greater than or equal to 65 percent titrated HF. The hydrocarbon products (UP) from the alkylation zone are added after separating the catalyst in a fractionation tower; distillation is carried out at 38-49 degrees and 1.03-1.3 NPa. The head fraction containing I and less than 50 molar percent C3H8 and also fraction I at the point below the input side of the UP which contains less than 8 molar percent C3H8 and fraction n-C4H10 at the point below the point of discharge of fraction I is drained from the tower. The alkylate is discharged at the bottom of the tower. According to the patent the tower operates at low pressure. This improves relative volatility of individual components and reduces heat consumption. The best results are obtained when a head fraction or the concentration C3H8 approximately 25 molar percent is discharged.

  1. Glutamine deficiency induces DNA alkylation damage and sensitizes cancer cells to alkylating agents through inhibition of ALKBH enzymes.

    Science.gov (United States)

    Tran, Thai Q; Ishak Gabra, Mari B; Lowman, Xazmin H; Yang, Ying; Reid, Michael A; Pan, Min; O'Connor, Timothy R; Kong, Mei

    2017-11-01

    Driven by oncogenic signaling, glutamine addiction exhibited by cancer cells often leads to severe glutamine depletion in solid tumors. Despite this nutritional environment that tumor cells often experience, the effect of glutamine deficiency on cellular responses to DNA damage and chemotherapeutic treatment remains unclear. Here, we show that glutamine deficiency, through the reduction of alpha-ketoglutarate, inhibits the AlkB homolog (ALKBH) enzymes activity and induces DNA alkylation damage. As a result, glutamine deprivation or glutaminase inhibitor treatment triggers DNA damage accumulation independent of cell death. In addition, low glutamine-induced DNA damage is abolished in ALKBH deficient cells. Importantly, we show that glutaminase inhibitors, 6-Diazo-5-oxo-L-norleucine (DON) or CB-839, hypersensitize cancer cells to alkylating agents both in vitro and in vivo. Together, the crosstalk between glutamine metabolism and the DNA repair pathway identified in this study highlights a potential role of metabolic stress in genomic instability and therapeutic response in cancer.

  2. Oxidative 1,2-carboamination of alkenes with alkyl nitriles and amines toward γ-amino alkyl nitriles

    Science.gov (United States)

    Liu, Yan-Yun; Yang, Xu-Heng; Song, Ren-Jie; Luo, Shenglian; Li, Jin-Heng

    2017-04-01

    Difunctionalization of alkenes has become a powerful tool for quickly increasing molecular complexity in synthesis. Despite significant progress in the area of alkene difunctionalization involving the incorporation of a nitrogen atom across the C-C double bonds, approaches for the direct 1,2-carboamination of alkenes to produce linear N-containing molecules are scarce and remain a formidable challenge. Here we describe a radical-mediated oxidative intermolecular 1,2-alkylamination of alkenes with alkyl nitriles and amines involving C(sp3)-H oxidative functionalization catalysed by a combination of Ag2CO3 with iron Lewis acids. This three-component alkene 1,2-alkylamination method is initiated by the C(sp3)-H oxidative radical functionalization, which enables one-step formation of two new chemical bonds, a C-C bond and a C-N bond, to selectively produce γ-amino alkyl nitriles.

  3. Efficient synthesis of N-alkyl-2,7-dihalocarbazoles by simultaneous carbazole ring closure and N-alkylation

    Czech Academy of Sciences Publication Activity Database

    Výprachtický, Drahomír; Kmínek, Ivan; Pokorná, Veronika; Cimrová, Věra

    2012-01-01

    Roč. 68, č. 25 (2012), s. 5075-5080 ISSN 0040-4020 R&D Projects: GA MŠk(CZ) 1M06031; GA ČR GAP106/12/0827 Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : carbazole ring closure * carbazole alkylation * heterocycles Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 2.803, year: 2012

  4. Balancing repair and tolerance of DNA damage caused by alkylating agents.

    Science.gov (United States)

    Fu, Dragony; Calvo, Jennifer A; Samson, Leona D

    2012-01-12

    Alkylating agents constitute a major class of frontline chemotherapeutic drugs that inflict cytotoxic DNA damage as their main mode of action, in addition to collateral mutagenic damage. Numerous cellular pathways, including direct DNA damage reversal, base excision repair (BER) and mismatch repair (MMR), respond to alkylation damage to defend against alkylation-induced cell death or mutation. However, maintaining a proper balance of activity both within and between these pathways is crucial for a favourable response of an organism to alkylating agents. Furthermore, the response of an individual to alkylating agents can vary considerably from tissue to tissue and from person to person, pointing to genetic and epigenetic mechanisms that modulate alkylating agent toxicity.

  5. Discovery and identification of a series of alkyl decalin isomers in petroleum geological samples.

    Science.gov (United States)

    Wang, Huitong; Zhang, Shuichang; Weng, Na; Zhang, Bin; Zhu, Guangyou; Liu, Lingyan

    2015-07-07

    The comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) has been used to characterize a crude oil and a source rock extract sample. During the process, a series of pairwise components between monocyclic alkanes and mono-aromatics have been discovered. After tentative assignments of decahydronaphthalene isomers, a series of alkyl decalin isomers have been synthesized and used for identification and validation of these petroleum compounds. From both the MS and chromatography information, these pairwise compounds were identified as 2-alkyl-decahydronaphthalenes and 1-alkyl-decahydronaphthalenes. The polarity of 1-alkyl-decahydronaphthalenes was stronger. Their long chain alkyl substituent groups may be due to bacterial transformation or different oil cracking events. This systematic profiling of alkyl-decahydronaphthalene isomers provides further understanding and recognition of these potential petroleum biomarkers.

  6. Polycyclic aromatic acids are primary metabolites of alkyl-PAHs - a case study with Nereis diversicolor

    DEFF Research Database (Denmark)

    Malmquist, Linus Mattias Valdemar; Selck, Henriette; Jørgensen, Kåre Bredeli

    2015-01-01

    Although concentrations of alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) in oil-contaminated sediments are higher than those of unsubstituted PAHs, only little attention has been given to metabolism and ecotoxicity of alkyl-PAHs. In this study we demonstrated that metabolism of alkyl-PA...... that carboxylic acid metabolites of alkyl-PAHs have the potential of constituting a new class of contaminants in marine waters that needs attention in relation to ecological risk assessments.......Although concentrations of alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) in oil-contaminated sediments are higher than those of unsubstituted PAHs, only little attention has been given to metabolism and ecotoxicity of alkyl-PAHs. In this study we demonstrated that metabolism of alkyl...

  7. Cytotoxicity of alkylating agents towards sensitive and resistant strains of Escherichia coli in relation to extent and mode of alkylation of cellular macromolecules and repair of alkylation lesions in deoxyribonucleic acids.

    Science.gov (United States)

    Lawley, P D; Brookes, P

    1968-09-01

    1. A quantitative study was made of the relationship between survival of colony-forming ability in Escherichia coli strains B/r and B(s-1) and the extents of alkylation of cellular DNA, RNA and protein after treatment with mono- or di-functional sulphur mustards, methyl methanesulphonate or iodoacetamide. 2. The mustards and methyl methanesulphonate react with nucleic acids in the cells, in the same way as found previously from chemical studies in vitro, and with proteins. Iodoacetamide reacts only with protein, principally with the thiol groups of cysteine residues. 3. The extents of alkylation of cellular constituents required to prevent cell division vary widely according to the strain of bacteria and the nature of the alkylating agent. 4. The extents of alkylation of the sensitive and resistant strains at a given dose of alkylating agent do not differ significantly. 5. Removal of alkyl groups from DNA of cells of the resistant strains B/r and 15T(-) after alkylation with difunctional sulphur mustard was demonstrated; the product di(guanin-7-ylethyl) sulphide, characteristic of di- as opposed to mono-functional alkylation, was selectively removed; the time-scale of this effect suggests an enzymic rather than a chemical mechanism. 6. The sensitive strain B(s-1) removed alkyl groups from DNA in this way only at very low extents of alkylation. When sensitized to mustard action by treatment with iodoacetamide, acriflavine or caffeine, the extent of alkylation of cellular DNA corresponding to a mean lethal dose was decreased to approximately 3 molecules of di(guanin-7-ylethyl) sulphide in the genome of this strain. 7. Relatively large numbers of monofunctional alkylations per genome can be withstood by this sensitive strain. Iodoacetamide had the weakest cytotoxic action of the agents investigated; methyl methanesulphonate was significantly weaker in effect than the monofunctional sulphur mustard, which was in turn weaker than the difunctional sulphur mustard. 8

  8. Protonation of 1-alkyl-2-allyllithium-0-carboranes and 1-methyl-2-allylmaonesium chloride-0-carborane

    International Nuclear Information System (INIS)

    Ivanova, N.N.; Kazantsev, A.V.; Zakharkin, L.I.

    1975-01-01

    The ratio of 1-alkyl-2-allyl and 1-alkyl-2-propenyl-0-carboranes generated in protonation of 1-alkyl-2-lithium allyl-0-carboranes with various protolytic agents in ether, THF and liquid ammonia depends on the nature of protolytic agent and solvent. The rat:o of these allyl and propenyl isomers is also affected by steric effects of the protolytic agent and 0-carborane nucleus

  9. Balancing repair and tolerance of DNA damage caused by alkylating agents

    OpenAIRE

    Fu, Dragony; Calvo, Jennifer A.; Samson, Leona D.

    2012-01-01

    Alkylating agents constitute a major class of frontline chemotherapeutic drugs that inflict cytotoxic DNA damage as their main mode of action, in addition to collateral mutagenic damage. Numerous cellular pathways, including direct DNA damage reversal, base excision repair (BER) and mismatch repair (MMR), respond to alkylation damage to defend against alkylation-induced cell death or mutation. However, maintaining a proper balance of activity both within and between these pathways is crucial ...

  10. SERIES: Genomic instability in cancer Balancing repair and tolerance of DNA damage caused by alkylating agents

    OpenAIRE

    Fu, Dragony; Calvo, Jennifer A.; Samson, Leona D

    2012-01-01

    Alkylating agents comprise a major class of frontline chemotherapeutic drugs that inflict cytotoxic DNA damage as their main mode of action, in addition to collateral mutagenic damage. Numerous cellular pathways, including direct DNA damage reversal, base excision repair (BER), and mismatch repair (MMR) respond to alkylation damage to defend against alkylation-induced cell death or mutation. However, maintaining a proper balance of activity both within and between these pathways is crucial fo...

  11. Highly enantio- and diastereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with allyl ketones

    KAUST Repository

    Tong, Guanghu

    2013-05-17

    The asymmetric allylic alkylation of Morita-Baylis-Hillman (MBH) carbonates with allyl ketones has been developed. The α-regioselective alkylation adducts, containing a hexa-1,5-diene framework with important synthetic value, were achieved in up to 83% yield, >99% ee, and 50:1 dr by using a commercially available Cinchona alkaloid as the catalyst. From the allylic alkylation adduct, a cyclohexene bearing two adjacent chiral centers was readily prepared. © 2013 American Chemical Society.

  12. Effects of Photo-chemically Activated Alkylating Agents of the FR900482 Family on Chromatin

    OpenAIRE

    Subramanian, Vidya; Ducept, Pascal; Williams, Robert M.; Luger, Karolin

    2007-01-01

    Bioreductive alkylating agents are an important class of clinical antitumor antibiotics that cross-link and mono-alkylate DNA. Here we use a synthetic photochemically activated derivative of FR400482 to investigate the molecular mechanism of this class of drugs in a biologically relevant context. We find that the organization of DNA into nucleosomes effectively protects it against drug-mediated cross-linking, while permitting mono-alkylation. This modification has the potential to form covale...

  13. Gold-catalyzed alkylation of silyl enol ethers with ortho-alkynylbenzoic acid esters

    Directory of Open Access Journals (Sweden)

    Yoshinori Yamamoto

    2011-05-01

    Full Text Available Unprecedented alkylation of silyl enol ethers has been developed by the use of ortho-alkynylbenzoic acid alkyl esters as alkylating agents in the presence of a gold catalyst. The reaction probably proceeds through the gold-induced in situ construction of leaving groups and subsequent nucleophilic attack on the silyl enol ethers. The generated leaving compound abstracts a proton to regenerate the silyl enol ether structure.

  14. Quantum molecular modeling of the interaction between guanine and alkylating agents--2--nitrogen mustard.

    Science.gov (United States)

    Hamza, A; Broch, H; Vasilescu, D

    1996-06-01

    The alkylation mechanism of guanine by nitrogen mustard (HN2) was studied by using a supermolecular modeling at the ab initio 6-31G level. Our computations show that interaction of guanine with the aziridinium form of HN2 necessitates a transition state for the N7 alkylation route. The pathway of N7-guanine alkylation by nitrogen and sulfur mustards is discussed on the basis of the Molecular Electrostatic Potential and HOMO-LUMO properties of these molecules.

  15. Highly enantio- and diastereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with allyl ketones

    KAUST Repository

    Tong, Guanghu; Zhu, Bo; Lee, Richmond; Yang, Wenguo; Tan, Davin; Yang, Caiyun; Han, Zhiqiang; Yan, Lin; Huang, Kuo-Wei; Jiang, Zhiyong

    2013-01-01

    The asymmetric allylic alkylation of Morita-Baylis-Hillman (MBH) carbonates with allyl ketones has been developed. The α-regioselective alkylation adducts, containing a hexa-1,5-diene framework with important synthetic value, were achieved in up to 83% yield, >99% ee, and 50:1 dr by using a commercially available Cinchona alkaloid as the catalyst. From the allylic alkylation adduct, a cyclohexene bearing two adjacent chiral centers was readily prepared. © 2013 American Chemical Society.

  16. Hydride Transfer versus Deprotonation Kinetics in the Isobutane–Propene Alkylation Reaction: A Computational Study

    OpenAIRE

    Liu, Chong; van Santen, Rutger A.; Poursaeidesfahani, Ali; Vlugt, Thijs J. H.; Pidko, Evgeny A.; Hensen, Emiel J. M.

    2017-01-01

    The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane–propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate o...

  17. Hydration of the Atlantis Massif: Halogen, Noble Gas and In-Situ δ18O Constraints

    Science.gov (United States)

    Williams, M. J.; Kendrick, M. A.; Rubatto, D.

    2017-12-01

    A combination of halogen (Cl, Br, I), noble gases (He, Ne, Ar, Kr and Xe) and in situ oxygen isotope analysis have been utilized to investigate the fluid-mobile element record of hydration and alteration processes at the Atlantis Massif (30°N on the Mid-Atlantic Ridge). The sample suite investigated includes serpentinite, talc-amphibole ± chlorite schist and hydrated gabbro recovered by seafloor drilling undertaken at sites on a transect across the Atlantis Massif during IODP Expedition 357. Serpentine mesh and veins analysed in-situ by SHRIMP SI exhibit δ18O from 6‰ down to ≈0‰, suggesting serpentinization temperatures of 150 to >280°C and water/rock ratios >5. Differences of 1.5-2.5‰ are observed between adjacent generations of serpentine, but the δ18O range is similar at each investigated drilling site. Halogen and noble gas abundances in serpentinites, talc-amphibole schist and hydrated gabbro have been measured by noble gas mass spectrometry of both irradiated and non-irradiated samples. Serpentinites contain low abundances of halogens and noble gases (e.g. 70-430 ppm Cl, 4.7-12.2 x 10-14 mol/g 36Ar) relative to other seafloor serpentinites. The samples have systematically different Br/Cl and I/Cl ratios related to their mineralogy. Serpentinites retain mantle-like Br/Cl with a wide variation in I/Cl that stretches toward seawater values. Talc-amphibole schists exhibit depletion of Br and I relative to Cl with increasing Cl abundances, suggesting tremolite exerts strong control on halogen abundance ratios. Serpentinites show no evidence of interaction with halogen-rich sedimentary pore fluids. Iodine abundances are variable across serpentinites, and are decoupled from Br and Cl; iodine enrichment (up to 530 ppb) is observed within relatively oxidised and clay-bearing samples. Serpentinized harzburgites exhibit distinct depletion of Kr and Xe relative to atmospheric 36Ar in seawater. Oxygen isotope compositions and low abundances of both halogens

  18. Mid-latitude Ozone Depletion Events Caused by Halogens from the Great Salt Lake in Utah

    Science.gov (United States)

    Fibiger, D. L.; Goldberger, L.; Womack, C.; McDuffie, E. E.; Dube, W. P.; Franchin, A.; Middlebrook, A. M.; Thornton, J. A.; Brown, S. S.

    2017-12-01

    Halogens are highly reactive chemicals and play an important role in atmospheric chemistry. They can be involved in many cycles which influence the oxidizing capacity of the atmosphere, including through destruction of ozone (O3). While the influence of halogens on O3 is well documented in the arctic, there are very few observations of O3 depletion driven by halogens in the mid-latitudes. To date, the most comprehensive study observed co-occurring plumes of BrO and depleted O3 near the Dead Sea in 1997. During the Utah Wintertime Fine Particulate Study (UWFPS) in winter 2017, simultaneous measurements of a comprehensive suite of halogen measurements by I- chemical ionization mass spectrometry and O3 from cavity ring-down spectroscopy, both at 1-second time resolution, were taken on a NOAA Twin Otter Aircraft over the Great Salt Lake and in the surrounding valleys. Many O3 depletion events were observed over the lake with O3 values sometimes below the instrument detection limit of 0.5 ppbv. Corresponding increases in BrO and/or ClO were observed. Many of these events were caused by extremely high levels of halogens (up to 1 ppmv Cl2) emitted from the U.S. Magnesium plant on the edge of the lake. The O3 depletion caused by U.S. Magnesium was usually isolated to a distinct vertical layer, but in other cases O3 depletion was vertically mixed and the origin of halogen activation was not immediately clear. The most complete O3 depletion was observed over the lake, but there were smaller events of a few ppbv observed in the adjacent valleys, including the highly populated Salt Lake Valley, with corresponding plumes of BrO and ClO, due to transport from the lake. Additionally, meteorology played a role in the observed O3 depletion. The strongest O3 depletion was observed during inversion events, when there is a low boundary layer and little mixing out of the air above the lake. During non-inversion conditions, only small depletions were observed, covering a much smaller

  19. Synthesis and evaluation of novel caged DNA alkylating agents bearing 3,4-epoxypiperidine structure.

    Science.gov (United States)

    Kawada, Yuji; Kodama, Tetsuya; Miyashita, Kazuyuki; Imanishi, Takeshi; Obika, Satoshi

    2012-07-14

    Previously, we reported that the 3,4-epoxypiperidine structure, whose design was based on the active site of DNA alkylating antitumor antibiotics, azinomycins A and B, possesses prominent DNA cleavage activity. In this report, novel caged DNA alkylating agents, which were designed to be activated by UV irradiation, were synthesized by the introduction of four photo-labile protecting groups to a 3,4-epoxypiperidine derivative. The DNA cleavage activity and cytotoxicity of the caged DNA alkylating agents were examined under UV irradiation. Four caged DNA alkylating agents showed various degrees of bioactivity depending on the photosensitivity of the protecting groups.

  20. Methods of producing alkylated hydrocarbons from an in situ heat treatment process liquid

    Science.gov (United States)

    Roes, Augustinus Wilhelmus Maria [Houston, TX; Mo, Weijian [Sugar Land, TX; Muylle, Michel Serge Marie [Houston, TX; Mandema, Remco Hugo [Houston, TX; Nair, Vijay [Katy, TX

    2009-09-01

    A method for producing alkylated hydrocarbons is disclosed. Formation fluid is produced from a subsurface in situ heat treatment process. The formation fluid is separated to produce a liquid stream and a first gas stream. The first gas stream includes olefins. The liquid stream is fractionated to produce at least a second gas stream including hydrocarbons having a carbon number of at least 3. The first gas stream and the second gas stream are introduced into an alkylation unit to produce alkylated hydrocarbons. At least a portion of the olefins in the first gas stream enhance alkylation.

  1. Conversion of alkyl radicals to allyl radicals in irradiated single crystal mats of polyethylene

    International Nuclear Information System (INIS)

    Fujimura, T.; Hayakawa, N.; Kuriyama, I.

    1978-01-01

    The decay of alkyl radicals, the conversion of alkyl radicals to allyl radicals and the trapping of allyl radicals in irradiated single crystal mats of polyethylene have been studied by electron spin resonance (e.s.r.). It has been suggested that in the crystal core alkyl radicals react with trans-vinylene double bonds and are converted into trans-vinylene allyl radicals; at the crystal surface, alkyl radicals react with vinyl end groups and are converted into allyl radicals with vinyl end groups. The decay of radical pairs and the formation of trans-vinylene double bonds are discussed. (author)

  2. The influence of microplastics and halogenated contaminants in feed on toxicokinetics and gene expression in European seabass (Dicentrarchus labrax)

    NARCIS (Netherlands)

    Granby, Kit; Rainieri, Sandra; Rasmussen, Rie Romme; Kotterman, Michiel J.J.; Sloth, Jens Jørgen; Cederberg, Tommy Licht; Barranco, Alex; Marques, António; Larsen, Bodil Katrine

    2018-01-01

    When microplastics pollute fish habitats, it may be ingested by fish, thereby contaminating fish with sorbed contaminants. The present study investigates how combinations of halogenated contaminants and microplastics associated with feed are able to alter toxicokinetics in European seabass and

  3. The Effects of Water Spray Cooling in Conjunction with Halogenated Extinguishants on Hydrogen Fluoride Generation and Decay

    National Research Council Canada - National Science Library

    Burch, Ian

    2007-01-01

    The halogenated extinguishants Halon 1301, HFC-227ea (FM200) and NAF-S-III used within Royal Australian Navy vessels for total flooding fire suppression applications have hydrogen fluoride (HF) toxicity concerns...

  4. Isomorphism of 2-methylnaphthalene and 2-halonaphthalenes as a revealer of a special interaction between methyl and halogen

    Science.gov (United States)

    Calvet, T.; Cuevas-Diarte, M. A.; Haget, Y.; Mondieig, D.; Kok, I. C.; Verdonk, M. L.; Van Miltenburg, J. C.; Oonk, H. A. J.

    1999-03-01

    The systems 2-methylnaphthalene+2-chloronaphthalene and 2-methylnaphthalene+2-bromonaphthalene belong to the exceptional group of binary systems where the formation of mixed crystals goes together with a solid-liquid phase diagram with a maximum. For these systems a thermodynamic analysis is presented which is based on new phase diagram and thermochemical data. The excess Gibbs energies, excess enthalpies, and excess entropies of the mixed crystalline state all are negative. These properties correspond to a net attraction between methyl and substituted halogen. Additional evidence of such an attraction is given by the outcome of a statistical search on intermolecular contacts, in the crystalline state of pure substances, among methyl+halogen, halogen+halogen, and methyl+methyl.

  5. Biogas from MSW landfill: Composition and determination of chlorine content with the AOX (adsorbable organically bound halogens) technique

    International Nuclear Information System (INIS)

    Rey, M.D.; Font, R.; Aracil, I.

    2013-01-01

    An exhaustive characterization of the biogas from some waste disposal facilities has been carried out. The analysis includes the main components (methane, carbon dioxide, nitrogen and oxygen) as well as trace components such as hydrogen sulphide, ammonia and VOCs (volatile organic compounds) including siloxanes and halogenated compounds. VOCs were measured by GC/MS (Gas Chromatography/Mass Spectrometry) using two different procedures: thermal desorption of the Tenax TA and Carbotrap 349 tubes and SPME (Solid Phase Micro-Extraction). A method has been established to measure the total halogen content of the biogas with the AOX (adsorbable organically bound halogens) technique. The equipment used to analyze the samples was a Total Organic Halogen Analyzer (TOX-100). Similar results were obtained when comparing the TOX (Total Organic Halogen) values with those obtained by GC/MS. The halogen content in all the samples was under 22 mg Cl/Nm 3 which is below the limit of 150 mg/Nm 3 proposed in the Spanish Regulations for any use of the biogas. The low chlorine content in the biogas studied, as well as the low content of other trace compounds, makes it suitable for use as a fuel for electricity generating engines

  6. Environmental and economic implications of a shift to halogen-free printed wiring boards

    Energy Technology Data Exchange (ETDEWEB)

    Bergendahl, C.G.; Johansson, G.; Zackrisson, M. [IVF Industrial Research and Development Corp., Moelndal (Sweden); Lichtenvort, K. [Technical Univ. of Berlin (Germany); Nyyssoenen, J. [Aspocomp Oy, Salo (Finland)

    2004-07-01

    The 'Restriction of Hazardous Substances Directive' (RoHS) and the 'Waste from Electrical and Electronic Equipment Directive' (WEEE) enforced by the European Commission require new materials and processes to be implemented in the production of electrical and electronic equipment (EEE). In response to this, the project grEEEn (Cost Management System for greening Electrical and Electronic Equipment) was defined and carried out within the 5th framework programme of the EU. This paper presents the grEEEn method and the outcome of applying the method on a case study. The study addressed the material shift in printed wiring boards (PWBs), from the traditional FR4 material containing halogenated flame retardants to halogen-free FR4 materials. The paper presents the product, process and scenario modelling and the results from analysing costs, environmental profile and legal compliance. (orig.)

  7. Attosecond Time Delay in Photoionization of Noble-Gas and Halogen Atoms

    Directory of Open Access Journals (Sweden)

    Liang-Wen Pi

    2018-02-01

    Full Text Available Ultrafast processes are now accessible on the attosecond time scale due to the availability of ultrashort XUV laser pulses. Noble-gas and halogen atoms remain important targets due to their giant dipole resonance and Cooper minimum. Here, we calculate photoionization cross section, asymmetry parameter and Wigner time delay using the time-dependent local-density approximation (TDLDA, which includes the electron correlation effects. Our results are consistent with experimental data and other theoretical calculations. The asymmetry parameter provides an extra layer of access to the phase information of the photoionization processes. We find that halogen atoms bear a strong resemblance on cross section, asymmetry parameter and time delay to their noble-gas neighbors. Our predicted time delay should provide a guidance for future experiments on those atoms and related molecules.

  8. UV-visible and resonance Raman spectroscopy of halogen molecules in clathrate hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Janda, K.C.; Kerenskaya, G.; Goldsheleger, I.U.; Apkarian, V.A.; Fleischer, E.B. [California Univ., Irvine, CA (United States). Dept. of Chemistry

    2008-07-01

    Resonance Raman spectroscopy was used to study halogen clathrate hydrate solids. In particular, this paper presented an ultraviolet-visible spectra for a polycrystalline sample of chlorine clathrate hydrate and two single crystal samples of bromine clathrate hydrate. UV-visible spectroscopy was used to study the interactions between the halogen guest molecule and the host water lattice. The spectrum for chlorine hydrate had a strong temperature dependence, while the spectra for bromine clathrate hydrate single crystals had a stable cubic type 2 structure as well as a tetragonal structure. A metastable cubic type 1 structure was also observed. Resonance Raman spectroscopy showed how the molecules fit into the host cages. 25 refs., 2 tabs., 7 figs.

  9. Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

    Energy Technology Data Exchange (ETDEWEB)

    Hissung, A; Isildar, M; von Sonntag, C [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany, F.R.). Inst. fuer Strahlenforschung; Witzel, H [Biochemisches Institut der Westfaelischen Wilhelms-Universitaet, Muenster, West Germany

    1981-02-01

    The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N/sub 2/O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10/sup 5/s/sup -1/) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10/sup 3/ M/sup -1/s/sup -1/ was estimated. Compound 4 has also been investigated by product analysis after 60-Co-..gamma..-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O/sub 2/ to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA.

  10. Degradation of halogenated aliphatic compounds by the ammonia- oxidizing bacterium Nitrosomonas europaea.

    Science.gov (United States)

    Vannelli, T; Logan, M; Arciero, D M; Hooper, A B

    1990-01-01

    Suspensions of Nitrosomonas europaea catalyzed the ammonia-stimulated aerobic transformation of the halogenated aliphatic compounds dichloromethane, dibromomethane, trichloromethane (chloroform), bromoethane, 1,2-dibromoethane (ethylene dibromide), 1,1,2-trichloroethane, 1,1,1-trichloroethane, monochloroethylene (vinyl chloride), gem-dichloroethylene, cis- and trans-dichloroethylene, cis-dibromoethylene, trichloroethylene, and 1,2,3-trichloropropane, Tetrachloromethane (carbon tetrachloride), tetrachloroethylene (perchloroethylene), and trans-dibromoethylene were not degraded. PMID:2339874

  11. Determination of halogen content in glass for assessment of melter decontamination factors

    International Nuclear Information System (INIS)

    Goles, R.W.

    1996-03-01

    Melter decontamination factor (DF) values for the halogens (fluorine, chlorine, and iodine) are important to the Hanford Waste Vitrification Plant (HWVP) process because of the potential influence of DF on secondary-waste recycle strategies (fluorine and chlorine) as well as its impact on off-gas emissions (iodine). This study directly establishes the concentrations of halides-in HWVP simulated reference glasses rather than relying on indirect off-gas data. For fluorine and chlorine, pyrohydrolysis coupled with halide (ion chromatographic) detection has proven to be a useful analytical approach suitable for glass matrices, sensitive enough for the range of halogens encountered, and compatible with remote process support applications. Results obtained from pyrohydrolytic analysis of pilot-scale ceramic melter (PSCM) -22 and -23 glasses indicate that the processing behavior of fluorine and chlorine is quite variable even under similar processing conditions. Specifically, PSCM-23 glass exhibited a ∼90% halogen (F and Cl) retention efficiency, while only 20% was incorporated in PSCM-22 glass. These two sets of very dissimilar test results clearly do not form a sufficient basis for establishing design DF values for fluorine and chlorine. Because the present data do not provide any new halogen volatility information, but instead reconfirm the validity of previously obtained offgas derived values, melter DF values of 4, 2, and 1 for fluorine, chlorine, and iodine, respectively, are recommended for adoption; these values were conservatively established by a team of responsible engineers at Westinghouse Hanford Company (WHC) and Pacific Northwest Laboratory (PNL) on the basis of average behavior for many comparable melter tests. In the absence of further HWVP process data, these average melter DFs are the best values currently available

  12. A simple and automated sample preparation system for subsequent halogens determination: Combustion followed by pyrohydrolysis.

    Science.gov (United States)

    Pereira, L S F; Pedrotti, M F; Vecchia, P Dalla; Pereira, J S F; Flores, E M M

    2018-06-20

    A simple and automated system based on combustion followed by a pyrohydrolysis reaction was proposed for further halogens determination. This system was applied for digestion of soils containing high (90%) and also low (10%) organic matter content for further halogens determination. The following parameters were evaluated: sample mass, use of microcrystalline cellulose and heating time. For analytes absorption, a diluted alkaline solution (6 mL of 25 mmol L -1  NH 4 OH) was used in all experiments. Up to 400 mg of soil with high organic matter content and 100 mg of soil with low organic matter content (mixed with 400 mg of cellulose) could be completely digested using the proposed system. Quantitative results for all halogens were obtained using less than 12 min of sample preparation step (about 1.8 min for sample combustion and 10 min for pyrohydrolysis). The accuracy was evaluated using a certified reference material of coal and spiked samples. No statistical difference was observed between the certified values and results obtained by the proposed method. Additionally, the recoveries obtained using spiked samples were in the range of 98-103% with relative standard deviation values lower than 5%. The limits of quantification obtained for F, Cl, Br and I for soil with high (400 mg of soil) and low (100 mg of soil) organic matter were in the range of 0.01-2 μg g -1 and 0.07-59 μg g -1 , respectively. The proposed system was considered as a simple and suitable alternative for soils digestion for further halogens determination by ion chromatography and inductively coupled plasma mass spectrometry techniques. Copyright © 2018 Elsevier B.V. All rights reserved.

  13. Possibilities of analyzing dump and sewage gas, and determination of halogen and sulfur compounds

    Energy Technology Data Exchange (ETDEWEB)

    Eisenmann, R

    1985-01-01

    In connection with the utilization of refuse and sewage gas efficacions analytical methods are gaining increasing importance especially with regard to halogen and sulfur compounds. The paper describes various possibilities to determine those substances. Besides gas chromatography it takes into account classic analytical methods which can be superior in biogas analytics to modern physical processes. The advantages and disadvantages of each method are discussed and practical experiences obtained by their application reported.

  14. Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

    International Nuclear Information System (INIS)

    Hissung, A.; Isildar, M.; Sonntag, C. von; Witzel, H.

    1981-01-01

    The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N 2 O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10 5 s -1 ) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10 3 M -1 s -1 was estimated. Compound 4 has also been investigated by product analysis after 60-Co-γ-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O 2 to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA. (author)

  15. Radiation-induced DNA damage in halogenated pyrimidine incorporated cells and its correlation with radiosensitivity

    International Nuclear Information System (INIS)

    Watanabe, R.; Nikjoo, H.

    2003-01-01

    Cells with DNA containing 5-halogenated pyrimidines in place of thymidine show significant reductions of slope (Do) and shoulder (Dq) of their radiation survival curves. Similar radiosensitization has also been observed in the yield of DNA strand breaks. The purpose of this study is to obtain an insight into the mechanism of cell lethality by examining the relationship between the spectrum of DNA damage and the cell survival. In this study we estimated the enhancement of strand breaks due to incorporation of halogenated pyrimidine, the complexity of DNA damage and the probability of the initial DNA damage leading to cell inactivation. Monte Carlo track structure methods were used to model and simulate the induction of strand breakage by X-rays. The increase of DNA strand break was estimated by assuming the excess strand break was caused by the highly reactive uracil radicals at the halouracil substituted sites. The assumption of the enhancement mechanism of strand breaks was examined and verified by comparison with experimental data for induction of SSB and DSB. The calculated DNA damage spectrum shows the increase in complexity of strand breaks is due to incorporation of halogenated pyrimidines. The increase in the yield of DSB and cell lethality show similar trend at various degrees of halogenated pyrimidine substitution. We asked the question whether this agreement supports the hypothesis that DSB is responsible for cell lethality? The estimated number of lethal damage from the cell survival using a linear-quadratic model is much less than the initial yield of DSB. This work examines the correlation of cell lethality as a function of frequencies of complex form of double strand breaks

  16. Reactive Halogens in the Marine Boundary Layer (RHaMBLe): the tropical North Atlantic experiments

    OpenAIRE

    J. D. Lee; G. McFiggans; J. D. Allan; A. R. Baker; S. M. Ball; A. K. Benton; L. J. Carpenter; R. Commane; B. D. Finley; M. Evans; E. Fuentes; K. Furneaux; A. Goddard; N. Good; J. F. Hamilton

    2010-01-01

    The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth...

  17. Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

    Science.gov (United States)

    Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

    2017-11-02

    Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Synthesis of 4-Halogenated 3-Fluoro-6-methoxyquinolines: Key Building Blocks for the Synthesis of Antibiotics

    DEFF Research Database (Denmark)

    Flagstad, Thomas; Petersen, Mette Terp; Hinnerfeldt, Daniel Michael

    2014-01-01

    A practical and scalable 4-step route is presented for the synthesis of 4-bromo-3-fluoro-6-methoxyoquinoline and 3-fluoro-4-iodo-6-methoxyoquinoline from readily available 2,4-dichloro-3-fluoroquinoline with an overall yield of 81-85%. Halogenated quinoline building blocks have found much use in ...... in antimicrobial drug discovery, and the method reported here would be useful for the synthesis of these compounds. © Georg Thieme Verlag....

  19. On Extension of the Current Biomolecular Empirical Force Field for the Description of Halogen Bonds

    Czech Academy of Sciences Publication Activity Database

    Kolář, Michal; Hobza, Pavel

    2012-01-01

    Roč. 8, č. 4 (2012), s. 1325-1333 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Grant - others:European Science Fund(XE) CZ.1.05/2.1.00/03.0058 Institutional research plan: CEZ:AV0Z40550506 Keywords : halogen bond * molecular mechanics * sigma-hole Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.389, year: 2012

  20. Cooperativity of halogen, chalcogen, and pnictogen bonds in infinite molecular chains by electronic structure theory.

    Science.gov (United States)

    George, Janine; Deringer, Volker L; Dronskowski, Richard

    2014-05-01

    Halogen bonds (XBs) are intriguing noncovalent interactions that are frequently being exploited for crystal engineering. Recently, similar bonding mechanisms have been proposed for adjacent main-group elements, and noncovalent "chalcogen bonds" and "pnictogen bonds" have been identified in crystal structures. A fundamental question, largely unresolved thus far, is how XBs and related contacts interact with each other in crystals; similar to hydrogen bonding, one might expect "cooperativity" (bonds amplifying each other), but evidence has been sparse. Here, we explore the crucial step from gas-phase oligomers to truly infinite chains by means of quantum chemical computations. A periodic density functional theory (DFT) framework allows us to address polymeric chains of molecules avoiding the dreaded "cluster effects" as well as the arbitrariness of defining a "large enough" cluster. We focus on three types of molecular chains that we cut from crystal structures; furthermore, we explore reasonable substitutional variants in silico. We find evidence of cooperativity in chains of halogen cyanides and also in similar chalcogen- and pnictogen-bonded systems; the bonds, in the most extreme cases, are amplified through cooperative effects by 79% (I···N), 90% (Te···N), and 103% (Sb···N). Two experimentally known organic crystals, albeit with similar atomic connectivity and XB characteristics, show signs of cooperativity in one case but not in another. Finally, no cooperativity is observed in alternating halogen/acetone and halogen/1,4-dioxane chains; in fact, these XBs weaken each other by up to 26% compared to the respective gas-phase dimers.

  1. Effect of halogenated benzenes on acetanilide esterase, acetanilide hydroxylase and procaine esterase in rats.

    Science.gov (United States)

    Carlson, G P; Dziezak, J D; Johnson, K M

    1979-07-01

    1,2,4-Trichlorobenzene, 1,3,5-trichlorobenzene, hexachlorobenzene, 1,2,4-tribromobenzene, 1,3,5-tribromobenzene and hexabromobenzene were compared for their abilities to induce acetanilide esterase, acentailide hydroxylase and procaine esterase. Except for hexabromobenzene all induced acetanilide esterase whereas the hydroxylation of acetanilide was seen only with the fully halogenated benzenes and with 1,3,5-tribromobenzene. Hepatic procaine esterase activity was increased by the three chlorinated benzenes and 1,2,4-tribromobenzene.

  2. Strength and Character of Halogen Bonds in Protein-Ligand Complexes

    Czech Academy of Sciences Publication Activity Database

    Riley, Kevin Eugene; Hobza, Pavel

    2011-01-01

    Roč. 11, č. 10 (2011), s. 4272-4278 ISSN 1528-7483 R&D Projects: GA MŠk LC512 Grant - others:Research and Development for Innovations of European Social Fund(XE) CZ.1.05/2.1.00/03.0058 Institutional research plan: CEZ:AV0Z40550506 Keywords : halogen bond * protein-ligand complexes * calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.720, year: 2011

  3. Monolayer structures of alkyl aldehydes: Odd-membered homologues

    International Nuclear Information System (INIS)

    Phillips, T.K.; Clarke, S.M.; Bhinde, T.; Castro, M.A.; Millan, C.; Medina, S.

    2011-01-01

    Crystalline monolayers of three aldehydes with an odd number of carbon atoms in the alkyl chain (C 7 , C 9 and C 11 ) at low coverages are observed by a combination of X-ray and neutron diffraction. Analysis of the diffraction data is discussed and possible monolayer crystal structures are proposed; although unique structures could not be ascertained for all molecules. We conclude that the structures are flat on the surface, with the molecules lying in the plane of the layer. The C 11 homologue is determined to have a plane group of either p2, pgb or pgg, and for the C 7 homologue the p2 plane group is preferred.

  4. Radioprotective action of 3-(imidazoline-2-alkyl)-5-methoxyindoles

    International Nuclear Information System (INIS)

    Bitny-Szlachto, S.; Kwiek, S.; Piotrowska, H.; Serafin, B.; Wejroch-Matacz, K.

    1977-01-01

    Radioprotective action in mice of four 3-(imidazoline-2'-alkyl)-5-methoxyindoles was examined and compared with that of 3-(2'-aminoethyl)-5-hydroxyindole (serotonine). The imidazoline-2-methyl derivatives (S 3 , S 4 ), applied in doses of 50 μmole/kg 10 min prior to irrdiation were found to reduce mortality of mice with LD 50 DRF of 1.14-1.15, while serotonine displayed DRF of 1.45. The imidazoline-2-ethyl derivatives (S 7 , S 8 ) have turned out to be ineffective. (author)

  5. [Methaemoglobinaemia induced by ingestion of alkyl nitrite, "poppers"].

    Science.gov (United States)

    Kragsfeldt, Celina Thelberg; Nissen, Christoffer B; Brandt, Frans

    2016-08-22

    We present a case report of an 18-year-old male who was referred to the emergency department with evidence of methaemoglobinaemia. He presented with classic symptoms with peripheral cyanosis and hypoxia. Arterial blood gas showed a methaemoglobin level of 36%. This was caused by ingestion of alkyl nitrate, a widespread party drug called "poppers". When inhaled it causes euphoria, reduced pain and relaxation of the anal sphincter, but oral use may induce life-threatening methaemoglobinaemia. The treatment of choice is the antidote methylene blue. After treatment the patient regained full recovery and was discharged on the following day. We discuss classic symptoms, diagnosis and treatment of intoxication with methylene blue.

  6. Alkylating HIV-1 Nef - a potential way of HIV intervention

    Directory of Open Access Journals (Sweden)

    Cai Catherine

    2010-07-01

    Full Text Available Abstract Background Nef is a 27 KDa HIV-1 accessory protein. It downregulates CD4 from infected cell surface, a mechanism critical for efficient viral replication and pathogenicity. Agents that antagonize the Nef-mediated CD4 downregulation may offer a new class of drug to combat HIV infection and disease. TPCK (N-α-p-tosyl-L-phenylalanine chloromethyl ketone and TLCK (N-α-p-tosyl-L-lysine chloromethyl ketone are alkylation reagents that chemically modify the side chain of His or Cys residues in a protein. In search of chemicals that inhibit Nef function, we discovered that TPCK and TLCK alkylated HIV Nef. Methods Nef modification by TPCK was demonstrated on reducing SDS-PAGE. The specific cysteine residues modified were determined by site-directed mutagenesis and mass spectrometry (MS. The effect of TPCK modification on Nef-CD4 interaction was studied using fluorescence titration of a synthetic CD4 tail peptide with recombinant Nef-His protein. The conformational change of Nef-His protein upon TPCK-modification was monitored using CD spectrometry Results Incubation of Nef-transfected T cells, or recombinant Nef-His protein, with TPCK resulted in mobility shift of Nef on SDS-PAGE. Mutagenesis analysis indicated that the modification occurred at Cys55 and Cys206 in Nef. Mass spectrometry demonstrated that the modification was a covalent attachment (alkylation of TPCK at Cys55 and Cys206. Cys55 is next to the CD4 binding motif (A56W57L58 in Nef required for Nef-mediated CD4 downregulation and for AIDS development. This implies that the addition of a bulky TPCK molecule to Nef at Cys55 would impair Nef function and reduce HIV pathogenicity. As expected, Cys55 modification reduced the strength of the interaction between Nef-His and CD4 tail peptide by 50%. Conclusions Our data suggest that this Cys55-specific alkylation mechanism may be exploited to develop a new class of anti HIV drugs.

  7. Separation of uranium from molybdenum by alkyl phosphoric acid extraction

    Energy Technology Data Exchange (ETDEWEB)

    Zhongshi, Li

    1986-08-01

    The regularities of separation of uranium from molybdenum by alkyl phosphoric acid extraction are described. Two parameters, i.e., density ratio of uranium to molybdenum in organic phase at first stage and density of uranium in raffinate at last stage are presented. The relationship between these parameters and purity of molybdenum and uranium products is given. The method of adjusting and controlling these parameters in experiments and production is worked out. The technical key problem in comprehensive utilization of sedimentary type uranium ore containing molybdenum with close concentration of these to elements has been solved.

  8. PARP inhibitors protect against sex- and AAG-dependent alkylation-induced neural degeneration.

    Science.gov (United States)

    Allocca, Mariacarmela; Corrigan, Joshua J; Fake, Kimberly R; Calvo, Jennifer A; Samson, Leona D

    2017-09-15

    Alkylating agents are commonly used to treat cancer. Although base excision repair (BER) is a major pathway for repairing DNA alkylation damage, under certain conditions, the initiation of BER produces toxic repair intermediates that damage healthy tissues. The initiation of BER by the alkyladenine DNA glycosylase (AAG, a.k.a. MPG) can mediate alkylation-induced cytotoxicity in specific cells in the retina and cerebellum of male mice. Cytotoxicity in both wild-type and Aag -transgenic ( AagTg ) mice is abrogated in the absence of Poly(ADP-ribose) polymerase-1 (PARP1). Here, we tested whether PARP inhibitors can also prevent alkylation-induced retinal and cerebellar degeneration in male and female WT and AagTg mice. Importantly, we found that WT mice display sex-dependent alkylation-induced retinal damage (but not cerebellar damage), with WT males being more sensitive than females. Accordingly, estradiol treatment protects males against alkylation-induced retinal degeneration. In AagTg male and female mice, the alkylation-induced tissue damage in both the retina and cerebellum is exacerbated and the sex difference in the retina is abolished. PARP inhibitors, much like Parp1 gene deletion, protect against alkylation-induced AAG-dependent neuronal degeneration in WT and AagTg mice, regardless of the gender, but their efficacy in preventing alkylation-induced neuronal degeneration depends on PARP inhibitor characteristics and doses. The recent surge in the use of PARP inhibitors in combination with cancer chemotherapeutic alkylating agents might represent a powerful tool for obtaining increased therapeutic efficacy while avoiding the collateral effects of alkylating agents in healthy tissues.

  9. Pharmacological evaluation of halogenated and non-halogenated arylpiperazin-1-yl-ethyl-benzimidazoles as D(2) and 5-HT(2A) receptor ligands.

    Science.gov (United States)

    Tomić, Mirko; Vasković, Djurdjica; Tovilović, Gordana; Andrić, Deana; Penjišević, Jelena; Kostić-Rajačić, Sladjana

    2011-05-01

    Five groups of previously synthesized and initially screened non-substituted and 4-halogenated arylpiperazin-1-yl-ethyl-benzimidazoles were estimated for their in-vitro binding affinities at the rat D(2) , 5-HT(2A) , and α(1) -adrenergic receptors. Among all these compounds, 2-methoxyphenyl and 2-chlorophenyl piperazines demonstrate the highest affinities for the tested receptors. The effects of 4-halogenation of benzimidazoles reveal that substitution with bromine may greatly increase the affinity of the compounds for the studied receptors, while the effect of substitution with chlorine is less remarkable. Most of the tested components show 5-HT(2A)/D(2) pK(i) binding ratios slightly above or less than 1, while only 4-chloro-6-(2-{4-[3-(trifluoromethyl)phenyl]piperazin-1-yl}ethyl)-1H-benzimidazole expresses an appropriate higher binding ratio (1.14), which was indicated for atypical neuroleptics. This compound exhibits a non-cataleptic action in rats and prevents d-amphetamine-induced hyperlocomotion in mice, which suggest its atypical antipsychotic potency. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Organohalide respiration in pristine environments: implications for the natural halogen cycle.

    Science.gov (United States)

    Atashgahi, Siavash; Häggblom, Max M; Smidt, Hauke

    2018-03-01

    Halogenated organic compounds, also termed organohalogens, were initially considered to be of almost exclusively anthropogenic origin. However, over 5000 naturally synthesized organohalogens are known today. This has also fuelled the hypothesis that the natural and ancient origin of organohalogens could have primed development of metabolic machineries for their degradation, especially in microorganisms. Among these, a special group of anaerobic microorganisms was discovered that could conserve energy by reducing organohalogens as terminal electron acceptor in a process termed organohalide respiration. Originally discovered in a quest for biodegradation of anthropogenic organohalogens, these organohalide-respiring bacteria (OHRB) were soon found to reside in pristine environments, such as the deep subseafloor and Arctic tundra soil with limited/no connections to anthropogenic activities. As such, accumulating evidence suggests an important role of OHRB in local natural halogen cycles, presumably taking advantage of natural organohalogens. In this minireview, we integrate current knowledge regarding the natural origin and occurrence of industrially important organohalogens and the evolution and spread of OHRB, and describe potential implications for natural halogen and carbon cycles. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

  11. The Halogenated Metabolism of Brown Algae (Phaeophyta, Its Biological Importance and Its Environmental Significance

    Directory of Open Access Journals (Sweden)

    Stéphane La Barre

    2010-03-01

    Full Text Available Brown algae represent a major component of littoral and sublittoral zones in temperate and subtropical ecosystems. An essential adaptive feature of this independent eukaryotic lineage is the ability to couple oxidative reactions resulting from exposure to sunlight and air with the halogenations of various substrates, thereby addressing various biotic and abiotic stresses i.e., defense against predators, tissue repair, holdfast adhesion, and protection against reactive species generated by oxidative processes. Whereas marine organisms mainly make use of bromine to increase the biological activity of secondary metabolites, some orders of brown algae such as Laminariales have also developed a striking capability to accumulate and to use iodine in physiological adaptations to stress. We review selected aspects of the halogenated metabolism of macrophytic brown algae in the light of the most recent results, which point toward novel functions for iodide accumulation in kelps and the importance of bromination in cell wall modifications and adhesion properties of brown algal propagules. The importance of halogen speciation processes ranges from microbiology to biogeochemistry, through enzymology, cellular biology and ecotoxicology.

  12. Development of an enzymatic fiber-optic biosensor for detection of halogenated hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Bidmanova, Sarka; Chaloupkova, Radka; Damborsky, Jiri; Prokop, Zbynek [Masaryk University, Loschmidt Laboratories, Department of Experimental Biology and Research Centre for Toxic Compounds in the Environment, Faculty of Science, Brno (Czech Republic)

    2010-11-15

    An enzyme-based biosensor was developed by co-immobilization of purified enzyme haloalkane dehalogenase (EC 3.8.1.5) and a fluorescence pH indicator on the tip of an optical fiber. Haloalkane dehalogenase catalyzes hydrolytic dehalogenation of halogenated aliphatic hydrocarbons, which is accompanied by a pH change influencing the fluorescence of the indicator. The pH sensitivity of several fluorescent dyes was evaluated. The selected indicator 5(6)-carboxyfluorescein was conjugated with bovine serum albumin and its reaction was tested under different immobilization conditions. The biosensor was prepared by cross-linking of the conjugate in tandem with haloalkane dehalogenase using glutaraldehyde vapor. The biosensor, stored for 24 h in 50 mM phosphate buffer (pH 7.5) prior to measurement, was used after 15 min of equilibration, the halogenated compound was added, and the response was monitored for 30 min. Calibration of the biosensor with 1,2-dibromoethane and 3-chloro-2-(chloromethyl)-1-propene showed an excellent linear dependence, with detection limits of 0.133 and 0.014 mM, respectively. This biosensor provides a new tool for continuous in situ monitoring of halogenated environmental pollutants. (orig.)

  13. Parent and halogenated polycyclic aromatic hydrocarbons in rice and implications for human health in China

    International Nuclear Information System (INIS)

    Ding Chao; Ni Honggang; Zeng Hui

    2012-01-01

    Rice is the staple food for approximate two thirds of the Chinese population. However, human exposure to parent and halogenated polycyclic aromatic hydrocarbons (PAHs) via rice consumption is still not clear for Chinese people so far. The goals of this work are to assess human exposure to PAHs and halogenated PAHs (HPAHs) via rice ingestion and the cancer risk for Chinese population. 16 PAHs and eight HPAHs were determined in rice samples collected from 18 provinces in China. In general terms, the general population in China was exposed to higher levels of PAHs via rice ingestion in comparison to that via cereals for other countries. The cancer risk values induced by exposure to PAHs and HPAHs for male and female on each age group were between the priority risk level (10 −4 ) and the acceptable risk level (10 −6 ). Children faced the highest cancer risk, followed by adolescents and adults. - Highlights: ► Dietary exposure to PAHs via rice ingestion for Chinese population was higher than that via cereals in other countries. ► The cancer risk induced by PAHs and HPAHs intakes via rice consumption were between 10 −6 and 10 −4 . ► Children faced the highest cancer risk, followed by adolescents and adults. ► Given all exposure routes were considered, the real cancer risk for Chinese people would be greater. - Human exposure to parent and halogenated PAHs via rice ingestion and the cancer risk for Chinese population were assessed.

  14. Gas-liquid partitioning of halogenated volatile organic compounds in aqueous cyclodextrin solutions

    Energy Technology Data Exchange (ETDEWEB)

    Ondo, Daniel; Barankova, Eva [Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic); Dohnal, Vladimir, E-mail: dohnalv@vscht.cz [Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic)

    2011-08-15

    Highlights: > Binding of halogenated VOCs with cyclodextrins examined through g-l partitioning. > Complex stabilities reflect host-guest size matching and hydrophobic interaction. > Presence of halogens in the guest molecule stabilizes the binding. > Thermodynamic origin of the binding varies greatly among the systems studied. > Results obey the guest-CD global enthalpy-entropy compensation relationship. - Abstract: Gas-liquid partitioning coefficients (K{sub GL}) were measured for halogenated volatile organic compounds (VOCs), namely 1-chlorobutane, methoxyflurane, pentafluoropropan-1-ol, heptafluorobutan-1-ol, {alpha},{alpha},{alpha}-trifluorotoluene, and toluene in aqueous solutions of natural {alpha}-, {beta}-, and {gamma}-cyclodextrins (CDs) at temperatures from (273.35 to 326.35) K employing the techniques of headspace gas chromatography and inert gas stripping. The binding constants of the 1:1 inclusion complex formation between the VOCs and CDs were evaluated from the depression of the VOCs volatility as a function of CD concentration. The host-guest size matching and the hydrophobic interaction concept were used to rationalize the observed widely different affinity of the VOC-CD pairs to form the inclusion complex. The enthalpic and entropic component of the standard Gibbs free energy of complex formation as derived from the temperature dependence of the binding constant indicate the thermodynamic origin of the binding to vary greatly among the systems studied, but follow the global enthalpy-entropy compensation relationships reported previously in the literature.

  15. Molecular Engineering of Non-Halogenated Solution-Processable Bithiazole based Electron Transport Polymeric Semiconductors

    KAUST Repository

    Fu, Boyi; Wang, Cheng-Yin; Rose, Bradley Daniel; Jiang, Yundi; Chang, Mincheol; Chu, Ping-Hsun; Yuan, Zhibo; Fuentes-Hernandez, Canek; Bernard, Kippelen; Bredas, Jean-Luc; Collard, David M.; Reichmanis, Elsa

    2015-01-01

    The electron deficiency and trans planar conformation of bithiazole is potentially beneficial for the electron transport performance of organic semiconductors. However, the incorporation of bithiazole into polymers through a facile synthetic strategy remains a challenge. Herein, 2,2’-bithiazole was synthesized in one step and copolymerized with dithienyldiketopyrrolopyrrole to afford poly(dithienyldiketopyrrolopyrrole-bithiazole), PDBTz. PDBTz exhibited electron mobility reaching 0.3 cm2V-1s-1 in organic field-effect transistor (OFET) configuration; this contrasts with a recently discussed isoelectronic conjugated polymer comprising an electron rich bithiophene and dithienyldiketopyrrolopyrrole, which displays merely hole transport characteristics. This inversion of charge carrier transport characteristics confirms the significant potential for bithiazole in the development of electron transport semiconducting materials. Branched 5-decylheptacyl side chains were incorporated into PDBTz to enhance polymer solubility, particularly in non-halogenated, more environmentally compatible solvents. PDBTz cast from a range of non-halogenated solvents exhibited film morphologies and field-effect electron mobility similar to those cast from halogenated solvents.

  16. Molecular Engineering of Non-Halogenated Solution-Processable Bithiazole based Electron Transport Polymeric Semiconductors

    KAUST Repository

    Fu, Boyi

    2015-04-01

    The electron deficiency and trans planar conformation of bithiazole is potentially beneficial for the electron transport performance of organic semiconductors. However, the incorporation of bithiazole into polymers through a facile synthetic strategy remains a challenge. Herein, 2,2’-bithiazole was synthesized in one step and copolymerized with dithienyldiketopyrrolopyrrole to afford poly(dithienyldiketopyrrolopyrrole-bithiazole), PDBTz. PDBTz exhibited electron mobility reaching 0.3 cm2V-1s-1 in organic field-effect transistor (OFET) configuration; this contrasts with a recently discussed isoelectronic conjugated polymer comprising an electron rich bithiophene and dithienyldiketopyrrolopyrrole, which displays merely hole transport characteristics. This inversion of charge carrier transport characteristics confirms the significant potential for bithiazole in the development of electron transport semiconducting materials. Branched 5-decylheptacyl side chains were incorporated into PDBTz to enhance polymer solubility, particularly in non-halogenated, more environmentally compatible solvents. PDBTz cast from a range of non-halogenated solvents exhibited film morphologies and field-effect electron mobility similar to those cast from halogenated solvents.

  17. Self-assembly of iodine in superfluid helium droplets. Halogen bonds and nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    He, Yunteng; Zhang, Jie; Lei, Lei; Kong, Wei [Department of Chemistry, Oregon State University, Corvallis, OR (United States)

    2017-03-20

    We present evidence of halogen bond in iodine clusters formed in superfluid helium droplets based on results from electron diffraction. Iodine crystals are known to form layered structures with intralayer halogen bonds, with interatomic distances shorter than the sum of the van der Waals radii of the two neighboring atoms. The diffraction profile of dimer dominated clusters embedded in helium droplets reveals an interatomic distance of 3.65 Aa, much closer to the value of 3.5 Aa in iodine crystals than to the van der Waals distance of 4.3 Aa. The profile from larger iodine clusters deviates from a single layer structure; instead, a bi-layer structure qualitatively fits the experimental data. This work highlights the possibility of small halogen bonded iodine clusters, albeit in a perhaps limited environment of superfluid helium droplets. The role of superfluid helium in guiding the trapped molecules into local potential minima awaits further investigation. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Development of halogen-free flame-retardant cable for nuclear power plant. 2

    International Nuclear Information System (INIS)

    Matsumoto, Tetsuo; Kimura, Hitoshi; Ishii, Nobuhisa

    1997-01-01

    Halogen-free flame-retardant cables were developed for PWR nuclear power stations. It was confirmed that the developed cables possess flame retardant property, corrosion resistance, low toxicity and low smoke generation, and withstand the normal operation in the environment in PWR containment vessels for 60 years and loss of coolant accident. In the advancement of LWR technology, it is important to improve the reliability of machinery and equipment, to extend the period of continuous operation, to optimize the operation cycle and to improve the maintenance of plants. By improving halogen-free flame-retardant material and applying it to the cables for nuclear power stations, it can contribute to the above purposes. The required characteristics of these cables are explained, and the targets of development are power cables, control cables, instrumentation cables and insulated wires which do not contain halogen. The basic material is polyolefin, in which flame retardant magnesium hydroxide and the agent for improving radiation resistance are mixed. The corrosive property and toxicity of gases, smoke generation and the prevention of spread of flame when the cables burn and the durability in environment were evaluated. (K.I.)

  19. Photofragmentation spectra of halogenated methanes in the VUV photon energy range

    Energy Technology Data Exchange (ETDEWEB)

    Cartoni, Antonella, E-mail: antonella.cartoni@uniroma1.it [Dipartimento di Chimica e Tecnologie del Farmaco, Sapienza Università di Roma, P.le Aldo Moro 5, Roma 00185 (Italy); Bolognesi, Paola; Fainelli, Ettore; Avaldi, Lorenzo [CNR-IMIP, Area della Ricerca di Roma 1, Monterotondo Scalo (Rm) 00015 (Italy)

    2014-05-14

    In this paper an investigation of the photofragmentation of dihalomethanes CH{sub 2}X{sub 2} (X = F, Cl, Br, I) and chlorinated methanes (CH{sub n}Cl{sub 4−n} with n = 0–3) with VUV helium, neon, and argon discharge lamps is reported and the role played by the different halogen atoms is discussed. Halogenated methanes are a class of molecules used in several fields of chemistry and the study of their physical and chemical proprieties is of fundamental interest. In particular their photodissociation and photoionization are of great importance since the decomposition of these compounds in the atmosphere strongly affects the environment. The results of the present work show that the halogen-loss is the predominant fragmentation channel for these molecules in the VUV photon energy range and confirm their role as reservoir of chlorine, bromine, and iodine atoms in the atmosphere. Moreover, the results highlight the peculiar feature of CH{sub 2}F{sub 2} as a source of both fluorine and hydrogen atoms and the characteristic formation of I{sub 2}{sup +} and CH{sub 2}{sup +} ions from the photofragmentation of the CH{sub 2}I{sub 2} molecule.

  20. Environmental levels and toxicological potencies of a novel mixed halogenated carbazole

    Directory of Open Access Journals (Sweden)

    Miren Pena-Abaurrea

    2016-09-01

    Full Text Available The present work involves an extensive analytical and toxicological description of a recently identified mixed halogenated carbazole found in sediment samples, 1,8-dibromo-3,6-dichloro-9H-carbazole (BCCZ. Concentrations and the relative effect potency (REP were calculated for the target BCCZ in a set of stream sediments collected in 2008 in Ontario, Canada. The levels calculated for BCCZ as compared to those previously assessed for legacy persistent organic pollutants (POPs in the same samples revealed a significant contribution of BCCZ to the total organic chemical contamination (<1%–95%; average 37%. The corresponding dioxin toxic equivalencies (TEQs of BCCZ in the sediment extracts were estimated from experimental REP data. The experimental data presented supports the classification of this emerging halogenated chemical as a contaminant of emerging environmental concern. Although potential emission sources could not be identified, this study highlights the importance of on-going research for complete characterization of halogenated carbazoles and related compounds.

  1. Evaluation of wear rate of dental composites polymerized by halogen or LED light curing units

    Directory of Open Access Journals (Sweden)

    Alaghehmand H.

    2006-08-01

    Full Text Available Background and Aim: Sufficient polymerization is a critical factor to obtain optimum physical properties and clinical efficacy of resin restorations. The aim of this study was to evaluate wear rates of composite resins polymerized by two different systems Light Emitting Diodes (LED to and Halogen lamps. Materials and Methods: In this laboratory study, 20 specimens of A3 Tetric Ceram composite were placed in brass molds of 2*10*10 mm dimensions and cured for 40 seconds with 1 mm distance from surface. 10 specimens were cured with LED and the other 10 were cured with Halogen unit. A device with the ability to apply force was developed in order to test the wear of composites. After storage in distilled water for 10 days, the specimens were placed in the wear testing machine. A chrome cobalt stylus with 1.12 mm diameter was applied against the specimens surfaces with a load of 2 kg. The weight of each samples before and after 5000, 10000, 20000, 40000, 80000 and 120000 cycles was measured using an electronic balance with precision of 10-4 grams. Data were analyzed using t test and paired t test. P0.05. Conclusion: Based on the results of this study, LED and halogen light curing units resulted in a similar wear rate in composite resin restorations.

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

    Directory of Open Access Journals (Sweden)

    Jarosław Poznański

    Full Text Available Halogen bonding in ligand-protein complexes is currently widely exploited, e.g. in drug design or supramolecular chemistry. But little attention has been directed to other effects that may result from replacement of a hydrogen by a strongly electronegative halogen. Analysis of almost 30000 hydrogen bonds between protein and ligand demonstrates that the length of a hydrogen bond depends on the type of donor-acceptor pair. Interestingly, lengths of hydrogen bonds between a protein and a halogenated ligand are visibly shorter than those estimated for the same family of proteins in complexes with non-halogenated ligands. Taking into account the effect of halogenation on hydrogen bonding is thus important when evaluating structural and/or energetic parameters of ligand-protein complexes. All these observations are consistent with the concept that halogenation increases the acidity of the proximal amino/imino/hydroxyl groups and thus makes them better, i.e. stronger, H-bond donors.

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

    Science.gov (United States)

    Poznański, Jarosław; Poznańska, Anna; Shugar, David

    2014-01-01

    Halogen bonding in ligand-protein complexes is currently widely exploited, e.g. in drug design or supramolecular chemistry. But little attention has been directed to other effects that may result from replacement of a hydrogen by a strongly electronegative halogen. Analysis of almost 30000 hydrogen bonds between protein and ligand demonstrates that the length of a hydrogen bond depends on the type of donor-acceptor pair. Interestingly, lengths of hydrogen bonds between a protein and a halogenated ligand are visibly shorter than those estimated for the same family of proteins in complexes with non-halogenated ligands. Taking into account the effect of halogenation on hydrogen bonding is thus important when evaluating structural and/or energetic parameters of ligand-protein complexes. All these observations are consistent with the concept that halogenation increases the acidity of the proximal amino/imino/hydroxyl groups and thus makes them better, i.e. stronger, H-bond donors.

  4. Selectivity of alkyl radical formation from branched alkanes studied by electron spin resonance and electron spin echo spectroscopy

    International Nuclear Information System (INIS)

    Tsuneki, Ichikawa; Hiroshi, Yoshida

    1992-01-01

    Alkyl radicals generated from branched alkanes by γ radiation are being measuring by electron spin resonance and electron spin echo spectroscopy. This research is being conducted to determine the mechanism of selective alkyl radical formation in low-temperature solids

  5. Rh(III-Catalyzed, Highly Selectively Direct C–H Alkylation of Indoles with Diazo Compounds

    Directory of Open Access Journals (Sweden)

    Kang Wan

    2016-06-01

    Full Text Available Rh(III-catalyzed regioselective alkylation of indoles with diazo compounds as a highly efficient and atom-economic protocol for the synthesis of alkyl substituted indoles has been developed. The reaction could proceed under mild conditions and afford a series of desired products in good to excellent yields.

  6. Modulation of the toxicity and antitumour activity of alkylating drugs by steroids.

    OpenAIRE

    Shepherd, R.; Harrap, K. R.

    1982-01-01

    The steroids prednisolone and progesterone significantly altered the therapeutic indices of the alkylating agents, nitrogen mustard, melphalan, cyclophosphamide, phenyl acetic mustard and chlorambucil. For nitrogen mustard, chlorambucil and phenyl acetic mustard, prednisolone reduced host toxicity in the rat and enhanced the antitumour effectiveness against alkylating-agent-resistant strains of the Yoshida sarcoma and Walker carcinosarcoma. Progesterone also increased the therapeutic index of...

  7. Detection and identification of alkylating agents by using a bioinspired "chemical nose".

    Science.gov (United States)

    Hertzog-Ronen, Carmit; Borzin, Elena; Gerchikov, Yulia; Tessler, Nir; Eichen, Yoav

    2009-10-12

    Alkylating agents are simple and reactive molecules that are commonly used in many and diverse fields such as organic synthesis, medicine, and agriculture. Some highly reactive alkylating species are also being used as blister chemical-warfare agents. The detection and identification of alkylating agents is not a trivial issue because of their high reactivity and simple structure. Herein, we report on a new multispot luminescence-based approach to the detection and identification of alkylating agents. In order to demonstrate the potential of the approach, seven pi-conjugated oligomers and polymers bearing nucleophilic pyridine groups, 1-7, were adsorbed onto a solid support and exposed to vapors of alkylators 8-15. The alkylation-induced color-shift patterns of the seven-spot array allow clear discrimination of the different alkylators. The spots are sensitive to minute concentrations of alkylators and, because the detection is based on the formation of new covalent bonds, these spots saturate at about 50 ppb.

  8. Synthesis of alkylated deoxyno irimycin and 1,5-dideoxy-1,5-iminoxylitol analogues:

    DEFF Research Database (Denmark)

    Szczepina, M.G.; Johnston, B.D; Yuan, Y.

    2004-01-01

    The syntheses of N-alkylated deoxynojirimycin and 1,5-dideoxy-1,5-iminoxylitol derivatives having either a D- or an L-erythritol-3-sulfate functionalized N-substituent are reported. The alkylating agent used was a cyclic sulfate derivative, whereby selective attack of the nitrogen atom at the least...

  9. Paraffin Alkylation Using Zeolite Catalysts in a slurry reactor: Chemical Engineering Principles to Extend Catalyst Lifetime

    NARCIS (Netherlands)

    Jong, K.P. de; Mesters, C.M.A.M.; Peferoen, D.G.R.; Brugge, P.T.M. van; Groot, C. de

    1996-01-01

    The alkylation of isobutane with 2-butene is carried out using a zeolitic catalyst in a well stirred slurry reactor. Whereas application of fixed bed technology using a solid acid alkylation catalyst has in the led to catalysts lifetimes in the range of minutes, in this work we report catalyst

  10. Comparative study of oxidative stress caused by anthracene and alkyl-anthracenes in

    Directory of Open Access Journals (Sweden)

    Ji-Yeon Roh

    2018-02-01

    Full Text Available Oxidative stress was evaluated for anthracene (Ant and alkyl-Ants (9-methylanthracene [9-MA] and 9,10-dimethylanthracene [9,10-DMA] in Caenorhabditis elegans to compare changes in toxicity due to the degree of alkylation. Worms were exposed at 1 the same external exposure concentration and 2 the maximum water-soluble concentration. Formation of reactive oxygen species, superoxide dismutase activity, total glutathione concentration, and lipid peroxidation were determined under constant exposure conditions using passive dosing. The expression of oxidative stress-related genes (daf-2, sir-2.1, daf-16, sod-1, sod-2, sod-3 and cytochrome 35A/C family genes was also investigated to identify and compare changes in the genetic responses of C. elegans exposed to Ant and alkyl-Ant. At the same external concentration, 9,10-DMA induced the greatest oxidative stress, as evidenced by all indicators, except for lipid peroxidation, followed by 9-MA and Ant. Interestingly, 9,10-DMA led to greater oxidative stress than 9-MA and Ant when worms were exposed to the maximum water-soluble concentration, although the maximum water-soluble concentration of 9,10-DMA is the lowest. Increased oxidative stress by alkyl-Ants would be attributed to higher lipid-water partition coefficient and the π electron density in aromatic rings by alkyl substitution, although this supposition requires further confirmation.

  11. Selective alkylation of T–T mismatched DNA using vinyldiaminotriazine–acridine conjugate

    Science.gov (United States)

    Onizuka, Kazumitsu; Usami, Akira; Yamaoki, Yudai; Kobayashi, Tomohito; Hazemi, Madoka E; Chikuni, Tomoko; Sato, Norihiro; Sasaki, Kaname; Katahira, Masato

    2018-01-01

    Abstract The alkylation of the specific higher-order nucleic acid structures is of great significance in order to control its function and gene expression. In this report, we have described the T–T mismatch selective alkylation with a vinyldiaminotriazine (VDAT)–acridine conjugate. The alkylation selectively proceeded at the N3 position of thymidine on the T–T mismatch. Interestingly, the alkylated thymidine induced base flipping of the complementary base in the duplex. In a model experiment for the alkylation of the CTG repeats DNA which causes myotonic dystrophy type 1 (DM1), the observed reaction rate for one alkylation increased in proportion to the number of T–T mismatches. In addition, we showed that primer extension reactions with DNA polymerase and transcription with RNA polymerase were stopped by the alkylation. The alkylation of the repeat DNA will efficiently work for the inhibition of replication and transcription reactions. These functions of the VDAT–acridine conjugate would be useful as a new biochemical tool for the study of CTG repeats and may provide a new strategy for the molecular therapy of DM1. PMID:29309639

  12. Selective alkylation of T-T mismatched DNA using vinyldiaminotriazine-acridine conjugate.

    Science.gov (United States)

    Onizuka, Kazumitsu; Usami, Akira; Yamaoki, Yudai; Kobayashi, Tomohito; Hazemi, Madoka E; Chikuni, Tomoko; Sato, Norihiro; Sasaki, Kaname; Katahira, Masato; Nagatsugi, Fumi

    2018-02-16

    The alkylation of the specific higher-order nucleic acid structures is of great significance in order to control its function and gene expression. In this report, we have described the T-T mismatch selective alkylation with a vinyldiaminotriazine (VDAT)-acridine conjugate. The alkylation selectively proceeded at the N3 position of thymidine on the T-T mismatch. Interestingly, the alkylated thymidine induced base flipping of the complementary base in the duplex. In a model experiment for the alkylation of the CTG repeats DNA which causes myotonic dystrophy type 1 (DM1), the observed reaction rate for one alkylation increased in proportion to the number of T-T mismatches. In addition, we showed that primer extension reactions with DNA polymerase and transcription with RNA polymerase were stopped by the alkylation. The alkylation of the repeat DNA will efficiently work for the inhibition of replication and transcription reactions. These functions of the VDAT-acridine conjugate would be useful as a new biochemical tool for the study of CTG repeats and may provide a new strategy for the molecular therapy of DM1.

  13. Alkylation damage causes MMR-dependent chromosomal instability in vertebrate embryos.

    NARCIS (Netherlands)

    Feitsma, H.; Akay, A.; Cuppen, E.

    2008-01-01

    S(N)1-type alkylating agents, like N-methyl-N-nitrosourea (MNU) and N-ethyl-N-nitrosourea (ENU), are potent mutagens. Exposure to alkylating agents gives rise to O(6)-alkylguanine, a modified base that is recognized by DNA mismatch repair (MMR) proteins but is not repairable, resulting in

  14. Chemistry of the pyrazolidines. 26. Alkylation of 4-benzyliden-1-phenyl-3,5-dioxopyrazolidines

    International Nuclear Information System (INIS)

    Moldarev, B.L.; Aronzon, M.E.; Adanin, V.M.; Zyakun, A.M.

    1986-01-01

    The reaction of 4-benzyliden-1-phenyl-3,5-dioxopyrazolidines with alkyl halides in the presence of sodium alkoxide gave 1-phenyl-2-alkyl-4-benzyliden- and 1-phenyl-2,4-dialkyl-4-(α-alkoxybenzyl)-3,4-dioxopyrazolines. The structures of these compounds were confirmed by UV, IR, and PMR spectroscopy, and by mass-spectrometry

  15. Synthesis of 2-substituted tryptophans via a C3- to C2-alkyl migration

    Directory of Open Access Journals (Sweden)

    Michele Mari

    2014-08-01

    Full Text Available The reaction of 3-substituted indoles with dehydroalanine (Dha derivatives under Lewis acid-mediated conditions has been investigated. The formation of 2-substituted tryptophans is proposed to occur through a selective alkylative dearomatization–cyclization followed by C3- to C2-alkyl migration and rearomatization.

  16. Industrial tests of a new technology for sulfuric acid alkylation of isobutane by olefines

    Energy Technology Data Exchange (ETDEWEB)

    Tarakanov, V.S.; Karamyshev, M.S.; Khadzhiyev, S.N.; Mel' man, A.Z.

    1971-01-01

    A complex of elements of a new technology for sulfuric acid alkylation of isobutane by alkenes with the use of a KSG-2 reactor and an acetic settler of a new design is realized as a result of the joint work of the Novo-Yaroslav oil refinery, GrozNII, VNIIOINeft and VNIINeftemash in an alkylation installation.

  17. Mechanism of alkylation of isobutane by olefins in the presence of sulfuric acid

    Energy Technology Data Exchange (ETDEWEB)

    Baiburskii, V.L.; Khadzhiev, S.N.; Ovsyannikov, V.P.

    1992-05-10

    The authors attempted here to examine the mechanism of alkylation of isobutane by olefins in the presence of sulfuric acid in terms of an initial stage of activation of isoparaffin. The version of formation of tert-alkyl cations and the role of the catalyst in this stage were analyzed. 10 refs., 1 fig., 1 tab.

  18. Model study of multiphase DMS oxidation with a focus on halogens

    Directory of Open Access Journals (Sweden)

    R. von Glasow

    2004-01-01

    Full Text Available We studied the oxidation of dimethylsulfide (DMS in the marine boundary layer (MBL with a one-dimensional numerical model and focused on the influence of halogens. Our model runs show that there is still significant uncertainty about the end products of the DMS addition pathway, which is especially caused by uncertainty in the product yield of the reaction of the intermediate product methyl sulfinic acid (MSIA with OH. BrO strongly increases the importance of the addition branch in the oxidation of DMS even when present at mixing ratios smaller than 0.5pmol mol-1. The inclusion of halogen chemistry leads to higher DMS oxidation rates and smaller DMS to SO2 conversion efficiencies. The DMS to SO2 conversion efficiency is also drastically reduced under cloudy conditions. In cloud-free model runs between 5 and 15% of the oxidized DMS reacts further to particulate sulfur, in cloudy runs this fraction is almost 100%. Sulfate production by HOClaq and HOBraq is important in cloud droplets even for small Br- deficits and related small gas phase halogen concentrations. In general, more particulate sulfur is formed when halogen chemistry is included. A possible enrichment of HCO3- in fresh sea salt aerosol would increase pH values enough to make the reaction of S(IV* (=SO2,aq+HSO3-+SO32- with O3 dominant for sulfate production. It leads to a shift from methyl sulfonic acid (MSA to non-sea salt sulfate (nss-SO42- production but increases the total nss-SO42- only somewhat because almost all available sulfur is already oxidized to particulate sulfur in the base scenario. We discuss how realistic this is for the MBL. We found the reaction MSAaq+OH to contribute about 10% to the production of nss-SO42- in clouds. It is unimportant for cloud-free model runs. Overall we find that the presence of halogens leads to processes that decrease the albedo of stratiform clouds in the MBL.

  19. Immunological detection of O6-methylguanine in alkylated DNA

    International Nuclear Information System (INIS)

    Briscoe, W.T.; Spizizen, J.; Tan, E.M.

    1978-01-01

    Antibodies to O 6 -methyldeoxyguanosine were produced in rabbits and utilized in a radioimmunoassay to detect this nucleoside at picomole levels. The specificity of the antibodies was demonstrated by the use of nucleoside analogues as inhibitors in the radioimmunoassay. The antibodies cross-reacted with O 6 -methylguanosine, O 6 -methylguanine, and O 6 -ethylguanosine. There was 10 4 to 10 6 times less sensitivity to inhibition by deoxyadenosine, deoxyguanosine, and guanosine than by O 6 -methyldeoxyguanosine. The radioimmunoassay also detected O 6 -methylguanine in DNA alkylated by agents known to produce O 6 -methylguanine, such as N'-methyl-N-nitrosourea. DNA alkylated with dimethyl sulfate, which does not produce O 6 -methylguanine in DNA, cross-reacted with the antibodies to a very limited extent. Such an assay system for modified nucleic acid components would be very useful in following the production, persistence, and repair of these lesions in a variety of cells and tissues treated with a broad spectrum of carcinogens and suspected carcinogens

  20. Pharmacology of dimethanesulfonate alkylating agents: busulfan and treosulfan.

    Science.gov (United States)

    Galaup, Ariane; Paci, Angelo

    2013-03-01

    Among the dimethanesulfonates, busulfan, in combination with other alkylating agents or nucleoside analogues, is the cornerstone of high-dose chemotherapy. It is used, and followed hematopoietic stem cell transplantation, for the treatment of various hematologic malignancies and immunodeficiencies. Treosulfan, which is a hydrophilic analogue of busulfan, was the first dimethanesufonate registered for the treatment of ovarian cancer. Recently, treosulfan has been investigated for the treatment of hematologic malignancies in combination with the same second agents before hematopoietic stem cell transplantation. This work reviews the pharmacological data of these two dimethanesulfonates alkylating agents. Specifically, the article looks at their chemistry, metabolism, anticancer activity, and their pharmacokinetics and pharmacodynamics. Busulfan has been investigated widely for more than three decades leading to a large and precise handling of this agent with numerous studies on activity and pharmacokinetics and pharmacodynamics. In contrast, the behavior of treosulfan is still under investigation and not fully described. The complexity of treosulfan's metabolism and mechanism of action gives rise to the need of a deeper understanding of its pharmacological activity in a context of high-dose chemotherapy. Specifically, there is a great need to better understand its pharmacokinetics/pharmacodynamics relationship.