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Sample records for n-alkylpentaethylene glycol n-alkyl

  1. Fabrication and properties of poly(polyethylene glycol n-alkyl ether vinyl ether)s as polymeric phase change materials

    International Nuclear Information System (INIS)

    Pei, Dong-fang; Chen, Sai; Li, Shu-qin; Shi, Hai-feng; Li, Wei; Li, Xuan; Zhang, Xing-xiang

    2016-01-01

    A series of poly(polyethylene glycol n-alkyl ether vinyl ether)s (PC m E n VEs) with various lengths of alkyl chains and polyethylene glycol spacers as side chain (m = 16,18; n = 1,2) were synthesized via two steps. First, monomers-ethylene glycol hexadecyl ether vinyl ether (C 16 E 1 VE), ethylene glycol octadecyl ether vinyl ether (C 18 E 1 VE), diethylene glycol hexadecyl ether vinyl ether (C 16 E 2 VE) and diethylene glycol octadecyl ether vinyl ether (C 18 E 2 VE) were synthesized by a modified Williamson etherification. Then, four new types of phase change materials were successfully fabricated by a living cationic polymerization. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were employed to characterize their composition, thermal properties and crystallization behavior. The results show that, the side chains of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are in a hexagonal lattice, and the onset temperatures for melting of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are 39.8 °C, 37.4 °C, 51.0 °C and 48.9 °C, the onset temperatures for crystallization are 36.7 °C, 35.2 °C, 47.4 °C and 46.3 °C, respectively. The enthalpy changes of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 100 J/g; on the contrary, it is 96 J/g for PC 16 E 1 VE. The enthalpy decrease is no more than 11% after 10 heating and cooling cycles. The 5 wt% mass loss temperatures of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 300 °C; on the contrary, it’s 283 °C for PC 16 E 1 VE. Using a weak polarity, flexible alkyl ether chain (-OCH 2 CH 2 O-) as a spacer to link the main chain and side chain is conducive to the crystallization of the alkyl side chain. These new phase change materials can be applied in heat storage, energy conservation, and environmental protection.

  2. 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

  3. 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...

  4. 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.

  5. 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.

  6. Structural Characterization of N-Alkylated Twisted Amides: Consequences for Amide Bond Resonance and N-C Cleavage.

    Science.gov (United States)

    Hu, Feng; Lalancette, Roger; Szostak, Michal

    2016-04-11

    Herein, we describe the first structural characterization of N-alkylated twisted amides prepared directly by N-alkylation of the corresponding non-planar lactams. This study provides the first experimental evidence that N-alkylation results in a dramatic increase of non-planarity around the amide N-C(O) bond. Moreover, we report a rare example of a molecular wire supported by the same amide C=O-Ag bonds. Reactivity studies demonstrate rapid nucleophilic addition to the N-C(O) moiety of N-alkylated amides, indicating the lack of n(N) to π*(C=O) conjugation. Most crucially, we demonstrate that N-alkylation activates the otherwise unreactive amide bond towards σ N-C cleavage by switchable coordination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Poly(mono/diethylene glycol n-tetradecyl ether vinyl ethers with Various Molecular Weights as Phase Change Materials

    Directory of Open Access Journals (Sweden)

    Dongfang Pei

    2018-02-01

    Full Text Available At present, research on the relationship of comb-like polymer phase change material structures and their heat storage performance is scarce. Therefore, this relationship from both micro and macro perspectives will be studied in this paper. In order to achieve a high phase change enthalpy, ethylene glycol segments were introduced between the vinyl and the alkyl side chains. A series of poly(mono/diethylene glycol n-tetradecyl ether vinyl ethers (PC14EnVEs (n = 1, 2 with various molecular weights were polymerized by living cationic polymerization. The results of PC14E1VE and PC14E2VE showed that the minimum number of carbon atoms required for side-chain crystallization were 7.7 and 7.2, which were lower than that reported in the literature. The phase change enthalpy 89 J/g (for poly(mono ethylene glycol n-tetradecyl ether vinyl ethers and 86 J/g (for poly(hexadecyl acrylate were approximately equal. With the increase of molecular weight, the melting temperature, the melting enthalpy, and the initial thermal decomposition temperature of PC14E1VE changed from 27.0 to 28.0 °C, from 95 to 89 J/g, and from 264 to 287 °C, respectively. When the number average molar mass of PC14EnVEs exceeded 20,000, the enthalpy values remained basically unchanged. The introduction of the ethylene glycol chain was conducive to the crystallization of alkyl side chains.

  8. Sleep-inducing N-alkyl-5-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinones and N-alkyl-3-(trifluoromethyl)cinnamamides.

    Science.gov (United States)

    Houlihan, W J; Gogerty, J H; Ryan, E A; Schmitt, G

    1985-01-01

    A series of N-alkyl-3-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinones and N-alkyl-3-(trifluoromethyl)-cinnamamides were prepared and screened in a series of tests designed to detect potential sleep inducers. The more active members of the series were evaluated for their ability to induce sleep in Cebus monkeys. The most active compound, N-methyl-5-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinone, was equal to methaqualone.

  9. 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.

  10. 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.

  11. Assessment of the combined approach of N-alkylation and salt formation to enhance aqueous solubility of tertiary amines using bupivacaine as a model drug

    DEFF Research Database (Denmark)

    Nielsen, Anders Bach; Frydenvang, Karla Andrea; Liljefors, Tommy

    2005-01-01

    as their iodide salts. Chloride, mesylate, formate, acetate, glycolate, and tosylate salts were obtained by anion exchange of the N-methyl-bupivacaine derivative. N-Alkylation and salt formation afforded quaternary ammonium salts possessing pH-independent aqueous solubilities far exceeding that of the parent......Quaternary prodrug types of poorly water-soluble tertiary amines have been shown to exhibit significantly enhanced solubilities as compared to the parent amine. In the present study the combined effect of N-alkylation and salt formation to enhance aqueous solubility of tertiary amines have been...

  12. Mechanochemical N-alkylation of imides

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    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.

  13. Alkylation of deoxyribonucleic acid by carcinogens dimethyl sulphate, ethyl methanesulphonate, N-ethyl-N-nitrosourea and N-methyl-N-nitrosourea

    International Nuclear Information System (INIS)

    Swenson, D.H.; Lawley, P.D.

    1978-01-01

    The ethyl phosphotriester of thymidylyl(3'-5')thymidine, dTp((Et) dT, was identified as a product from the reaction of DNA with N-ethyl-N-nitrosourea. Enzymic degradation to yield alkyl phosphotriesters from DNA alkylated by this carcinogen, and by N-methyl-N-nitrosourea, dimethyl sulphate and ethyl methanesulphonate was studied quantitatively, and the relative yields of the triesters dTp(Alk)dT were determined. The relative reactivity of the phosphodiester group dTpdT to each of the four carcinogens was thus obtained, and compared with that of DNA overall, or with that of the N-7 atom of guanine in DNA. The results are related to steric factors, and the electrophilic character of each carcinogen. (author)

  14. Synthesis of no-carrier-added radiobrominated n-alkylated analogues of spiperone

    International Nuclear Information System (INIS)

    Moerlein, S.M.; Laufer, P.; Stoecklin, G.

    1985-01-01

    The synthesis of a series of p-bromo-3-N-alkyl spiperone analogues is described. N-alkylation was achieved via reaction of the potassium salt of the spiperone lactam ring with alkyl iodide; subsequent reactions with elemental bromine gave the p-brominated isomers. Optimization studies using no-carrier-added (n.c.a.) 77 Br - indicated that radio-bromination of N-alkyl spiperone analogues occurs with higher yields and in shorter reaction times when dichloramine-T (DCT) is used rather than H 2 0 2 /acetic acid as an oxidant. The production of the title compounds in high effective specific activity with radiochemical yields of 20-30 % using n.c.a. 77 Br - and DCT is reported. (author)

  15. Comparative analysis of oxidative synthesis of N-alkyl, N,N-dialkyl and N-cykloalkyl-O-isobutyl thioncarbamate

    Directory of Open Access Journals (Sweden)

    Sovrlić Milica Ž.

    2011-01-01

    Full Text Available A optimized synthesis of N-alkyl, N,N-dialkyl- and N-cycloalkyl-O-isobutyl thioncarbamates by aminolysis of sodium isobutylxanthogenic acid (NaiBXAc and primary, secondary and cycloalkyl amines was developed at laboratory scale and applied at semi-industrial level. Studies on dependence of N-n-propyl-O-isopropylthiocarbamate yield and purity with respect to reaction parameters: reaction time and molar ratio of n-propylamine and NaiBXAc, were performed. In such way, optimal reaction conditions for synthesis of N-alkyl, N,N-dialkyl- and N-cycloalkyl-O-isobutyl thioncarbamates, by aminolysis of NaiBXAc, were established. Also, comparative results of thioncarbamates synthesis starting from potassium isobutyl xanthate (KiBX and corresponding amines in presence of different oxidants: hydrogen peroxide, sodium hypochlorite and new oxidative agent potassium peroxodisulfate were evaluated. Synthesized compounds have been fully characterized by FTIR, 1H and 13C NMR and MS data, elemental analysis and purity have been determined by gas chromatographic method (GC. According to our knowledge, ten synthesized thioncarbamates are for the first time characterized. Synthesized compounds could be used as selective reagents for flotation of copper and zinc ores. The presented methods offer several benefits, namely, high product yields and purity, simple operation, mild reaction conditions without use of hazardous organic solvents, while some of them could be implemented on industrial scale production.

  16. CORRELATION ANALYSIS OF IR, 1 H- AND 13 C-NMR SPECTRAL DATA OF N-ALKYL AND N-CYCLOALKYL CYANOACETAMIDES

    Directory of Open Access Journals (Sweden)

    Aleksandar D. Marinković

    2011-09-01

    Full Text Available Linear free energy relationships (LFER were applied to the IR, 1H- and 13C--NMR spectral data in N-alkyl and N-cycloalkyl cyanoacetamides. N-alkyl and N-cycloalkyl cyanocetamides were synthesized from corresponding amine and ethyl cyanoacetate. A number of substituents were employed for alkyl substitution, and fairly good correlations were obtained, using simple Hammett equation. In N-alkyl and N-cycloalkyl cyanoacetamides substituent cause SCS of N-H hydrogen primarily by steric interaction, polar subtituent effect influences SCS shift of C=O carbon, while steric effect of N-alkyl substituent causes IR stretching frequencies of N-H, C=O and CN group. The conformations of investigated compounds have been studied by the use of semiempirical PM6 method, and together with LFER analysis, give a better insight into the influence of such a structure on the transmission of electronic substituent effects. Negative ρ values for several correlations (reverse substituent effect were found.

  17. 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.

  18. Synthesis and Biological Evaluation of N-Alkyl-3-(alkylamino-pyrazine-2-carboxamides

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    Lucia Semelkova

    2015-05-01

    Full Text Available A series of N-alkyl-3-(alkylaminopyrazine-2-carboxamides and their N-alkyl-3-chloropyrazine-2-carboxamide precursors were prepared. All compounds were characterized by analytical methods and tested for antimicrobial and antiviral activity. The antimycobacterial MIC values against Mycobacterium tuberculosis H37Rv of the most effective compounds, 3-(hexylamino-, 3-(heptylamino- and 3-(octylamino-N-methyl-pyrazine-2-carboxamides 14‒16, was 25 μg/mL. The compounds inhibited photosystem 2 photosynthetic electron transport (PET in spinach chloroplasts. This activity was strongly connected with the lipophilicity of the compounds. For effective PET inhibition longer alkyl chains in the 3-(alkylamino substituent in the N-alkyl-3-(alkylaminopyrazine-2-carboxamide molecule were more favourable than two shorter alkyl chains.

  19. N,N'-(Hexane-1,6-diylbis(4-methyl-N-(oxiran-2-ylmethylbenzenesulfonamide: Synthesis via cyclodextrin mediated N-alkylation in aqueous solution and further Prilezhaev epoxidation

    Directory of Open Access Journals (Sweden)

    Julian Fischer

    2013-12-01

    Full Text Available N-alkylation of N,N'-(hexane-1,6-diylbis(4-methylbenzenesulfonamide with allyl bromide and subsequent Prilezhaev reaction with m-chloroperbenzoic acid to give N,N'-(hexane-1,6-diylbis(4-methyl-N-(oxiran-2-ylmethylbenzenesulfonamide is described. This twofold alkylation was performed in aqueous solution, whereby α-, and randomly methylated β-cyclodextrin were used as adequate phase transfer catalysts and the cyclodextrin–guest complexes were characterized by 1H NMR and 2D NMR ROESY spectroscopy. Finally, the curing properties of the diepoxide with lysine-based α-amino-ε-caprolactam were analyzed by rheological measurements.

  20. 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.

  1. 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

  2. Amphetamine in rat brain after intraperitoneal injection of N-alkylated analogues.

    Science.gov (United States)

    Nazarali, A J; Baker, G B; Coutts, R T; Pasutto, F M

    1983-01-01

    Three N-alkylated analogues of amphetamine were administered intraperitoneally to male Sprague-Dawley rats and whole brain levels of amphetamine (AM) and the N-alkyl analogue were determined one hour after injection of the N-alkylated compounds. The drugs administered were the N-2-cyanoethyl-(I) (fenproporex), the N-3-chloropropyl-(II) (mefenorex) and the N-n-propyl-(III) derivatives of AM: the first two of these are used clinically as anorexiants, and the latter has been used extensively to study aspects of metabolism of AM-like compounds. Analysis of AM, I, II and III was performed using electron-capture gas chromatography with a capillary column after reaction of compounds with pentafluorobenzoyl chloride under aqueous conditions. In a second comparative study, equimolar doses (0.05 mMole/kg) of I or AM were administered intraperitoneally to the rats and brain levels determined after one hour. Results indicate extensive N-dealkylation occurs for compounds I, II and III in the rat.

  3. 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%.

  4. Thermodynamic Interactions between Polystyrene and Long-Chain Poly(n-Alkyl Acrylates) Derived from Plant Oils.

    Science.gov (United States)

    Wang, Shu; Robertson, Megan L

    2015-06-10

    Vegetable oils and their fatty acids are promising sources for the derivation of polymers. Long-chain poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) are readily derived from fatty acids through conversion of the carboxylic acid end-group to an acrylate or methacrylate group. The resulting polymers contain long alkyl side-chains with around 10-22 carbon atoms. Regardless of the monomer source, the presence of alkyl side-chains in poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) provides a convenient mechanism for tuning their physical properties. The development of structured multicomponent materials, including block copolymers and blends, containing poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) requires knowledge of the thermodynamic interactions governing their self-assembly, typically described by the Flory-Huggins interaction parameter χ. We have investigated the χ parameter between polystyrene and long-chain poly(n-alkyl acrylate) homopolymers and copolymers: specifically we have included poly(stearyl acrylate), poly(lauryl acrylate), and their random copolymers. Lauryl and stearyl acrylate were chosen as model alkyl acrylates derived from vegetable oils and have alkyl side-chain lengths of 12 and 18 carbon atoms, respectively. Polystyrene is included in this study as a model petroleum-sourced polymer, which has wide applicability in commercially relevant multicomponent polymeric materials. Two independent methods were employed to measure the χ parameter: cloud point measurements on binary blends and characterization of the order-disorder transition of triblock copolymers, which were in relatively good agreement with one another. The χ parameter was found to be independent of the alkyl side-chain length (n) for large values of n (i.e., n > 10). This behavior is in stark contrast to the n-dependence of the χ parameter predicted from solubility parameter theory. Our study complements prior work investigating the interactions between

  5. N-fluoroalkylated and N-alkylated analogues of the dopaminergic D-2 receptor antagonist raclopride

    International Nuclear Information System (INIS)

    Lannoye, G.S.; Moerlein, S.M.; Parkinson, D.; Welch, M.J.

    1990-01-01

    A series of raclopride [(S)-2-[(3,5-dichloro-6-methoxy-2- hydroxybenzamido)methyl]-1-ethylpyrrolidine] derivatives bearing pyrrolidino N-fluoroalkyl or -alkyl substituents were synthesized and evaluated as potential dopaminergic receptor-based positron tomography radiopharmaceuticals. Radiosynthetic procedures for producing the corresponding N-[18F]fluoroalkylated analogues of raclopride from 18F- (beta+, t1/2 = 110 min) in high specific activity were also developed. In vitro binding assays using competitive displacement of [3H]spiperone from primate caudate tissue indicated that the N-alkylated analogues of raclopride had Ki values of 5-40 nM, whereas the corresponding values for analogous N-fluoroalkylated derivatives ranged from 90-160 nM. The relatively low D-2 binding affinity of these fluorinated salicylamides was corroborated by in vivo tissue biodistribution results in rodents. On the basis of structure-binding correlations, the impact of intramolecular hydrogen bonding, ligand basicity, and steric bulk on the affinity of the benzamides for D-2 receptor binding are discussed. Strategies are presented for the development of alternative fluorinated salicylamides that are both receptor active and metabolically stable

  6. 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.

  7. [The biochemical mechanisms of the action of N-alkyl-N-nitrosoureas. The possible reasons for drug resistance to these compounds].

    Science.gov (United States)

    Syrkin, A B; Gorbacheva, L B

    1996-01-01

    N-alkyl-N-nitrosoureas exhibit a wide spectrum of antitumor activity. They react as alkylating agents at nucleophilic sites in purine and pyrimidine moieties of DNA. The predominant site of this alkylation is N7 of guanine, which is followed by the site N3 of adenine and 06 of guanine. The formation and persistence of 0(6)-alkylguanine (0(6)-AG) may be of primary importance in cytotoxicity of the nitrosoureas. 0(6)-AG adducts of DNA of the tumor cells are repaired by protein 0(6)-alkylguanine-DNA transferase (0(6)-AGT) which transfers the alkyl group to internal cysteine residue being the acceptor protein for the alkyl group in an irreversible transfer reaction. 0(6)-AGT can protect the tumor cells against 0(6)-AG adducts by the way of inhibiting the formation of the DNA interstrand cross-links 0(6)-AGT plays an important role in the drug resistance because it repairs the DNA alkyl adducts at the 0(6) position of guanine. The 0(6)-AGT activity inversely correlates with the cytotoxic effect of the nitrosoureas. The agents like 0(6)-methylguanosine, 0(6)-methyl-2'-deoxyguanosine, and some 0(6)-benzylated guanine derivatives are effective inactivators of 0(6)-AGT, and thus can be used to enhance the cytotoxicity of N-nitrosoureas. The activation of 0(6)-AGT and other repairing enzymes such as alpha and beta DNA-polymerases as well as an increase in the level of reduced glutathione may be used in developing the resistance to the nitrosoureas.

  8. Extracting properties of N,N,N'N'-tetraalkyl-2 alkyl propane -1,3 diamides

    International Nuclear Information System (INIS)

    Nigond, L.

    1992-01-01

    N,N,N',N'-tetraalkyl -2 alkyl propane -1,3 diamides (RR'NCO) 2 CHR'' are investigated in the aim to separate actinides from nuclear wastes. N,N'-dimethyl N,N'-dibutyl tetradecylmalonamide (DMDBTDMA) was selected. This molecule can extract trivalent actinides in aliphatic diluents. Americium extraction is faster than iron extraction, hydrolytic degradation and solubility in aqueous phase are satisfactory. In non acidic media, diamides form aggregates, the size of which is function of diluent and diamide concentration. Extraction equilibria of HNO 3 , UO 2 2+ , Pu 4+ , Am 3+ and Fe 3+ are investigated.Four complexes are formed with nitric acid: L 2 HNO 3 , LHNO 3 , L 2 (HNO 3 ) 2 and L(HNO 3 ) 3 with L=DMDBTDMA. UO 2 2+ and Pu 4+ extraction takes place via the formation of neutral complexes: LUO 2 (NO 3 ) 2 , LPu(NO 3 ) 4 and L 2 Pu(NO 3 ) 4 for any nitric acid concentration. Am 3+ extraction takes place via the formation of LAm(NO 3 ) 3 and L 2 Am(NO 3 ) 3 for low nitric acid concentration and L x H y Am(NO 3 ) 3+y at higher acidity. Fe 3+ extraction involves anionic complexes L x HFe(NO 3 ) 4 for any acid concentration. In the presence of metallic cations, two kinds of interactions are observed: in the inner sphere of the metal diamide-metal ion complexation and in the outer sphere diamide-metallic complex interaction. The malonamide DMDBTDMA can be used to separate (III), (IV) and (VI) actinides from radioactive wastes

  9. Building blocks for ionic liquids: Vapor pressures and vaporization enthalpies of 1-(n-alkyl)-imidazoles

    International Nuclear Information System (INIS)

    Emel'yanenko, Vladimir N.; Portnova, Svetlana V.; Verevkin, Sergey P.; Skrzypczak, Andrzej; Schubert, Thomas

    2011-01-01

    Highlights: → We measured vapor pressures of the 1-(n-alkyl)-imidazoles by transpiration method. → Variations on the alkyl chain length n were C 3 , C 5 -C 7 , and C 9 -C 10 . → Enthalpies of vaporization were derived from (p, T) dependencies. → Enthalpies of vaporization at 298.15 K were linear dependent on the chain length. - Abstract: Vapor pressures of the linear 1-(n-alkyl)-imidazoles with the alkyl chain C 3 , C 5 -C 7 , and C 9 -C 10 have been measured by the transpiration method. The molar enthalpies of vaporization Δ l g H m of these compounds were derived from the temperature dependencies of vapor pressures. A linear correlation of enthalpies of vaporization Δ l g H m (298.15 K) of the 1-(n-alkyl)-imidazoles with the chain length has been found.

  10. Tribology of monolayer films: comparison between n-alkanethiols on gold and n-alkyl trichlorosilanes on silicon.

    Science.gov (United States)

    Booth, Brandon D; Vilt, Steven G; McCabe, Clare; Jennings, G Kane

    2009-09-01

    This Article presents a quantitative comparison of the frictional performance for monolayers derived from n-alkanethiolates on gold and n-alkyl trichlorosilanes on silicon. Monolayers were characterized by pin-on-disk tribometry, contact angle analysis, ellipsometry, and electrochemical impedance spectroscopy (EIS). Pin-on-disk microtribometry provided frictional analysis at applied normal loads from 10 to 1000 mN at a speed of 0.1 mm/s. At low loads (10 mN), methyl-terminated n-alkanethiolate self-assembled monolayers (SAMs) exhibited a 3-fold improvement in coefficient of friction over SAMs with hydroxyl- or carboxylic-acid-terminated surfaces. For monolayers prepared from both n-alkanethiols on gold and n-alkyl trichlorosilanes on silicon, a critical chain length of at least eight carbons is required for beneficial tribological performance at an applied load of 9.8 mN. Evidence for disruption of chemisorbed alkanethiolate SAMs with chain lengths n tribology wear tracks. The direct comparison between the tribological stability of alkanethiolate and silane monolayers shows that monolayers prepared from n-octadecyl dimethylchlorosilane and n-octadecyl trichlorosilane withstood normal loads at least 30 times larger than those that damaged octadecanethiolate SAMs. Collectively, our results show that the tribological properties of monolayer films are dependent on their internal stabilities, which are influenced by cohesive chain interactions (van der Waals) and the adsorbate-substrate bond.

  11. Read-across of ready biodegradability based on the substrate specificity of N-alkyl polypropylene polyamine-degrading microorganisms

    NARCIS (Netherlands)

    Geerts, R.; Ginkel, van C.G.; Plugge, C.M.

    2017-01-01

    The biodegradation of N-alkyl polypropylene polyamines (NAPPs) was studied using pure and mixed cultures to enable read-across of ready biodegradability test results. Two Pseudomonas spp. were isolated from activated sludge with N-oleyl alkyl propylene diamine and N-coco alkyl dipropylene triamine,

  12. Copper(II)/amine synergistically catalyzed enantioselective alkylation of cyclic N-acyl hemiaminals with aldehydes.

    Science.gov (United States)

    Sun, Shutao; Mao, Ying; Lou, Hongxiang; Liu, Lei

    2015-07-07

    The first catalytic asymmetric alkylation of N-acyl quinoliniums with aldehydes has been described. A copper/amine synergistic catalytic system has been developed, allowing the addition of functionalized aldehydes to a wide range of electronically varied N-acyl quinoliniums in good yields with excellent enantiocontrol. The synergistic catalytic system was also effective for N-acyl dihydroisoquinoliniums and β-caboliniums, demonstrating the general applicability of the protocol in the enantioselective alkylation of diverse cyclic N-acyl hemiaminals.

  13. Alkylation of deoxyribonucleic acid by carcinogens dimethyl sulphate, ethyl methanesulphonate, N-ethyl-N-nitrosourea and N-methyl-N-nitrosourea. Relative reactivity of the phosphodiester site thymidylyl(3'-5')thymidine.

    Science.gov (United States)

    Swenson, D H; Lawley, P D

    1978-01-01

    1. The ethyl phosphotriester of thymidylyl(3'-5')thymidine, dTp(Et)dT, was identified as a product from reaction of DNA with N-ethyl-N-nitrosourea, by procedures parallel to those reported previously for the methyl homologue produced by N-methyl-N-nitrosourea. 2. Enzymic degradation to yield alkyl phosphotriesters from DNA alkylated by these carcinogens and by dimethyl sulphate and ethyl methanesulphonate was studied quantitatively, and the relative yields of the triesters dTp(Alk)dT were determined. The relative reactivity of the phosphodiester group dTpdT to each of the four carcinogens was thus obtained, and compared with that of DNA overall, or with that of the N-7 atom of guanine in DNA. Relative reactivity of the phosphodiester group was lowest towards dimethyl sulphate, the least electrophilic of the reagents used, and was highest towards N-ethyl-N-nitrosourea, the most electrophilic reagent. 3. The nature of the alkyl group transferred also influenced reactivity of the phosphodiester site, since this site was relatively more reactive towards ethylation than would be predicted simply from the known Swain-Scott s values of the alkylating agents. It was therefore suggested that the steric accessibility of the weakly nucleophilic phosphodiester group on the outside of the DNA macromolecule favours its reaction with ethylating, as opposed to methylating, reagents. 4. Taking a value of the Swain-Scott nucleophilicity (n) of 2.5 for an average DNA nucleotide unit [Walles & Ehrenberg (1969) Acta Chem. Scand. 23, 1080-1084], a value of n of about 1 for the phosphodiester group was deduced, and this value was found to be 2-3 units less than that for the N-7 atom of guanine in DNA. 5. The reactivity of DNA overall was markedly high towards the alkylnitrosoureas, despite their relatively low s values. This was ascribed to an electrostatic factor that favoured reaction of the negatively charged polymer with alkyldiazonium cation intermediates. PMID:208508

  14. Synthesis and evaluation of N,N-di-alkyl-2-methoxyacetamides for the separation of U(VI) and Pu(IV) from nitric acid medium

    Energy Technology Data Exchange (ETDEWEB)

    Kumaresan, R.; Prathibha, T.; Selvan, B. Robert; Venkatesan, K.A.; Antony, M.P. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

    2017-07-01

    The homologs of N,N-di-alkyl-2-methoxyacetamides (DAMeOA) having three different alkyl chains varying from hexyl to decyl (C{sub 6}, C{sub 8} and C{sub 10}) were synthesized and characterized by NMR and IR spectral analyses. Extraction behavior of U(VI) and Pu(IV) from nitric acid medium in a solution of 0.5 M of DAMeOA in n-dodecane (n-DD) was studied and the results were compared with those obtained using N,N-di-hexyloctanamide (DHOA) in n-dodecane. The effect of various parameters on the distribution ratio of U(VI) and Pu(IV) in DAMeOA was studied. The extraction of nitric acid increased with decrease in chain length of alkyl group attached to amidic nitrogen atom of DAMeOA and the conditional nitric acid extraction constant was determined. The extraction of nitric acid in DAMeOA/n-DD resulted in the formation of third phase in organic phase and the third phase occurred early with DAMeOA having smaller alkyl chain length. In contrast to this, the distribution ratio (D) of U(VI) and Pu(IV) in DAMeOA/n-DD increased with increase in the concentration of nitric acid and with increase in the chain length of alkyl group attached to amidic nitrogen atom of DAMeOA. The stoichiometry of the metal - solvate was determined from the slope of extraction data. Quantitative recovery of uranium and plutonium from the loaded organic phase was achieved using dilute nitric acid.

  15. Synthesis and enzyme inhibitory studies of some new N-alkylated/aralkylated N-(4-ethoxyphenyl)-2,3-drobenzo-(1,4)-dioxin-6-sulfonamides

    International Nuclear Information System (INIS)

    Abbasi, M.A.; Islam, M.; Rehman, A.U.; Siddiqui, S.Z.

    2016-01-01

    The research endeavor was aimed to synthesize N-alkyl/aralkylated-N-(4-ethoxyphenyl)-2,3-dihydrobenzo-(1,4)-dioxine-6 sulfonamides and to evaluate their enzyme inhibitory potential. The target molecules were synthesized in two steps. The first step involved the reaction of 4-ethoxyaniline (1) with N-2,3-dihydrobenzo(1,4)-dioxin-6-sulfonyl chloride (2) under dynamic pH control maintained by 10% aqueous Na/sub 2/CO/sub 3/ to yield N-(4-ethoxyphenyl)-2,3-dihydrobenzo-(1,4)-dioxine-6-sulfonamide (3). In second step parent compound 3 was reacted with various alkyl/aralkyl halides (4a-l) in N,N'-dimethylformamide and catalytic amount of lithium hydride to accomplish some new N-alkyl/aralkylated-N-(4-ethoxyphenyl)-2,3-dihydrobenzo-(1,4)-dioxine-6 sulfonamides (5a-l). Probable structures of the synthesized compounds were characterized by contemporary spectral techniques i.e. IR, 1H-NMR and EIMS and were finally evaluated for enzyme inhibitory potential against a-glucosidase and urease. The synthesized compounds exhibited moderate to weak therapeutic potential throughout the series. (author)

  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. Masked N-Heterocyclic Carbene-Catalyzed Alkylation of Phenols with Organic Carbonates.

    Science.gov (United States)

    Lui, Matthew Y; Yuen, Alexander K L; Masters, Anthony F; Maschmeyer, Thomas

    2016-09-08

    An easily prepared masked N-heterocyclic carbene, 1,3-dimethylimidazolium-2-carboxylate (DMI-CO2 ), was investigated as a "green" and inexpensive organocatalyst for the alkylation of phenols. The process made use of various low-toxicity and renewable alkylating agents, such as dimethyl- and diethyl carbonate, in a focused microwave reactor. DMI-CO2 was found to be a very active catalyst and excellent yields of a range of aryl alkyl ethers were obtained under relatively benign conditions. The observed difference in the conversion behavior of phenol methylation, in the presence of either the carbene or 1,8-diazabicycloundec-7-ene (DBU) catalyst, was rationalized on the basis of mechanistic investigations. The primary mode of action for the N-heterocyclic carbene is nucleophilic catalysis. Activation of the dialkyl carbonate electrophile results in concomitant evolution of an organo-soluble alkoxide, which deprotonates the phenolic starting material. In contrast, DBU is initially protonated by the phenol and thus consumed. Subsequent regeneration and participation in nucleophilic catalysis only becomes significant after some phenolate alkylation occurs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Study on the Alkylation Reactions of N(7)-Unsubstituted 1,3-Diazaoxindoles.

    Science.gov (United States)

    Kókai, Eszter; Halász, Judit; Dancsó, András; Nagy, József; Simig, Gyula; Volk, Balázs

    2017-05-19

    The chemistry of the 5,7-dihydro-6 H -pyrrolo[2,3- d ]pyrimidin-6-one (1,3-diazaoxindole) compound family, possessing a drug-like scaffold, is unexplored. In this study, the alkylation reactions of N (7)-unsubstituted 5-isopropyl-1,3-diazaoxindoles bearing various substituents at the C (2) position have been investigated. The starting compounds were synthesized from the C (5)-unsubstituted parent compounds by condensation with acetone and subsequent catalytic reduction of the 5-isopropylidene moiety. Alkylation of the thus obtained 5-isopropyl derivatives with methyl iodide or benzyl bromide in the presence of a large excess of sodium hydroxide led to 5,7-disubstituted derivatives. Use of butyllithium as the base rendered alkylation in the C (5) position possible with reasonable selectivity, without affecting the N (7) atom. During the study on the alkylation reactions, some interesting by-products were also isolated and characterized.

  19. Tripodal (N-alkylated) CMP(O) and malonamide ligands: synthesis, extraction of metal ions, and potentiometric studies

    International Nuclear Information System (INIS)

    Janczewski, D.; Reinhoudt, D.N.; Verboom, W.; Malinowska, E.; Pietrzak, M.; Hill, C.; Allignol, C.

    2007-01-01

    Tripodal ligands build on the C-pivot (9b-e, 13b-d, and 17a-d) and tri-alkyl-benzene platforms (10a,b, 11, 12, 14a,b, and 18a,b) bearing (N-alkylated) carbamoyl-methyl-phosphine oxide (CMPO), carbamoyl-methyl-phosphonate (CMP), and malonamide moieties were synthesized. Extraction studies with Am 3+ and Eu 3+ show that in general there is a positive influence of the N-alkyl substituents in C-pivot CMP(O) ligands on the D(distribution) coefficients. The tri-alkyl-benzene CMPO ligands 10a,b, 11, and 12 have considerably larger D coefficients than the corresponding C-pivot analogues 9a-e, although hardly having any selectivity, while N-alkylation gives rise to smaller D coefficients. Although less effective the extraction behavior of the C-pivot CMP analogues 13b-d shows more or less the same trend as the corresponding CMPO ligands 9b-e upon substitution of the carboxamide N-atom with different alkyl chains. The different malonamide ligands 17a-d and 18a,b are bad extractants, while N-alkylation makes them even worse. Potentiometric studies of CMP(O) and malonamide ligands in polymeric membranes on Pb 2+ , Cu 2+ , Ca 2+ , Mg 2+ , Na + , and K + salts revealed that N-alkyl substituents increase the stability constants of ion-ionophore complexes compared to unsubstituted ligands. In polymeric membrane electrodes the ligands induce a selectivity pattern that differs significantly from the so-called Hofmeister series, giving the highest selectivity coefficients for UO 2 2+ among all examined cations (Pb 2+ , Cu 2+ , Ca 2+ , Mg 2+ , Na + , K + ). (authors)

  20. 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.

  1. Thermal phase behaviour of N-alkyl-N-methylpyrrolidinium and piperidinium bis(trifluoromethanesulfonyl)imide salts

    International Nuclear Information System (INIS)

    Henderson, W A; Jr, V G Young; Pearson, W; Passerini, S; Long, H C De; Trulove, P C

    2006-01-01

    The phases, ion crystal packing and thermal properties of the N-alkyl-N-methylpyrrolidinium and piperidinium bis(trifluoromethanesulfonyl)imide (PYR 1R TFSI and PIP 1R TFSI (subscript R = 1 for methyl and 2 for ethyl), respectively) salts are compared using powder and single-crystal x-ray diffraction (XRD) and differential scanning calorimetry (DSC). The crystal structure of PIP 12 TFSI has been determined at 123 K. The salt crystallizes in the triclinic space group P1-bar with Z 8. Structural data are also reported for PYR 11 TFSI at 153 K and PIP 12 TFSI at 223 K. PIP 11 TFSI has identical ion crystal packing to the analogous pyrrolidinium salt PYR 11 TFSI. Since increasing the cation alkyl chain length to propyl or butyl (R = 3 or 4) reduces the melting point of the salts below room temperature, this study may provide valuable insight into why these pyrrolidinium and piperidinium salts form room-temperature ionic liquids

  2. Pd@[nBu₄][Br] as a Simple Catalytic System for N-Alkylation Reactions with Alcohols.

    Science.gov (United States)

    Cacciuttolo, Bastien; Pascu, Oana; Aymonier, Cyril; Pucheault, Mathieu

    2016-08-10

    Palladium nanoparticles, simply and briefly generated in commercial and cheap onium salts using supercritical carbon dioxide, have been found to be an effective catalytic system for additive free N-alkylation reaction using alcohols via cascade oxidation/condensation/reduction steps.

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

    Science.gov (United States)

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

    2011-10-13

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

  4. N- and C-alkylation of seven-membered iminosugars generates potent glucocerebrosidase inhibitors and F508del-CFTR correctors.

    Science.gov (United States)

    Désiré, J; Mondon, M; Fontelle, N; Nakagawa, S; Hirokami, Y; Adachi, I; Iwaki, R; Fleet, G W J; Alonzi, D S; Twigg, G; Butters, T D; Bertrand, J; Cendret, V; Becq, F; Norez, C; Marrot, J; Kato, A; Blériot, Y

    2014-11-28

    The glycosidase inhibitory properties of synthetic C-alkyl and N-alkyl six-membered iminosugars have been extensively studied leading to therapeutic candidates. The related seven-membered iminocyclitols have been less examined despite the report of promising structures. Using an in house ring enlargement/C-alkylation as well as cross-metathesis methodologies as the key steps, we have undertaken the synthesis and biological evaluation of a library of fourteen 2C- and eight N-alkyl tetrahydroxylated azepanes starting from an easily available glucopyranose-derived azidolactol. Four, six, nine and twelve carbon atom alkyl chains have been introduced. The study of two distinct D-gluco and L-ido stereochemistries for the tetrol pattern as well as R and S configurations for the C-2 carbon bearing the C-alkyl chain is reported. We observed that C-alkylation of the L-ido tetrahydroxylated azepane converts it from an α-L-fucosidase to a β-glucosidase and β-galactosidase inhibitor while N-alkylation of the D-gluco iminosugar significantly improves its inhibition profile leading to potent β-glucosidase, β-galactosidase, α-L-rhamnosidase and β-glucuronidase inhibitors whatever the stereochemistry of the alkyl chain. Interestingly, the N-alkyl chain length usually parallels the azepane inhibitor potency as exemplified by the identification of a potent glucocerebrosidase inhibitor (Ki 1 μM) bearing a twelve carbon atom chain. Additionally, several C-alkyl azepanes demonstrated promising F508del-CFTR correction unlike the parent tetrahydroxyazepanes. None of the C-alkyl and N-alkyl azepanes did inhibit ER α-glucosidases I or II.

  5. 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.

  6. Tripodal (N-alkylated) CMP(O) and malonamide ligands: synthesis, extraction of metal ions, and potentiometric studies

    Energy Technology Data Exchange (ETDEWEB)

    Janczewski, D.; Reinhoudt, D.N.; Verboom, W. [Twente Univ., Lab. of Supramolecular Chemistry and Technology, Mesa Research Institute for Nanotechnology, Enschede (Netherlands); Malinowska, E.; Pietrzak, M. [Warsaw Univ. of Technology, Dept. of Analytical Chemistry, Faculty of Chemistry (Poland); Hill, C.; Allignol, C. [CEA Valrho, 30 - Marcoule (France)

    2007-01-15

    Tripodal ligands build on the C-pivot (9b-e, 13b-d, and 17a-d) and tri-alkyl-benzene platforms (10a,b, 11, 12, 14a,b, and 18a,b) bearing (N-alkylated) carbamoyl-methyl-phosphine oxide (CMPO), carbamoyl-methyl-phosphonate (CMP), and malonamide moieties were synthesized. Extraction studies with Am{sup 3+} and Eu{sup 3+} show that in general there is a positive influence of the N-alkyl substituents in C-pivot CMP(O) ligands on the D(distribution) coefficients. The tri-alkyl-benzene CMPO ligands 10a,b, 11, and 12 have considerably larger D coefficients than the corresponding C-pivot analogues 9a-e, although hardly having any selectivity, while N-alkylation gives rise to smaller D coefficients. Although less effective the extraction behavior of the C-pivot CMP analogues 13b-d shows more or less the same trend as the corresponding CMPO ligands 9b-e upon substitution of the carboxamide N-atom with different alkyl chains. The different malonamide ligands 17a-d and 18a,b are bad extractants, while N-alkylation makes them even worse. Potentiometric studies of CMP(O) and malonamide ligands in polymeric membranes on Pb{sup 2+}, Cu{sup 2+}, Ca{sup 2+}, Mg{sup 2+}, Na{sup +}, and K{sup +} salts revealed that N-alkyl substituents increase the stability constants of ion-ionophore complexes compared to unsubstituted ligands. In polymeric membrane electrodes the ligands induce a selectivity pattern that differs significantly from the so-called Hofmeister series, giving the highest selectivity coefficients for UO{sub 2}{sup 2+} among all examined cations (Pb{sup 2+}, Cu{sup 2+}, Ca{sup 2+}, Mg{sup 2+}, Na{sup +}, K{sup +}). (authors)

  7. TRANSPORT PROPERTIES FOR 1-ETHYL-3-METHYLIMIDAZOLIUM n-ALKYL SULFATES: POSSIBLE EVIDENCE OF GROTTHUSS MECHANISM

    International Nuclear Information System (INIS)

    García-Garabal, S.; Vila, J.; Rilo, E.; Domínguez-Pérez, M.; Segade, L.; Tojo, E.; Verdía, P.; Varela, L.M.; Cabeza, O.

    2017-01-01

    The objective of this work was to study the effect of the temperature and the lengthening of the linear alkyl chain of the anion in the transport physical properties of the pure ionic liquids 1-ethyl-3-methyl imidazolium n-alkyl sulphate (being n = 0, 1, 2, 4, 6 and 8). Density, viscosity and electrical conductivities were measured at atmospheric pressure in a wide temperature range. In the bibliography, data existed for these magnitudes for all ionic liquids studied but none of these had information about the electrical conductivity of 1-ethyl-3-methyl imidazolium n-alkyl sulfate whith n = 0, 4, 6 and 8. The experimental results show clearly 1-ethyl-3-methyl imidazolium hydrogen sulphate cannot be considered part of the 1-ethyl-3-methyl imidazolium n-alkyl sulphate family because of its hydrogen bonding ability. Results of density and viscosity behave as expected. However, in the case of the electrical conductivity due to the lack of alkyl chain in the hydrogen sulfate we expected to get extreme values but in practise, we obtained intermediate values between 1-ethyl-3-methyl imidazolium butyl sulphate and 1-ethyl-3-methyl imidazolium hexyl sulphate. This suggests that a Grotthus mechanism exists as result of a protonic current in addition to ionic conductivity, being Waldeńs plot consistent with this idea.

  8. 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...

  9. Effects of derivatization reagents consisting of n-alkyl chloroformate/n-alcohol combinations in LC-ESI-MS/MS analysis of zwitterionic antiepileptic drugs.

    Science.gov (United States)

    Kostić, Nađa; Dotsikas, Yannis; Malenović, Anđelija; Medenica, Mirjana

    2013-11-15

    In the current study, three antiepileptic drugs with zwitterionic properties, namely vigabatrin, pregabalin and gabapentin, were chosen as model analytes to undergo derivatization by applying various n-alkyl chloroformate/n-alcohol combinations, followed by LC-ESI-MS/MS analysis. The employment of 16 combinations per drug using methyl, ethyl, propyl or butyl chloroformate coupled with methanol, ethanol, propanol or butanol, greatly affected a series of parameters of the derivatives, such as retention time on C8 column, signal expressed via areas, limit of detection values, as well as the yields of the main and side reactions. Practically, even slight modification of n-alkyl group of either chloroformate or alcohol resulted in significant changes in the chromatographic and mass spectrometric behavior of the novel derivative. It was clearly demonstrated that all the estimated parameters were highly correlated with the length of n-alkyl groups of the involved chloroformate and alcohol. The most significant influence was monitored in peak area values, indicating that the length of the n-alkyl chain plays an important role in electrospray ionization efficiency. For this parameter, increasing the n-alkyl chain from methyl to butyl led to increment up to 2089%, 508.7% and 1075% for area values of derivatized vigabatrin, pregabalin and gabapentin, respectively. These changes affected also the corresponding values of limits of detection, with the estimated improvements up to 1553%, 397.7% and 875.0% for the aforementioned derivatized drugs, respectively. Besides the obvious utilization of these conclusions in the development of bioanalytical methods for these analytes with the current protocol, this study offers valuable data which can be useful in more general approaches, giving insights into the effects of this derivatization reaction and its performances. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Mechanism of the protective effects of long chain n-alkyl glucopyranosides against ultrasound-induced cytolysis of HL-60 cells.

    Science.gov (United States)

    Cheng, Jason Y; Riesz, Peter

    2007-07-01

    Recently it has been shown that long chain (C5-C8) n-alkyl glucopyranosides completely inhibit ultrasound-induced cytolysis [J.Z. Sostaric, N. Miyoshi, P. Riesz, W.G. DeGraff, and J.B. Mitchell, Free Radical Biol. Med., 39 (2005) 1539]. This protective effect has possible applications in HIFU (high intensity focused ultrasound) for tumor treatment, and in ultrasound assisted drug delivery and gene therapy. n-Alkyl glucopyranosides with hexyl (5mM), heptyl (3mM), octyl (2mM) n-alkyl chains protected 100% of HL-60 cells in vitro from 1.057 MHz ultrasound-induced cytolysis under a range of conditions that resulted in 35-100% cytolysis in the absence of glucopyranosides. However the hydrophilic methyl-beta-d-glucopyranoside did not protect cells. The surface active n-alkyl glucopyranosides accumulate at the gas-liquid interface of cavitation bubbles. The OH radicals and H atoms formed in collapsing cavitation bubbles react by H-atom abstraction from either the n-alkyl chain or the glucose moiety of the n-alkyl glucopyranosides. Owing to the high concentration of the long chain surfactants at the gas-liquid interface of cavitation bubbles, the initially formed carbon radicals on the alkyl chains are transferred to the glucose moieties to yield radicals which react with oxygen leading to the formation of hydrogen peroxide. In this work, we find that the sonochemically produced hydrogen peroxide yields from oxygen-saturated solutions of long chain (hexyl, octyl) n-alkyl glucopyranosides at 614 kHz and 1.057 MHz ultrasound increase with increasing n-alkyl glucopyranoside concentration but are independent of concentration for methyl-beta-D-glucopyranoside. These results are consistent with the previously proposed mechanism of sonoprotection [J.Z. Sostaric, N. Miyoshi, P. Riesz, W.G. DeGraff, and J.B. Mitchell, Free Radical Biol. Med., 39 (2005) 1539]. This sequence of events prevents sonodynamic cell killing by initiation of lipid peroxidation chain reactions in cellular

  11. Determination of rate constants of N-alkylation of primary amines by 1H NMR spectroscopy.

    Science.gov (United States)

    Li, Chenghong

    2013-09-05

    Macromolecules containing N-diazeniumdiolates of secondary amines are proposed scaffolds for controlled nitrogen oxide (NO) release medical applications. Preparation of these compounds often involves converting primary amine groups to secondary amine groups through N-alkylation. However, N-alkylation results in not only secondary amines but tertiary amines as well. Only N-diazeniumdiolates of secondary amines are suitable for controlled NO release; therefore, the yield of secondary amines is crucial to the total NO load of the carrier. In this paper, (1)H NMR spectroscopy was used to estimate the rate constants for formation of secondary amine (k1) and tertiary amine (k2) for alkylation reagents such as propylene oxide (PO), methyl acrylate (MA), and acrylonitrile (ACN). At room temperature, the ratio of k2/k1 for the three reactions was found to be around 0.50, 0.026, and 0.0072.

  12. Neighbor-directed histidine N(τ) alkylation. A route to imidazolium-containing phosphopeptide macrocycles

    Energy Technology Data Exchange (ETDEWEB)

    Qian, Wen-Jian [National Cancer Inst., Frederick, MD (United States); Park, Jung-Eun [National Cancer Inst., Bethesda, MD (United States); Grant, Robert [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lai, Christopher C. [National Cancer Inst., Frederick, MD (United States); Kelley, James A. [National Cancer Inst., Frederick, MD (United States); Yaffe, Michael B. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lee, Kyung S. [National Cancer Inst., Bethesda, MD (United States); Burke, Terrence R. [National Cancer Inst., Frederick, MD (United States)

    2015-07-07

    Our recently discovered, selective, on-resin route to N(τ)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In this, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. These cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation. Furthermore, neighbor-directed histidine N(τ)-alkylation opens the door to new families of phosphopeptidomimetics for use in a range of chemical biology contexts.

  13. Design rules for carbazole derivatized n-alkyl methacrylate polymeric memristors

    Czech Academy of Sciences Publication Activity Database

    McFarlane, T. M.; Zdyrko, B.; Bandera, Y.; Worley, D.; Klep, O.; Jurča, M.; Tonkin, C.; Foulger, S. H.; Vilčáková, J.; Sáha, P.; Pfleger, Jiří

    2018-01-01

    Roč. 6, č. 10 (2018), s. 2533-2545 ISSN 2050-7526 Institutional support: RVO:61389013 Keywords : n-alkyl methacrylate polymers * charge transport * composites Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 5.256, year: 2016

  14. Synthesis of triated N1'-alkyl derivatives of the delta opioid receptor ligand naltrindole

    International Nuclear Information System (INIS)

    Lever, J.R.; Johnson, S.M.

    1997-01-01

    Tritiated N1'-methyl and N1'-ethyl analogues of naltrindole (NTI) have been synthesized for evaluation as radioligands for studies of delta opioid receptors. The two N1'-alkyl-5',7'-dibromoNTI precursors for radiolabeling were prepared by base-promoted alkylation of 2,4-dibromophenylhydrazine with either iodomethane or iodoethane followed by condensation with naltrexone using the Fischer indole synthesis. Catalytic debromotritiation followed by HPLC purification afforded [ 3 H]MeNTI (17.3 Ci/mmol) and [ 3 H]EtNTI (22.5 Ci/mmol) with high chemical and radiochemical purities (≥ 99.8%). (author)

  15. Pd@[nBu4][Br] as a Simple Catalytic System for N-Alkylation Reactions with Alcohols

    Directory of Open Access Journals (Sweden)

    Bastien Cacciuttolo

    2016-08-01

    Full Text Available Palladium nanoparticles, simply and briefly generated in commercial and cheap onium salts using supercritical carbon dioxide, have been found to be an effective catalytic system for additive free N-alkylation reaction using alcohols via cascade oxidation/condensation/reduction steps.

  16. Time course evaluation of N-nitrosodialkylamines-induced DNA alkylation and oxidation in liver of mosquito fish

    International Nuclear Information System (INIS)

    Chao, M.-R.; Chang, Y.-Z.; Wong, R.-H.; Hu, C.-W.

    2009-01-01

    Here we simultaneously measured N7-alkylguanines and 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) in liver of small fish, respectively, to assess the time course of the formation and removal of alkylation and oxidative damage to DNA caused by N-nitrosodialkylamines. Mosquito fish (Gambusia affinis) were killed at various times during (4 days) and post-exposure (16 days) to N-nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA) alone or their combination with concentrations of 10 and 50 mg/l. The modified guanine adducts were sensitively and selectively quantitated by isotope-dilution LC-MS/MS methods. During exposure, N7-methylguanine (N7-MeG) and N7-ethylguanine (N7-EtG) in liver DNA increased with the duration and dose of N-nitrosodialkylamine exposure, while 8-oxodG was dose-dependently induced within 1 day. It was found that NDMA formed substantially more N7-alkylated guanines and 8-oxodG than NDEA on the basis of adducts formed per micromolar concentration, suggesting that NDMA can be more easily bioactivated than NDEA to form reactive alkylating agents with the concomitant formation of oxygen radicals. After cessation of exposure, N7-alkylguanines remained elevated for 1 day and then gradually decreased over time but still higher than the background levels, even at day 16 (half-lives of 7-8 days). However, 8-oxodG was excised quickly from liver DNA and returned to the background level within 4 days post-exposure (half-lives less than 2 days). Taken together, this study firstly demonstrated that in addition to alkylation, N-nitrosodialkylamines can concurrently cause oxidative damage to DNA in vivo

  17. Time course evaluation of N-nitrosodialkylamines-induced DNA alkylation and oxidation in liver of mosquito fish

    Energy Technology Data Exchange (ETDEWEB)

    Chao, M -R [Department of Occupational Safety and Health, Chung Shan Medical University, Taichung 402, Taiwan (China); Institute of Medical and Molecular Toxicology, Chung Shan Medical University, Taichung 402, Taiwan (China); Chang, Y -Z [Institute of Medical and Molecular Toxicology, Chung Shan Medical University, Taichung 402, Taiwan (China); Wong, R -H [Department of Public Health, Chung Shan Medical University, Taichung 402, Taiwan (China); Hu, C.-W. [Department of Public Health, Chung Shan Medical University, Taichung 402, Taiwan (China)], E-mail: windyhu@csmu.edu.tw

    2009-01-15

    Here we simultaneously measured N7-alkylguanines and 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) in liver of small fish, respectively, to assess the time course of the formation and removal of alkylation and oxidative damage to DNA caused by N-nitrosodialkylamines. Mosquito fish (Gambusia affinis) were killed at various times during (4 days) and post-exposure (16 days) to N-nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA) alone or their combination with concentrations of 10 and 50 mg/l. The modified guanine adducts were sensitively and selectively quantitated by isotope-dilution LC-MS/MS methods. During exposure, N7-methylguanine (N7-MeG) and N7-ethylguanine (N7-EtG) in liver DNA increased with the duration and dose of N-nitrosodialkylamine exposure, while 8-oxodG was dose-dependently induced within 1 day. It was found that NDMA formed substantially more N7-alkylated guanines and 8-oxodG than NDEA on the basis of adducts formed per micromolar concentration, suggesting that NDMA can be more easily bioactivated than NDEA to form reactive alkylating agents with the concomitant formation of oxygen radicals. After cessation of exposure, N7-alkylguanines remained elevated for 1 day and then gradually decreased over time but still higher than the background levels, even at day 16 (half-lives of 7-8 days). However, 8-oxodG was excised quickly from liver DNA and returned to the background level within 4 days post-exposure (half-lives less than 2 days). Taken together, this study firstly demonstrated that in addition to alkylation, N-nitrosodialkylamines can concurrently cause oxidative damage to DNA in vivo.

  18. Time course evaluation of N-nitrosodialkylamines-induced DNA alkylation and oxidation in liver of mosquito fish

    Energy Technology Data Exchange (ETDEWEB)

    Chao, M.-R. [Department of Occupational Safety and Health, Chung Shan Medical University, Taichung 402, Taiwan (China); Institute of Medical and Molecular Toxicology, Chung Shan Medical University, Taichung 402, Taiwan (China); Chang, Y.-Z. [Institute of Medical and Molecular Toxicology, Chung Shan Medical University, Taichung 402, Taiwan (China); Wong, R.-H. [Department of Public Health, Chung Shan Medical University, Taichung 402, Taiwan (China); Hu, C.-W. [Department of Public Health, Chung Shan Medical University, Taichung 402, Taiwan (China)], E-mail: windyhu@csmu.edu.tw

    2009-01-15

    Here we simultaneously measured N7-alkylguanines and 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) in liver of small fish, respectively, to assess the time course of the formation and removal of alkylation and oxidative damage to DNA caused by N-nitrosodialkylamines. Mosquito fish (Gambusia affinis) were killed at various times during (4 days) and post-exposure (16 days) to N-nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA) alone or their combination with concentrations of 10 and 50 mg/l. The modified guanine adducts were sensitively and selectively quantitated by isotope-dilution LC-MS/MS methods. During exposure, N7-methylguanine (N7-MeG) and N7-ethylguanine (N7-EtG) in liver DNA increased with the duration and dose of N-nitrosodialkylamine exposure, while 8-oxodG was dose-dependently induced within 1 day. It was found that NDMA formed substantially more N7-alkylated guanines and 8-oxodG than NDEA on the basis of adducts formed per micromolar concentration, suggesting that NDMA can be more easily bioactivated than NDEA to form reactive alkylating agents with the concomitant formation of oxygen radicals. After cessation of exposure, N7-alkylguanines remained elevated for 1 day and then gradually decreased over time but still higher than the background levels, even at day 16 (half-lives of 7-8 days). However, 8-oxodG was excised quickly from liver DNA and returned to the background level within 4 days post-exposure (half-lives less than 2 days). Taken together, this study firstly demonstrated that in addition to alkylation, N-nitrosodialkylamines can concurrently cause oxidative damage to DNA in vivo.

  19. Ruthenium-complex catalyzed N-(cyclo)alkylation of aromatic amines with diols. Selective synthesis of N-(n-hydroixyalkyl)anilines of type PhNH(CH2)nOH and of some bioactive arylpiperazines,

    NARCIS (Netherlands)

    Koten, G. van; Abbenhuis, R.A.T.M.; Boersma, J.

    1998-01-01

    A new class of well-defined neutral mono-, and dicationic ruthenium(II) complexes containing a neutral terdentate donor system [C5H3N(CH2E)(2)-2,6] (E = PPh2 (PNP) or NMe2 (NN'N)) has been found effective as catalyst precursor in N-(cyclo)alkylation reactions of aromatic amines with diols

  20. Kinetic investigation of the oxidation of N-alkyl anilines by ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 112; Issue 6. Kinetic investigation of the oxidation of N-alkyl anilines by peroxomonophosphoric acid in anionic surfactant sodium lauryl sulphate. G P Panigrahi Jagannath Panda. Physical and Theoretical Volume 112 Issue 6 December 2000 pp 615-622 ...

  1. 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.

  2. N- versus O-alkylation: utilizing NMR methods to establish reliable primary structure determinations for drug discovery.

    Science.gov (United States)

    LaPlante, Steven R; Bilodeau, François; Aubry, Norman; Gillard, James R; O'Meara, Jeff; Coulombe, René

    2013-08-15

    A classic synthetic issue that remains unresolved is the reaction that involves the control of N- versus O-alkylation of ambident anions. This common chemical transformation is important for medicinal chemists, who require predictable and reliable protocols for the rapid synthesis of inhibitors. The uncertainty of whether the product(s) are N- and/or O-alkylated is common and can be costly if undetermined. Herein, we report an NMR-based strategy that focuses on distinguishing inhibitors and intermediates that are N- or O-alkylated. The NMR strategy involves three independent and complementary methods. However, any combination of two of the methods can be reliable if the third were compromised due to resonance overlap or other issues. The timely nature of these methods (HSQC/HMQC, HMBC. ROESY, and (13)C shift predictions) allows for contemporaneous determination of regioselective alkylation as needed during the optimization of synthetic routes. Copyright © 2013 Elsevier Ltd. All rights reserved.

  3. 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

  4. Solvation of ionic liquids based on N-methyl-N-alkyl morpholinium cations in dimethylsulfoxide – volumetric and compressibility studies

    International Nuclear Information System (INIS)

    Marcinkowski, Łukasz; Kloskowski, Adam; Czub, Jacek; Namieśnik, Jacek; Warmińska, Dorota

    2015-01-01

    Highlights: • In DMSO both volumes and compressibilities of ionic liquids were studied. • Molecular dynamics simulations were performed for all studied ionic liquids. • V Φ of DMSO solutions of [Mor 1,R ][TFSI] decrease with increasing IL concentration. • Results indicate that [Mor 1,R ][TFSI] are structure breakers in dimethylsulfoxide. • Obtained results are the consequence of the cation size of the ionic liquid. - Abstract: The density and sound velocity of the solutions of ionic liquids based on N-alkyl-N-methyl-morpholinium cations, N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, N-methyl-N-octyl-morpholinium bis(trifluoromethanesulfonyl)imide and N-decyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide in dimethylsulfoxide were measured at T = (298.15 to 318.15) K and at atmospheric pressure. The apparent molar volume and apparent molar compressibility values were evaluated from density and sound velocity values and fitted to the Masson equation from which the partial molar volume and partial molar isentropic compressibility of the ILs at infinite dilution were also calculated at working temperatures. By using the density values, the limiting apparent molar expansibilities were estimated. The effect of the alkyl chain length of the ILs and experimental temperature on these thermodynamic properties is discussed. In addition, molecular dynamics simulations were used to interpret the measured properties in terms of interactions of ILs with solvent molecules. Both, volumetric measurements results and molecular dynamics simulations for ionic liquids in dimethylsulfoxide were compared and discussed with results obtained for the same IL in acetonitrile

  5. N-mercapto acetyl-N'-octyl-O, N″-glycol chitosan as an efficiency oral delivery system of paclitaxel.

    Science.gov (United States)

    Huo, Meirong; Fu, Ying; Liu, Yanhong; Chen, Qinyu; Mu, Yan; Zhou, Jianping; Li, Lingchao; Xu, Wei; Yin, Tingjie

    2018-02-01

    Herein, thioglycolic acid modified N-octyl-O, N'-glycol chitosan (N-mercapto acetyl-N'-octyl-O, N″-glycol chitosan, abbreviated as SH-OGC) was synthesized to improve the oral bioavailability of paclitaxel (PTX). PTX was readily solubilized into the hydrophobic inner core of SH-OGC. Pharmacokinetic studies demonstrated that the bioavailability of PTX was greatly enhanced when delivered by SH-OGC compared to Taxol ® or non-sulfhydrylated OGC micelles. Caco-2 cell experiments confirmed PTX or rhodamine-123-loaded SH-OGC demonstrated effective cellular accumulation via caveola-mediated endocytosis along with the inhibition of P-gp efflux. Furthermore, Caco-2 transport studies demonstrated that the mechanistic basis of SH-OGC efficacy was attributed to P-gp inhibition, enhanced permeability of tight junctions and clathrin-mediated transcytosis across the endothelium. In addition, SH-OGC exhibited increased intestinal retention through thiol-mediated mucoadhesion compared with OGC according to results of mucoadhesion evaluation on freshly excised rat intestine. In summary, SH-OGC micelles may present as a promising delivery vehicle for enhancing the oral bioavailability of P-gp substrates. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. the influence of acidity of zeolite H-BEA catalyzed isobutane/n-butene alkylation

    NARCIS (Netherlands)

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

    1998-01-01

    The influence of the concentration of acid sites for isobutane/n-butene alkylation on zeolite BEA with varying degrees of Na+ ion exchange is reported. All catalysts studied showed complete n-butene conversion over a significant time-on-stream. Isooctanes were the dominating products over H-BEA,

  7. Activated N-nitrosocarbamates for regioselective synthesis of N-nitrosoureas.

    Science.gov (United States)

    Martinez, J; Oiry, J; Imbach, J L; Winternitz, F

    1982-02-01

    A practical and convenient method for synthesizing antitumor compounds, N-alkyl-N-nitrosoureas, regioselectively nitrosated on the nitrogen atom bearing the alkyl group is proposed. N-Alkyl-N-nitrosocarbamates are interesting intermediates in these syntheses and yield, by reaction with amino compounds, the regioselectively nitrosated N-alkyl-N-nitrosoureas. As an interesting example, N,N'-bis[(2-chloroethyl)nitrosocarbamoyl]cystamine, a new attractive oncostatic derivative, has been prepared. The cytotoxic activity of these various compounds were tested on L1210 leukemia.

  8. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

    KAUST Repository

    Giovannitti, Alexander

    2018-04-24

    We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

  9. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

    KAUST Repository

    Giovannitti, Alexander; Maria, Iuliana P.; Hanifi, David; Donahue, Mary J.; Bryant, Daniel; Barth, Katrina J.; Makdah, Beatrice E.; Savva, Achilleas; Moia, Davide; Zetek, Matyá š; Barnes, Piers R.F.; Reid, Obadiah G.; Inal, Sahika; Rumbles, Garry; Malliaras, George G.; Nelson, Jenny; Rivnay, Jonathan; McCulloch, Iain

    2018-01-01

    We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

  10. Read-across of ready biodegradability based on the substrate specificity of N-alkyl polypropylene polyamine-degrading microorganisms.

    Science.gov (United States)

    Geerts, R; van Ginkel, C G; Plugge, C M

    2017-04-01

    The biodegradation of N-alkyl polypropylene polyamines (NAPPs) was studied using pure and mixed cultures to enable read-across of ready biodegradability test results. Two Pseudomonas spp. were isolated from activated sludge with N-oleyl alkyl propylene diamine and N-coco alkyl dipropylene triamine, respectively. Both strains utilized all NAPPs tested as the sole source of carbon, nitrogen and energy for growth. Mineralization of NAPPs was independent of the alkyl chain length and the size of the polyamine moiety. NAPPs degraded in closed bottle tests (CBTs) using both river water and activated sludge. However, ready biodegradability of NAPPs with alkyl chain lengths of 16-18 carbon atoms and polyamine moieties with three and four nitrogen atoms could not be demonstrated. Biodegradation in the CBT was hampered by their limited bioavailability, making assessment of the true ready biodegradability of these highly adsorptive surfactants impossible. All NAPPs are therefore classified as readily biodegradable through read-across. Read-across is justified by the broad substrate specificity of NAPP-degrading microorganisms, their omnipresence and the mineralization of NAPPs.

  11. Effect of alkyl-N-phenylcarbamates on photochemical activity of spinach chloroplasts

    International Nuclear Information System (INIS)

    Sersen, F.; Kralova, K.; Macho, V.

    1999-01-01

    This study is aimed to investigate the effect of alkyl-N-phenylcarbamates on photosynthetic electron transport in spinach chloroplasts, to determine site of action in the photosynthetic apparatus of spinach chloroplasts and to find correlations between their structure and biological activity. (authors)

  12. Mechanism of the protective effects of long chain n-alkyl glucopyranosides against ultrasound-induced cytolysis of HL-60 cells

    OpenAIRE

    Cheng, Jason Y.; Riesz, Peter

    2007-01-01

    Recently it has been shown that long chain (C5 to C8) n-alkyl glucopyranosides completely inhibit ultrasound-induced cytolysis [1]. This protective effect has possible applications in HIFU (high intensity focused ultrasound) for tumor treatment, and in ultrasound assisted drug delivery and gene therapy. n-Alkyl glucopyranosides with hexyl (5mM), heptyl (3mM), octyl (2mM) n-alkyl chains protected 100% of HL-60 cells in-vitro from 1.057 MHz ultrasound induced cytolysis under a range of conditio...

  13. Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines.

    Science.gov (United States)

    Ikawa, Takashi; Fujita, Yuki; Mizusaki, Tomoteru; Betsuin, Sae; Takamatsu, Haruki; Maegawa, Tomohiro; Monguchi, Yasunari; Sajiki, Hironao

    2012-01-14

    Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH(4)OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.

  14. Dynamic studies of poly(di-n-alkyl itaconate)s

    CERN Document Server

    Arrighi, V; Gagliardi, S; McEwen, I J; Telling, M T F

    2002-01-01

    We report a preliminary dynamic study of poly(di-n-alkyl itaconate)s with varying side chain length n. QENS measurements were carried out on two backscattering spectrometers, IRIS at ISIS and IN10 at the ILL in the temperature range of 4 to 350 K. We show that molecular motion can be detected well below the polymer glass transition for all samples. It is possible to distinguish different dynamic processes. The temperature range over which these are observed is dependent on the length of the side chain, n. The intermediate scattering function, I(Q,t), was determined from the IRIS and found to obey time-temperature superposition. We show that the I(Q,t) data at different temperatures can be overlapped using the same time-scale shift factors, indicating that the relaxation process is common to all the polymers investigated. (orig.)

  15. Mitsunobu mischief: Neighbor-directed histidine N(π)–alkylation provides access to peptides containing selectively functionalized imidazolium heterocycles

    Science.gov (United States)

    Qian, Wen-Jian

    2015-01-01

    There are few methodologies that yield peptides containing His residues with selective N(π), N(π)-bis-alkylated imidazole rings. We have found that, under certain conditions, on-resin Mitsunobu coupling of alcohols with peptides having a N(π)-alkylated His residue results in selective and high-yield alkylation of the imidazole N(π) nitrogen. The reaction requires the presence of a proximal phosphoric, carboxylic or sulfonic acid, and proceeds through an apparent intramolecular mechanism involving Mitsunobu intermediates. These transformations have particular application to phosphopeptides, where “charge masking” of one phosphoryl anionic charge by the cationic histidine imidazolium ion is now possible. This chemistry opens selective access to peptides containing differentially functionalized imidazolium heterocycles, which provide access to new classes of peptides and peptide mimetics. PMID:25739367

  16. Production of n-alkyl lipids in living plants and implications for the geologic past

    Science.gov (United States)

    Diefendorf, Aaron F.; Freeman, Katherine H.; Wing, Scott L.; Graham, Heather V.

    2011-12-01

    Leaf waxes (i.e., n-alkyl lipids or n-alkanes) are land-plant biomarkers widely used to reconstruct changes in climate and the carbon isotopic composition of the atmosphere. There is little information available, however, on how the production of leaf waxes by different kinds of plants might influence the abundance and isotopic composition of n-alkanes in sedimentary archives. This lack of information increases uncertainty in interpreting n-alkyl lipid abundance and δ 13C signals in ancient settings. We provide here n-alkyl abundance distributions and carbon isotope fractionation data for deciduous and evergreen angiosperm and gymnosperm leaves from 46 tree species, representing 24 families. n-Alkane abundances are significantly higher in angiosperms than gymnosperms; many of the gymnosperm species investigated did not produce any n-alkanes. On average, deciduous angiosperms produce 200 times more n-alkanes than deciduous gymnosperms. Although differences between angiosperms and gymnosperms dominate the variance in n-alkane abundance, leaf life-span is also important, with higher n-alkane abundances in longer-lived leaves. n-Alkanol abundances covary with n-alkanes, but n-alkanoic acids have similar abundances across all plant groups. Isotopic fractionation between leaf tissue and individual alkanes ( ɛlipid) varies by as much as 10‰ among different chain lengths. Overall, ɛlipid values are slightly lower (-4.5‰) for angiosperm than for gymnosperm (-2.5‰) n-alkanes. Angiosperms commonly express slightly higher Δleaf (photosynthetic discrimination) relative to gymnosperms under similar growth conditions. As a result, angiosperm n-alkanes are expected to be generally 3-5‰ more depleted in 13C relative to gymnosperm alkanes for the same locality. Differences in n-alkane production indicate the biomarker record will largely (but not exclusively) reflect angiosperms if both groups were present, and also that evergreen plants will likely be overrepresented

  17. Study of the reaction between polyethylene glycol and epoxy resins using N,N-dimethylbenzylamine as catalyst

    International Nuclear Information System (INIS)

    Zacharuk, Mario; Coelho, Luiz A.F.; Pezzin, Sergio H.; Becker, Daniela

    2009-01-01

    In this work the use of N,N-dimethylbenzylamine as a catalyst of the reaction of polyethylene glycol (PEG) and epoxy resin (DGEBA) was studied. The reaction products were evaluated by infra-red spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and viscosity measurements. Samples cured with a polyamine-based hardener were also submitted to tensile tests and differential scanning calorimetry (DSC). The results of the viscosity analyses, FTIR and RMN ( 1 H) had confirmed the occurrence of the reaction between DGEBA epoxy groups and PEG hydroxyl groups in the presence of N, N-dimethylbenzylamine as catalyst, at 100 deg C. DSC analyses and tensile tests of cured systems showed that the reaction of DGEBA with PEG leads to a reduction of the Tg, generating a more flexible material. (author)

  18. Dynamic adsorption properties of n-alkyl glucopyranosides determine their ability to inhibit cytolysis mediated by acoustic cavitation

    OpenAIRE

    Sostaric, Joe Z.; Miyoshi, Norio; Cheng, Jason Y.; Riesz, Peter

    2008-01-01

    Suspensions of human leukemia (HL-60) cells readily undergo cytolysis when exposed ultrasound above the acoustic cavitation threshold. However, n-alkyl glucopyranosides (hexyl-,heptyl- and octyl-) completely inhibit ultrasound-induced (1057 kHz) cytolysis (Sostaric, et al., Free Radic. Biol. Med. 2005, 39, 1539–1548). The efficacy of protection from ultrasound-induced cytolysis was determined by the n-alkyl chain length of the glucopyranosides, indicating that protection efficacy depended on ...

  19. Synthesis and pharmacology of N-alkylated derivatives of the excitotoxin ibotenic acid

    DEFF Research Database (Denmark)

    Madsen, U; Dumpis, M A; Bräuner-Osborne, Hans

    1998-01-01

    Three amino-alkylated derivatives of the naturally occurring excitatory amino acid (EAA) receptor agonist ibotenic acid (Ibo) have been synthesized and tested pharmacologically. N-Methyl-Ibo (1a) and N-ethyl-Ibo (1b) were shown to be agonists at NMDA receptors (EC50 = 140 and 320 micro......-c and the potent NMDA agonist 2-amino-2-(3-hydroxy-5-methyl-4-isoxazolyl)acetic acid (AMAA) in order to elucidate the observed structure-activity data....

  20. Molecular structure, supramolecular organization and thermotropic phase behavior of N-acylglycine alkyl esters with matched acyl and alkyl chains.

    Science.gov (United States)

    Reddy, S Thirupathi; Swamy, Musti J

    2017-11-01

    N-Acylglycines (NAGs), the endogenous single-tailed lipids present in rat brain and other mammalian tissues, play significant roles in cell physiology and exhibit interesting pharmacological properties. In the present study, a homologous series of N-acylglycine alkyl esters (NAGEs) with matched chains were synthesized and characterized. Results of differential scanning calorimetric studies revealed that all NAGEs exhibit a single sharp phase transition and that the transition enthalpy and entropy show a linear dependence on the N-acyl and ester alkyl chain length. The structure of N-myristoylglycine myristyl ester (NMGME), solved by single-crystal X-ray diffraction, showed that the molecule adopts a linear geometry and revealed that the structure of N-myristoyl glycyl moiety in NMGME is identical to that in N-myristoylglycine. The molecules are packed in layers with the polar functional groups of the ester and amide functionalities located at the center of the layer. The crystal packing is stabilized by NH⋯O hydrogen bonds between the amide CO and NH groups of adjacent molecules as well as by CH⋯O hydrogen bonds between the amide carbonyl and the methylene CH adjacent to the ester carbonyl of neighboring molecules as well as between ester carbonyl and methylene group of the glycine moiety of adjacent molecules. Powder X-ray diffraction studies showed a linear dependence of the d-spacings on the acyl chain length, suggesting that all NAGEs adopt a structure similar to the packing exhibited in the crystal lattice of NMGME. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Synthetic Routes to N-9 Alkylated 8-Oxoguanines; Weak Inhibitors of the Human DNA Glycosylase OGG1

    Directory of Open Access Journals (Sweden)

    Tushar R. Mahajan

    2015-09-01

    Full Text Available The human 8-oxoguanine DNA glycosylase OGG1 is involved in base excision repair (BER, one of several DNA repair mechanisms that may counteract the effects of chemo- and radiation therapy for the treatment of cancer. We envisage that potent inhibitors of OGG1 may be found among the 9-alkyl-8-oxoguanines. Thus we explored synthetic routes to 8-oxoguanines and examined these as OGG1 inhibitors. The best reaction sequence started from 6-chloroguanine and involved N-9 alkylation, C-8 bromination, and finally simultaneous hydrolysis of both halides. Bromination before N-alkylation should only be considered when the N-substituent is not compatible with bromination conditions. The 8-oxoguanines were found to be weak inhibitors of OGG1. 6-Chloro-8-oxopurines, byproducts in the hydrolysis of 2,6-halopurines, turned out to be slightly better inhibitors than the corresponding 8-oxoguanines.

  2. Dopamine D(3) receptor antagonists. 1. Synthesis and structure-activity relationships of 5,6-dimethoxy-N-alkyl- and N-alkylaryl-substituted 2-aminoindans.

    Science.gov (United States)

    Haadsma-Svensson, S R; Cleek, K A; Dinh, D M; Duncan, J N; Haber, C L; Huff, R M; Lajiness, M E; Nichols, N F; Smith, M W; Svensson, K A; Zaya, M J; Carlsson, A; Lin, C H

    2001-12-20

    5,6-Dimethoxy-2-(N-dipropyl)-aminoindan (3, PNU-99194A) was found to be a selective dopamine D(3) receptor antagonist with potential antipsychotic properties in animal models. To investigate the effects of nitrogen substitution on structure-activity relationships, a series of 5,6-dimethoxy-N-alkyl- and N-alkylaryl-substituted 2-aminoindans were synthesized and evaluated in vitro for binding affinity and metabolic stability. The results indicate that substitution at the amine nitrogen of the 2-aminoindans is fairly limited to the di-N-propyl group in order to achieve selective D(3) antagonists. Thus, combinations of various alkyl groups were generally inactive at the D(3) receptor. Although substitution with an N-alkylaryl or N-alkylheteroaryl group yields compounds with potent D(3) binding affinity, the D(2) affinity is also enhanced, resulting in a less than 4-fold preference for the D(3) receptor site, and no improvements in metabolic stability were noted. A large-scale synthesis of the D(3) antagonist 3 has been developed that has proven to be reproducible with few purification steps. The improvements include the use of 3,4-dimethoxybenzaldehyde as a low-cost starting material to provide the desired 5,6-dimethoxy-1-indanone 5c in good overall yield (65%) and the formation of a soluble silyl oxime 17 that was reduced efficiently with BH(3).Me(2)S. The resulting amino alcohol was alkylated and then deoxygenated using a Lewis acid and Et(3)SiH to give the desired product 3 in good overall yield of ( approximately 65%) from the indanone 5c.

  3. Gas chromatography-mass spectrometric studies of O-alkyl O-2-(N,N-dialkylamino) ethyl alkylphosphonites(phosphonates) for chemical weapons convention verification.

    Science.gov (United States)

    Saeidian, Hamid; Babri, Mehran; Ramezani, Atefeh; Ashrafi, Davood; Sarabadani, Mansour; Naseri, Mohammad Taghi

    2013-01-01

    The electron ionization (EI) mass spectra of a series of O-alkyl O-2-(N,N-dialkylaminolethyl alkylphosphonites(phosphonates), which are precursors of nerve agents, were studied for Chemical Weapons Convention (CWC) verification. General El fragmentation pathways were constructed and discussed. Proposed fragment structures were confirmed through analyzing fragment ions of deuterated analogs and density functional theory (DFT) calculations. The observed fragment ions are due to different fragmentation pathways such as hydrogen and McLafferty+1 rearrangements, alkene, amine and alkoxy elimination by alpha- or beta-cleavage process. Fragment ions distinctly allow unequivocal identification of the interested compounds including those of isomeric compounds. The presence and abundance of fragment ions were found to depend on the size and structure of the alkyl group attached to nitrogen, phosphorus and oxygen atoms.

  4. Ionic conductivity of N-alkyl pyridinium halides mesophases

    International Nuclear Information System (INIS)

    Meftah, Ahmed

    1980-01-01

    The quasi anhydrous N-alkyl pyridinium halides undergo at a temperature T c a phase transition from a crystalline isolating state to a conducting mesophase (σ = 3.10 -2 Ω -1 cm -1 ). The transition temperature depends on the nature on counter-ion and on the aliphatic chain length. The present study is devoted to the N-alkyl pyridinium chlorides, bromides and iodides varying the number of carbon atoms in the chain from ten to twenty two. The transition temperatures T c were found to increase from 30 deg. C up to 110 deg. C by a step of 10 deg. C for two added carbon atoms in the chain. The electrical measurements have shown that the conductivity of the mesophases which is ionic in origin is due to a large mobility of counter-ions in hydrophilic parts. At high frequencies (F > 10 3 Hz) ionic conductivity predominates in the bulk and does not depend on frequency. At low frequencies (F 3 Hz) the most important are interface phenomena depending on the square root of inverse frequency (ω -1/2 ) and being due to an electronic exchange limited by diffusion velocity of counter-ions. The electrical conductivity depends weekly on the chain length and the mesophases textures. The most conducting mesophase is the optically isotropic. The conductivity increases with increasing water content of the system and decreases with increasing atomic number of counter-ion. The diffusion measurements by radioactive tracers confirm the ionic character of charge carriers although the diffusion factors obtained by this method are largely higher than the calculated ones from the conductivity values. (author) [fr

  5. 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.

  6. 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.

  7. L-β-N-methylamino-l-alanine (BMAA) nitrosation generates a cytotoxic DNA damaging alkylating agent: An unexplored mechanism for neurodegenerative disease.

    Science.gov (United States)

    Potjewyd, G; Day, P J; Shangula, S; Margison, G P; Povey, A C

    2017-03-01

    L-β-N-methylamino-l-alanine (BMAA) is a non-proteinic amino acid, that is neurotoxic in vitro and in animals, and is implicated in the causation of amyotrophic lateral sclerosis and parkinsonism-dementia complex (ALS-PDC) on Guam. Given that natural amino acids can be N-nitrosated to form toxic alkylating agents and the structural similarity of BMAA to other amino acids, our hypothesis was that N-nitrosation of BMAA might result in a toxic alkylating agent, providing a novel mechanistic hypothesis for BMAA action. We have chemically nitrosated BMAA with sodium nitrite to produce nitrosated BMAA (N-BMAA) which was shown to react with the alkyl-trapping agent, 4-(p-nitrobenzyl)pyridine, cause DNA strand breaks in vitro and was toxic to the human neuroblastoma cell line SH-SY5Y under conditions in which BMAA itself was minimally toxic. Our results indicate that N-BMAA is an alkylating agent and toxin suggesting a plausible and previously unrecognised mechanism for the neurotoxic effects of BMAA. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Densities, refractive indices, and viscosities of N,N-diethylethanol ammonium chloride–glycerol or –ethylene glycol deep eutectic solvents and their aqueous solutions

    International Nuclear Information System (INIS)

    Siongco, Kathrina R.; Leron, Rhoda B.; Li, Meng-Hui

    2013-01-01

    Highlights: • The densities, refractive indices, and viscosities of aqueous DES solutions were measured. • DES are made from N,N-diethylethanol ammonium chloride + glycerol or ethylene glycol. • The temperature studied was (298.15 to 343.15) K. • The measured data were reported as functions of temperature and composition. • The measured data were represented satisfactorily by the applied correlations. -- Abstract: In this work, we report new experimental data on density, ρ, refractive index, n D, and viscosity, η, of two deep eutectic solvents, N,N-diethylethanol ammonium chloride–glycerol (DEACG) and N,N-diethylethanol ammonium chloride–ethylene glycol (DEACEG), and their aqueous solutions, over the complete composition range, at temperatures from (298.15 to 343.15) K. Densities and viscosities were measured using the vibrating tube and the falling ball techniques, respectively, while the refractive index at the sodium D line was measured using an automatic refractometer. We aimed to represent the measured properties as a function of temperature and composition, and correlated them using the Redlich–Kister-type equation, for density, a polynomial function, for refractive index, and the Vogel–Fulcher–Tammann (VFT) equation, for viscosity

  9. Smiles Rearrangement Based Practical One-pot Synthesis of N-Alkyl/aryl-6-aminoquinolines from 6-Hydroxylquinoline

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Yongsheng; Vijaykumar, B. V. D.; Jang, Kiwan; Choi, Kyungmin; Shin, Dongsoo [Changwon National Univ., Changwon (Korea, Republic of); Zuo, Hua [Southwest Univ., Chongqing (Korea, Republic of); Yoon, Yongjin [Gyeongsang National Univ., Chinju (Korea, Republic of)

    2013-12-15

    The C-N coupling protocol reported herein represents a convenient and practical synthesis of N-alkyl/aryl-6-aminoquinolines in a three-step one-pot manner by simple addition of 6-hydroxyquinoline and N-alkyl/aryl-2-chloroacetamides with Cs{sub 2}CO{sub 3} or K{sub 2}CO{sub 3} in DMF at 150 .deg. C via Smiles rearrangement. An electron donating substituent on the nitrogen counterpart would accelerate the rearrangement process to achieve various anilines in good yields. We currently engaged in making a chemical library including multifarious N-substituted-6-aminoquinolines, to be used in the screening for specific AChEI activity. Furthermore, this work extends the scope of preparing different heterocyclic synthons in drug design for various biological activities. Aminoquinolines and their derivatives are important chemical entities that are widely used as pro-drugs and drugs due to their antimicrobial, cytotoxic and anti-malarial activities etc.

  10. Alkylation of amide linkages and cleavage of the C chain in the enzyme-activated-substrate inhibition of alpha-chymotrypsin with N-nitrosamides

    International Nuclear Information System (INIS)

    Donadio, S.; Perks, H.M.; Tsuchiya, K.; White, E.H.

    1985-01-01

    Active-site-directed N-nitrosamides inhibit alpha-chymotrypsin through an enzyme-activated-substrate mechanism. In this work, the activation results in the release--in the active site--of benzyl carbonium ions, which alkylate and inhibit the enzyme. The final ratio of benzyl groups to enzyme molecules is 1.0, but the alkyl groups are scattered over a number of sites. Reduction and alkylation of the inhibited enzyme generate peptides insoluble in most media. Guanidine hydrochloride at 6 M proved a good solvent, and its use as an eluant on G-75 Sephadex permitted separation of the peptides. In the case of 14 C-labeled enzyme, such an approach has shown that all of the alkylation occurs on the C chain of the enzyme, the chain of which the active site is constructed. Chemical modification of the peptides with ethylenediamine and N-[3-(dimethylamino)propyl]-N'-ethylcarbodiimide rendered them soluble in dilute acid, permitting high-performance liquid chromatographic separation. Model studies have shown that the benzyl carbonium ions are highly reactive, alkylating amide linkages at both oxygen and nitrogen. Chromatography of this mixture and also 13 C NMR spectroscopy of the intact inhibited enzyme have shown that three major N-alkylations have occurred. Tryptic digestion of the C chain of chymotrypsin, which contains all of the alkylation sites, provides evidence that the stable N sites are principally located between residue 216 and residue 230

  11. N-alkylvaline levels in globin as a new type of biomarker in risk assessment of alkylating agents.

    Science.gov (United States)

    Lewalter, J

    1996-01-01

    Adducts with the N-terminal valine of erythrocyte globin can serve as individual biomarkers of systemic and cellular exposure to endogenous and exogenous alkylating agents. In contrast to "detoxification markers" of this kind of mecapturic acids derived from alkylation of glutathione, individual N-alkylations of valine in globin reflect the formally "toxifying" part of the stress due to alkylating agents transformed into the ultimate toxicant. Thus, in contrast to the traditional methods of biological monitoring this approach enables a better evaluation of systemic exposure to reactive agents, adapted more sensibly to the exposure situation over the whole life span of erythrocytes, and it can serve as a specific biomarker of exposure for the purpose of health surveillance in occupational medicine. An individual evaluation of exposures in comparison with the range of corresponding background levels is discussed from the point of view of supplementary risk assessment in medical surveillance of occupationally exposed persons.

  12. Dynamic adsorption properties of n-alkyl glucopyranosides determine their ability to inhibit cytolysis mediated by acoustic cavitation.

    Science.gov (United States)

    Sostaric, Joe Z; Miyoshi, Norio; Cheng, Jason Y; Riesz, Peter

    2008-10-09

    Suspensions of human leukemia (HL-60) cells readily undergo cytolysis when exposed to ultrasound above the acoustic cavitation threshold. However, n-alkyl glucopyranosides (hexyl, heptyl, and octyl) completely inhibit ultrasound-induced (1057 kHz) cytolysis (Sostaric, et al. Free Radical Biol. Med. 2005, 39, 1539-1548). The efficacy of protection from ultrasound-induced cytolysis was determined by the n-alkyl chain length of the glucopyranosides, indicating that protection efficacy depended on adsorption of n-alkyl glucopyranosides to the gas/solution interface of cavitation bubbles and/or the lipid membrane of cells. The current study tests the hypothesis that "sonoprotection" (i.e., protection of cells from ultrasound-induced cytolysis) in vitro depends on the adsorption of glucopyranosides at the gas/solution interface of cavitation bubbles. To test this hypothesis, the effect of ultrasound frequency (from 42 kHz to 1 MHz) on the ability of a homologous series of n-alkyl glucopyranosides to protect cells from ultrasound-induced cytolysis was investigated. It is expected that ultrasound frequency will affect sonoprotection ability since the nature of the cavitation bubble field will change. This will affect the relative importance of the possible mechanisms for ultrasound-induced cytolysis. Additionally, ultrasound frequency will affect the lifetime and rate of change of the surface area of cavitation bubbles, hence the dynamically controlled adsorption of glucopyranosides to their surface. The data support the hypothesis that sonoprotection efficiency depends on the ability of glucopyranosides to adsorb at the gas/solution interface of cavitation bubbles.

  13. Inhibition of β-bungarotoxin binding to brain membranes by mast cell degranulating peptide, toxin I, and ethylene glycol bis(β-aminoethyl ether)-N,N,N',N'-tetraacetic acid

    International Nuclear Information System (INIS)

    Schmidt, R.R.; Betz, H.; Rehm, H.

    1988-01-01

    The presynaptically active snake venom neurotoxin β-bungarotoxin (β-Butx) is known to affect neurotransmitter release by binding to a subtype of voltage-activated K + channels. Here the authors show that mast cell degranulating (MCD) peptide from bee venom inhibits the binding of 125 I-labeled β-Butx to chick and rat brain membranes with apparent K/sub i/ values of 180 nM and 1100 nM, respectively. The mechanisms of inhibition of MCD peptide is noncompetitive, as is inhibition of 125 I-β-Butx binding by the protease inhibitor homologue from mamba venom, toxin I. β-Butx and its binding antagonists thus bind to different sites of the same membrane protein. Removal of Ca 2+ by ethylene glycol bis(β-aminoethyl ether)-N,N,N',N'-tetraacetic acid inhibits the binding of 125 I-β-Butx by lowering its affinity to brain membranes

  14. Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Dae Won; Oh, Sun Wha; Park, Hea Jung; Yoon, Ung Chan [Pusan National University, Busan (Korea, Republic of); Kim, Dong Uk [Daegu National University of Education, Daegu (Korea, Republic of); Xue, Jin Ying [Harbin Normal University, Harbin (China); Mariano, Patrick S. [University of New Mexico, Albuquerque (United States)

    2010-09-15

    Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and γ-hydrogen abstraction pathways.

  15. Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

    International Nuclear Information System (INIS)

    Cho, Dae Won; Oh, Sun Wha; Park, Hea Jung; Yoon, Ung Chan; Kim, Dong Uk; Xue, Jin Ying; Mariano, Patrick S.

    2010-01-01

    Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and γ-hydrogen abstraction pathways

  16. (Vapour + liquid) equilibria in the ternary system (acetonitrile + n-propanol + ethylene glycol) and corresponding binary systems at 101.3 kPa

    International Nuclear Information System (INIS)

    Qian, Guo-fei; Liu, Wen; Wang, Li-tao; Wang, Dao-cai; Song, Hang

    2013-01-01

    Highlights: • We adopted a new extractive solvent “ethylene glycol” to separate the mixture. • We measured the VLE data of binary system n-propanol + ethylene glycol. • We reinforce the VLE data of binary system acetonitrile + ethylene glycol. • We predicted the VLE data for the ternary system successfully. -- Abstract: Experimental isobaric (Vapour + liquid) equilibrium (VLE) data at 101.3 kPa were determined for three binary systems, viz. {acetonitrile (1) + n-propanol (2)}, {acetonitrile (1) + ethylene glycol (3)} and {n-propanol (2) + ethylene glycol (3)} and for one ternary system {acetonitrile (1) + n-propanol (2) + ethylene glycol (3)}. The measurements were performed using an improved Rose equilibrium still. The VLE data of the binary systems passed thermodynamic consistency tests and were correlated by Wilson and NRTL models. Good results were achieved. The phase behaviour of the ternary system was predicted directly by the parameters of two models obtained from the experimental binary results. The results showed an excellent agreement with experimental values

  17. Study on selective separation of uranium(VI) by new N,N-dialkyl carboxy-amides

    International Nuclear Information System (INIS)

    Suzuki, Shinichi; Sugo, Yumi; Kimura, Takaumi; Yaita, Tsuyoshi

    2007-01-01

    The Feasibility study (FS) on commercialized FR cycle systems has been carried out in Japan. In this Feasibility study, 'Advanced Aqueous' reprocessing was designed as a new reprocessing concept to enhance nuclear non-proliferation by recycling U, Pu and minor actinides (MA) with some fission products (FP). The crystallization and U(VI)/TRU(transuranics) co-extraction technique have been selected as candidate technique in the 'Advanced Aqueous' reprocessing. In JAEA, the result of Feasibility study was received and Fast Reactor Cycle Technology Development Project (FaCT) was started. In the nuclear spent fuel reprocessing, FBR spent fuels will coexist with LWR spent fuels for several decades until FBR cycle begins to operate. For the treatment of LWR spent fuels, high decontamination factor for FP was required for U(VI) storage, and solvent extraction technique was selected in the nuclear fuel treatment. In our laboratory, N,N-di-alkyl carboxy-amides have been developed as extractant based on solvent extraction technique for one of a back-up technology of 'Advanced Aqueous' reprocessing in FBR spent fuel treatments. N,N-di-alkyl carboxy-amides were noted as one of the alternative extractant of tri-butylphosphate (TBP) in the field of nuclear fuel reprocessing. Extraction behavior of U(VI) and Pu(IV) with N,N-di-alkyl carboxy-amides was almost similar to those with TBP. N,N-di-alkyl carboxy-amides have some advantages, namely, their complete incinerability (CHON principle) and high stability for hydrolysis and radiolysis. Their main degradation products are carboxylic acids and secondary amines which hardly affect the separation of U(VI) and Pu(IV) from fission products. Further, the synthesis of N,N-di-alkyl carboxy-amides was relatively easy with reaction of carboxylic chloride and secondary amine. The main purpose of this solvent extraction technique using N,N-di-alkyl carboxy-amides is selective separation of Uranium(VI) with branched N,N-di-alkyl carboxy

  18. Critical effects of alkyl chain length on fibril structures in benzene-trans(RR)- or (SS)-N,N'-alkanoyl-1,2-diaminocyclohexane gels.

    Science.gov (United States)

    Sato, Hisako; Nakae, Takahiro; Morimoto, Kazuya; Tamura, Kenji

    2012-02-28

    Vibrational circular dichroism (VCD) spectra were recorded on benzene-d(6) gels formed by chiral low molecular mass gelators (LMGs), trans(RR)- or trans(SS)-N,N'-alkanoyl-1,2-diaminocyclohexane (denoted by RR-C(n) or SS-C(n), respectively; n = the number of carbon atoms in an introduced alkanoyl group). Attention was focused on the effects of alkyl chain length on the structures of the gels. When n was changed from 6 to 12, the signs of the coupled peaks around 1550 cm(-1) in the VCD spectra, which were assigned to the symmetric and asymmetric C=O stretching vibrations from the higher to lower wavenumber, respectively, critically depended on the alkyl chain length. In the case of RR-C(n), for example, the signs of the couplet were plus and minus for n = 8, 9, 10 and 12, while the signs of the same couplet were reversed for n = 6 and 7. The conformations of LMGs in fibrils were determined by comparing the observed IR and VCD spectra with those calculated for a monomeric molecule. The observed reversal of signs in the C=O couplet was rationalized in terms of the different modes of hydrogen bonding. In the case of C(8), C(9), C(10) and C(12), gelator molecules were stacked with their cyclohexyl rings in parallel, forming double anti-parallel chains of intermolecular hydrogen bonds using two pairs of >NH and >C=O groups. In case of C(6) and C(7), gelator molecules were stacked through a single chain of intermolecular hydrogen bonds using a pair of >NH and >C=O groups. The remaining pair of >NH and >C=O groups formed an intramolecular hydrogen bond.

  19. Definitive characterization of human thymine glycol N-glycosylase activity

    International Nuclear Information System (INIS)

    Higgins, S.A.; Frenkel, K.; Cummings, A.; Teebor, G.W.

    1987-01-01

    An N-glycosylase activity that released cis-[ 3 H]-5,6-dihydroxy-5,6-dihydrothymine (thymine glycol, TG) from chemically oxidized poly(dA-[ 3 H]dT) was unambiguously characterized both in extracts of HeLa cells and in purified Escherichia coli endonuclease III. This was accomplished by use of a microderivatization procedure that quantitatively converted cis-TG to 5-hydroxy-5-methylhydantoin (HMH). The reaction products were analyzed by high-pressure liquid chromatography before and after derivation by using cis-[ 14 C]TG and [ 14 C]HMH, which had been independently synthesized, as reference compounds. This technique facilitated construction of a v/[E]/sub t/ plot for the enzyme activity in HeLa cells, permitting estimation of its specific activity. The results obtained prove the existence of both human and bacterial N-glycosylase activities that effect removal of TG from DNA

  20. 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

  1. Inhibition of. beta. -bungarotoxin binding to brain membranes by mast cell degranulating peptide, toxin I, and ethylene glycol bis(. beta. -aminoethyl ether)-N,N,N',N'-tetraacetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, R.R.; Betz, H.; Rehm, H.

    1988-02-09

    The presynaptically active snake venom neurotoxin ..beta..-bungarotoxin (..beta..-Butx) is known to affect neurotransmitter release by binding to a subtype of voltage-activated K/sup +/ channels. Here the authors show that mast cell degranulating (MCD) peptide from bee venom inhibits the binding of /sup 125/I-labeled ..beta..-Butx to chick and rat brain membranes with apparent K/sub i/ values of 180 nM and 1100 nM, respectively. The mechanisms of inhibition of MCD peptide is noncompetitive, as is inhibition of /sup 125/I-..beta..-Butx binding by the protease inhibitor homologue from mamba venom, toxin I. ..beta..-Butx and its binding antagonists thus bind to different sites of the same membrane protein. Removal of Ca/sup 2 +/ by ethylene glycol bis(..beta..-aminoethyl ether)-N,N,N',N'-tetraacetic acid inhibits the binding of /sup 125/I-..beta..-Butx by lowering its affinity to brain membranes.

  2. The chemotherapeutic potential of glycol alkyl ethers: structure-activity studies of nine compounds in a Fischer-rat leukemia transplant model.

    Science.gov (United States)

    Dieter, M P; Jameson, C W; Maronpot, R R; Langenbach, R; Braun, A G

    1990-01-01

    Structure-activity studies with nine glycol alkyl ethers were conducted with a cellular leukemia transplant model in male Fischer rats. This in vivo assay measures the effects of chemical treatment on neoplastic progression in transplant recipients. Chemicals were given ad libitum in the drinking water simultaneously with the transplants and continued throughout the study. In all, 20 million leukemic cells were injected s.c. into syngeneic rats, which after 60 days resulted in a 10-fold increase in relative spleen weights, a 100-fold increase in white blood cell counts, and a 50% reduction in red blood cell (RBC) indices and platelet counts. At this interval, ethylene glycol monomethyl ether (2-ME) given at a dose of 2.5 mg/ml in the drinking water completely eliminated all clinical, morphological, and histopathological evidence of leukemia, whereas the same dose of ethylene glycol monoethyl ether (2-EE) reduced these responses by about 50%. Seven of the glycol ethers were ineffective as anti-leukemic agents, including ethylene glycol, the monopropyl, monobutyl, and monophenyl ethylene glycol ethers, diethylene glycol, and the monomethyl and monoethyl diethylene glycol ethers. 2-ME more than doubled the latency period of leukemia expression and extended survival for at least 210 days. A minimal effective dose for a 50% reduction in the leukemic responses was 0.25 mg/ml 2-ME in the drinking water (15 mg/kg body weight), whereas a 10-fold higher dose of 2-EE was required for equivalent antileukemic activity. In addition, the in vitro exposure of a leukemic spleen mononuclear cell culture to 2-ME caused a dose- and time-dependent reduction in the number of leukemia cells after a single exposure to 1-100 microM concentrations, whereas the 2-ME metabolite, 2-methoxyacetic acid, was only half as effective. The two glycol alkyl ethers with demonstrable anti-leukemic activity, 2-ME and 2-EE, also exhibited a favorable efficacy-to-toxicity ratio and should be considered for

  3. Homogeneous synthesis of cellulose acrylate-g-poly (n-alkyl acrylate) solid-solid phase change materials via free radical polymerization.

    Science.gov (United States)

    Qian, Yong-Qiang; Han, Na; Bo, Yi-Wen; Tan, Lin-Li; Zhang, Long-Fei; Zhang, Xing-Xiang

    2018-08-01

    A novel solid-solid phase change materials, namely, cellulose acrylate-g-poly (n-alkyl acrylate) (CA-g-PAn) (n = 14, 16 and 18) were successfully synthesized by free radical polymerization in N, N-dimethylacetamide (DMAc). The successful grafting was confirmed by fourier transform infrared spectra (FT-IR) and nuclear magnetic resonance (NMR). The properties of the CA-g-PAn copolymers were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The phase change temperatures and the melting enthalpies of CA-g-PAn copolymers are in the range of 10.1-53.2 °C and 15-95 J/g, respectively. It can be adjusted by the contents of poly (n-alkyl acrylate) and the length of alkyl side-chain. The thermal resistant temperatures of CA-g-PA14, 16 and 18 copolymers are 308 °C, 292 °C and 273 °C, respectively. It show that all of grafting materials exhibit good thermal stability and shape stability. Therefore, it is expected to be applied in the cellulose-based thermos-regulating field. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. Thermodynamic calculation of simultaneous reactions of n-butane isomerization and isobutane alkylation with ethylene

    Energy Technology Data Exchange (ETDEWEB)

    Batyrshin, N.N.; Beresneva, L.D.; Sidorov, V.A.

    1981-08-01

    Industrial production of ethylene alkylate has gained further development in connection with worldwide ecological problems and the planned changeover of automobile transport to unleaded gasolines, but the scale of production is still substantially less than that of sulfuric acid or hydrogen fluoride alkylates. This is due both to the instability of market prices for ethylene and the shortage of isobutane - a raw material for these large-tonnage production processes and for the synthetic rubber industry. The latter difficulty can be overcome by combining processes of isomerization of n-butane and alkylation of the resultant isobutane with ethylene in a single reaction unit. The possibility of combining these reactions using AlCl/sub 3/-based catalysts has been pointed out previously but in the literature there are no theoretical developments of technology or thermodynamic substantiation of a combined process. We have made a thermodynamic calculation of the consecutive (series-parallel) reactions of isomerization and alkylation with the goal of determining suitable technological conditions for carrying them out simultaneously and establishing the expected equilibrium yields of target products and the compositions of the reaction mixture.

  5. Extraction of gold(I) cyanide by the methyl tri-n-alkyl ammonium chloride

    International Nuclear Information System (INIS)

    Zhang Tianxi; Yan Wenfei; Wu Jinguang

    2000-01-01

    The solvent extraction of KAu(CN) 2 from alkaline solution by the tri-n-alkyl ammonium chloride (N263) using 198 Au tracer has been investigated. The effects of various parameters, such as gold (I) concentration in aqueous phase, cosolvent, phase ratio on the extraction of gold (I) are studied. The results demonstrate that almost all of gold (I) in aqueous phase can be extracted into the organic phase. Water concentration decreases significantly with the increase of gold (I) concentration in the organic phase. No water molecule could be involved in the extraction of gold (I)

  6. Synthesis and Cytotoxicity Evaluation of 13-n-Alkyl Berberine and Palmatine Analogues as Anticancer Agents

    Directory of Open Access Journals (Sweden)

    Lei Zhang

    2012-09-01

    Full Text Available By introducing long carbon-chain alkyl groups at the C-13 position of berberine and palmatine, 13-n-hexyl/13-n-octyl berberine and palmatine chloride analogues 4ad were synthesized and examined by MTT assays for cytotoxic activity in seven human cancer cell lines (7701QGY, SMMC7721, HepG2, CEM, CEM/VCR, KIII, Lewis, yielding IC50 values of 0.02 ± 0.01–13.58 ± 2.84 μM. 13-n-Octyl palmatine (compound 4d gave the most potent inhibitor activity, with an IC50 of 0.02 ± 0.01 μM for SMMC7721. In all cases, the 13-n-alkyl berberine and palmatine analogues 4ad were more cytotoxic than berberine and palmatine. In addition, compounds 4ad also exhibited more potent cytotoxicity than berberine and palmatine in mice with S180 sarcoma xenografted in vivo. The primary screening results indicated that the 13-n-hexyl/13-n-octyl berberine and palmatine analogues might be valuable source for new potent anticancer drug candidates.

  7. Cyanobacterial Lactate Oxidases Serve as Essential Partners in N2 Fixation and Evolved into Photorespiratory Glycolate Oxidases in Plants[w

    Science.gov (United States)

    Hackenberg, Claudia; Kern, Ramona; Hüge, Jan; Stal, Lucas J.; Tsuji, Yoshinori; Kopka, Joachim; Shiraiwa, Yoshihiro; Bauwe, Hermann; Hagemann, Martin

    2011-01-01

    Glycolate oxidase (GOX) is an essential enzyme involved in photorespiratory metabolism in plants. In cyanobacteria and green algae, the corresponding reaction is catalyzed by glycolate dehydrogenases (GlcD). The genomes of N2-fixing cyanobacteria, such as Nostoc PCC 7120 and green algae, appear to harbor genes for both GlcD and GOX proteins. The GOX-like proteins from Nostoc (No-LOX) and from Chlamydomonas reinhardtii showed high l-lactate oxidase (LOX) and low GOX activities, whereas glycolate was the preferred substrate of the phylogenetically related At-GOX2 from Arabidopsis thaliana. Changing the active site of No-LOX to that of At-GOX2 by site-specific mutagenesis reversed the LOX/GOX activity ratio of No-LOX. Despite its low GOX activity, No-LOX overexpression decreased the accumulation of toxic glycolate in a cyanobacterial photorespiratory mutant and restored its ability to grow in air. A LOX-deficient Nostoc mutant grew normally in nitrate-containing medium but died under N2-fixing conditions. Cultivation under low oxygen rescued this lethal phenotype, indicating that N2 fixation was more sensitive to O2 in the Δlox Nostoc mutant than in the wild type. We propose that LOX primarily serves as an O2-scavenging enzyme to protect nitrogenase in extant N2-fixing cyanobacteria, whereas in plants it has evolved into GOX, responsible for glycolate oxidation during photorespiration. PMID:21828292

  8. Synthesis and structure-activity relationship of N-alkyl Gly-boro-Pro inhibitors of DPP4, FAP, and DPP7.

    Science.gov (United States)

    Hu, Yi; Ma, Lifu; Wu, Min; Wong, Melissa S; Li, Bei; Corral, Sergio; Yu, Zhizhou; Nomanbhoy, Tyzoon; Alemayehu, Senaiet; Fuller, Stacy R; Rosenblum, Jonathan S; Rozenkrants, Natasha; Minimo, Lauro C; Ripka, William C; Szardenings, Anna K; Kozarich, John W; Shreder, Kevin R

    2005-10-01

    The structure-activity relationship of various N-alkyl Gly-boro-Pro derivatives against three dipeptidyl peptidases (DPPs) was studied. In a series of N-cycloalkyl analogs, DPP4 and fibroblast activation protein-alpha (FAP) optimally preferred N-cycloheptyl whereas DPP7 tolerated even larger cycloalkyl rings. Gly alpha-carbon derivatization of N-cyclohexyl or N-(2-adamantyl) Gly-boro-Pro resulted in a significant decrease in potency against all the three DPPs.

  9. Supramolecular recognition control of polyethylene glycol modified N-doped graphene quantum dots: tunable selectivity for alkali and alkaline-earth metal ions.

    Science.gov (United States)

    Yang, Siwei; Sun, Jing; Zhu, Chong; He, Peng; Peng, Zheng; Ding, Guqiao

    2016-02-07

    The graphene quantum dot based fluorescent probe community needs unambiguous evidence about the control on the ion selectivity. In this paper, polyethylene glycol modified N-doped graphene quantum dots (PN-GQDs) were synthesized by alkylation reaction between graphene quantum dots and organic halides. We demonstrate the tunable selectivity and sensitivity by controlling the supramolecular recognition through the length and the end group size of the polyether chain on PN-GQDs. The relationship formulae between the selectivity/detection limit and polyether chains are experimentally deduced. The polyether chain length determines the interaction between the PN-GQDs and ions with different ratios of charge to radius, which in turn leads to a good selectivity control. Meanwhile the detection limit shows an exponential growth with the size of end groups of the polyether chain. The PN-GQDs can be used as ultrasensitive and selective fluorescent probes for Li(+), Na(+), K(+), Mg(2+), Ca(2+) and Sr(2+), respectively.

  10. Investigation of Unanticipated Alkylation at the N(π) Position of a Histidyl Residue Under Mitsunobu Conditions and Synthesis of Orthogonally Protected Histidine Analogues

    Science.gov (United States)

    Qian, Wenjian; Liu, Fa; Burke, Terrence R.

    2011-01-01

    We had previously reported that Mitsunobu-based introduction of alkyl substituents onto the imidazole N(π)-position of a key histidine residue in phosphothreonine-containing peptides can impart high binding affinity against the polo box domain of polo like kinase 1. Our current paper investigates the mechanism leading to this N(π)-alkylation and provides synthetic methodologies that permit the facile synthesis of histidine N(π)-modified peptides. These agents represent new and potentially important tools for biological studies. PMID:21950469

  11. Phase behavior of polystyrene-block-poly(n-alkyl methacrylate) copolymers investigated by SANS, SAXS, and temperature-dependent FTIR spectroscopy

    International Nuclear Information System (INIS)

    Ryu, Du Yeol; Lee, Dong Hyun; Kim, Hye Jeong; Kim, Jin Kon; Jung, Y. M.; Kim, S. B.

    2005-01-01

    The phase behavior of polystyrene-block -poly(n-alkyl methacrylate) (PS-PnAMA) copolymer were investigated by Small-Angle Neutron Scattering (SANS), Small-Angle X-ray Scattering (SAXS), and temperature-dependent Fourier Transform Infrared (FTIR) spectroscopy. Also, the effect of hydrostatic pressure on the transition temperatures was studied by using SANS with pressure controller. Phase behavior was changed significantly with the change of alkyl number (n). For n = 2∼4, only Lower Disordered-to-Order Tansition (LDOT) was observed, whereas the Ordered-to-Disorder (ODT) was found for n =1 and n =6. Finally, a closed-loop phase behavior was found for n =5. Using incompressible random phase approximation, the segmental interactions (χ) between PS and PnAMA for all n values were obtained. The standard expression of χ = a + b/T (where T is the absolute temperature) was valid only for n =1 and n =6. But, this relationship was not valid any more for n = 2∼4. For n =5, a more complex behavior of χ upon temperature was observed. We investigated, by using temperature-dependent FTIR, the mechanism why as closed loop phase behavior was observed for n =5. Interestingly, the conformation of C-C-O stretching band of the PnPMA chain (n=5) (and thus the directional enthapic gain) was different in the two disordered states, and, therefore, the driving force to induce the disordered state at lower temperatures was different from that at higher temperatures

  12. Cyanobacterial lactate oxidases serve as essential partners in N2-fixation and evolved into photorespiratory glycolate oxidases in plants.

    NARCIS (Netherlands)

    Hackenberg, C.; Kern, R.; Hüge, J; Stal, L.J.; Tsuji, Y.; Kopka, J.; Shiraiwa, Y.; Bauwe, H.; Hagemann, M.

    2011-01-01

    Glycolate oxidase (GOX) is an essential enzyme involved in photorespiratory metabolism in plants. In cyanobacteria and green algae, the corresponding reaction is catalyzed by glycolate dehydrogenases (GlcD). The genomes of N2-fixing cyanobacteria, such as Nostoc PCC 7120 and green algae, appear to

  13. Cyanobacterial lactate oxidases serve as essential partners of N2-fixation and evolved to photorespiratory glycolate oxidases in plants

    NARCIS (Netherlands)

    Hackenberg, C.; Kern, R.; Hüge, J.; Stal, L.J.; Tsuji, Y.; Kopka, J.; Shiraiwa, Y.; Bauwe, H.; Hagemann, M.

    2011-01-01

    Glycolate oxidase (GOX) is an essential enzyme involved in photorespiratory metabolism in plants. In cyanobacteria and green algae, the corresponding reaction is catalyzed by glycolate dehydrogenases (GlcD). The genomes of N2-fixing cyanobacteria, such as Nostoc PCC 7120 and green algae, appear to

  14. Iridium-catalyzed direct synthesis of tryptamine derivatives from indoles: exploiting n-protected β-amino alcohols as alkylating agents.

    Science.gov (United States)

    Bartolucci, Silvia; Mari, Michele; Bedini, Annalida; Piersanti, Giovanni; Spadoni, Gilberto

    2015-03-20

    The selective C3-alkylation of indoles with N-protected ethanolamines involving the "borrowing hydrogen" strategy is described. This method provides convenient and sustainable access to several tryptamine derivatives.

  15. Surface mobility and structural transitions of poly(n-alkyl methacrylates) probed by dynamic contact angle measurements

    NARCIS (Netherlands)

    van Damme, H.S.; Hogt, A.H.; Feijen, Jan

    1986-01-01

    Dynamic contact angles and contact-angle hysteresis of a series of poly(n-alkyl methacrylates) (PAMA) were investigated using the Wilhelmy plate technique. The mobility of polymer surface chains, segments, and side groups affected the measured contact angles and their hysteresis. A model is

  16. Molecular and component volumes of N,N-dimethyl-N-alkylamine N-oxides in DOPC bilayers

    DEFF Research Database (Denmark)

    Belicka, Michal; Klacsova, Maria; Karlovska, Janka

    2014-01-01

    The volumetric properties of fluid bilayers formed of dioleoylphosphatidylcholine (DOPC) with incorporated N ,N -dimethyl-N -alkylamine N -oxides (Cn NO, n = 6, 10–18 is the even number of carbons in alkyl chain) were studied by vibrating tube densitometry in the temperature interval from 20 °C...... to 50 °C. It was found that the DOPC and Cn NO mixed ideally in the investigated composition range and hence the molecular volumes of DOPC (V DOPC) and incorporated Cn NO (V CnNO) were constant and additive within error limits. From the temperature dependencies of the molecular volumes of DOPC and Cn...... NO their coefficients of isobaric thermal expansivities in the investigated temperature interval were obtained. The V CnNO volumes of Cn NO incorporated into DOPC bilayers showed linear dependencies on the Cn NO alkyl chain length at all measured temperatures. This allowed to calculate the component volume of the Cn...

  17. Molecular Mobility of n-Ethylene Glycol Dimethacrylate Glass Formers Upon Free Radical Polymerization

    Science.gov (United States)

    Plaza, Maria Teresa Viciosa

    the highly crosslinked network originating a clear phase separation (Chapter 4). Knowing that phase separation occurs upon the polymerization reaction, the next step was the separate study of the isothermal polymerization of di-, tri- and tetra- EGDMA, giving special attention to the changes in the unreacted monomer's mobility. With the restrictions imposed by the formation of chemical bonds, the alpha and beta relaxations detected in bulk monomers tend to vanish in the newly formed polymer network, while the secondary gamma relaxation kept almost unaffected. The high sensitivity of the beta relaxation to low contents of unreacted monomer was used as a probe of the reaction's advance. These different behaviours shown under polymerization allowed the assignment of the molecular origin of the secondary processes: the gamma relaxation associated to the ethylene glycol twisting motions, while the rotation of the carboxyl groups seems to be related to the beta relaxation (Chapter 5). In what concerns the polymer itself, an additional secondary process was found, betapol, namely in poly-DEGDMA, poly-TrEGDMA and poly-TeEGDMA, with similar characteristics to the one found in poly( n-alkyl methacrylates). This process was confirmed and well characterized when the copolymerization of TrEGDMA with methyl acrylate (MA) was studied varying its composition (Chapter 6). Finally, EGDMA, the smaller monomer of this family, apart from vitrifying, also shows a high tendency to crystallize by coming from both melt and glassy states. The formation of a rigid phase affects mainly the alpha-process whose intensity decreases without suffering significant changes in the temperature dependence of the characteristic relaxation time. On the other hand, the secondary beta process becomes very well defined and narrowest, indicating a more homogeneous environment around the local-motions (Chapter 7).

  18. Globular, Sponge-like to Layer-like Morphological Transition in 1-n-Alkyl-3-methylimidazolium Octylsulfate Ionic Liquid Homologous Series.

    Science.gov (United States)

    Kapoor, Utkarsh; Shah, Jindal K

    2018-01-11

    Segregation of polar and nonpolar domains in ionic liquids for which either the cation or anion is responsible for inducing nonpolar domains is well understood. On the other hand, information regarding the nanoscale heterogeneities originating due to the presence of nonpolar content on both the ions is rudimentary at this point. The present contribution is aimed at addressing this question and focuses on a molecular dynamics simulation study to probe nanoscale structural and aggregation features of the 1-n-alkyl-3-methylimidazolium [C n mim] octylsulfate [C 8 SO 4 ] ionic liquid homologous series (n = 2, 4, 6, 8, 10, and 12). The objective of this work is to determine the effect of increasing alkyl chain length in the cation on nonpolar domain formation, especially when the alkyl chain lengths from both the ions participate in defining such domains. The results indicate that all the ionic liquids form nonpolar domains, morphology of which gradually changes from globular, sponge-like to layer-like structure with increase in the cationic alkyl chain length. The length of the nonpolar domains calculated from the total structure factor for [C 10 mim][C 8 SO 4 ] is considerably higher than that reported for other imidazolium-based ionic liquid containing smaller anions. The structure factor for [C 12 mim][C 8 SO 4 ] ionic liquid contains multiple intermediate peaks separating the charge alternation peak and pre-peak, which points to nonpolar domains of varying lengths, an observation that remains to be validated. Analysis of the heterogeneous order parameters and orientational correlation functions of the alkyl chains further suggests an increase in the spatial heterogeneity and long-range order along the homologous series. The origin of rich diversity of structures obtained by introducing nonpolar content on both the ions is discussed.

  19. Synthesis of multiple deuterated N-n-propyl-norapomorphine N-(d/sub 7/) and derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Yigong; Trainor, T.M.; Vouros, Paul; Neumeyer, J.L.

    1988-03-01

    Novapomorphine has been labelled using n-propyl iodide through alkylation of norcodeine followed by a multistep route which also affords the related deuterated analogs N-n-propylnorapocodeine, the prodrug 10,11-methylenedioxy-NPA and 10,11-dimethoxy-NPA.

  20. Formaldehyde and tobacco smoke as alkylating agents: the formation of N-methylenvaline in pathologists and in plastic laminate workers.

    Science.gov (United States)

    Bono, Roberto; Romanazzi, Valeria; Pirro, Valentina; Degan, Raffaella; Pignata, Cristina; Suppo, Elisa; Pazzi, Marco; Vincenti, Marco

    2012-01-01

    Aim of this study was to investigate the relationships between the concentration of formaldehyde in air and the alkylation of hemoglobin to form a terminal N-methylenvaline residue in three occupationally exposed groups: a) technicians of pathology wards, b) workers of the plastic laminates industry, and c) a control group. All subjects recruited in this study were also tested on their smoking habits. Formaldehyde adsorbed on passive air samplers was quantified by HPLC with UV detection (360 nm), cotinine was quantified by GC-MS. Terminal hemoglobin N-methylenvaline was determined by treating globine under reducing conditions with pentafluorophenyl isothiocyanate to yield a derivative, subsequently detected by GC-MS. One-way analysis of variance was performed to compare among the three groups the biomarkers considered in this study. For air-FA and N-methylenvaline a difference between the three groups was detected (p alkylation to form N-methylenvaline molecular adduct in two occupationally exposed groups of subjects considered in the present study. In comparison with occupational exposition, tobacco smoke proved to have a minor impact on the formation of N-methylenvaline molecular adduct. Copyright © 2011 Elsevier B.V. All rights reserved.

  1. 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...

  2. Effect of DNA sequence, ionic strength, and cationic DNA affinity binders on the methylation of DNA by N-methyl-N-nitrosourea

    International Nuclear Information System (INIS)

    Wurdeman, R.L.; Gold, B.

    1988-01-01

    DNA alkylation by N-alkyl-N-nitrosoureas is generally accepted to be responsible for their mutagenic, carcinogenic, and antineoplastic activities. The exact nature of the ultimate alkylating intermediate is still controversial, with a variety of species having been nominated. The sequence specificity for DNA alkylation by simple N-alkyl-N-nitrosoureas has not been reported, although such information is basic in understanding the specific point mutations induced by these compounds in oncogene targets. These two points are addressed by using N-methyl-N-nitrosourea methylation of a 576 base-pair 32 P-end-labeled DNA restriction fragment and high-resolution polyacrylamide sequencing gels. This method provides information on the formation of N 7 -methylguanine, by the generation of single-strand breaks upon exposure to piperidine

  3. S - and N-alkylating agents diminish the fluorescence of fluorescent dye-stained DNA.

    Science.gov (United States)

    Giesche, Robert; John, Harald; Kehe, Kai; Schmidt, Annette; Popp, Tanja; Balzuweit, Frank; Thiermann, Horst; Gudermann, Thomas; Steinritz, Dirk

    2017-01-25

    Sulfur mustard (SM), a chemical warfare agent, causes DNA alkylation, which is believed to be the main cause of its toxicity. SM DNA adducts are commonly used to verify exposure to this vesicant. However, the required analytical state-of-the-art mass-spectrometry methods are complex, use delicate instruments, are not mobile, and require laboratory infrastructure that is most likely not available in conflict zones. Attempts have thus been made to develop rapid detection methods that can be used in the field. The analysis of SM DNA adducts (HETE-G) by immunodetection is a convenient and suitable method. For a diagnostic assessment, HETE-G levels must be determined in relation to the total DNA in the sample. Total DNA can be easily visualized by the use of fluorescent DNA dyes. This study examines whether SM and related compounds affect total DNA staining, an issue that has not been investigated before. After pure DNA was extracted from human keratinocytes (HaCaT cells), DNA was exposed to different S- and N-alkylating agents. Our experiments revealed a significant, dose-dependent decrease in the fluorescence signal of fluorescent dye-stained DNA after exposure to alkylating agents. After mass spectrometry and additional fluorescence measurements ruled out covalent modifications of ethidium bromide (EthBr) by SM, we assumed that DNA crosslinks caused DNA condensation and thereby impaired access of the fluorescent dyes to the DNA. DNA digestion by restriction enzymes restored fluorescence, a fact that strengthened our hypothesis. However, monofunctional agents, which are unable to crosslink DNA, also decreased the fluorescence signal. In subsequent experiments, we demonstrated that protons produced during DNA alkylation caused a pH decrease that was found responsible for the reduction in fluorescence. The use of an appropriate buffer system eliminated the adverse effect of alkylating agents on DNA staining with fluorescent dyes. An appropriate buffer system is thus

  4. Deposition of radiation energy in solids as visualized by the distribution, structure and properties of alkyl radicals in γ-irradiated n-alkane single crystals

    International Nuclear Information System (INIS)

    Gillbro, T.; Lund, A.

    1976-01-01

    This paper summarizes results obtained earlier from ESR studies of γ-irradiated n-alkane single crystals. It also contains some new experimental results that serve to give a more complete picture of the deposition of radiation energy in solid alkanes. The experiments performed with solid n-alkanes have thus far provided structural data that permit the nature and even the conformation of alkyl radicals to be clearly understood. Two types of radical exist namely, one where the unpaired electron is located next to the end methyl group and one with the unpaired electron in the interior of the chain. The first type has a conformation which differs from that of the undamaged molecule. Microwave saturation data show that there is a difference in relaxation properties of these radicals which can be understood in terms of a difference in mobility. Relative yield measurements give the distribution of isomeric alkyl, the result differing from that obtained using product analysis in liquids. For protiated n-alkanes n-alkyl is lacking and the 2-alkyl concentration is higher than expected. For deuterated n-alkanes the ESR spectrum is mainly that of radicals with the unpaired electron located in the interior of the carbon chain. This isotope effect is again contrary to observations in liquid n-alkanes. The broad lines observed in protiated alkanes irradiated at 77 K and deuterated alkanes irradiated at 4.2 K are not believed to arise from strong spin-spin interactions. They are thought instead to arise from distorted crystal and radical structures relating to the damaged regions of the crystals. (Auth.)

  5. Fabrication and tribological properties of self-assembled monolayer of n-alkyltrimethoxysilane on silicon: Effect of SAM alkyl chain length

    International Nuclear Information System (INIS)

    Huo, Lixia; Du, Pengcheng; Zhou, Hui; Zhang, Kaifeng; Liu, Peng

    2017-01-01

    Highlights: • n-Alkyltrimethoxysilanes with various chain lengths were self-assembled on silicon. • Effect of alkyl chain lengths (C6, C12, or C18) on the SAMs was investigated. • Surface roughness of the SAMs decreased with increasing the alkyl chain lengths. • The C 12 -SAM possessed superior friction reduction and wear resistance. - Abstract: It is well known that the self-assembled organic molecules on a solid surface exhibit the friction-reducing performance. However, the effect of the molecular size of the self-assembled organic molecules has not been established. In the present work, self-assembled monolayers (SAMs) of n-alkyltrimethoxysilanes with different alkyl chain lengths (C 6 , C 12 , or C 18 ) were fabricated on silicon substrate. The water contact angles of the SAMs increased from 26.8° of the hydroxylated silicon substrate to near 60° after self-assembly. The atomic force microscopy (AFM) analysis results showed that the mean roughness (R a ) of the SAMs decreased with increasing the alkyl chain length. The tribological properties of the SAMs sliding against Al 2 O 3 ball were evaluated on an UMT-2 tribometer, and the worn surfaces of the samples were analyzed by means of Nano Scratch Tester and surface profilometry. It was found that lowest friction coefficient and smallest width of wear were achieved with the SAMs of C 12 alkyl chain (C 12 -SAM). The superior friction reduction and wear resistance of the SAMs in comparison with the bare silicon substrate are attributed to good adhesion of the self-assembled films to the substrate, especially the C 12 -SAM with desirable alkyl chain length.

  6. Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes

    Science.gov (United States)

    Elangovan, Saravanakumar; Neumann, Jacob; Sortais, Jean-Baptiste; Junge, Kathrin; Darcel, Christophe; Beller, Matthias

    2016-01-01

    Borrowing hydrogen (or hydrogen autotransfer) reactions represent straightforward and sustainable C–N bond-forming processes. In general, precious metal-based catalysts are employed for this effective transformation. In recent years, the use of earth abundant and cheap non-noble metal catalysts for this process attracted considerable attention in the scientific community. Here we show that the selective N-alkylation of amines with alcohols can be catalysed by defined PNP manganese pincer complexes. A variety of substituted anilines are monoalkylated with different (hetero)aromatic and aliphatic alcohols even in the presence of other sensitive reducible functional groups. As a special highlight, we report the chemoselective monomethylation of primary amines using methanol under mild conditions. PMID:27708259

  7. Some features of formation and dissolution of a series of Pu(IV) and Zr alkyl and butyl alkyl phosphates in the system TBP -n-dodecane - nitric acid - water

    International Nuclear Information System (INIS)

    Markov, G.S.; Moshkov, M.M.; Kokina, S.A.

    1990-01-01

    The formation and composition of salts produced on interaction of a series of alkyl- and butylalkylphosphoric acids having alkyl radical chain lengths from C 4 to C 1 0 with Pu(IV) and Zr in organic and aqueous phases of the system TBP - n-dodecane -nitric acid - water were studied. The composition of compounds was found to depend on the conditions of their formation, defined first of all by the HNO 3 concentration in aqueous and organic phases. (author) 12 refs.; 4 figs.; 1 tab

  8. Fabrication and tribological properties of self-assembled monolayer of n-alkyltrimethoxysilane on silicon: Effect of SAM alkyl chain length

    Energy Technology Data Exchange (ETDEWEB)

    Huo, Lixia [National Key Laboratory of Science and Technology on Vacuum Technology and Physics, Lanzhou Institute of Physics, Lanzhou, Gansu 730010 (China); Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Lanzhou University, Gansu 730000 (China); Du, Pengcheng [Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Lanzhou University, Gansu 730000 (China); Zhou, Hui; Zhang, Kaifeng [National Key Laboratory of Science and Technology on Vacuum Technology and Physics, Lanzhou Institute of Physics, Lanzhou, Gansu 730010 (China); Liu, Peng, E-mail: pliu@lzu.edu.cn [Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Lanzhou University, Gansu 730000 (China)

    2017-02-28

    Highlights: • n-Alkyltrimethoxysilanes with various chain lengths were self-assembled on silicon. • Effect of alkyl chain lengths (C6, C12, or C18) on the SAMs was investigated. • Surface roughness of the SAMs decreased with increasing the alkyl chain lengths. • The C{sub 12}-SAM possessed superior friction reduction and wear resistance. - Abstract: It is well known that the self-assembled organic molecules on a solid surface exhibit the friction-reducing performance. However, the effect of the molecular size of the self-assembled organic molecules has not been established. In the present work, self-assembled monolayers (SAMs) of n-alkyltrimethoxysilanes with different alkyl chain lengths (C{sub 6}, C{sub 12}, or C{sub 18}) were fabricated on silicon substrate. The water contact angles of the SAMs increased from 26.8° of the hydroxylated silicon substrate to near 60° after self-assembly. The atomic force microscopy (AFM) analysis results showed that the mean roughness (R{sub a}) of the SAMs decreased with increasing the alkyl chain length. The tribological properties of the SAMs sliding against Al{sub 2}O{sub 3} ball were evaluated on an UMT-2 tribometer, and the worn surfaces of the samples were analyzed by means of Nano Scratch Tester and surface profilometry. It was found that lowest friction coefficient and smallest width of wear were achieved with the SAMs of C{sub 12} alkyl chain (C{sub 12}-SAM). The superior friction reduction and wear resistance of the SAMs in comparison with the bare silicon substrate are attributed to good adhesion of the self-assembled films to the substrate, especially the C{sub 12}-SAM with desirable alkyl chain length.

  9. Ab initio Study of Alkyl-oxonium Cations CnH2n+1OH2+, n=1,2,3,4

    Directory of Open Access Journals (Sweden)

    Francis F. Muguet

    2004-08-01

    Full Text Available ABSTRACT: Within the framework of the itinerant radical model, the solvated electron in liquid alcohols is understood as an itinerant alkyl-oxonium ROH2. radical. As a first step in the investigation of those radicals, this study deals with the optimization of related ROH2+ alky-oxonium cations: CnH2n+1OH2+,n=1,2,3,4. The structures were optimized at the MP2/6-31G**++ level with the help of the GAMESS ab initio package. Optimized structures are reported for the following cations: MethylOxonium; EthylOxonium; 1-PropylOxonium, 2-PropylOxonium and 1-ButylOxonium, 2-ButylOxonium, IsoButylOxonium, TertButylOxonium. Optimized geometries are displayed with the help of the ChemApp Java applet. Vibrational frequencies and ZPEs have been computed, and visual depictions of expected experimental IR spectra have been simulated with the help of Lorentzian functions.

  10. 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.

  11. In vivo detection of central dopaminergic processes: studies with 1-C-11-dopa and C-11-labelled N-alkylated ADTN derivatives

    International Nuclear Information System (INIS)

    Werf, J.F. van der; Molen, H.D. Beerling-Van der; Paans, A.M.J.; Wiegman, T.; Korf, J.; Vaalburg, W.

    1982-01-01

    N-alkyl derivatives of 2-amino-6,7-dihydroxy-1,2,3,4-tetrahydro-naphthalene were labelled with 11 C by methylation with methyl iodide. They are dopamine agonists and have been found to bind, with high affinity, to dopamine receptors, in vitro and in vivo, after intracerebral administration. These compounds can pass the blood-brain barrier while the non-alkyl compound (ADTN) cannot. (U.K.)

  12. 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.

  13. 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,

  14. Investigating Spectrum of Biological Activity of 4- and 5-Chloro-2-hydroxy-N-[2-(arylamino-1-alkyl-2-oxoethyl]benzamides

    Directory of Open Access Journals (Sweden)

    Jirina Stolarikova

    2011-03-01

    Full Text Available In this study, a series of twenty-two 5-chloro-2-hydroxy-N-[2-(arylamino-1-alkyl-2-oxoethyl]benzamides and ten 4-chloro-2-hydroxy-N-[2-(arylamino-1-alkyl-2-oxoethyl]benzamides is described. The compounds were analyzed using RP-HPLC to determine lipophilicity. Primary in vitro screening of the synthesized compounds was performed against mycobacterial, bacterial and fungal strains. They were also evaluated for their activity related to the inhibition of photosynthetic electron transport (PET in spinach (Spinacia oleracea L. chloroplasts. The compounds showed biological activity comparable with or higher than the standards isoniazid, fluconazole, penicillin G or ciprofloxacin. For all the compounds, the relationships between the lipophilicity and the chemical structure of the studied compounds as well as their structure-activity relationships are discussed.

  15. Design and synthesis of BODIPY sensitizers with long alkyl chains tethered to N-carbazole and their application for dye sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Cheema, Hammad [Polymer and Color Chemistry Program, North Carolina State University, Raleigh, NC, 27695 (United States); Younts, Robert; Gautam, Bhoj; Gundogdu, Kenan [Physics Department, North Carolina State University, Raleigh, NC, 27695 (United States); El-Shafei, Ahmed, E-mail: Ahmed_El-Shafei@ncsu.edu [Polymer and Color Chemistry Program, North Carolina State University, Raleigh, NC, 27695 (United States)

    2016-12-01

    In this study, three boron dipyrromethenes (BODIPY) dyes with extended conjugation and electron donating carbazole groups with different alkyl chain lengths tethered to N-carbazole were synthesized and characterized for dye-sensitized solar cells. The goal was to study the effect of different alkyl chain lengths on dye aggregation at TiO{sub 2} surface. The proposed molecular strategy resulted in BODIPY dyes which showed interesting electronic absorption and fluorescence properties. It was observed that intramolecular energy transfer decreases with the increase in alkyl chain length possibly due to induced changes in molecular geometry caused by long alkyl chains. Additionally, interface analysis by impedance spectroscopy in comparison to N719 sensitized TiO{sub 2} solar cell showed significant charge transport related losses (Nyquist plot) most likely due to impedance resulted from aggregated BODIPY dye on TiO{sub 2} surface. Femtosecond transient absorption studies showed the loss of excited electrons by recombination with oxidized ground state of the sensitizers. - Highlights: • BODIPY dyes with carbazole electron donating groups are characterized. • Photophysics is discussed based on transient and steady state spectroscopy results. • Impedance spectroscopy found huge charge transport related losses on TiO{sub 2.}.

  16. Design and synthesis of BODIPY sensitizers with long alkyl chains tethered to N-carbazole and their application for dye sensitized solar cells

    International Nuclear Information System (INIS)

    Cheema, Hammad; Younts, Robert; Gautam, Bhoj; Gundogdu, Kenan; El-Shafei, Ahmed

    2016-01-01

    In this study, three boron dipyrromethenes (BODIPY) dyes with extended conjugation and electron donating carbazole groups with different alkyl chain lengths tethered to N-carbazole were synthesized and characterized for dye-sensitized solar cells. The goal was to study the effect of different alkyl chain lengths on dye aggregation at TiO_2 surface. The proposed molecular strategy resulted in BODIPY dyes which showed interesting electronic absorption and fluorescence properties. It was observed that intramolecular energy transfer decreases with the increase in alkyl chain length possibly due to induced changes in molecular geometry caused by long alkyl chains. Additionally, interface analysis by impedance spectroscopy in comparison to N719 sensitized TiO_2 solar cell showed significant charge transport related losses (Nyquist plot) most likely due to impedance resulted from aggregated BODIPY dye on TiO_2 surface. Femtosecond transient absorption studies showed the loss of excited electrons by recombination with oxidized ground state of the sensitizers. - Highlights: • BODIPY dyes with carbazole electron donating groups are characterized. • Photophysics is discussed based on transient and steady state spectroscopy results. • Impedance spectroscopy found huge charge transport related losses on TiO_2_.

  17. Order in poly(di-n-alkyl itaconate)s revealed by X-ray scattering experiments

    International Nuclear Information System (INIS)

    Holmes, P.F.; Arrighi, V.; McEwen, I.J.; Qian, H.; Terrill, N.J.

    2003-01-01

    The effects of both blending and copolymersiation on local ordering in poly(di-n-alkyl itaconate)s is investigated, as a function of side chain length, using small-angle X-ray scattering. Preliminary results show that local ordering is unaffected by blending in these immiscible materials, however copolymerisation leads to different behaviour. For short side chains the characteristic distance varies smoothly with copolymer composition, but with longer side chains the characteristic separations found for the homopolymers are observed, and these remain unchanged with composition

  18. Order in poly(di-n-alkyl itaconate)s revealed by X-ray scattering experiments

    Energy Technology Data Exchange (ETDEWEB)

    Holmes, P.F.; Arrighi, V. E-mail: v.arrighi@hw.ac.uk; McEwen, I.J.; Qian, H.; Terrill, N.J

    2003-01-01

    The effects of both blending and copolymersiation on local ordering in poly(di-n-alkyl itaconate)s is investigated, as a function of side chain length, using small-angle X-ray scattering. Preliminary results show that local ordering is unaffected by blending in these immiscible materials, however copolymerisation leads to different behaviour. For short side chains the characteristic distance varies smoothly with copolymer composition, but with longer side chains the characteristic separations found for the homopolymers are observed, and these remain unchanged with composition.

  19. Saturated amine oxides: Part 8. Hydroacridines: Part 27. Effects of N-oxidation and of N-quaternization on the 15N NMR chemical shifts of N-methylpiperidine-derived mono-, bi-, and tricycloaliphatic tertiary amines.

    Science.gov (United States)

    Potmischil, Francisc; Duddeck, Helmut; Nicolescu, Alina; Deleanu, Calin

    2007-03-01

    The (15)N chemical shifts of 13 N-methylpiperidine-derived mono-, bi- and tricycloaliphatic tertiary amines, their methiodides and their N-epimeric pairs of N-oxides were measured, and the contributions of specific structural parameters to the chemical shifts were determined by multilinear regression analysis. Within the examined compounds, the effects of N-oxidation upon the (15)N chemical shifts of the amines vary from +56 ppm to +90 ppm (deshielding), of which approx. +67.7 ppm is due to the inductive effect of the incoming N(+)--O(-) oxygen atom, whereas the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The effects of quaternization vary from -3.1 ppm to +29.3 ppm, of which approx. +8.9 ppm is due to the inductive effect of the incoming N(+)--CH(3) methyl group, and the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The shift effects of the C-alkyl substituents in the amines, the N-oxides and the methiodides are discussed. Copyright (c) 2007 John Wiley & Sons, Ltd.

  20. Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

    Science.gov (United States)

    Fu, Ming-Chen; Shang, Rui; Cheng, Wan-Min; Fu, Yao

    2015-07-27

    A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Synthesis, in vitro and in vivo studies, and molecular modeling of N-alkylated dextromethorphan derivatives as non-competitive inhibitors of α3β4 nicotinic acetylcholine receptor.

    Science.gov (United States)

    Jozwiak, Krzysztof; Targowska-Duda, Katarzyna M; Kaczor, Agnieszka A; Kozak, Joanna; Ligeza, Agnieszka; Szacon, Elzbieta; Wrobel, Tomasz M; Budzynska, Barbara; Biala, Grazyna; Fornal, Emilia; Poso, Antti; Wainer, Irving W; Matosiuk, Dariusz

    2014-12-15

    9 N-alkylated derivatives of dextromethorphan are synthesized and studied as non-competitive inhibitors of α3β4 nicotinic acetylcholine receptors (nAChRs). In vitro activity towards α3β4 nicotinic acetylcholine receptor is determined using a patch-clamp technique and is in the micromolar range. Homology modeling, molecular docking and molecular dynamics of ligand-receptor complexes in POPC membrane are used to find the mode of interactions of N-alkylated dextromethorphan derivatives with α3β4 nAChR. The compounds, similarly as dextromethorphan, interact with the middle portion of α3β4 nAChR ion channel. Finally, behavioral tests confirmed potential application of the studied compounds for the treatment of addiction. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Investigation of J-shaped dose-responses induced by exposure to the alkylating agent N-methyl-N-nitrosourea.

    Science.gov (United States)

    Chapman, Katherine E; Hoffmann, George R; Doak, Shareen H; Jenkins, Gareth J S

    2017-07-01

    Hormesis is defined as a biphasic dose-response where biological effects of low doses of a stressor demonstrate the opposite effect to high-dose effects of the same stressor. Hormetic, or J-shaped, dose-response relationships are relatively rarely observed in toxicology, resulting in a limited understanding and even some skepticism of the concept. Low dose-response studies for genotoxicity endpoints have been performed at Swansea University for over a decade. However, no statistically significant decreases below control genotoxicity levels have been detected until recently. A hormetic-style dose-response following a 24h exposure to the alkylating agent N-methyl-N-nitrosourea (MNU) was observed in a previous study for HPRT mutagenesis in the human lymphoblastoid cell line AHH-1. A second recent study demonstrated a J-shaped dose-response for the induction of micronuclei by MNU in a 24h treatment in a similar test system. Following mechanistic investigations, it was hypothesized that p53 may be responsible for the observed hormetic phenomenon. As genotoxic carcinogens are a major causative factor of many cancers, consideration of hormesis in carcinogenesis could be important in safety assessment. The data examined here offer possible insights into hormesis, including its estimated prevalence, underlying mechanisms and lack of generalizability. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Synthesis and inhibition of N-alkyl-2-(4-hydroxybut-2-ynyl) pyridinium bromide for mild steel in acid solution: Box–Behnken design optimization and mechanism probe

    International Nuclear Information System (INIS)

    Gu, Tianbin; Chen, Zhengjun; Jiang, Xiaohui; Zhou, Limei; Liao, Yunwen; Duan, Ming; Wang, Hu; Pu, Qiang

    2015-01-01

    Highlights: • N-alkyl-2-(4-hydroxybut-2-ynyl) pyridinium bromide prepared is new type of inhibitor. • Box–Behnken experiment design-based optimization model is used to maximize inhibition efficiency. • O-n adsorbing on X70 steel surface enhances the resistance of the steel to acid corrosion. • O-n acts as mix-type inhibitor to suppress both the anodic and cathodic reaction of X70 steel. - Abstract: N-alkyl-2-(4-hydroxybut-2-ynyl) pyridinium bromides (designated as O-n) was synthesized and characterized by 1 H and 13 C NMR and FTIR. Box–Behnken design (BBD)-based optimization was engaged to analyze the factors and the interaction of the factors that influence the corrosion inhibition efficiency of O-n for X70 steel. The inhibition mechanism was also probed by means of X-ray photoelectron spectroscopy (XPS), Tafel polarization and electrochemical impedance spectroscopy (EIS) techniques

  4. Effects of alkyl chain length and solvents on thermodynamic dissociation constants of the ionic liquids with one carboxyl group in the alkyl chain of imidazolium cations.

    Science.gov (United States)

    Chen, Yuehua; Wang, Huiyong; Wang, Jianji

    2014-05-01

    Thermodynamic dissociation constants of the Brønsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-Hückel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions.

  5. 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

  6. A convenient method to synthesize N-[3H]methyl-N-nitrosocarbamate transfer reagents

    International Nuclear Information System (INIS)

    Mehta, P.; Gold, B.; Konakahara, T.

    1992-01-01

    Activated N-alkyl-N-nitrosocarbamates are useful acyl transfer reagents that are employed in the synthesis of N-alkyl-N-nitrosoureas and related N-nitroso compounds. The nitrosourea products are of chemical and biological interest because they provide access to the in situ generation of highly reactive carbonium type intermediates, which, depending on their structure, can be powerful carcinogens or antineoplastic agents. The availability of radiolabeled nitrosoureas greatly facilitates studies on their chemical and biological activities. Generally, the synthesis of activated nitrosocarbamates requires condensation of radiolabeled alkylisocyanates with the appropriate alcohol. Because radiolabeled alkylisocyanates are not commercially available and/or troublesome to synthesize, we have developed an easy and economical method for preparing N-[ 3 H]methyl-N-nitrosocarbamates suitable for use as transfer reagents utilizing 1,2,2,2-tetrachloroethyl chloroformate and [ 3 H]methylamine hydrochloride as starting materials. (author)

  7. Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

    KAUST Repository

    Behenna, Douglas C.

    2011-12-18

    The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures. © 2012 Macmillan Publishers Limited. All rights reserved.

  8. Palladium(II)-catalyzed ortho-C-H arylation/alkylation of N-benzoyl α-amino ester derivatives.

    Science.gov (United States)

    Misal Castro, Luis C; Chatani, Naoto

    2014-04-14

    The palladium-catalyzed arylation/alkylation of ortho-C-H bonds in N-benzoyl α-amino ester derivatives is described. In such a system both the NH-amido and the CO2R groups in the α-amino ester moieties play a role in successful C-H activation/C-C bond formation using iodoaryl coupling partners. A wide variety of functional groups and electron-rich/deficient iodoarenes are tolerated. The yields obtained range from 20 to 95%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. A convenient method to synthesize N-[[sup 3]H]methyl-N-nitrosocarbamate transfer reagents

    Energy Technology Data Exchange (ETDEWEB)

    Mehta, P.; Gold, B. (Nebraska Univ., Omaha, NE (United States). Eppley Inst. for Research in Cancer); Konakahara, T. (Science Univiversity of Tokyo, Noda, Chiba (Japan). Faculty of Science and Technology)

    1992-11-01

    Activated N-alkyl-N-nitrosocarbamates are useful acyl transfer reagents that are employed in the synthesis of N-alkyl-N-nitrosoureas and related N-nitroso compounds. The nitrosourea products are of chemical and biological interest because they provide access to the in situ generation of highly reactive carbonium type intermediates, which, depending on their structure, can be powerful carcinogens or antineoplastic agents. The availability of radiolabeled nitrosoureas greatly facilitates studies on their chemical and biological activities. Generally, the synthesis of activated nitrosocarbamates requires condensation of radiolabeled alkylisocyanates with the appropriate alcohol. Because radiolabeled alkylisocyanates are not commercially available and/or troublesome to synthesize, we have developed an easy and economical method for preparing N-[[sup 3]H]methyl-N-nitrosocarbamates suitable for use as transfer reagents utilizing 1,2,2,2-tetrachloroethyl chloroformate and [[sup 3]H]methylamine hydrochloride as starting materials. (author).

  10. The corrosion inhibition of pure zinc in NH{sub 4}Cl aqueous solutions by N-Alkyl quaternary ammonium bromides

    Energy Technology Data Exchange (ETDEWEB)

    Branzoi, V.; Pilan, Luisa; Pruna, Alina [University ' Politehnica' of Bucharest, Faculty of Industrial Chemistry, Department of Physical Chemistry and Electrochemistry, Calea Grivitei, 132, Bucharest (Romania); Branzoi, Florina [Institute of Physical Chemistry Bucharest, Splaiul Independentei, 202, Bucharest (Romania)

    2004-07-01

    The corrosion of zinc in NH{sub 4}Cl solutions of different concentrations has been studied by potentiostatic and potentiodynamic methods and by impedance measurements. The results obtained in a potential region near the zinc corrosion potential showed that the cathodic reaction of hydrogen discharge does not fit a simple exponential law because the Tafel coefficient appears to be electrode potential dependent. At low overvoltages, in the anodic region, the corrosion process is under activation control, while at high overvoltages the process is under diffusion control. N-dodecyl, n-tetra-decyl and n-hexa-decyl ammonium bromides were used as organic inhibitors. The potentiostatic and potentiodynamic polarization studies and EIS measurements showed that each quaternary ammonium salt inhibits the corrosion of pure zinc in 1M NH{sub 4}Cl at 30 deg. C. The inhibition efficiency of the cations was discussed on the basis of Coulomb adsorption behaviour, using molecular coverage areas and polar substituent constant. The inhibition efficiency obtained from the corrosion currents was found to increase linearly with an increase in the molecular coverage area (A) for the series of tetra-alkyl ammonium ions. The efficiency of the cations increased with an increase in the positive charge of the nitrogen atom, which was due to the inductive effect of the electron-attractive groups. This effect on the Coulomb adsorption of the cations was, however, far less than that of the electron donating groups on the chemisorption of un-protonated amines. The steric requirements for the adsorption of the quaternaries with branched alkyl chains were small. Each organic compound exhibits Langmuir behaviour and inhibition increases with increasing alkyl chain length. This is attributed to cohesive Van der Waals forces between the positive head groups co-adsorbed with bromide ions on the positively charged zinc surface. (authors)

  11. Biosynthetic mechanism of glycolate in Chromatium, 4

    International Nuclear Information System (INIS)

    Asami, Sumio; Takabe, Tetsuo; Akazawa, Takashi

    1977-01-01

    The metabolic transformation of glycolate to glycine occurring in photosynthesizing cells of Chromatium was investigated by the radioisotopic technique and by amino acid analysis. By analyzing the distribution of radiocarbon upon feeding (1- 14 C) glycolate, (2- 14 C) glyoxylate and (1- 14 C) glycine to bacterial cells, it was demonstrated that glycolate is converted to glycine via glyoxylate, and both glycolate and glycine are excreted extracellularly. Although the formation of serine was barely detected by the above two techniques in both N 2 and O 2 atmospheres, it was found that 14 CO 2 is evolved quite markedly from both (1- 14 C) glycolate and (1- 14 C) glycine fed to the Chromatium cells. Analytical results of transient changes in amino acid compositions under atmospheric changes of N 2 →O 2 and by the addition of exogenous glycolate in N 2 confirm the notion that glycolate is converted to glycine. Acidic amino acids (glutamic acid and aspartic acid) appear to take part in glycine formation as amino donors. The formation of glycine from glycolate in a N 2 atmosphere suggests that an unknown glycolate dehydrogenation reaction may operate in the overall process. (auth.)

  12. Determination of the enthalpy of vaporization and prediction of surface tension for ionic liquid 1-alkyl-3-methylimidazolium propionate [C(n)mim][Pro](n = 4, 5, 6).

    Science.gov (United States)

    Tong, Jing; Yang, Hong-Xu; Liu, Ru-Jing; Li, Chi; Xia, Li-Xin; Yang, Jia-Zhen

    2014-11-13

    With the use of isothermogravimetrical analysis, the enthalpies of vaporization, Δ(g)lH(o)m(T(av)), at the average temperature, T(av) = 445.65 K, for the ionic liquids (ILs) 1-alkyl-3-methylimidazolium propionate [C(n)mim][Pro](n = 4, 5, 6) were determined. Using Verevkin's method, the difference of heat capacities between the vapor phase and the liquid phase, Δ(g)lC(p)(o)m, for [C(n)mim][Pro](n = 2, 3, 4, 5, 6), were calculated based on the statistical thermodynamics. Therefore, with the use of Δ(g)lC(p)(o)m, the values of Δ(g)lH(o)m(T(av)) were transformed into Δ(g)lH(o)m(298), 126.8, 130.3, and 136.5 for [C(n)mim][Pro](n = 4, 5, 6), respectively. In terms of the new scale of polarity for ILs, the order of the polarity of [C(n)mim][Pro](n = 2, 3, 4, 5, 6) was predicted, that is, the polarity decreases with increasing methylene. A new model of the relationship between the surface tension and the enthalpy of vaporization for aprotic ILs was put forward and used to predict the surface tension for [C(n)mim][Pro](n = 2, 3, 4, 5, 6) and others. The predicted surface tension for the ILs is in good agreement with the experimental one.

  13. 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.

  14. Interaction between N-methyl-N'-nitro-N-nitrosoguanidine and ultraviolet irradiation on Bacillus subtilis

    International Nuclear Information System (INIS)

    Lotareva, O.V.

    1990-01-01

    The mutagenic interaction between ultraviolet-irradiation and the alkylating agent N-methyl-N'-nitro-N-nitrosoguanidine was studied in a repaid-competent and excision-deficient strains of Bacillus subtilis. Pre-exposure to low doses of MNNG with following treatment by low and intermediate doses of UV-light increase the resistance of Bac. subtilis to UV-radiation (antagonistic effect). Probably pre-exposition with MNNG leads to induction of enzymes reparation, UV-damages being controlled with adaptive respons genes

  15. 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

  16. Effect of ionic strength and cationic DNA affinity binders on the DNA sequence selective alkylation of guanine N7-positions by nitrogen mustards

    International Nuclear Information System (INIS)

    Hartley, J.A.; Forrow, S.M.; Souhami, R.L.

    1990-01-01

    Large variations in alkylation intensities exist among guanines in a DNA sequence following treatment with chemotherapeutic alkylating agents such as nitrogen mustards, and the substituent attached to the reactive group can impose a distinct sequence preference for reaction. In order to understand further the structural and electrostatic factors which determine the sequence selectivity of alkylation reactions, the effect of increase ionic strength, the intercalator ethidium bromide, AT-specific minor groove binders distamycin A and netropsin, and the polyamine spermine on guanine N7-alkylation by L-phenylalanine mustard (L-Pam), uracil mustard (UM), and quinacrine mustard (QM) was investigated with a modification of the guanine-specific chemical cleavage technique for DNA sequencing. The result differed with both the nitrogen mustard and the cationic agent used. The effect, which resulted in both enhancement and suppression of alkylation sites, was most striking in the case of netropsin and distamycin A, which differed from each other. DNA footprinting indicated that selective binding to AT sequences in the minor groove of DNA can have long-range effects on the alkylation pattern of DNA in the major groove

  17. Inhibition of mutagenicity of N-methyl-N-nitrosourea by ellagic acid

    International Nuclear Information System (INIS)

    Dixit, R.; Gold, B.

    1986-01-01

    Ellagic acid (EA), a plant phenol present in a variety of soft fruits and vegetables, has been shown to possess antimutagenic and anticarcinogenic properties against bay region diol epoxide of polycyclic aromatic hydrocarbons. It is suggested that EA forms an adduct with diol epoxide of benzo (α) pyrene and thus prevents its binding to DNA. To better understand the mechanism of reactivity and inhibition properties of EA, we studied the effect of EA on mutagenicity and DNA alkylation of carcinogenic N-nitroso compounds, including N-methyl-N-nitrosourea (MNU) and N-methyl-N'-nitro-Nnitrosoguanidine (MNNG). MNU and MNNG are direct-acting mutagens requiring no metabolic activation. MNU showed a linear dose response between the concentration range of 50 to 400 nmole in an Ames/Salmonella mammalian mutagenicity test. EA at concentrations of 100, 250, 500, and 1,000 nmole inhibited the mutagenicity of MNU (400 nmole) by 3, 13, 45,and 60%, respectively. MNNG produced a nonlinear dose response in mutagenicity between the concentrations of 0.5 to 4 nmole. EA showed no appreciable inhibition of MNNG mutagenicity. Inhibition of DNA alkylation by MNU and MNNG by EA was studied by preincubating 50 to 200 nmole of EA with 200 nmole of ( 3 H)-MNU or ( 3 H)-MNNG for 10 min at 37 0 c, followed by incubation of polymer deoxyguanosine: deoxycytosine (poly dG:dC) (1 unit) overnight. EA caused no inhibitory effect on MNNG alkylation of poly dG:dC. Experiments on the effect of EA on alkylation of DNA and formation of nucleoside adducts by MNU are in progress, and results will be discussed with reference to MNU and MNNG mutagenicity and EA inhibition

  18. Synthesis, NMR spectral and antimicrobial studies of some [N-methyl-3t-alkyl-2r,6c-diarylpiperidin-4-ylidine]-5‧-methylthiazolidine-4-ones

    Science.gov (United States)

    Prakash, S. M.; Pandiarajan, K.; Kumar, S.

    2013-06-01

    Four new [N-methyl-3t-alkyl-2r,6c-diaryl-4-ylidine]-5'-methylthiozolidin-4-ones 9-12 have been synthesized by the condensation of N-methyl-3t-alkyl-2r,6c-diarylpiperidin-4-one thiosemicarbazones with ethyl 2-bromopropionate. These compounds have been characterized using FT-IR, 1H NMR, 13C NMR spectral techniques. HOMOCOSY, HSQC and HMBC spectral study have been done for [N-methyl-3,3-dimethyl-2r,6c-bis(p-methoxyphenyl)piperidin-4-ylidine]-5'-methylthiazolidine-4-one (12). Two geometrical isomers are formed in this reaction. In all these compounds piperidin rings adopt chair conformation. The rotation of the aryl group at C-2 is rather slow in 10-12. Antimicrobial activities have also been studied for 9-12. These compounds are active against all the tested bacterial and fungal strains.

  19. Preparation of Second Generation Ionic Liquids by Efficient Solvent-Free Alkylation of N-Heterocycles with Chloroalkanes

    Directory of Open Access Journals (Sweden)

    Werner Bonrath

    2008-01-01

    Full Text Available Non-conventional techniques, such as microwave (MW and power ultrasound(US as well as combined MW/US irradiation, have been used to promote one-potsynthesis of second-generation ionic liquids (ILs, cutting down reaction times andimproving yields. However, the use of chloroalkanes in the alkylation of N-heterocyclesrequires more drastic conditions if results are to match those obtained with more reactivealkyl halides. The present paper describes a series of MW- or MW/US-promoted ILpreparations starting from chloroalkanes and classic heterocycles (1-methylimidazole,pyridine and 1-methylpyrrolidine. When reactions were carried out under conventionalheating in an oil bath they required longer reaction times and gave poorer yields. 1H-NMRanalysis and ion-exchange chromatography showed that the present solventless procedureafforded ILs of satisfactory purity. The observed high yields (usually 70-98% isolated,and short reaction times showed that a straightforward access to ILs can be also achievedwith the use of alkyl chlorides, resulting in a considerable reduction of costs.

  20. N-Alkylated dinitrones from isosorbide as cross-linkers for unsaturated bio-based polyesters

    Directory of Open Access Journals (Sweden)

    Oliver Goerz

    2014-04-01

    Full Text Available Isosorbide was esterified with acryloyl chloride and crotonic acid yielding isosorbide diacrylate (9a and isosorbide dicrotonate (9b, which were reacted with benzaldehyde oxime in the presence of zinc(II iodide and boron triflouride etherate as catalysts to obtain N-alkylated dinitrones 10a/b. Poly(isosorbide itaconite -co- succinate 13 as a bio-based unsaturated polyester was cross-linked by a 1,3-dipolar cycloaddition with the received dinitrones 10a/b. The 1,3-dipolar cycloaddition led to a strong change of the mechanical properties which were investigated by rheological measurements. Nitrones derived from methyl acrylate (3a and methyl crotonate (3b were used as model systems and reacted with dimethyl itaconate to further characterize the 1,3-dipolaric cycloaddition.

  1. SYNTHESIS OF 4’-ALLYLBENZO-3N-CROWN-N ETHERS AND THEIR MASS SPECTRA COMPARED WITH BENZO-3N-CROWN-N ETHERS

    OpenAIRE

    Anwar, Chairil

    2008-01-01

    Synthesis of 4’allylbenzo-3n-crown-n ethers was carried out by reacting demethylated eugenol with α,ω-dichloro-oligoethylene glycols in 1-butanol under basic condition. The mass spectra of 4’allylbenzo-3n-crown-n and benzo-3n-crown-n were investigated by mass spectrometry using electron impact under 70 eV of electron bombardment as ionisation method. The difference between the group of compounds is only the present of allyl moiety as a side chain at the other side of benzene ring. The first g...

  2. 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

  3. Fabrication and tribological properties of self-assembled monolayer of n-alkyltrimethoxysilane on silicon: Effect of SAM alkyl chain length

    Science.gov (United States)

    Huo, Lixia; Du, Pengcheng; Zhou, Hui; Zhang, Kaifeng; Liu, Peng

    2017-02-01

    It is well known that the self-assembled organic molecules on a solid surface exhibit the friction-reducing performance. However, the effect of the molecular size of the self-assembled organic molecules has not been established. In the present work, self-assembled monolayers (SAMs) of n-alkyltrimethoxysilanes with different alkyl chain lengths (C6, C12, or C18) were fabricated on silicon substrate. The water contact angles of the SAMs increased from 26.8° of the hydroxylated silicon substrate to near 60° after self-assembly. The atomic force microscopy (AFM) analysis results showed that the mean roughness (Ra) of the SAMs decreased with increasing the alkyl chain length. The tribological properties of the SAMs sliding against Al2O3 ball were evaluated on an UMT-2 tribometer, and the worn surfaces of the samples were analyzed by means of Nano Scratch Tester and surface profilometry. It was found that lowest friction coefficient and smallest width of wear were achieved with the SAMs of C12 alkyl chain (C12-SAM). The superior friction reduction and wear resistance of the SAMs in comparison with the bare silicon substrate are attributed to good adhesion of the self-assembled films to the substrate, especially the C12-SAM with desirable alkyl chain length.

  4. Asymmetric Alkyl Side-Chain Engineering of Naphthalene Diimide-Based n-Type Polymers for Efficient All-Polymer Solar Cells.

    Science.gov (United States)

    Jia, Tao; Li, Zhenye; Ying, Lei; Jia, Jianchao; Fan, Baobing; Zhong, Wenkai; Pan, Feilong; He, Penghui; Chen, Junwu; Huang, Fei; Cao, Yong

    2018-02-13

    The design and synthesis of three n-type conjugated polymers based on a naphthalene diimide-thiophene skeleton are presented. The control polymer, PNDI-2HD, has two identical 2-hexyldecyl side chains, and the other polymers have different alkyl side chains; PNDI-EHDT has a 2-ethylhexyl and a 2-decyltetradecyl side chain, and PNDI-BOOD has a 2-butyloctyl and a 2-octyldodecyl side chain. These copolymers with different alkyl side chains exhibit higher melting and crystallization temperatures, and stronger aggregation in solution, than the control copolymer PNDI-2HD that has the same side chain. Polymer solar cells based on the electron-donating copolymer PTB7-Th and these novel copolymers exhibit nearly the same open-circuit voltage of 0.77 V. Devices based on the copolymer PNDI-BOOD with different side chains have a power-conversion efficiency of up to 6.89%, which is much higher than the 4.30% obtained with the symmetric PNDI-2HD. This improvement can be attributed to the improved charge-carrier mobility and the formation of favorable film morphology. These observations suggest that the molecular design strategy of incorporating different side chains can provide a new and promising approach to developing n-type conjugated polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Neighbor-Directed Histidine N (s)–Alkylation: A Route to Imidazolium-Containing Phosphopeptide Macrocycles-Biopolymers | Center for Cancer Research

    Science.gov (United States)

    Our recently discovered, selective, on-resin route to N(s)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In this, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. Interestingly, these cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation.

  6. N-methylpurine DNA glycosylase inhibits p53-mediated cell cycle arrest and coordinates with p53 to determine sensitivity to alkylating agents.

    Science.gov (United States)

    Song, Shanshan; Xing, Guichun; Yuan, Lin; Wang, Jian; Wang, Shan; Yin, Yuxin; Tian, Chunyan; He, Fuchu; Zhang, Lingqiang

    2012-08-01

    Alkylating agents induce genome-wide base damage, which is repaired mainly by N-methylpurine DNA glycosylase (MPG). An elevated expression of MPG in certain types of tumor cells confers higher sensitivity to alkylation agents because MPG-induced apurinic/apyrimidic (AP) sites trigger more strand breaks. However, the determinant of drug sensitivity or insensitivity still remains unclear. Here, we report that the p53 status coordinates with MPG to play a pivotal role in such process. MPG expression is positive in breast, lung and colon cancers (38.7%, 43.4% and 25.3%, respectively) but negative in all adjacent normal tissues. MPG directly binds to the tumor suppressor p53 and represses p53 activity in unstressed cells. The overexpression of MPG reduced, whereas depletion of MPG increased, the expression levels of pro-arrest gene downstream of p53 including p21, 14-3-3σ and Gadd45 but not proapoptotic ones. The N-terminal region of MPG was specifically required for the interaction with the DNA binding domain of p53. Upon DNA alkylation stress, in p53 wild-type tumor cells, p53 dissociated from MPG and induced cell growth arrest. Then, AP sites were repaired efficiently, which led to insensitivity to alkylating agents. By contrast, in p53-mutated cells, the AP sites were repaired with low efficacy. To our knowledge, this is the first direct evidence to show that a DNA repair enzyme functions as a selective regulator of p53, and these findings provide new insights into the functional linkage between MPG and p53 in cancer therapy.

  7. The monofunctional alkylating agent N-methyl-N'-nitro-N-nitrosoguanidine triggers apoptosis through p53-dependent and -independent pathways

    International Nuclear Information System (INIS)

    Kim, W.-J.; Beardsley, Dillon I.; Adamson, Aaron W.; Brown, Kevin D.

    2005-01-01

    One of the cellular responses to DNA damaging events is the activation of programmed cell death, also known as apoptosis. Apoptosis is an important process in limiting tumorigenesis by eliminating cells with damaged DNA. This view is reinforced by the finding that many genes with pro-apoptotic function are absent or altered in cancer cells. The tumor suppressor p53 performs a significant role in apoptotic signaling by controlling expression of a host of genes that have pro-apoptotic or pro-survival function. The S N 1 DNA alkylating agent N-methyl-N'-nitro-N-nitrosoguanidine (MNNG) triggers apoptosis and the upregulation/phosphorylation of p53; however, the mechanism(s) governing MNNG-induced cell death remain unresolved. We observed that the human lymphoblastoid cell line WTK-1, which expresses mutant p53, shows far less sensitivity to the cytotoxic effects of MNNG than the closely related, p53-normal line TK-6. Exposure to 15 μM MNNG (LD50 at 24 h in TK-6) leads to a kinetically slower rate of apoptotic onset in WTK-1 cells compared to TK-6 as judged by viability assays and approaches that directly examine apoptotic onset. Similar results were obtained using an unrelated human lymphoblastoid line B310 expressing reduced levels of p53 due to E6 oncoprotein expression, indicating that MNNG activates both p53-dependent and -independent apoptotic mechanisms and that these two mechanisms are discernable by the rates which they trigger apoptotic onset. We document, during time points corresponding to peak apoptotic response in TK6, WTK-1, B310, and B310-E6, that these cell lines show marked decreases in mitochondrial transmembrane potential and increases in cytochrome c within the cytosolic fraction of MNNG-treated cells. Consistent with these events, we observed that both caspase-9 and -3 are activated in our panel of lymphoblastoid cells after MNNG exposure. We also found, using both broad spectrum and specific inhibitors, that blocking caspase activity in TK-6 and

  8. Toxicokinetics of amphetamines: metabolism and toxicokinetic data of designer drugs, amphetamine, methamphetamine, and their N-alkyl derivatives.

    Science.gov (United States)

    Kraemer, Thomas; Maurer, Hans H

    2002-04-01

    This paper reviews the toxicokinetics of amphetamines. The designer drugs MDA (methylenedioxy-amphetamine, R,S-1-(3;,4;-methylenedioxyphenyl)2-propanamine), MDMA (R,S-methylenedioxymethamphetamine), and MDE (R,S-methylenedioxyethylamphetamine), as well as BDB (benzodioxolylbutanamine; R,S-1-(1;,3;-benzodioxol-5;-yl)-2-butanamine or R,S-1-(3;,4;-methylenedioxyphenyl)-2-butanamine) and MBDB (R,S-N-methyl-benzodioxolylbutanamine), were taken into consideration, as were the following N-alkylated amphetamine derivatives: amphetaminil, benzphetamine, clobenzorex, dimethylamphetamine, ethylamphetamine, famprofazone, fencamine, fenethylline, fenproporex, furfenorex, mefenorex, mesocarb, methamphetamine, prenylamine, and selegiline. English-language publications from 1995 to 2000 were reviewed. Papers describing identification of metabolites or cytochrome P450 isoenzyme-dependent metabolism and papers containing pharmacokinetic/toxicokinetic data were considered and summarized. The implications of toxicokinetics for toxicologic assessment or for interpretation in forensic cases are discussed.

  9. Poly(N-vinylimidazole/ethylene glycol dimethacrylate) for the purification and isolation of phenolic acids

    Energy Technology Data Exchange (ETDEWEB)

    Schemeth, Dieter; Noël, Jean-Christophe [Institute of Analytical Chemistry and Radiochemistry, Leopold-Franzens University of Innsbruck, CCB—Center of Chemistry and Biomedicine, Innrain 80-82, 6020 Innsbruck (Austria); Jakschitz, Thomas [Austrian Drug Screening Institute, Innrain 66a, 6020 Innsbruck (Austria); Rainer, Matthias, E-mail: m.rainer@uibk.ac.at [Institute of Analytical Chemistry and Radiochemistry, Leopold-Franzens University of Innsbruck, CCB—Center of Chemistry and Biomedicine, Innrain 80-82, 6020 Innsbruck (Austria); Tessadri, Richard [Institute of Mineralogy and Petrography, Leopold-Franzens University of Innsbruck, Innrain 52, 6020 Innsbruck (Austria); Huck, Christian W. [Institute of Analytical Chemistry and Radiochemistry, Leopold-Franzens University of Innsbruck, CCB—Center of Chemistry and Biomedicine, Innrain 80-82, 6020 Innsbruck (Austria); Bonn, Günther K. [Institute of Analytical Chemistry and Radiochemistry, Leopold-Franzens University of Innsbruck, CCB—Center of Chemistry and Biomedicine, Innrain 80-82, 6020 Innsbruck (Austria); Austrian Drug Screening Institute, Innrain 66a, 6020 Innsbruck (Austria)

    2015-07-23

    Highlights: • Free-radical polymerization of protonable vinylimidazole with EGMDA. • Polymer-optimization by maximum loading capacity of phenolic acids. • Performs better than SiO{sub 2} and Al{sub 2}O{sub 3} in normal phase mode using acetonitrile. • Performs equal or even better in anion-exchange mode compared to Oasis-MAX. • Efficient purification of phenolic compounds from crude extract. - Abstract: In this study we report the novel polymeric resin poly(N-vinyl imidazole/ethylene glycol dimethacrylate) for the purification and isolation of phenolic acids. The monomer to crosslinker ratio and the porogen composition were optimized for isolating phenolic acids diluted in acetonitrile at normal phase chromatography conditions, first. Acetonitrile serves as polar, aprotic solvent, dissolving phenolic acids but not interrupting interactions with the stationary phase due to the approved Hansen solubility parameters. The optimized resin demonstrated high loading capacities and adsorption abilities particularly for phenolic acids in both, acetonitrile and aqueous solutions. The adsorption behavior of aqueous standards can be attributed to ion exchange effects due to electrostatic interactions between protonated imidazole residues and deprotonated phenolic acids. Furthermore, adsorption experiments and subsequent curve fittings provide information of maximum loading capacities of single standards according to the Langmuir adsorption model. Recovery studies of the optimized polymer in the normal-phase and ion-exchange mode illustrate the powerful isolation properties for phenolic acids and are comparable or even better than typical, commercially available solid phase extraction materials. In order to prove the applicability, a highly complex extract of rosemary leaves was purified by poly(N-vinyl imidazole/ethylene glycol dimethacrylate) and the isolated compounds were identified using UHPLC–qTOF-MS.

  10. Structure and thermal performance of poly(ethylene glycol) alkyl ether (Brij)/porous silica (MCM-41) composites as shape-stabilized phase change materials

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lingjian; Shi, Haifeng, E-mail: haifeng.shi@gmail.com; Li, Weiwei; Han, Xu; Zhang, Xingxiang, E-mail: zhangpolyu@gmail.com

    2013-10-20

    Graphical abstract: The maximum 50 wt% Brij58 is loaded into the porous MCM-41 networks, and a new peak at 18.8° in XRD patterns confirmed the changes of crystallization behavior of Brij58 against the bulk one. - Highlights: • Poly(ethylene glycol) hexadecyl ether and poly(ethylene glycol) octadecyl ether have the good thermal storage ability. • New peak at 18.8° proved the coexisted confined crystallization and nucleation-induced crystallization. • Poly(ethylene glycol) alkyl ether/MCM-41 PCMs exhibits the good thermal stability. - Abstract: A series of shape-stabilized phase change materials (PCMs), composed of poly(ethylene glycol) hexadecyl ether (Brij58) or poly(ethylene glycol) octadecyl ether (Brij76) and porous silica (MCM-41), were prepared by the physical mixing method. The structure, thermal stability, energy storage ability and crystallization behavior of these composites are deeply investigated and characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD) and thermogravimetric analysis (TGA). Obvious phase transition behavior and energy storage capability are observed for these Brij/MCM-41 composites, and the heat storage efficiency increased with the weight of Brij component. New peak at 18.8° demonstrated that the pore size and the surface adsorption ability of MCM-41 affect the crystallization behavior of Brij molecule. The crystalline structure and energy storage ability of these Brij/MCM-41 composites are discussed based on the crystallization process.

  11. 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

  12. Synthesis and aggregation behavior of cyclic single- and double-tailed phosphate amphiphiles: A novel class of phosphate surfactants - Comparison with the aggregation behavior of sodium di-n-alkyl phosphates

    NARCIS (Netherlands)

    Buwalda, Rixt; Wagenaar, Anno; Engberts, Jan B.F.N.

    Herein we describe the synthesis and aggregation of the sodium salts of a series of 5-alkyl-2-hydroxy-1,3,2-dioxaphosphorinan-2-ones and 5,5-dialkyl-2-hydroxy-1,3,2-dioxaphosphorinan-2-ones in aqueous solution. The results are compared with properties of previously studied sodium di-n-alkyl

  13. Thermochemical properties of 4-N,N-dialkylamino-7-nitrobenzofurazan derivatives (alkyl = methyl, ethyl)

    International Nuclear Information System (INIS)

    Santos, Ana Filipa L.O.M.; Silva, Ana L.R.; Santiago, Otília D.F.; Gonçalves, Jorge M.; Pandey, Siddharth; Acree, W.E.; Ribeiro da Silva, Maria D.M.C.

    2014-01-01

    Highlights: • Combustion of 4-N,N-dialkylamino-7-nitrobenzofurazan by static bomb calorimetry. • Enthalpies of sublimation of 4-N,N-dialkylamino-7-nitrobenzofurazan. • Gaseous enthalpies of formation of 4-N,N-dialkylamino-7-nitrobenzofurazan. • Comparison between experimental and calculated (G3(MP2)//B3LYP approach) enthalpies of formation, in the gaseous phase. - Abstract: The standard (p° = 0.1 MPa) molar enthalpies of formation, at T = 298.15 K, in the gaseous phase, for two nitrobenzofurazan derivatives, 4-N,N-dimethylamino-7-nitrobenzofurazan (DMANBF) and 4-N,N-diethylamino-7-nitrobenzofurazan (DEANBF), were derived from their enthalpies of combustion and sublimation, obtained by static bomb calorimetry and by the Knudsen effusion technique, respectively. The results are compared with the corresponding data calculated by the G3(MP2)//B3LYP approach. Computationally, the molecular structures of both compounds were established and the geometrical parameters were determined at the B3LYP/6-31G(d) level of theory

  14. Prediction of the vapor pressure and vaporization enthalpy of 1-n-alkyl-3-methylimidazolium-bis-(trifluoromethanesulfonyl) amide ionic liquids.

    Science.gov (United States)

    Diedenhofen, Michael; Klamt, Andreas; Marsh, Kenneth; Schäfer, Ansgar

    2007-09-07

    The vapor pressures and vaporization enthalpies of a series of 1-n-alkyl-3-methylimidazolium-bis-(trifluoromethanesulfonyl) amide ionic liquids have been predicted with two different approaches using the COSMO-RS method and quantum chemical gas phase calculations. While the calculated enthalpies are in good agreement with the experimental data, COSMO-RS seems to underestimate the vapor pressures by roughly 0.5-4 log units dependent on the IL and approach used.

  15. The influence of tannin, pectin and polyethylene glycol on attachment of 15N-labelled rumen microorganisms to cellulose

    International Nuclear Information System (INIS)

    Bento, M.H.L.; Acamovic, T.; Makkar, H.P.S.

    2005-01-01

    The microbial attachment to and gas production from α-cellulose (Sigma; C-8002) without and with mimosa tannin (MT), pectin (P), polyethylene glycol (PEG), MT + P or MT + PEG, were investigated using the in vitro gas production system. Microbial attachment based on 15 N-labelled rumen microorganisms in the residual pellet after 24 h incubation was estimated, which varied from 113.7 to 161.3 μg 15 N per g residual pellet. C + MT had the lowest microbial attachment (P 2 = 0.84, P 15 N) in the residual pellet measured for C + MT (0.054) and C + MT + P (0.159), compared with the other treatments (0.32 for C; 0.34 for C + P; 0.33 for C + PEG; and 0.33 for C + MT + PEG). A MT concentration of 194 g/kg diet reduced microbial attachment and activity of rumen microorganisms in vitro. Polyethylene glycol counteracted the effect of MT on microbial attachment and activity. Pectin exerted a beneficial effect on attachment and fermentation in the initial hours of incubation. A ratio of pectin to MT of 1:1 improved microbial activity of C + MT but inhibition of microbial activity by MT remained at 24 h as indicated by the lower gas production of C + MT + P compared with the control. The results support the hypothesis that there is considerable interaction between tannins, microbes and non-starch-polysaccharides (NSP) in animal feeds and that these interactions may influence the functional ability of microbes in the gastrointestinal tract of animals. (author)

  16. Facile synthesis of thiol-polyethylene glycol functionalized magnetic titania nanomaterials for highly efficient enrichment of N-linked glycopeptides.

    Science.gov (United States)

    Wang, Jiawen; Yao, Jizong; Sun, Nianrong; Deng, Chunhui

    2017-08-25

    As protein N-glycosylation involved in generation and development of various cancers and diseases, it is vital to capture glycopeptides from complex biological samples for biomarker discovery. In this work, by taking advantages of the interaction between titania and thiol groups, thiol-polyethylene glycol functionalized magnetic titania nanomaterials (denoted as Fe 3 O 4 @TiO 2 @PEG) were firstly fabricated as an excellent hydrophilic adsorbent of N-linked glycopeptides. On one hand, the special interaction of titanium-thiol makes the synthetic manipulation simple and provides a new idea for design and synthesis of novel nanomaterials; on the other hand, strong magnetic response could realize rapid separation and the outstanding hydrophilicity of polyethylene glycol makes Fe 3 O 4 @TiO 2 @PEG nanomaterials show superior performance for glycopeptides enrichment with ultralow limit of detection (0.1mol/μL) and high selectivity (1:100). As a result, 24 and 33 glycopeptides enriched from HRP and IgG digests were identified respectively by MALDI-TOF MS, and 300 glycopeptides corresponding to 106 glycoproteins were recognized from merely 2μL human serum, indicating a great potential of Fe 3 O 4 @TiO 2 @PEG nanomaterials for glycoproteomic research. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Identification and Characterization of uvrA, a DNA Repair Gene of Deinococcus radiodurans

    Science.gov (United States)

    1996-01-01

    alkylating agents , such as methyl-N-nitro~N~nitrosoguanidine(MNNG), N-methyl-N~ nitrosourea (MNU), and to a lesser extent methyl methanesulfonate (MMS...6,4) Photoproduct 17 c. Thymine Glycols and Cross-links 17 3. Ionizing Radiation Damage " 17 4. Chemical Damage 20 a. Alkylating Agents .20 b. Cross...Examples of base damage induced by ionizing radiation 19 6. Nucleotide centers in DNA that are most reactive to alkylating agents 21 7. Schematic

  18. Ag@polypyrrole: A highly efficient nanocatalyst for the N-alkylation of amines using alcohols.

    Science.gov (United States)

    Mandi, Usha; Kundu, Sudipta K; Salam, Noor; Bhaumik, Asim; Islam, Sk Manirul

    2016-04-01

    We have synthesized Ag@polypyrrole nanomaterial by dispersing ultrafine silver nanoparticles (Ag NPs) over the organic polymer polypyrrole. The Ag@polypyrrole material has been characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), electron paramagnetic resonance (EPR), Fourier transform infrared (FT-IR), ultraviolet-visible absorption (UV-vis) and atomic adsorption spectroscopy (AAS), and thermogravimetric analysis (TGA). The XRD pattern suggested the cubic crystalline phase of Ag NPs in Ag@polypyrrole. TEM image analysis revealed that silver nanoparticles are highly dispersed in the polymer matrix. The Ag@polypyrrole acts as an efficient and versatile heterogeneous nanocatalyst in the N-alkylation of amines using alcohols. The catalyst can be easily prepared, highly robust and reused several times without decrease in its catalytic activity. Copyright © 2016 Elsevier Inc. All rights reserved.

  19. Influence of bulky substituents on the regioselective group-transfer reactions of diorganozinc compounds with N,N'-bis(2,6-di-isopropylphenyl)-1,4-diaza-1,3-butadiene

    NARCIS (Netherlands)

    Koten, G. van; Wissing, E.; Gorp, K. van; Boersma, J.

    1994-01-01

    Diorganozinc compounds R{2}Zn (R=alkyl or aryl) react with N, N'-bis(2,6-di-isopropylphenyl)-1,4-diaza-1,3-butadiene, (i-Pr{2}Ph)N@?CHCHp@?N(i-Pr{2}Ph) (i-Pr{2}Ph-DAB) to give thermally unstable 1:1 coordination complexes R{2}Zn(i-Pr2Ph-DAB), which subsequently undergo a slow regioselective alkyl or

  20. Oxidation and N-alkylation of galactomannan extracted from Caesalpinia ferrea var. ferrea seeds

    International Nuclear Information System (INIS)

    Souza, Clayton F. de; Lucyszyn, Neoli; Ferraz, Fernando A.; Sierakowski, Maria Rita

    2009-01-01

    The objective of this work was the synthesis and characterization of carboxyl (polyelectrolyte, GMPFOXT) and amino alkylate (amphiphilic, GMPFOXD) derivatives of the galactomannan extracted from the seeds of native specie Pau-ferro (Caesalpinia ferrea - GMPF). The derivatives were obtained by selective modification of GMPF at C-6 in the presence of TEMPO reagent (N-oxil-2,2,6,6-tetramethyl-piperidine) and dodecylamine showed high yields (∼ 77 and 94% for GMPFOXT and GMPFOXD, respectively). The characteristics of the derivatives were confirmed by spectroscopic techniques of FTIR and 13 C-NMR. By gel permeation chromatography (GPC), was observed a decrease of molar mass values and increase in polydispersity after derivatization, indicating change in the aggregation state in solution, caused by modification on the superficial structure. The development of these products can expand the use of them in different areas such as cosmetics and pharmaceutics, among others. (author)

  1. 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

  2. No-carrier-added (NCA) N-(3-[18F]fluoropropyl)-N-norbuprenorphine and N-(3-[18F]fluoropropyl)-N-nordiprenorphine -synthesis, anatomical distribution in mice and rats, and tomographic studies in a baboon

    International Nuclear Information System (INIS)

    Lanqin Bai; Renrui Teng; Chyngyann Shiue; Wolf, A.P.; Dewey, S.L.; Holland, M.J.; Simon, E.J.

    1990-01-01

    N-(3-Fluoropropyl)-N-norbuprenorphine (3a) and N-(3-fluoropropyl)-N-nordiprenorphine (4a) were synthesized by N-alkylation of norbuprenorphine (1) and nordiprenorphine (2) with 1-bromo-3-fluoropropane. The corresponding no-carrier-added (NCA) N-(3-[ 18 F]fluoropropyl)-N-norbuprenorphine (3b) and N-(3-[ 18 F]fluoropropyl)-N-nordiprenorphine (4b) were synthesized by N-alkylation of 1 and 2 with NCA 1-[ 18 F]fluoro-3-iodopropane. In vitro studies indicate that in the absence of sodium chloride, compounds 3a, 4a, N-propyl-N-norbuprenorphine (5), buprenorphine and diprenorphine are reasonably comparable in binding affinity for opioid receptors. In the presence of 100 mM sodium chloride, however, compounds 3a, 4a and 5, are clearly less potent than buprenorphine and diprenorphine. The anatomical distribution study of compound 3b in mice shows radioactivity accumulating in bone. Rat studies of both compounds 3b and 4b indicate the specific distribution of these two radioligands within certain cortical and subcortical regions of rat brain. However, the absolute uptake of compound 4b in rat brain was only half that of compound 3b. PET studies of 3b in a baboon revealed specific binding of compound 3b in striatum and cerebellum. At 1 h after injection, ratios of specific/non-specific binding of 3b in striatum and cerebellum of a baboon were 1.9 and 1.7 respectively. (author)

  3. Catalytic dehydroaromatization of n-alkanes by pincer-ligated iridium complexes

    Science.gov (United States)

    Ahuja, Ritu; Punji, Benudhar; Findlater, Michael; Supplee, Carolyn; Schinski, William; Brookhart, Maurice; Goldman, Alan S.

    2011-02-01

    Aromatic hydrocarbons are among the most important building blocks in the chemical industry. Benzene, toluene and xylenes are obtained from the high temperature thermolysis of alkanes. Higher alkylaromatics are generally derived from arene-olefin coupling, which gives branched products—that is, secondary alkyl arenes—with olefins higher than ethylene. The dehydrogenation of acyclic alkanes to give alkylaromatics can be achieved using heterogeneous catalysts at high temperatures, but with low yields and low selectivity. We present here the first catalytic conversion of n-alkanes to alkylaromatics using homogeneous or molecular catalysts—specifically ‘pincer’-ligated iridium complexes—and olefinic hydrogen acceptors. For example, the reaction of n-octane affords up to 86% yield of aromatic product, primarily o-xylene and secondarily ethylbenzene. In the case of n-decane and n-dodecane, the resulting alkylarenes are exclusively unbranched (that is, n-alkyl-substituted), with selectivity for the corresponding o-(n-alkyl)toluene.

  4. Biosynthetic mechanism of glycolate in Chromatium, (3)

    International Nuclear Information System (INIS)

    Asami, Sumio; Akazawa, Takashi

    1976-01-01

    The effects of α-hydroxy-2-pyridinemethanesulfonate (α-HPMS), 2,3-epoxypropionate(glycidate), and cyanide on the photosynthetic activity of Chromatium were investigated. The α-HPMS stimulated the photosynthetic CO 2 fixation in the bacterial cells in both N 2 and O 2 environments. The formation and subsequent excretion of both glycolate and glycine in the O 2 atmosphere were markedly enhanced by the HPMS. In contrast to the recent report that glycidate especially inhibits the glycolate formation in tabacco leaf disks, the authors found that it had no influence on the CO 2 fixation by Chromatium in either N 2 or O 2 atmosphere, and that the synthesis and extracellular excretion of glycolate were markedly stimulated by glycidate treatment. The cyanide (0.01 - 1mM) exerted some marked inhibitory effect on the photosynthetic CO 2 fixation in N 2 . In O 2 atmosphere, the photosynthesis was stimulated by the 0.01 mM cyanide, and inhibited by it above this level. Both the incorporation of 14 CO 2 into glycolate and the total synthesis of glycolate in light were also enhanced by the 0.01 mM cyanide, and strongly inhibited above that concentration. (J.P.N.)

  5. Studies on the obtention and characterization of N,N,N-trimethyl chitosan (TMC)

    International Nuclear Information System (INIS)

    Curti, Elisabete; Campana Filho, Sergio P.

    2001-01-01

    In this work, a study was developed on the obtention of N,N,N-trimethyl chitosan (TMC) aiming the preparation of samples with different average degrees of quaternization under controlled experimental conditions. The effects of previous treatments of chitosan on the reactivity toward its N-alkylation were evaluated and it was concluded that the purification method previously applied to chitosan strongly influenced the reaction yield. The average degrees of quaternization of the TMC samples were determined by nuclear magnetic resonance spectroscopy and they ranged from 4,0% to 22%, depending on the previous treatment to which the chitosan was submitted and on the reaction conditions. It was also concluded that an average degree of quaternization close to 4,0% is already high enough to impart water solubility to this chitosan derivative. (author)

  6. Imperfections and phase transformations by mono-N-alkylammonium-uranium glimmers

    International Nuclear Information System (INIS)

    Kammermeier, H.

    1982-01-01

    Uranium glimmers have a layered structure. Bimolecular intermediate layered films of parallel ordered alkyl chains can be produced by exchange of the intermediate layer kations with the mono-n-alkylammonium ions and the succession of soaking with n-alkanols. Phase changes can occur in these films that are accompanied by a change of the layer distance of the solid inorganic basic matrix. N-alkyl ammonium-n-alkanol-intercalcation compounds of uranium glimmers represent systems that can conveniently be examined with X-rays. Thermal phase changes can be performed easily. This paper describes how one can derive conclusions on the reaction mechanism of phase changes in bimolecular alkyl chain films by means of a profile analysis of X-ray reflexes. (orig./HBR) [de

  7. 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.

  8. Rigid Dipeptide Mimics: Synthesis of Enantiopure 5- and 7-Benzyl and 5,7-Dibenzyl Indolizidinone Amino Acids via Enolization and Alkylation of delta-Oxo alpha,omega-Di-[N-(9-(9-phenylfluorenyl))amino]azelate Esters.

    Science.gov (United States)

    Polyak, Felix; Lubell, William D.

    1998-08-21

    Azabicyclo[X.Y.0]alkane amino acids are tools for constructing mimics of peptide structure and templates for generating combinatorial libraries for drug discovery. Our methodology for synthesizing these conformationally rigid dipeptides has been elaborated such that alkyl groups can be appended onto the heterocycle to generate mimics of peptide backbone and side-chain structure. Inexpensive glutamic acid was employed as chiral educt in a Claisen condensation/ketone alkylation/reductive amination/lactam cyclization sequence that furnished alkyl-branched azabicyclo[4.3.0]alkane amino acid. Enantiopure 5-benzyl-, 7-benzyl-, and 5,7-dibenzylindolizidinone amino acids 2-4 were stereoselectively synthesized via efficient reaction sequences featuring the alkylation of di-tert-butyl alpha,omega-di-[N-(PhF)amino]azelate delta-ketone 5. A variety of alkyl halides were readily added to the enolate of ketone 5 to provide mono- and dialkylated ketones 6 and 7. Hydride additions to 6 and 7, methanesulfonations, and intramolecular S(N)2 displacements by the PhF amine gave 5-alkylprolines that were converted by lactam cyclizations into 7- and 5-benzyl-, as well as 5,7-dibenzyl-2-oxo-3-N-(BOC)amino-1-azabicyclo[4.3.0]nonane-9-carboxylate methyl esters 10, 11, and 14. Epimerization of the alkyl-branched stereocenter via an iminium-enaminium equilibrium proved effective for controlling diastereoselectivity in reductive aminations with 6 and 7 in order to furnish 5-alkylprolines that were similarly converted to 7- benzyl- and 5,7-dibenzylindolizidinone N-(BOC)amino esters 10 and 14. Ester hydrolysis with hydroxide ion and potassium trimethylsilanolate then gave enantiopure indolizidinone amino acids 2-4. Epimerization at C-9 of benzylindolizidinone amino esters was also used to provide alternative diastereomers of 10, 11, and 14. This practical methodology for introducing side-chain groups onto the heterocycle with regioselective and diastereoselective control is designed to enhance

  9. 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)

  10. No-carrier-added (NCA) N-(3-( sup 18 F)fluoropropyl)-N-norbuprenorphine and N-(3-( sup 18 F)fluoropropyl)-N-nordiprenorphine -synthesis, anatomical distribution in mice and rats, and tomographic studies in a baboon

    Energy Technology Data Exchange (ETDEWEB)

    Bai, Lanqin; Teng, Renrui; Shiue, Chyngyann; Wolf, A P; Dewey, S L [Brookhaven National Lab., Upton, NY (USA); Holland, M J; Simon, E J [New York Univ., NY (USA). Medical Center

    1990-01-01

    N-(3-Fluoropropyl)-N-norbuprenorphine (3a) and N-(3-fluoropropyl)-N-nordiprenorphine (4a) were synthesized by N-alkylation of norbuprenorphine (1) and nordiprenorphine (2) with 1-bromo-3-fluoropropane. The corresponding no-carrier-added (NCA) N-(3-({sup 18}F)fluoropropyl)-N-norbuprenorphine (3b) and N-(3-({sup 18}F)fluoropropyl)-N-nordiprenorphine (4b) were synthesized by N-alkylation of 1 and 2 with NCA 1-({sup 18}F)fluoro-3-iodopropane. In vitro studies indicate that in the absence of sodium chloride, compounds 3a, 4a, N-propyl-N-norbuprenorphine (5), buprenorphine and diprenorphine are reasonably comparable in binding affinity for opioid receptors. In the presence of 100 mM sodium chloride, however, compounds 3a, 4a and 5, are clearly less potent than buprenorphine and diprenorphine. The anatomical distribution study of compound 3b in mice shows radioactivity accumulating in bone. Rat studies of both compounds 3b and 4b indicate the specific distribution of these two radioligands within certain cortical and subcortical regions of rat brain. However, the absolute uptake of compound 4b in rat brain was only half that of compound 3b. PET studies of 3b in a baboon revealed specific binding of compound 3b in striatum and cerebellum. At 1 h after injection, ratios of specific/non-specific binding of 3b in striatum and cerebellum of a baboon were 1.9 and 1.7 respectively. (author).

  11. 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.

  12. 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

  13. Thermodynamics of Triethylene Glycol and Tetraethylene Glycol Containing Systems Described by the Cubic-Plus-Association Equation of State

    DEFF Research Database (Denmark)

    Breil, Martin Peter; Kontogeorgis, Georgios

    2009-01-01

    A thorough investigation of triethylene glycol (TEG) containing systems has been performed. The introduction of a new six-site association scheme for the TEG molecule has shown to be advantageous. Glycols are often modeled using a four-site scheme (abbreviated as 4C) hence ignoring the internal...... lone pairs of oxygen. The new association scheme also takes these sites into account. The new parameters of TEG are based on the vapor pressure data, liquid density data, and liquid-liquid equilibria (LLE) data (n-heptane), and they are tested for binary systems (methane, n-octane, n-nonane, n...

  14. N-Methylamino Pyrimidyl Amides (MAPA): Highly Reactive, Electronically-Activated Amides in Catalytic N-C(O) Cleavage.

    Science.gov (United States)

    Meng, Guangrong; Lalancette, Roger; Szostak, Roman; Szostak, Michal

    2017-09-01

    Despite recent progress in catalytic cross-coupling technologies, the direct activation of N-alkyl-N-aryl amides has been a challenging transformation. Here, we report the first Suzuki cross-coupling of N-methylamino pyrimidyl amides (MAPA) enabled by the controlled n N → π Ar conjugation and the resulting remodeling of the partial double bond character of the amide bond. The new mode of amide activation is suitable for generating acyl-metal intermediates from unactivated primary and secondary amides.

  15. Reduced DNA repair in mouse satellite DNA after treatment with methylmethanesulfonate, and N-methyl-N-nitrosourea.

    Science.gov (United States)

    Bodell, W J; Banerjee, M R

    1976-01-01

    We have measured DNA repair in mouse satellite and main band DNA as resolved by Ag+-Cs2SO4 centrifugation in response to treatment with the alkylating agents, methyl methanesulfonate, and N-methyl-N-nitrosourea. We find that there is a statistically significant lower incorporation of 3H-Tdr into the satellite DNA as compared to the main band at varying periods after treatment with the alkylating agents. This suggests a reduced repair activity in the satellite DNA. We have measured the extent of binding of 14C-methyl methanesulfonate to the satellite, and main band DNA, and no difference in binding was observed, indicating that the reduced repair activity of satellite DNA is not due to a difference in binding of alkylating agents. We believe that the reduced incorporation of 3H-Tdr into satellite DNA may be due to its location in the condensed chromatin fraction. PMID:184436

  16. C- and N-Metalated Nitriles: The Relationship between Structure and Selectivity.

    Science.gov (United States)

    Yang, Xun; Fleming, Fraser F

    2017-10-17

    Metalated nitriles are exceptional nucleophiles capable of forging highly hindered stereocenters in cases where enolates are unreactive. The excellent nucleophilicity emanates from the powerful inductive stabilization of adjacent negative charge by the nitrile, which has a miniscule steric demand. Inductive stabilization is the key to understanding the reactivity of metalated nitriles because this permits a continuum of structures that range from N-metalated ketenimines to nitrile anions. Solution and solid-state analyses reveal two different metal coordination sites, the formally anionic carbon and the nitrile nitrogen, with the site of metalation depending intimately on the solvent, counterion, temperature, and ligands. The most commonly encountered structures, C- and N-metalated nitriles, have either sp 3 or sp 2 hybridization at the nucleophilic carbon, which essentially translates into two distinct organometallic species with similar but nonidentical stereoselectivity, regioselectivity, and reactivity preferences. The hybridization differences are particularly important in S N i displacements of cyclic nitriles because the orbital orientations create very precise trajectories that control the cyclization selectivity. Harnessing the orbital differences between C- and N-metalated nitriles allows selective cyclization to afford nitrile-containing cis- or trans-hydrindanes, decalins, or bicyclo[5.4.0]undecanes. Similar orbital constraints favor preferential S N i displacements with allylic electrophiles on sp 3 centers over sp 2 centers. The strategy permits stereoselective displacements on secondary centers to set contiguous tertiary and quaternary stereocenters or even contiguous vicinal quaternary centers. Stereoselective alkylations of acyclic nitriles are inherently more challenging because of the difficulty in creating steric differentiation in a dynamic system with rotatable bonds. However, judicious substituent placement of vicinal dimethyl groups and a

  17. Comparison of N-alkyl acridine orange dyes as fluorescence probes for the determination of cardiolipin

    Energy Technology Data Exchange (ETDEWEB)

    Kaewsuya, P.; Miller, J.D. [Department of Chemistry and Biochemistry, Miami University, Oxford, OH 45056 (United States); Danielson, N.D. [Department of Chemistry and Biochemistry, Miami University, Oxford, OH 45056 (United States)], E-mail: danielnd@muohio.edu; Sanjeevi, J.; James, P.F. [Department of Zoology, Miami University, Oxford, OH 45056 (United States)

    2008-09-26

    The phospholipid (PL), cardiolipin (CL), is found almost exclusively in the inner membrane of mitochondria and loss of CL is considered as an important indication of cell apoptosis. Previously, 10-N-nonyl acridine orange (NAO) has been used as a fluorescent probe for the visualization of CL in mitochondrial cell membranes and in solution. In this work for the determination of CL, we have synthesized two new fluorescent probes, n-tetradecyl acridine orange (C14-AO), and n-octadecyl acridine orange (C18-AO) by reacting acridine orange with the corresponding n-alkyl bromide. Using excitation and emission wavelengths at about 500 and 525 nm and varying the percentage of methanol in water as the solvent, no interaction between CL and the fluorescent probes at 75% is noted but a proportional quenching of the fluorescence signal by CL is observed at 50% or less for C14-AO and 60% or less for C18-AO. Binding efficiency of these fluorescent probes to CL is compared using dye concentrations of 5, 10, and 20 {mu}M. C18-AO shows a better sensitivity than C14-AO and NAO, respectively, but is less selective. For C14-AO, the detection limit and limit of quantitation are 0.07 and 0.21 {mu}M, respectively, which are better than those previously reported for NAO. One anionic PL, phosphatidic acid, shows some quenching interference to both the C14 and C18 dyes but only at concentrations above the working range for sample analysis. The CL in mitochondrial membrane samples is determined by standard addition using C14-AO. The level of CL in the outer mitochondrial membrane compared to the inner membrane is significantly increased due to the addition of cadmium chloride into the cells causing cell apoptosis.

  18. Mutants of Aspergillus nidulans with increased resistance to the alkylating agent, N-methyl-N'-nitro-N-nitrosoguanidine.

    Science.gov (United States)

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

    1988-05-01

    The isolation and characterisation of mutants of Aspergillus nidulans showing resistance to MNNG is described. Such isolates were stable through prolonged subculture in the absence of the selective agent, and resistance segregated as an allele of a single gene in meiotic and mitotic analysis. MNNG-resistant strains showed an increase in resistance to EMS and UV irradiation but no cross-resistance to MMS was detected. Possible mechanisms of resistance to alkylating agents are discussed.

  19. 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.

  20. The effect of the head group on branched-alkyl chain surfactants in glycolipid/n-octane/water ternary system.

    Science.gov (United States)

    Nainggolan, Irwana; Radiman, Shahidan; Hamzah, Ahmad Sazali; Hashim, Rauzah

    2009-10-01

    Two novel glycolipids have been synthesized and their phase behaviour studied. They have been characterized using FT-IR, FAB and 13C NMR and 1H NMR to ensure the purity of novel glycolipids. The two glycolipids are distinguished based on the head group of glycolipids (monosaccharide/glucose and disaccharide/maltose). These two novel glycolipids have been used as surfactant to perform two phase diagrams. Phase behaviours that have been investigated are 2-hexyldecyl-beta-D-glucopyranoside (2-HDG)/n-octane/water ternary system and 2-hexyldecyl-beta-D-maltoside (2-HDM)/n-octane/water ternary system. SAXS and polarizing optical microscope have been used to study the phase behaviours of these two surfactants in ternary phase diagram. Study of effect of the head group on branched-alkyl chain surfactants in ternary system is a strategy to derive the structure-property relationship. For comparison, 2-HDM and 2-HDG have been used as surfactant in the same ternary system. The phase diagram of 2-hexyldecyl-beta-D-maltoside/n-octane/water ternary system exhibited a Lalpha phase at a higher concentration regime, followed with two phases and a micellar solution region in a lower concentration regime. The phase diagram of 2-HDG/water/n-octane ternary system shows hexagonal phase, cubic phase, rectangular ribbon phase, lamellar phase, cubic phase as the surfactant concentration increase.

  1. 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.

  2. 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.

  3. EI/MS/MS SPECTRA OF N-MONOSUBS-TITUTED CYANOACETAMIDES

    Directory of Open Access Journals (Sweden)

    NATAŠA ILIĆ

    2010-12-01

    Full Text Available The electron-ionization induced mass spectra of twenty six N-monosubstituted cyanoacetamides were recorded and their fragmentation patterns were stu¬died. The effect of N-alkyl and N-aryl substituents to the fragmentation of the investigated compounds was discussed. Mechanistic generalization lead to a conclusion that fission of the carbon-carbon bonds next to carbonyl function or nitrogen were processes common for N-alkyl and N-(4-substituted phenyl cya¬noacetamides. In some amides, the elimination of the acyl group by a ketene fragment gave rise to the more stable ion. Cycloalkyl amides could not frag¬ment by single carbon-carbon bond fission, but subsequent rearrangement resulted in formation of stable even electron ion. N-(4-substituted phenyl cyanoacetamides were more stable showing also characteristic fragmentation depending on substituent present at phenyl ring.

  4. Separation of yttrium (III) from lanthanoids (III) by solvent extraction with substituted N-Alkylcarbonyl-N-phenylhydroxylamines

    International Nuclear Information System (INIS)

    Haraguchi, K.; Ogata, T.; Nakagawa, K.; Saitoh, T.; Kamidate, T.; Watanabe, H.

    1996-01-01

    A series of substituted N-alkylcarbonyl-N-phenylhydroxylamines(R-PHAs) were synthesized and utilized for the extraction of yttrium(III) and lanthanoids(III) in order to obtain effective extractants for the separation of yttrium(III) from the lanthanoids(III) and the mutual separation of the lanthanoids(III). The distribution ratio of yttrium(III) and the lanthanoids(III) between the carbon tetrachloride and the aqueous phases was measured as functions of the pH and the extractant concentration at 298 K at an ionic strength of 0.1 (NaNO 3 ). Yttrium(III) and the lanthanoids(III) were extracted with R-PHAs(HL) as self-adducted chelates of the form, ML 3 (HL) x , where 'x' is 1, 2 or 3 depending on the extraction system. The extractability of the metal ions decreased in the order of R-PHA having a primary, a secondary and a tertiary alkyl substituent attached to the carbonyl group because of the steric hindrance of the alkyl group. The separation factors for both Yb/Eu and Yb/Y pairs increased with increasing branching of the alkyl group of R-PHA. The excellent selectivity of R-PHAs having a tertiary alkyl group was attributable to a greater inductive effect of the tertiary alkyl group than those of the primary and secondary alkyl groups. The substituents at the phenyl group of R-PHAs gave no significant effect on the selectivity, while the extractability was enhanced considerably by introduction of electron withdrawing substituents at appropriate positions of the phenyl group of R-PHAs. (authors)

  5. Designing Efficient Solar-Thermal Fuels with [n.n](9,10)Anthracene Cyclophanes: A Theoretical Perspective.

    Science.gov (United States)

    Ganguly, Gaurab; Sultana, Munia; Paul, Ankan

    2018-01-18

    Molecular solar thermal storage (MOST) systems have been largely limited to three classes of molecular motifs: azo-benzene, norbornadiene, and transition metal based fulvalene-tetracarbonyl systems. Photodimerization of anthracene has been known for a century; however, this photoprocess has not been successfully exploited for MOST purposes due to its poor energy storage. Using well-calibrated theoretical methods on a series of [n.n](9,10)bis-anthracene cyclophanes, we have exposed that they can store solar energy into chemical bonds and can release in the form of heat energy on demand under mild conditions. The storage is mainly attributed to the strain in the rings formed by the alkyl linkers upon photoexcitation. Our results demonstrate that the gravimetric energy storage density for longer alkyl-chain linkers (n > 3) are comparable to those for the best-known candidates; however, it lacks some of the deleterious attributes of known systems, thus making the proposed molecules desirable targets for MOST applications.

  6. Synthesis of Lipophilic Guanine N-9 Derivatives

    DEFF Research Database (Denmark)

    Wamberg, Michael C; Pedersen, Pernille L; Löffler, Philipp M G

    2017-01-01

    the synthesis of five new guanine-N9 derivatives bearing alkyl chains with different attachment chemistries, exploiting a synthesis pathway that allows a flexible choice of hydrophobic anchor moiety. In this study, these guanine derivatives were functionalized with C10 chains for insertion into decanoic acid...... bilayer structures, in which both alkyl chain length and attachment chemistry determined their interaction with the membrane. Incubation of these guanine conjugates, as solids, with a decanoic acid vesicle suspension, showed that ether- and triazole-linked C10 anchors yielded an increased partitioning...... of the guanine derivative into the membranous phase compared to directly N-9-linked saturated alkyl anchors. Decanoic acid vesicle membranes could be loaded with up to 5.5 mol % guanine derivative, a 6-fold increase over previous limits. Thus, anchor chemistries exhibiting favorable interactions with a bilayer...

  7. Differential trace labeling of calmodulin: investigation of binding sites and conformational states by individual lysine reactivities. Effects of beta-endorphin, trifluoperazine, and ethylene glycol bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Giedroc, D.P.; Sinha, S.K.; Brew, K.; Puett, D.

    1985-11-05

    The CaS -dependent association of beta-endorphin and trifluoperazine with porcine testis calmodulin, as well as the effects of removing CaS by ethylene glycol bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA) treatment, were investigated by the procedure of differential kinetic labeling. This technique permitted determination of the relative rates of acylation of each of the epsilon-amino groups of the seven lysyl residues on calmodulin by (TH)acetic anhydride under the different conditions. In all cases, less than 0.52 mol of lysyl residue/mol of calmodulin was modified, thus ensuring that the labeling pattern reflects the microenvironments of these groups in the native protein. Lysines 75 and 94 were found to be the most reactive amino groups in CaS -saturated calmodulin. In the presence of CaS and under conditions where beta-endorphin and calmodulin were present at a molar ratio of 2.5:1, the amino groups of lysines 75 and 148 were significantly reduced in reactivity compared to calmodulin alone. At equimolar concentrations of peptides and proteins, essentially the same result was obtained except that the magnitudes of the perturbation of these two lysines were less pronounced. With trifluoperazine, at a molar ratio to calmodulin of 2.5:1, significant perturbations of lysines 75 and 148, as well as Lys 77, were also found. These results further substantiate previous observations of a commonality between phenothiazine and peptide binding sites on calmodulin. Lastly, an intriguing difference in CaS -mediated reactivities between lysines 75 and 77 of calmodulin is demonstrated. In the CaS -saturated form of the protein, both lysines are part of the long connecting helix between the two homologous halves of the protein.

  8. Microsynthesis and electron ionization mass spectral studies of O(S)-alkyl N,N-dimethyl alkylphosphono(thiolo)thionoamidates for Chemical Weapons Convention verification.

    Science.gov (United States)

    Saeidian, Hamdollah; Babri, Mehran; Abdoli, Morteza; Sarabadani, Mansour; Ashrafi, Davood; Naseri, Mohammad Taghi

    2012-12-15

    The availability of mass spectra and interpretation skills are essential for unambiguous identification of the Chemical Weapons Convention (CWC)-related chemicals. The O(S)-alkyl N,N-dimethyl alkylphosphono(thiolo)thionoamidates are included in the list of scheduled CWC-related compounds, but there are very few spectra from these compounds in the literature. This paper examines these spectra and their mass spectral fragmentation routes. The title chemicals were prepared through microsynthetic protocols and were analyzed using electron ionization mass spectrometry with gas chromatography as a MS-inlet system. Structures of fragments were confirmed using analysis of fragment ions of deuterated analogs, tandem mass spectrometry and density functional theory (DFT) calculations. Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as alkene and amine elimination and McLafferty-type rearrangements. The most important fragmentation route of the chemicals is the thiono-thiolo rearrangement. DFT calculations are used to support MS results and to reveal relative preference formation of fragment ions. The retention indices (RIs) of all the studied compounds are also reported. Mass spectra of the synthesized compounds were investigated with the aim to enrich the Organization for the Prohibition of Chemical Weapons (OPCW) Central Analytical Database (OCAD) which may be used for detection and identification of CWC-related chemicals during on-site inspection and/or off-site analysis such as OPCW proficiency tests. Copyright © 2012 John Wiley & Sons, Ltd.

  9. Effect of alkyl chain length on the rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imides.

    Science.gov (United States)

    Gangamallaiah, V; Dutt, G B

    2013-10-10

    Rotational diffusion of a nonpolar solute 9-phenylanthracene (9-PA) and a cationic solute rhodamine 110 (R110) has been examined in a series of 1-alkyl-3-methylimidazolium (alkyl = octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl) bis(trifluoromethylsulfonyl)imides to understand the influence of alkyl chain length on solute rotation. In this study, reorientation times (τr) have been measured as a function of viscosity (η) by varying the temperature (T) of the solvents. These results have been analyzed using the Stokes-Einstein-Debye (SED) hydrodynamic theory along with the ones obtained for the same solutes in 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides (Gangamallaiah and Dutt, J. Phys. Chem. B 2012, 116, 12819-12825). It has been noticed that the data for 9-PA and R110 follows the relation τr = A(η/T)(n) with A being the ratio of hydrodynamic volume of the solute to the Boltzmann constant and n = 1 as envisaged by the SED theory. However, upon increasing the alkyl chain length from methyl to octadecyl significant deviations from the SED theory have been observed especially from the octyl derivative onward. From methyl to octadecyl derivatives, the value of A decreases by a factor of 3 for both the solutes and n by a factor of 1.4 and 1.6 for 9-PA and R110, respectively. These observations have been rationalized by taking into consideration the organized structure of the ionic liquids, whose influence appears to be pronounced when the number of carbon atoms in the alkyl chain attached to the imidazolium cation exceeds eight.

  10. Rapid NIR determination of alkyl esters in virgin olive oil; Determinación rápida de ésteres alquílicos en aceite de oliva virgen para detección temprana de defectos sensoriales

    Energy Technology Data Exchange (ETDEWEB)

    Cayuela, J.A.

    2017-07-01

    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%. [Spanish] La reglamentación de la Unión Europea para el aceite de oliva y el orujo de oliva ha establecido el límite de 35 mg·kg-1 al contenido de ésteres etílicos de ácidos grasos en los aceites de oliva virgen extra, para campañas de molienda posteriores a 2016. En este trabajo se han establecido modelos predictivos para medir los ésteres etílicos y metílicos de ácidos grasos y para la medida de los ésteres alquílicos de ácidos grasos totales basados en la espectroscopía de infrarrojo cercano (NIRS) y utilizados con éxito para este propósito. Los coeficientes de correlación de los ejercicios de validación externa realizados con estos modelos predictivos oscilaron entre 0,84 y 0,91. Diferentes pruebas de clasificación utilizando los mismos modelos con respecto a los umbrales de 35 mg·kg-1 para ésteres etílicos y 75 mg·kg-1 para ésteres alquílicos, proporcionaron porcentajes de éxito del 75,0% al 95,2%.

  11. Sequence-specific DNA alkylation by tandem Py-Im polyamide conjugates.

    Science.gov (United States)

    Taylor, Rhys Dylan; Kawamoto, Yusuke; Hashiya, Kaori; Bando, Toshikazu; Sugiyama, Hiroshi

    2014-09-01

    Tandem N-methylpyrrole-N-methylimidazole (Py-Im) polyamides with good sequence-specific DNA-alkylating activities have been designed and synthesized. Three alkylating tandem Py-Im polyamides with different linkers, which each contained the same moiety for the recognition of a 10 bp DNA sequence, were evaluated for their reactivity and selectivity by DNA alkylation, using high-resolution denaturing gel electrophoresis. All three conjugates displayed high reactivities for the target sequence. In particular, polyamide 1, which contained a β-alanine linker, displayed the most-selective sequence-specific alkylation towards the target 10 bp DNA sequence. The tandem Py-Im polyamide conjugates displayed greater sequence-specific DNA alkylation than conventional hairpin Py-Im polyamide conjugates (4 and 5). For further research, the design of tandem Py-Im polyamide conjugates could play an important role in targeting specific gene sequences. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Relationship between the Composition of Polymer of n-Alkyl Substituted Acrylate and Vinyl Amine and Their Performance on Pour Point Depression

    Institute of Scientific and Technical Information of China (English)

    Jiang Qingzhe; Luo Fangmin; Song Zhaozheng; Ke Ming

    2005-01-01

    Polymer of n-alkyl substituted acrylate (PA) with the alkyl side chains C16- 30 were synthesized.Their crystallinity, solubility and effect on pour point depression were studied. Results showed that only carbon atoms located far away from polar groups of PA pour point depressants participated in crystallization.When the number of carbon atoms that participated in crystallization is about three fourths of the average carbon number of wax in crude, the effect of PA is the best. The molecular weight distribution of PA pour point depressant has little influence on the effect of pour point depression, and the average molecular weight of PA in the range of (1.5- 2.2)× 104 shows the best effect. The introduction of polar groups into the molecule of PA can improve its performance. However, a too high content of polar groups in PA would cause deterioration, and even lead to loss of PA's performance for pour point depression.

  13. Hydroperoxide Measurements During Low-Temperature Gas-Phase Oxidation of n-Heptane and n-Decane

    KAUST Repository

    Rodriguez, Anne

    2017-02-13

    A wide range of hydroperoxides (C-C alkyl hydroperoxides, C-C alkenyl hydroperoxides, C ketohydroperoxides, and hydrogen peroxide (HO)), as well as ketene and diones, have been quantified during the gas-phase oxidation of n-heptane. Some of these species, as well as C alkenyl hydroperoxides and ketohydroperoxides, were also measured during the oxidation of n-decane. These experiments were performed using an atmospheric-pressure jet-stirred reactor at temperatures from 500 to 1100 K and one of three analytical methods, time-of-flight mass spectrometry combined with tunable synchrotron photoionization with a molecular beam sampling: time-of-flight mass spectrometry combined with laser photoionization with a capillary tube sampling, continuous wave cavity ring-down spectroscopy with sonic probe sampling. The experimental temperature at which the maximum mole fraction is observed increases significantly for alkyl hydroperoxides, alkenyl hydroperoxides, and then more so again for hydrogen peroxide, compared to ketohydroperoxides. The influence of the equivalence ratio from 0.25 to 4 on the formation of these peroxides has been studied during n-heptane oxidation. The up-to-date detailed kinetic oxidation models for n-heptane and for n-decane found in the literature have been used to discuss the possible pathways by which these peroxides, ketene, and diones are formed. In general, the model predicts well the reactivity of the two fuels, as well as the formation of major intermediates. (Figure Presented).

  14. Hydroperoxide Measurements During Low-Temperature Gas-Phase Oxidation of n-Heptane and n-Decane

    KAUST Repository

    Rodriguez, Anne; Herbinet, Olivier; Meng, Xiangzan; Fittschen, Christa; Wang, Zhandong; Xing, Lili; Zhang, Lidong; Battin-Leclerc, Fré dé rique

    2017-01-01

    A wide range of hydroperoxides (C-C alkyl hydroperoxides, C-C alkenyl hydroperoxides, C ketohydroperoxides, and hydrogen peroxide (HO)), as well as ketene and diones, have been quantified during the gas-phase oxidation of n-heptane. Some of these species, as well as C alkenyl hydroperoxides and ketohydroperoxides, were also measured during the oxidation of n-decane. These experiments were performed using an atmospheric-pressure jet-stirred reactor at temperatures from 500 to 1100 K and one of three analytical methods, time-of-flight mass spectrometry combined with tunable synchrotron photoionization with a molecular beam sampling: time-of-flight mass spectrometry combined with laser photoionization with a capillary tube sampling, continuous wave cavity ring-down spectroscopy with sonic probe sampling. The experimental temperature at which the maximum mole fraction is observed increases significantly for alkyl hydroperoxides, alkenyl hydroperoxides, and then more so again for hydrogen peroxide, compared to ketohydroperoxides. The influence of the equivalence ratio from 0.25 to 4 on the formation of these peroxides has been studied during n-heptane oxidation. The up-to-date detailed kinetic oxidation models for n-heptane and for n-decane found in the literature have been used to discuss the possible pathways by which these peroxides, ketene, and diones are formed. In general, the model predicts well the reactivity of the two fuels, as well as the formation of major intermediates. (Figure Presented).

  15. 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...

  16. Chain-Length Distribution and Hydrogen Isotopic Fraction of n-alkyl Lipids in Aquatic and Terrestrial Plants: Implications for Paleoclimate Reconstructions

    Science.gov (United States)

    Gao, L.; Littlejohn, S.; Hou, J.; Toney, J.; Huang, Y.

    2008-12-01

    Recent studies demonstrate that in lacustrine sediments, aquatic plant lipids (e.g., C22-fatty acid) record lake water D/H ratio variation, while long-chain fatty acids (C26-C32, major components of terrestrial plant leaf waxes), record D/H ratios of precipitation (especially in arid regions). However, there are insufficient literature data for the distribution and hydrogen isotopic fractionation of n-alkyl lipids in aquatic and terrestrial plants. In this study, we determined the chain-length distributions and D/H ratios of n-alkyl lipids from 17 aquatic plant species (9 emergent, 4 floating and 4 submerge species) and 13 terrestrial plant species (7 grasses and 6 trees) from Blood Pond, Massachusetts. Our results are consistent with previous studies and provide a solid basis for the paleoclimatic reconstruction using D/H ratios of aquatic and terrestrial plant biomarkers. In addition, systematic hydrogen isotopic analyses on leaf waxes, leaf, stem and soil waters from trees and grasses significantly advance our understanding of our previously observed large D/H ratio difference between tree and grass leaf waxes. Our data indicate that the observed difference is not due to differences in leaf water D/H ratios. In comparison with grasses, trees use greater proportion of D-enriched residual or stored carbohydrates (as opposed to current photosynthetic carbohydrates) for leaf wax biosynthesis, resulting in higher leaf wax D/H ratios. The residual carbohydrates are enriched in deuterium because of the preferential consumption of light-hydrogen substrates during plant metabolism.

  17. Synthesis and crystal structures of new complexes of Np(V) glycolate with 2,2'-bipyridine, [NpO2(C10H8N2)(OOC2H2OH)].1.5H2O and [NpO2(C10H8N2)(OOC2H2OH)].2.5H2O

    International Nuclear Information System (INIS)

    Charushnikova, I.A.; Krot, N.N.; Starikova, Z.A.

    2009-01-01

    Single crystals were prepared, and the structures of two complexes of Np(V) glycolate with 2,2'-bipyridine of the compositions [NpO 2 (C 10 H 8 N 2 )(OOC 2 H 2 OH)].1.5H 2 O (I) and [NpO 2 (C 10 H 8 N 2 )(OOC 2 H 2 OH)]2.5H 2 O (II) were studied. The structures of the compounds are based on neptunyl-glycolate chains in which the glycolate anion manifests its complexation ability in different manner. In structure I, the bidentate-bridging anion links the adjacent NpO 2 - cations through the oxygen atoms of the carboxylate group. The neptunyl-glycolate chains of I exhibits the mutual coordination of the NpO 2 - cations acting toward each other simultaneously as ligands and coordinating centers. In compound II, the glycolate anion is bidentately coordinated to one neptunium atom to form a planar five-membered metallocycle [NpOCCO]. The O atom external with respect to the metallocycle is in the coordination environment of the adjacent neptunyl. The nitrogen-containing molecular ligand Bipy is included into the coordination environment of Np. The coordination polyhedron of the Np atoms in both structures is a pentagonal bipyramid in which the average Np-N bond length is 2.666 Aa (I) and 2.596 Aa (II). (orig.)

  18. Models for cytochrome P450 prosthetic heme alkylation. Reaction of diazoacetophenone with (tetraphenylporphyrinato)iron(II) chloride

    International Nuclear Information System (INIS)

    Komives, E.A.; Tew, D.; Olmstead, M.M.; Ortiz de Montellano, P.R.

    1988-01-01

    The reaction of diazoacetophenone with (tetraphenylporphyrinato)iron(II) yields [N-(2-phenyl-2-oxoethyl)tetraphenylporphyrinato]iron(II) chloride. The structure of this product has been established by spectroscopic methods and by x-ray crystallography. The crystal structure shows that the first carbon of the N-alkyl group is 2.94 angstrom from the iron atom and that the oxygen of the N-alkyl group points away from the iron. No evidence is seen for the Fe-C-N product expected from insertion of the diazo carbon into the metalloporphyrin iron-nitrogen bond or for intermediates in which the oxygen of the N-(2-phenyl-2-oxoethyl) group is coordinated to the iron. These results suggest it is unlikely that carbene-insertion or oxygen-coordinated intermediates will be detected during the N-alkylation of cytochrome P450 by diazo ketones. The results also rationalize the failure to detect iron-chelated enol species during N-alkylation of the prosthetic group of cytochrome P450 by catalytically activated phenylacetylene. 43 references, 5 figures, 4 tables

  19. An Efficient Synthesis of 1-Alkyl-2-phenyl-4-quinolones from 2-Halobenzoic Acids

    International Nuclear Information System (INIS)

    Song, Yoon Ju; Choi, Jin Sun; Lee, Jae In

    2013-01-01

    The present method offers an efficient synthesis of 1-alkyl-2-phenyl-4-quinolones from 2-haloben-zoic acids. It has the advantages with respect to (i) synthesis of 2 equiv of alkynones 5 from 1 equiv of 4,6-pyrimidyl di(2-halobenzoates) 3, (ii) synthesis of versatile 1-alkyl-2-phenyl-4-quinolones in high overall yields, and (iii) use of readily available and cheap starting materials. Therefore, this method could be utilized as a practical synthesis of 1-alkyl-2-phenyl-4-quinolones. Several methods have been developed to synthesize 1-alkyl-2-phenyl-4-quinolones from 2'-substituted acetophenones, anilines, and 2-halobenzoyl chlorides as starting materials. The reaction of N-methylisatoic anhydride with the lithium enolate of an 4'-methoxyacetophenone afforded the 1-methyl-2-phenyl-4-quinolone in a short sequence, but the yield was low. N-(2-Acetylphenyl)benzamides, prepared by Friedel-Crafts acylation of N-phenyl benzamides with acetyl chloride or benzoylation of 2'-aminoacetophenones with benzoyl chlorides,8 were cyclized with potassium t-butoxide to yield 2-aryl-4-quinolones, which were further alkylated with alkyl iodides to give 1-alkyl-2-aryl-4-quinolones

  20. An Efficient Synthesis of 1-Alkyl-2-phenyl-4-quinolones from 2-Halobenzoic Acids

    Energy Technology Data Exchange (ETDEWEB)

    Song, Yoon Ju; Choi, Jin Sun; Lee, Jae In [Duksung Women' s Univ., Seoul (Korea, Republic of)

    2013-10-15

    The present method offers an efficient synthesis of 1-alkyl-2-phenyl-4-quinolones from 2-haloben-zoic acids. It has the advantages with respect to (i) synthesis of 2 equiv of alkynones 5 from 1 equiv of 4,6-pyrimidyl di(2-halobenzoates) 3, (ii) synthesis of versatile 1-alkyl-2-phenyl-4-quinolones in high overall yields, and (iii) use of readily available and cheap starting materials. Therefore, this method could be utilized as a practical synthesis of 1-alkyl-2-phenyl-4-quinolones. Several methods have been developed to synthesize 1-alkyl-2-phenyl-4-quinolones from 2'-substituted acetophenones, anilines, and 2-halobenzoyl chlorides as starting materials. The reaction of N-methylisatoic anhydride with the lithium enolate of an 4'-methoxyacetophenone afforded the 1-methyl-2-phenyl-4-quinolone in a short sequence, but the yield was low. N-(2-Acetylphenyl)benzamides, prepared by Friedel-Crafts acylation of N-phenyl benzamides with acetyl chloride or benzoylation of 2'-aminoacetophenones with benzoyl chlorides,8 were cyclized with potassium t-butoxide to yield 2-aryl-4-quinolones, which were further alkylated with alkyl iodides to give 1-alkyl-2-aryl-4-quinolones.

  1. 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.

  2. Solvation of ionic liquids based on N-alkyl-N-methylmorpholinium cations in N,N-dimethylformamide and dimethyl sulfoxide – A volumetric and acoustic study

    International Nuclear Information System (INIS)

    Marcinkowski, Łukasz; Szepiński, Emil; Kloskowski, Adam; Namieśnik, Jacek; Warmińska, Dorota

    2017-01-01

    Highlights: • V ϕ of DMSO and DMF solutions of [Mor1,R][BF 4 ] increase with increasing IL concentration at all investigated temperatures. • Ion–ion interaction are stronger for DMF solutions than corresponding for DMSO. • DMSO interacts more effectively with ionic liquids studied than DMF. • Obtained results are the consequence of the cation size of the ionic liquid. - Abstract: Apparent molar volumes and molar isentropic compressibilities for N-ethyl-N-methylmorpholinium and N-decyl-N-methylmorpholinium tetrafluoroborates in N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) have been determined from density and speed of sound measurements over the temperature range T = (298.15, 303.15, 308.15, 313.15, 318.15 and 328.15) K at experimental pressure p = 0.1 MPa. This data has been used to calculate partial molar volumes and partial molar isentropic compressibilities at infinite dilution. The partial molar expansion coefficients and their secondary derivative have been estimated as well. The obtained results indicate that dimethyl sulfoxide interacts more effectively with ionic liquids studied than N,N-dimetylformamide and ion–ion interaction are stronger for N,N-dimetylformamide solutions than corresponding in dimethyl sulfoxide. Moreover the temperature dependence of the limiting apparent molar volumes and compressibilities is a result of temperature influence on the electrostriction effect, the ordering of a bulk solvent and number solvent molecules in the nearest presence of the salt.

  3. Application of N,N-dialkyl aliphatic amides in the separation of some actinides

    International Nuclear Information System (INIS)

    Gasparini, G.M.; Grossi, G.

    1980-01-01

    N,N-dialkyl substituted alkyl amides are known to be good extractants of some actinides such as U, Pu, and Th. Their stability is comparable to that of TBP, and their degradation products do not interfere as do the degradation products of TBP. On the other hand, the principal disadvantage of the amides is their tendency to form poorly soluble U adducts in organic diluents. A systematic investigation has been carried out on the extractive behavior of two typical alkyl amides of different structures with respect to the actinide ions UO/sub 2/ /sup 2+/, Th /sup 4+/, Np /sup +4/, Pu /sup +4/, NpO /sub 2/ /sup 2+/, PuO /sub 2/ / sup 2+/, Pu /sup 3+/, and Am /sup 3+/, as well as with respect to the most significant fission products. The results obtained have been compared with those obtained using TBP in the same experimental conditions, verifying the applicability of amides in the separation of U from Th

  4. Structure-property relationships for n-alkyl-isocyanate-containing polymers

    Science.gov (United States)

    Aronson, Carl Lawrence

    Poly(n-hexyl isocyanate) (PHIC), poly(n-butyl-isocyanate) (PBIC), poly(n-butyl-co-cyclohexyl isocyanate) (PBCHIC), poly(n-hexyl isocyanate-b-isoprene) (HI), poly(n-butyl isocyanate-b-isoprene) (BI) and poly(n-hexyl isocyanate-b-isoprene- b-styrene) (MS) were synthesized and characterized with respect to composition, molecular Weight and polydispersity. PHIC, HI and HIS were found to be lyotropic liquid crystalline whereas PBIC, PBCHIC and BI were found to be non-lyotropic. A lyotropic-nematic liquid crystalline phase diagram was determined for the PHIC/xylene system. A novel and reversible electric-field-induced biphasic-paranematic phase transition was found for the PHIC/xylene system from the dynamics of topological defects. The electric-field-induced phase diagram for PHIC/xylene agreed with the theoretically predicted field-induced phase diagram of Khokhlov and Semenov for semiflexible-persistent polymers. The dielectric characteristics, steady-state electrically induced birefringence and steady-state electroheological (ER) activity of PHIC, PBIC and PBCHIC solutions were compared as a function of polymer concentration. The role of lyotropic liquid crystalline ordering in the functional ER mechanism of poly( n-hexyl isocyanate) solutions is presented. PBCHIC was found to thermally decompose by a first-order rate process which became slower with increasing cyclohexyl isocyanate content from thermal gravimetric analysis. Competition between monomer dissociation and degradative trimerization as well as a non-alternating sequence distribution were determined for PBCHIC from direct pyrolysis/mass spectrometry. The Arrhenius activation energy, pre-exponential factor and entropy for diffusion and evaporation of xylene from PHIC, were found to be functions of initial polymer concentration whereas the intrinsic diffusion coefficient of the solvent was found to be independent of initial polymer concentration. The cross polarized/magic angle spinning solid state 13C

  5. 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.

  6. 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.

  7. Phosphorus-containing podands. 14. Effect of alkyl substituents at phosphorus atom on complexing ability of neutral monopodands. On the nature of abnormal alkyl effect

    International Nuclear Information System (INIS)

    Tsvetkov, E.N.; Evreinov, V.I.; Bondarenko, N.A.; Safronova, Z.V.

    1996-01-01

    The previously revealed unusual effect of alkyl substituents at phosphorus atom in phosphorus-containing monopodands of the general formula o-R 2 P(O)C 6 H 4 (OCH 2 CH 2 ) n OC 6 H 4 P(O)R 2 -o, n=1-5, R = Alk, Ph, OEt on their complexing ability towards alkali metals cations has been interpreted. Alkyl radicals create great spatial obstacles to rotation of R 2 P(O) fragments around the C-P bond as compared with other substituents, which gives rise to the appearance of anomalous alkyl effect. Solvation is an additional factor, which can bring about the anomalous effect appearance or a change in the degree of its pronouncement. 47 refs.; 3 figs.; 7 tabs

  8. Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 C-H bond and Lewis acid catalysis.

    Science.gov (United States)

    Wang, Ming-Zhong; Zhou, Cong-Ying; Wong, Man-Kin; Che, Chi-Ming

    2010-05-17

    Ruthenium porphyrins (particularly [Ru(2,6-Cl(2)tpp)CO]; tpp=tetraphenylporphinato) and RuCl(3) can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82% based on 60-95% substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron-withdrawing or electron-donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N-arylindoles to 3-{[(N-aryl-N-alkyl)amino]methyl}indoles (yield: up to 82%, conversion: up to 95%) and the alkylation of N-alkyl or N-H indoles to 3-[p-(dialkylamino)benzyl]indoles (yield: up to 73%, conversion: up to 92%). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp(3) C-H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N-arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three-component coupling reaction of the in situ generated formaldehyde with an N-alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium-labeling experiments are consistent with the alkylation of N-alkylindoles via pathway B. The relative reaction rates of [Ru(2,6-Cl(2)tpp)CO]-catalyzed oxidative coupling reactions of 4-X-substituted N,N-dimethylanilines with N-phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants sigma (R(2)=0.989), giving a rho value of -1.09. This rho value and the magnitudes of the intra- and intermolecular deuterium isotope effects (k(H)/k(D)) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4-X-substituted N,N-dimethylanilines. Ruthenium-catalyzed three-component reaction of N-alkyl/N-H indoles

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-04-30

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

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

    International Nuclear Information System (INIS)

    Frimpong, Reynolds A; Hilt, J Zach

    2008-01-01

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

  11. Oxidation and N-alkylation of galactomannan extracted from Caesalpinia ferrea var. ferrea seeds;Oxidacao e N-alquilacao de galactomanana de sementes de Caesalpina ferrea var. ferrea

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Clayton F. de; Lucyszyn, Neoli; Ferraz, Fernando A.; Sierakowski, Maria Rita, E-mail: clayton@quimica.ufpr.b [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Quimica

    2009-07-01

    The objective of this work was the synthesis and characterization of carboxyl (polyelectrolyte, GMPFOXT) and amino alkylate (amphiphilic, GMPFOXD) derivatives of the galactomannan extracted from the seeds of native specie Pau-ferro (Caesalpinia ferrea - GMPF). The derivatives were obtained by selective modification of GMPF at C-6 in the presence of TEMPO reagent (N-oxil-2,2,6,6-tetramethyl-piperidine) and dodecylamine showed high yields (approx 77 and 94% for GMPFOXT and GMPFOXD, respectively). The characteristics of the derivatives were confirmed by spectroscopic techniques of FTIR and {sup 13}C-NMR. By gel permeation chromatography (GPC), was observed a decrease of molar mass values and increase in polydispersity after derivatization, indicating change in the aggregation state in solution, caused by modification on the superficial structure. The development of these products can expand the use of them in different areas such as cosmetics and pharmaceutics, among others. (author)

  12. Effects of alkylating agents on dopamine D(3) receptors in rat brain: selective protection by dopamine.

    Science.gov (United States)

    Zhang, K; Weiss, N T; Tarazi, F I; Kula, N S; Baldessarini, R J

    1999-11-13

    Dopamine D(3) receptors are structurally highly homologous to other D(2)-like dopamine receptors, but differ from them pharmacologically. D(3) receptors are notably resistant to alkylation by 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline (EEDQ), which readily alkylates D(2) receptors. We compared EEDQ with N-(p-isothiocyanatophenethyl)spiperone (NIPS), a selective D(2)-like receptor alkylating agent, for effects on D(3) and D(2) receptors in rat brain using autoradiographic analysis. Neither agent occluded D(3) receptors in vivo at doses that produced substantial blockade of D(2) receptors, even after catecholamine-depleting pretreatments. In vitro, however, D(3) receptors were readily alkylated by both NIPS (IC(50)=40 nM) and EEDQ (IC(50)=12 microM). These effects on D(3) sites were blocked by nM concentrations of dopamine, whereas microM concentrations were required to protect D(2) receptors from the alkylating agents. The findings are consistent with the view that alkylation of D(3) receptors in vivo is prevented by its high affinity for even minor concentrations of endogenous dopamine.

  13. 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.

  14. Estudo da reação entre polietileno glicol e resina epoxídica na presença de N,N-dimetilbenzilamina Study of the reaction between polyethylene glycol and epoxy resins Using N,N-dimethylbenzylamine as catalyst

    Directory of Open Access Journals (Sweden)

    Mario Zacharuk

    2011-01-01

    Full Text Available Neste trabalho foi estudada a reação entre polietileno glicol (PEG e uma resina epoxídica à base de diglicidil éter de bisfenol A (DGEBA, na presença de N,N-dimetilbenzilamina (DMBA, sendo os produtos desta reação avaliados por espectroscopia no infravermelho (FTIR, espectroscopia de ressonância magnética nuclear de próton (RMN-1H e medidas de viscosidade cone-prato. Amostras curadas com um endurecedor à base de poliamina foram também submetidas a ensaios de tração e calorimetria exploratória diferencial (DSC. Os resultados das análises de viscosidade, FTIR e RMN (1H confirmaram a ocorrência da reação entre grupos epóxi do DGEBA e grupos hidroxila do PEG na presença de DMBA, a 100 ºC. As análises de DSC e os ensaios de tração dos sistemas curados mostram que a reação de DGEBA com PEG gera um material com temperatura de transição vítrea (Tg significativamente menor, em conjunto com o aumento da deformação na ruptura e decréscimo do modulo de elasticidade, quando comparados ao sistema epoxídico de referência (DGEBA.In this work the reaction of polyethylene glycol (PEG and epoxy resin (BADGE in the presence of N,N-dimethylbenzylamine (DMBA was studied. The reaction products were evaluated by infrared spectroscopy (FTIR, nuclear magnetic resonance spectroscopy (NMR and viscosity measurements. Samples cured with a polyamine-based hardener were also submitted to tensile tests and differential scanning calorimetry (DSC. The results of the viscosity analyses, FTIR and RMN (¹H confirmed the reaction between DGEBA epoxy groups and PEG hydroxyl groups in the presence of DMBA, at 100 ºC. DSC analyses and tensile tests of cured systems showed that the reaction of DGEBA with PEG leads to a reduction of Tg, generating a more flexible material.

  15. DNA alkylation damage as a sensor of nitrosative stress in Mycobacterium tuberculosis

    OpenAIRE

    Durbach, S I; Springer, B; Machowski, E E; North, R J; Papavinasasundaram, K G; Colston, M J; Böttger, E C; Mizrahi, V

    2003-01-01

    One of the cellular consequences of nitrosative stress is alkylation damage to DNA. To assess whether nitrosative stress is registered on the genome of Mycobacterium tuberculosis, mutants lacking an alkylation damage repair and reversal operon were constructed. Although hypersensitive to the genotoxic effects of N-methyl-N′-nitro-N-nitrosoguanidine in vitro, the mutants displayed no phenotype in vivo, suggesting that permeation of nitrosative stress to the level of cytotoxic DNA damage is res...

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

    Science.gov (United States)

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

    2013-12-01

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

  17. Direct dehydroxytrifluoromethylthiolation of alcohols using silver(I) trifluoromethanethiolate and tetra-n-butylammonium iodide.

    Science.gov (United States)

    Liu, Jian-Bo; Xu, Xiu-Hua; Chen, Zeng-Hao; Qing, Feng-Ling

    2015-01-12

    An unprecedented reaction for the direct trifluoromethylthiolation and fluorination of alkyl alcohols using AgSCF3 and nBu4NI has been developed. The trifluoromethylthiolated compounds and alkyl fluorides were selectively formed by changing the ratio of AgSCF3/nBu4NI. This protocol is tolerant of different functional groups and might be applicable to late-stage trifluoromethylthiolation of alcohols. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Rational design, efficient syntheses and biological evaluation of N,N '-symmetrically bis-substituted butylimidazole analogs as a new class of potent Angiotensin II receptor blockers

    Czech Academy of Sciences Publication Activity Database

    Agelis, G.; Resvani, A.; Koukoulitsa, C.; Tůmová, Tereza; Slaninová, Jiřina; Kalavrizioti, D.; Spyridaki, K.; Afantitis, A.; Melagraki, G.; Siafaka, A.; Gkini, E.; Megariotis, G.; Grdadolnik, S. G.; Papadopoulos, M. G.; Vlahakos, D.; Maragoudakis, M.; Liapakis, G.; Mavromoustakos, T.; Matsoukas, J.

    2013-01-01

    Roč. 62, Apr (2013), s. 352-370 ISSN 0223-5234 Institutional support: RVO:61388963 Keywords : AT1 receptor blockers * N,N '-Bis-alkylated butylimidazole analogs * synthesis * Wittig reaction * hydroxymethylation * structure elucidation Subject RIV: CC - Organic Chemistry Impact factor: 3.432, year: 2013

  19. U.v.-induced and N-methyl-N'-nitrosoguanidine-induced mutagenesis in Bacillus thuringiensis

    International Nuclear Information System (INIS)

    Auffray, Y.; Boutibonnes, P.

    1987-01-01

    The lethal and mutagenic effects of u.v. light and N-methyl-N'-nitro-N-nitrosoguanidine (MNNG) on Bacillus thuringiensis were investigated. Lethality studies demonstrated that B. thuringiensis was relatively sensitive to these agents. This bacterium was mutated at the rifampicin resistance marker by u.v. light and to a lesser extent by the direct acting alkylating agent MNNG. One mutant selected for its greater sensitivity to u.v. light expressed a higher frequency of mutagenesis after u.v. light treatment and appeared to be defective in an excision repair pathway. However, this mutant was only slightly mutable by MNNG in comparison with the wild-type strain. This unusual phenotype does not yet have a parallel among the radiation sensitive mutants described in other bacterial species. (author)

  20. Direct-acting DNA alkylating agents present in aqueous extracts of areca nut and its products.

    Science.gov (United States)

    Hu, Chiung-Wen; Chao, Mu-Rong

    2012-11-19

    Areca nut is a carcinogen to humans and has been strongly associated with oral premalignant and malignant diseases. Previous studies speculated the presence of unknown direct-acting mutagens present in aqueous extracts of areca nut. We hypothesized whether any direct-acting alkylating agents are present in areca nut and its commercial products. In this study, calf thymus DNA was treated with four different aqueous extracts obtained from unripe and ripe areca nuts or their commercial products, namely, pan masala (without tobacco) and gutkha (with tobacco). Three N-alkylated purines including N7-methylguanine (N7-MeG), N3-methyladenine (N3-MeA), and N7-ethylguanine (N7-EtG) were detected using sensitive and specific isotope-dilution liquid chromatography-tandem-mass spectrometry (LC-MS/MS) methods. The results showed that four types of aqueous extracts significantly induced the formation of N7-MeG and N3-MeA in a linear dose-response manner. Extracts from unripe areca nut exhibited higher methylating potency than those of ripe areca nut, while gutkha had higher methylating potency than pan masala. Meanwhile, gutkha made with areca nut and tobacco, was the only extract found to induce the formation of N7-EtG. Overall, this study first demonstrated that the presence of direct-acting alkylating agents in areca nut and its commercial products exist at a level that is able to cause significant DNA damage. Our findings may provide another mechanistic rationale for areca nut-mediated oral carcinogenesis and also highlight the importance and necessity of the identification of these direct-acting alkylating agents.

  1. A Modular Synthesis of N-Benzotriazole Ureas Using Alkylation of 5-Nitrobenzotriazole

    Czech Academy of Sciences Publication Activity Database

    Machara, A.; Konvalinka, Jan; Kotora, M.

    2016-01-01

    Roč. 1, č. 1 (2016), s. 101-107 ISSN 2365-6549 R&D Projects: GA ČR GA13-19561S Institutional support: RVO:61388963 Keywords : benzotriazole * alkylation * urea * isocyanate * reduction Subject RIV: CE - Biochemistry

  2. Sequential metabolism of secondary alkyl amines to metabolic-intermediate complexes: opposing roles for the secondary hydroxylamine and primary amine metabolites of desipramine, (s)-fluoxetine, and N-desmethyldiltiazem.

    Science.gov (United States)

    Hanson, Kelsey L; VandenBrink, Brooke M; Babu, Kantipudi N; Allen, Kyle E; Nelson, Wendel L; Kunze, Kent L

    2010-06-01

    Three secondary amines desipramine (DES), (S)-fluoxetine [(S)-FLX], and N-desmethyldiltiazem (MA) undergo N-hydroxylation to the corresponding secondary hydroxylamines [N-hydroxydesipramine, (S)-N-hydroxyfluoxetine, and N-hydroxy-N-desmethyldiltiazem] by cytochromes P450 2C11, 2C19, and 3A4, respectively. The expected primary amine products, N-desmethyldesipramine, (S)-norfluoxetine, and N,N-didesmethyldiltiazem, are also observed. The formation of metabolic-intermediate (MI) complexes from these substrates and metabolites was examined. In each example, the initial rates of MI complex accumulation followed the order secondary hydroxylamine > secondary amine > primary amine, suggesting that the primary amine metabolites do not contribute to formation of MI complexes from these secondary amines. Furthermore, the primary amine metabolites, which accumulate in incubations of the secondary amines, inhibit MI complex formation. Mass balance studies provided estimates of the product ratios of N-dealkylation to N-hydroxylation. The ratios were 2.9 (DES-CYP2C11), 3.6 [(S)-FLX-CYP2C19], and 0.8 (MA-CYP3A4), indicating that secondary hydroxylamines are significant metabolites of the P450-mediated metabolism of secondary alkyl amines. Parallel studies with N-methyl-d(3)-desipramine and CYP2C11 demonstrated significant isotopically sensitive switching from N-demethylation to N-hydroxylation. These findings demonstrate that the major pathway to MI complex formation from these secondary amines arises from N-hydroxylation rather than N-dealkylation and that the primary amines are significant competitive inhibitors of MI complex formation.

  3. Toxicological evaluation and metabolism of two N-alkyl benzamide umami flavour compounds: N-(heptan-4-ylbenzo[d][1,3]dioxole-5-carboxamide and (R-N-(1-methoxy-4-methylpentan-2-yl-3,4-dimethylbenzamide

    Directory of Open Access Journals (Sweden)

    Donald S. Karanewsky

    Full Text Available Toxicological evaluations of two N-alkyl benzamide umami flavour compounds, N-(heptan-4-ylbenzo[d][1,3]dioxole-5-carboxamide (S807, CAS 745047-51-2 and (R-N-(1-methoxy-4-methylpentan-2-yl-3,4-dimethylbenzamide (S9229, CAS 851669-60-8, were completed for the purpose of assessing their safety for use in food and beverage applications. Both S807 and S9229 undergo rapid oxidative metabolism by both rat and human liver microsomes in vitro. In pharmacokinetic studies in rats, the systemic exposure to S9229 on oral administration is very low at all doses (% F < 1%, while that of S807 demonstrated a non-linear dose dependence. In metabolism studies in rats, hydroxylation of the C-4 aryl methyl group was found to be the dominant metabolic pathway for S9229. The dominant metabolic pathway for S807 in the rat involved oxidative scission of the methylenedioxy moiety to produce the corresponding 3,4-dihydroxybenamide which is further converted by Phase II metabolic enzymes to the 3- and 4-O-methyl ethers as well as their corresponding glucuronides. Both S807 and S9229 were not found to be mutagenic or clastogenic in vitro, and did not induce micronuclei in polychromatic erythrocytes in vivo. In a subchronic oral toxicity study in rats, the no-observed-effect-level (NOEL for S807 was 20 mg/kg bw/day when administered in the diet for 13 weeks. The no-observed-adverse-effect-level (NOAEL for S9229 in rats was 100 mg/kg bw/day (highest dose tested when administered in the diet for 28 consecutive days. Keywords: S807, S9229, FEMA GRAS, Subchronic toxicological evaluation, Genetic toxicological evaluation

  4. Quantitative and subcellular localization analysis of the nuclear isoform dUTP pyrophosphatase in alkylating agent-induced cell responses

    International Nuclear Information System (INIS)

    Hu, Xiaolan; Yu, Yingnian; Li, Qian; Wu, Danxiao; Tan, Zhengning; Wang, Cheng; Wang, Jvping; Wu, Meiping

    2011-01-01

    Highlights: → MNNG-induced appearance of DUT-N in the extracellular fluid has cellular specificity. → MNNG alters the subcellular distribution of DUT-N in human cells in different ways. → DUT-N may be a potential biomarker to assess the risk of alkylating agents exposure. -- Abstract: Our previous proteome analysis showed that the nuclear isoform of dUTP pyrophosphatase (DUT-N) was identified in the culture medium of human amnion FL cells after exposure to the alkylating agent N-methyl-N'-nitro-N-nitrosoguanidine (MNNG). These results suggest that DUT-N may be a potential early biomarker to assess the risk of alkylating agents exposure. DUT-N is one of the two isoforms of deoxyuridine triphosphate nucleotidohydrolase (dUTPase). Our current knowledge of DUT-N expression in human cells is very limited. In the current study, we first investigated the appearance of DUT-N in the culture medium of different human cell lines in response to a low concentration of MNNG exposure. We verified that the MNNG-induced appearance of DUT-N in the extracellular environment is cell-specific. Western blot analysis confirmed that the intracellular DUT-N changes responded to MNNG in a concentration-dependent and cell-specific manner. Furthermore, subcellular fraction experiments showed that 0.25 μM MNNG treatment dramatically increased the DUT-N expression levels in the cytoplasmic extracts prepared from both FL and HepG2 cells, increased DUT-N levels in nuclear extracts prepared from HepG2 cells, and decreased DUT-N levels in nuclear extracts from FL cells. Morphological studies using immunofluorescence showed that a low concentration of MNNG could alter the distribution of DUT-N in FL and HepG2 cells in different ways. Taken together, these studies indicate a role of DUT-N in alkylating agent-induced cell responses.

  5. Fluorescence quenching of N,N-bis(2,5-di-tert-butylphenyl)-3,4:9,10-perylenebis(dicarboximide) (DBPI) by silver nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    El-Daly, Samy A., E-mail: samyeldaly@yahoo.com [Chemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589 (Saudi Arabia); Chemistry Department, Faculty of Science, Tanta University, Tanta 2173 (Egypt); Rahman, Mohammed M. [Chemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589 (Saudi Arabia); Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University, PO Box 80203, Jeddah 21589 (Saudi Arabia); Alamry, Kahlid A. [Chemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589 (Saudi Arabia); Asiri, Abdullah M. [Chemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589 (Saudi Arabia); Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University, PO Box 80203, Jeddah 21589 (Saudi Arabia)

    2014-04-15

    The interaction of a perylene derivative namely N,N-bis(2,5-di-tert-butylphenyl)-3,4:9,10-perylenebis(dicarboximide) (DBPI) with colloidal silver nanoparticles (AgNPs) was studied in ethanol and ethylene glycol using steady state fluorescence quenching measurements. The Stern–Volmer quenching rate constant (K{sub sv}) was calculated as 4.03×10{sup 9} and 29.14×10{sup 9} M{sup −1} in ethanol and ethylene glycol, respectively. From fluorescence quenching data, static quenching and energy transfer play a major role in the fluorescence quenching of DBPI by AgNPs. The apparent association constant (k{sub app}) was calculated as 1.26×10{sup 8} M{sup −1} in EtOH and 1.83×10{sup 9} M{sup −1} in ethylene glycol. Due to potential AgNPs interaction with DBPI, the average AgNPs size is increased slightly from ∼37.1 nm (As-prepared) to 48.9 nm. -- Highlights: • Fluorescence quenching of photostable DBPI by AgNPs. • Static quenching mechanism of interaction between DBPI and AgNPs. • Enhancement of fluorescence quenching of DBPI in ethylene glycol.

  6. Experimental and theoretical study of surface tension of binary mixtures of (n-alkyl acetates + heptane, benzene, and toluene)

    International Nuclear Information System (INIS)

    Rafati, Amir Abbas; Ghasemian, Ensieh

    2009-01-01

    Surface properties of binary mixtures of (n-alkyl acetates + heptane, benzene, and toluene) have been measured by surface tension method at T = 298.15 K and atmospheric pressure. Also, the surface tension has been predicted based on the Suarez method. This method combines a model for the description of surface tension of liquid mixtures with a group contribution method for the calculation of activity coefficient. The mean relative standard deviations obtained from the comparison of experimental (measured) and calculated surface tension values for the eight binary systems are less than 1.5%, which leads to concluding that the model shows a good accuracy in different situations in comparison with other predicted equations. In addition, the relative Gibbs adsorption and the surface mole fraction have been evaluated using this model. The surface tension deviations were calculated from experimental results and have been fitted to the Redlich-Kister type polynomial relation

  7. Nitric oxide donors attenuate clongenic potential in rat C6 glioma cells treated with alkylating chemotherapeutic agents.

    Science.gov (United States)

    Yang, Jir-Jei; Yin, Jiu-Haw; Yang, Ding-I

    2007-05-11

    1,3-Bis(2-chloroethyl)-1-nitrosourea (BCNU) kills tumor cells via multiple actions including alkylation and carbamoylation. Previously, we have reported that formation of S-nitrosoglutathione (GSNO) in glioma cells overexpressing inducible nitric oxide synthase (iNOS) contributed to nitric oxide (NO)-dependent carbamoylating chemoresistance against BCNU. To further characterize the effects of NO on alkylating cytotoxicity, colony formation assay was applied to evaluate the effects of various NO donors on rat C6 glioma cells challenged with alkylating agents. We demonstrate that NO donors including GSNO, diethylamine NONOate (DEA/NO), and sodium nitroprusside (SNP) substantially reduced the extent of colony formation in glioma cells treated with alkylating agents, namely methyl methanesulfonate (MMS), N-methyl-N-nitrosourea (MNU), and N-ethyl-N-nitrosourea (ENU). Without alkylating agents these NO-releasing agents alone had no effects on clongenic potential of rat C6 glioma cells. Among these three NO donors used, the effectiveness in potentiating alkylating cytotoxicity is in the order of "GSNO>DEA/NO>SNP" when applied at the same dosages. GSNO also exerted similar synergistic actions reducing the extents of colony formation when co-administrated with 1,2-bis(methylsulfonyl)-1-(2-chloroethyl)-hydrazine (compound #1), another alkylating agent that mimics the chloroethylating action of BCNU. Together with our previous findings, we propose that NO donors may be used as adjunct chemotherapy with alkylating agents for such malignant brain tumors as glioblastoma multiforme (GBM). In contrast, production of NO as a result of iNOS induction, such as that occurring after surgical resection of brain tumors, may compromise the efficacy of carbamoylating chemotherapy.

  8. Exposure to glycols and their renal effects in motor servicing workers.

    Science.gov (United States)

    Laitinen, J; Liesivuori, J; Savolainen, H

    1995-10-01

    Ten car mechanics frequently exposed to glycol-based cooling liquids were followed during a workshift. Airborne ethylene and propylene glycol concentrations in the car mechanics' environment were measured. The car mechanics gave urine samples after the workshift and their excretion of ethylene glycol, propylene glycol, oxalic acid, calcium and ammonia was analysed and compared to that of unexposed office workers. Urinary succinate dehydrogenase activity and glycosaminoglycans were also measured in both groups. Airborne ethylene and propylene glycol concentrations in the car mechanics' environment were negligible. Urinary ethylene glycol excretion in exposed workers was significantly higher than that in unexposed workers, but propylene glycol excretion was at the same levels as in controls. In the exposed group, the excretion of the end metabolite of ethylene glycol, oxalic acid (47 +/- 11 mmol/mol creatinine, mean +/- SD, n = 10) differed slightly from that of controls (36 +/- 14 mmol/mol creatinine, mean +/- SD, n = 10). Urinary excretion of ammonia was higher among exposed workers than office workers. The excretion of calcium did not differ from that of controls. A marginally decreased urinary succinate dehydrogenase activity was found in the exposed men. The excretion of glycosaminoglycans was significantly lower in exposed workers. Therefore, it seems that ethylene glycol is absorbed by skin contact. The internal body burden is associated with oxaluria and increased ammoniagenesis typical of chronic acidosis.

  9. Synthesis, resolution and radioiodination of S(-)trans-5-hydroxy-2-[N-n-propyl-N-(3'-iodo-2'-propenyl)amino]tet ralin-S(-)trans-5-OH-PIPAT: a new dopamine D2-like receptor ligand

    International Nuclear Information System (INIS)

    Chumpradit, Sumalee; Meiping Kung; Vessotskie, Janet; Kung, H.F.

    1995-01-01

    A new dopamine D2-like receptor ligand, (R,S)trans-5-hydroxy-2-[N-n0propyl-N-(3'-iodo-2'-propeny)amino]tet ralin ((R,S)trans-5-OH-PIPAT,3), based on high affinity dopamine receptor agonist 5-hydroxy-2-[N,N-(di-n-propyl)-2-amino]tetralin (5-OH-DPAT,1), was prepared. The synthesis was achieved by a reductive amination of 5-methoxy-2-tetralone with n-propylamine, followed by N-alkylation, to afford 5-methoxy-N-propyl-N-2'-aminotetralin,7. Reduction of 7 with tributyltin hydride gave the tri-n-butyl tin derivative,8, which was converted to 9 by an iododemetalation reaction. Demethylation of 9 gave the desired compound, (R,S)trans-5-OH-PIPAT,3. The resolved (R) and (S)trans-5-OH-PIPAT,3 were also quantitatively prepared. (author)

  10. Reaction of the diimine pyridine ligand with aluminum alkyls: An unexpectedly complex reaction

    NARCIS (Netherlands)

    Knijnenburg, Q.; Smits, J.M.M.; Budzelaar, P.H.M.

    2006-01-01

    The diimine pyridine ligand 2,6-{2,6-(Pr2C6H3N)-Pr-i=CMe}(2)C5H3N (1) was reacted with a series of aluminum alkyls (Me3Al, Et3Al, (Bu3Al)-Bu-i, (Bu2AlH)-Bu-i, Et2AlCl). Depending on the choice of alkyl, addition to the imine carbon and the pyridine C2 and C4 positions was observed. Addition to C2

  11. Ada response – a strategy for repair of alkylated DNA in bacteria

    Science.gov (United States)

    Mielecki, Damian; Grzesiuk, Elżbieta

    2014-01-01

    Alkylating agents are widespread in the environment and also occur endogenously. They can be cytotoxic or mutagenic to the cells introducing alkylated bases to DNA or RNA. All organisms have evolved multiple DNA repair mechanisms to counteract the effects of DNA alkylation: the most cytotoxic lesion, N3-methyladenine (3meA), is excised by AlkA glycosylase initiating base excision repair (BER); toxic N1-methyladenine (1meA) and N3-methylcytosine (3meC), induced in DNA and RNA, are removed by AlkB dioxygenase; and mutagenic and cytotoxic O6-methylguanine (O6meG) is repaired by Ada methyltransferase. In Escherichia coli, Ada response involves the expression of four genes, ada, alkA, alkB, and aidB, encoding respective proteins Ada, AlkA, AlkB, and AidB. The Ada response is conserved among many bacterial species; however, it can be organized differently, with diverse substrate specificity of the particular proteins. Here, an overview of the organization of the Ada regulon and function of individual proteins is presented. We put special effort into the characterization of AlkB dioxygenases, their substrate specificity, and function in the repair of alkylation lesions in DNA/RNA. PMID:24810496

  12. Modified reaction mechanism of aerated n-dodecane liquid flowing over heated metal tubes

    Science.gov (United States)

    Reddy, K. T.; Cernansky, N. P.; Cohen, R. S.

    1988-01-01

    The degradation mechanism of the n-dodecane was studied using a modified jet fuel thermal oxidation tester containing a sample withdrawal system as a reaction vessel. The reaction products were identified using gas chromatography and mass spectorometry. The soluble products were found to consist mainly of C5-C10 n-alkanes and 1-alkenes, C7-C10 aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, dodecyl hydroperoxide (ROOH) decomposition products, and C24 alkane isomers. The data from the experiments agreed with those of Hazlett et al. (1977). It was found that alkyl peroxide radical reactions dominate in the autooxidation temperature regime (at T not above 300 C); the dominant path is for the alkyl peroxyl radical to react bimolecularly with fuel to yield primarily alkyl hydroperoxides. The alkyl peroxide radical also undergoes self-termination and unimolecular isomerization and decomposition reactions, to yield smaller amounts of C12 alcohol plus ketone products and tetrahydrofuran derivatives, respectively.

  13. Ada response - a strategy for repair of alkylated DNA in bacteria.

    Science.gov (United States)

    Mielecki, Damian; Grzesiuk, Elżbieta

    2014-06-01

    Alkylating agents are widespread in the environment and also occur endogenously. They can be cytotoxic or mutagenic to the cells introducing alkylated bases to DNA or RNA. All organisms have evolved multiple DNA repair mechanisms to counteract the effects of DNA alkylation: the most cytotoxic lesion, N(3)-methyladenine (3meA), is excised by AlkA glycosylase initiating base excision repair (BER); toxic N(1)-methyladenine (1meA) and N(3)-methylcytosine (3meC), induced in DNA and RNA, are removed by AlkB dioxygenase; and mutagenic and cytotoxic O(6)-methylguanine (O(6) meG) is repaired by Ada methyltransferase. In Escherichia coli, Ada response involves the expression of four genes, ada, alkA, alkB, and aidB, encoding respective proteins Ada, AlkA, AlkB, and AidB. The Ada response is conserved among many bacterial species; however, it can be organized differently, with diverse substrate specificity of the particular proteins. Here, an overview of the organization of the Ada regulon and function of individual proteins is presented. We put special effort into the characterization of AlkB dioxygenases, their substrate specificity, and function in the repair of alkylation lesions in DNA/RNA. © 2014 The Authors. FEMS Microbiology Letters published by John Wiley & Sons Ltd on behalf of Federation of European Microbiological Societies.

  14. Induction of 6-thioguanine-resistant lymphocytes in Fischer 344 rats following in vivo exposure to N-ethyl-N-nitrosourea and cyclophosphamide

    International Nuclear Information System (INIS)

    Aidoo, A.; Lyn-Cook, L.E.; Mittelstaedt, R.A.; Heflich, R.H.; Casciano, D.A.

    1991-01-01

    The authors have developed a limiting dilution clonal assay for determining the frequency of 6-thioguanine-resistant (TG r ) lymphocytes produced in rats by in vivo exposure to genotoxic agents. Lymphocyte cloning efficiencies (CEs) were highest in plates containing both irradiated TK6 cells and irradiated autologous feeder cells. To measure the effects of chemical mutagens on the frequency of TG r lymphocytes, rats were given a single i.p. injection of N-ethyl-N-nitrosourea (ENU), a direct-acting alkylating agent, cyclophosphamide (CP), an indirect acting alkylating agent. Lymphocytes were isolated, primed, and cloned at 4 weeks after CP treatment and at 1,2,4 and 6 weeks after ENU treatment. CE in these cultures ranged from 12% to 27%. Cultures were also established for measuring CE in the presence of 6-thioguanine (TG). The dose-dependent responses obtained with both ENU and CP treatments suggest that rat lymphocytes are sensitive to direct- and indirect-acting alkylating agents administered in vivo and that the rat lymphocyte assay is a useful complement to the in vivo/in vitro mouse assay for determining the mutagenicity of environmental toxicants

  15. New iodocuprates(I) with N-heterocyclic molecules as the cations

    International Nuclear Information System (INIS)

    Zhao, Jin-Jing; Zhang, Xiao; Wang, Yan-Ning; Jia, Hong-Li; Yu, Jie-Hui; Xu, Ji-Qing

    2013-01-01

    Under the hydrothermal conditions, the reactions between CuI, KI and bp/bpp (bp=4,4′-bipiperidine, bpp=1,3-bis(4-piperidyl)propane) in an acidic alcohol solution produced three new organically templated iodocuprates(I) as [H 2 bp] 2 [Cu 2 I 6 ] 1, [tmbp][Cu 2 I 4 ] 2 and [tmbpp] 2 [Cu 4 I 8 ]·2H 2 O 3 (tmbp 2+ =N,N,N′,N′-tetramethyl-4,4′-bipiperidinium; tmbpp 2+ =N,N,N′,N′-tetramethyl-1,3-bis(4-piperidyl)propane dication). X-ray analysis revealed that (i) tmbp 2+ and tmbpp 2+ in compounds 2 and 3 originated from the complete N-alklation of bp/bpp with CH 3 OH; (ii) templated by H 2 bp 2+ , the inorganic anion [Cu 2 I 6 ] 2− of 1 possesses a dinuclear structure, whereas templated by tmbp 2+ , the inorganic anion [Cu 2 I 4 ] 2− of 2 exhibits a one-dimensional (1D) chain structure; (iii) templated by tmbpp 2+ , the inorganic anion [Cu 4 I 8 ] 4− of 3 shows a cubane-like structure modified by four terminal I − ions. The photoluminescence analysis indicates that compounds 1 and 2 emit blue light, while compound 3 emits green light. - Graphical abstract: By employing hydrothermal in situ N-alkylation of bp/bpp with CH 3 OH, three new organically templated iodocuprates(I) were obtained. Display Omitted - Highlights: • Three new organically templated iodocuprates(I) were reported. • Cations tmbp 2+ and tmbpp 2+ originated from in situ alkylation of bp/bpp with CH 3 OH. • H + and I − play a key role in alkylation of bp/bpp with CH 3 OH. • Photoluminescence emission for iodocuprates(I) is related to Cu···Cu interaction

  16. Randomized cross-over trial of polyethylene glycol electrolyte solution and water for colostomy irrigation.

    Science.gov (United States)

    O'Bichere, Austin; Green, Colin; Phillips, Robin K S

    2004-09-01

    Water for colostomy irrigation is largely absorbed by the colon, which may result in less efficient expulsion of stool. This study compared the outcome of colonic cleansing with water and polyethylene glycol solution. In a cross-over study, 41 colostomy irrigators were randomly assigned to water or polyethylene glycol solution irrigation first and then the other regimen, each for one week. Patients recorded fluid inflow time, total washout time, cramps, leakage episodes, number of stoma pouches used, and satisfaction scores (Visual Analog Scale, 1-10: 1 = poor, and 10 = excellent). The median and interquartile range for each variable was calculated, and the two treatments were compared (Wilcoxon's test). Eight patients failed to complete the study. Thirty-three patients (20 females; mean age, 55 (range, 39-73) years) provided 352 irrigation sessions: water (n = 176), and polyethylene glycol solution (n = 176). Irrigation was performed every 24, 48, and 72 hours by 17, 9, and 7 patients respectively, using 500 ml (n = 1), 750 ml (n = 2), 1,000 ml (n = 16), 1,500 ml (n = 11), 2,000 ml (n = 2), and 3,500 ml (n = 1) of fluid. The median and interquartile range for water vs. polyethylene glycol solution were: fluid inflow time (6 (range, 4.4-10.8) vs. 6.3 (range, 4.1-11) minutes; P = 0.48), total washout time (53 (range, 33-69) vs. 38 (range, 28-55) minutes; P = 0.01), leakage episodes (2.3 (range, 1.7-3.8) vs. 0.7 (range, 0.2-1); P colostomy irrigation.

  17. Non-random alkylation of DNA sequences induced in vivo by chemical mutagens

    Energy Technology Data Exchange (ETDEWEB)

    Durante, M.; Geri, C.; Bonatti, S.; Parenti, R. (Universita di Pisa (Italy))

    1989-08-01

    Previous studies of the interaction of alkylating agents on the eukaryotic genome support the idea that induction of DNA adducts is at specific genomic sites. Here we show molecular and cytological evidence that alkylation is rather specific. Mammalian cell cultures were exposed to different doses of mutagens and the DNA was analyzed by density gradient ultracentrifugation, hydroxylapatite fractionation, and by restriction enzyme analysis. Studies with the labelled mutagens N-ethyl-N-nitrosourea and N-methyl-N'-nitro-N-nitrosoguanidine show that there is a non-random distribution of the adducts. The adducts are found more frequently in A-T, G-C rich satellite DNA and highly repetitive sequences. Analysis with restriction enzymes shows that both methyl and ethyl groups influence the restriction patterns of the enzymes HpaII and MspI that recognize specific endogenous DNA methylation. These data suggest, as a subsequent mechanism, a modification in the pattern of the normal endogenous methylation of 5-methylcytosine.

  18. 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.

  19. Interaction mechanisms of ionic liquids [Cnmim]Br (n=4, 6, 8, 10) with bovine serum albumin

    International Nuclear Information System (INIS)

    Yan Hua; Wu Junyong; Dai Guoliang; Zhong Aiguo; Chen Hao; Yang Jianguo; Han Deman

    2012-01-01

    It is important to study the interaction of ionic liquids (ILs) with protein for the applications of ILs in biochemical process, and help the researchers to choose and design the better ILs to serve as a solvent. In this work, the interaction between 1-alkyl-3-methylimidazolium bromide [C n mim]Br (n=4, 6, 8, 10) and bovine serum albumin (BSA) was systematically investigated for the first time by multi-spectroscopic approach (fluorescence, UV–vis and FT-IR spectroscopy) and density functional theory (DFT). [C n mim]Br (n=4, 6, 8, 10) can bind to BSA by H-bond interaction between their cationic headgroups and Asp/Glu amino acid residue at the surface of BSA, and hydrophobic interaction between their hydrocarbon chains and the hydrophobic amino acid residues in the interior of BSA. On the basis of thermodynamic parameters and the similar structure of [C n mim]Br (n=4, 6, 8, 10), it can be inferred that the hydrophobic interaction plays a major role in the interaction of [C 10 mim]Br with BSA, while the hydrogen bond and van der Waals force play a major role in the interaction of [C n mim]Br (n=4, 6, 8) with BSA. Synchronous fluorescence and FT-IR spectra indicate that [C 10 mim]Br could markedly change the secondary structure of BSA, while [C n mim]Br (n=4, 6, 8) could slightly change the secondary structure of BSA. The results allowed us to understand (i) the effect of the alkyl chain length of the cation on the mechanism of ILs–protein interaction and (ii) the effect of the alkyl chain length of the cation on the protein secondary structure. - Highlights: ► Interaction of [C n mim]Br with BSA was investigated by spectroscopy and DFT. ► Interaction mechanisms and BSA secondary structure were discussed. ► Effects of the alkyl chain length of cation were presented.

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

    Science.gov (United States)

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

    2016-11-10

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

  1. 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

  2. System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO{sub 2}, n-alkanes, and poly(ethylene glycol) dimethyl ethers

    Energy Technology Data Exchange (ETDEWEB)

    Moultos, Othonas A.; Economou, Ioannis G. [Chemical Engineering Program, Texas A& M University at Qatar, P.O. Box 23847, Doha (Qatar); Zhang, Yong; Maginn, Edward J., E-mail: ed@nd.edu [Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Tsimpanogiannis, Ioannis N. [Chemical Engineering Program, Texas A& M University at Qatar, P.O. Box 23847, Doha (Qatar); Environmental Research Laboratory, National Center for Scientific Research “Demokritos,” 15310 Aghia Paraskevi Attikis (Greece)

    2016-08-21

    Molecular dynamics simulations were carried out to study the self-diffusion coefficients of CO{sub 2}, methane, propane, n-hexane, n-hexadecane, and various poly(ethylene glycol) dimethyl ethers (glymes in short, CH{sub 3}O–(CH{sub 2}CH{sub 2}O){sub n}–CH{sub 3} with n = 1, 2, 3, and 4, labeled as G1, G2, G3, and G4, respectively) at different conditions. Various system sizes were examined. The widely used Yeh and Hummer [J. Phys. Chem. B 108, 15873 (2004)] correction for the prediction of diffusion coefficient at the thermodynamic limit was applied and shown to be accurate in all cases compared to extrapolated values at infinite system size. The magnitude of correction, in all cases examined, is significant, with the smallest systems examined giving for some cases a self-diffusion coefficient approximately 15% lower than the infinite system-size extrapolated value. The results suggest that finite size corrections to computed self-diffusivities must be used in order to obtain accurate results.

  3. 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...

  4. Anionic subsites of the acetylcholinesterase from Torpedo californica: affinity labelling with the cationic reagent N,N-dimethyl-2-phenyl-aziridinium.

    OpenAIRE

    Weise, C; Kreienkamp, H J; Raba, R; Pedak, A; Aaviksaar, A; Hucho, F

    1990-01-01

    Several peptides of acetylcholinesterase of Torpedo californica labelled with the alkylating reagent [3H]N,N-dimethyl-2-phenyl-aziridinium (DPA) were localized within the primary structure. One peptide had the sequence KPQELIDVE (positions 270-278); the incorporation of DPA into this peptide could be specifically suppressed by propidium, which suggests that it is part of the peripheral anionic site. The incorporation of DPA into two other peptides was insensitive to propidium but could be pre...

  5. Protective efficacy of menthol propylene glycol carbonate compared to N, N-diethyl-methylbenzamide against mosquito bites in Northern Tanzania

    Directory of Open Access Journals (Sweden)

    Kweka Eliningaya J

    2012-09-01

    Full Text Available Abstract Background The reduction of malaria parasite transmission by preventing human-vector contact is critical in lowering disease transmission and its outcomes. This underscores the need for effective and long lasting arthropod/insect repellents. Despite the reduction in malaria transmission and outcomes in Tanzania, personal protection against mosquito bites is still not well investigated. This study sought to determine the efficacy of menthol propylene glycol carbonate (MR08, Ocimum suave as compared to the gold standard repellent N, N-diethyl-methylbenzamide (DEET, either as a single dose or in combination (blend, both in the laboratory and in the field against Anopheles gambiae s.l and Culex quinquefasciatus. Methods In the laboratory evaluations, repellents were applied on one arm while the other arm of the same individual was treated with a base cream. Each arm was separately exposed in cages with unfed female mosquitoes. Repellents were evaluated either as a single dose or as a blend. Efficacy of each repellent was determined by the number of mosquitoes that landed and fed on treated arms as compared to the control or among them. In the field, evaluations were performed by human landing catches at hourly intervals from 18:00 hr to 01:00 hr. Results A total of 2,442 mosquitoes were collected during field evaluations, of which 2,376 (97.30% were An. gambiae s.l while 66 (2.70% were Cx. quinquefaciatus. MR08 and DEET had comparatively similar protective efficacy ranging from 92% to 100 for both single compound and blends. These findings indicate that MR08 has a similar protective efficacy as DEET for personal protection outside bed nets when used singly and in blends. Because of the personal protection provided by MR08, DEET and blends as topical applicants in laboratory and field situations, these findings suggest that, these repellents could be used efficiently in the community to complement existing tools. Overall, Cx

  6. 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.

  7. Copper-catalyzed transformation of ketones to amides via C(CO)-C(alkyl) bond cleavage directed by picolinamide.

    Science.gov (United States)

    Ma, Haojie; Zhou, Xiaoqiang; Zhan, Zhenzhen; Wei, Daidong; Shi, Chong; Liu, Xingxing; Huang, Guosheng

    2017-09-13

    Copper catalyzed chemoselective cleavage of the C(CO)-C(alkyl) bond leading to C-N bond formation with chelation assistance of N-containing directing groups is described. Inexpensive Cu(ii)-acetate serves as a convenient catalyst for this transformation. This method highlights the emerging strategy to transform unactivated alkyl ketones into amides in organic synthesis and provides a new strategy for C-C bond cleavage.

  8. Vaporization enthalpies of imidazolium based ionic liquids. A thermogravimetric study of the alkyl chain length dependence

    International Nuclear Information System (INIS)

    Verevkin, Sergey P.; Zaitsau, Dzmitry H.; Emel’yanenko, Vladimir N.; Ralys, Ricardas V.; Yermalayeu, Andrei V.; Schick, Christoph

    2012-01-01

    Highlights: ► Enthalpies of vaporization of ionic liquids were measured with thermogravimetry. ► We studied 1-alkyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide. ► The linear alkyl chain length was 4, 6, 8, 10, 12, 14, 16, and 18 C-atoms. ► A linear dependence on the chain length of the alkyl-imidazolium cation was found. - Abstract: Vaporization enthalpies for a series of ten ionic liquids (ILs) 1-alkyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide [C n mim][NTf 2 ], with the alkyl chain length n = 4, 6, 8, 10, 12, 14, 16, and 18 were determined using the thermogravimetric method. An internally consistent set of experimental data and vaporization enthalpies at 540 K was obtained. Vaporization enthalpies at 540 K have shown a linear dependence on the chain length of the alkyl-imidazolium cation in agreement with the experimental results measured previously with a quartz crystal microbalance. Ambiguity of Δ l g C pm o -values required for the extrapolation of experimental vaporization enthalpies to the reference temperature 298 K has been discussed.

  9. Effect of the Alkyl Chain Length on the Adsorption Properties of Malonamide Chelating Resins

    International Nuclear Information System (INIS)

    Ismail, I.M.; Nogami, M.; Suzuki, K.

    2004-01-01

    In order to investigate the effect of the alkyl chain length of malonamide chelating resins on the rate of uptake of U(VI) ions and Ce(III) Ions, lV,N,N',N'-tetraethyl malonamide (TEMA), N,N,N',N'-tetra-n-propyl malonamide (TPrMA), lV,lV,N',N'-tetra-n-butyl malonamide (TBMA) and N,l V,N',N'-tetra-n-pentyl malonamide (Tamp) chelating resins were synthesized by chemically bonding these function groups to CMS-DVB co-polymer beads. N,lV,N',N'-tetraphenyl malonamide (TPhMA) chelating resin was also investigated and the results of these resins were compared with those of N,lY,N',N-tetra methylmalonamide (TMMA) previously reported. The batch technique was used to study the thermodynamic equilibrium, in terms of distribution coefficient, and the kinetics of the adsorption U(VI) and Ce(III) ions from 3 M HNO 3 , Acid, and 3 M NaNO 3 + 0.05 M HNO 3 , Salt, media. The introduction ratio of the function group into the polymer base and the uptake of U(VI) ions and C(III) ions were found to decrease with the increase in the alkyl chain length. The uptake was found to diminish in case of TPhMA resin due to the decrease of the function group ratio and the steric-hinder effect

  10. Nature of chromosome gaps induced by alkylating agents and γ-rays as revealed by caffeine treatment

    International Nuclear Information System (INIS)

    Dimitrov, B.

    1981-01-01

    In the cells of primary roots of Crepis capillaris, post-treatment with caffeine increased the frequency of gaps and chromosomal aberrations induced by the alkylating agents ethyleneimine and N-nitroso-N-methylurethane and γ-rays. The increase in the frequency of gaps was considerably lower than that observed in chromosomal aberrations, this being more strongly expressed in the case fo the alkylating agents. The potentiating effect of caffeine on the γ-ray-induced chromosomal gaps was a little higher in S as compared in G 2 . These results lead to the conclusion that the alkylating agents and the γ-rays might induce 2 types of chromosomal gap. (orig.)

  11. Quantum molecular modeling of the interaction between guanine and alkylating agents--1--sulfur mustard.

    Science.gov (United States)

    Broch, H; Hamza, A; Vasilescu, D

    1996-06-01

    Interaction between Guanine and the episulfonium form of Sulfur mustard (HD) was studied using the ab initio LCAO-MO method at the HF/6-31G level. The alkylation mechanism on guanine-N7 was analyzed by using a supermolecular modeling. Our stereostructural results associated with the molecular electrostatic potentials and HOMO-LUMO properties, show that in vacuum the alkylation of the N7 of guanine by HD in the aggressive episulfonium form is a direct process without transition state and of which the pathway is determined.

  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. Pseudomonas aeruginosa cytochrome c551 denaturation by five systematic urea derivatives that differ in the alkyl chain length.

    Science.gov (United States)

    Kobayashi, Shinya; Fujii, Sotaro; Koga, Aya; Wakai, Satoshi; Matubayasi, Nobuyuki; Sambongi, Yoshihiro

    2017-07-01

    Reversible denaturation of Pseudomonas aeruginosa cytochrome c 551 (PAc 551 ) could be followed using five systematic urea derivatives that differ in the alkyl chain length, i.e. urea, N-methylurea (MU), N-ethylurea (EU), N-propylurea (PU), and N-butylurea (BU). The BU concentration was the lowest required for the PAc 551 denaturation, those of PU, EU, MU, and urea being gradually higher. Furthermore, the accessible surface area difference upon PAc 551 denaturation caused by BU was found to be the highest, those by PU, EU, MU, and urea being gradually lower. These findings indicate that urea derivatives with longer alkyl chains are stronger denaturants. In this study, as many as five systematic urea derivatives could be applied for the reversible denaturation of a single protein, PAc 551 , for the first time, and the effects of the alkyl chain length on protein denaturation were systematically verified by means of thermodynamic parameters.

  14. N-(3-( sup 18 F)fluoropropyl)-N-nordiprenorphine: Synthesis and characterization of a new agent for imaging opioid receptors with positron emission tomography

    Energy Technology Data Exchange (ETDEWEB)

    Chesis, P.L.; Hwang, D.R.; Welch, M.J. (Washington Univ. School of Medicine, St. Louis, MO (USA))

    1990-05-01

    A series of N-fluoroalkyl (1-5) and N-alkyl (6-8) analogues of the high-affinity opioid receptor antagonist diprenorphine (9) has been synthesized and evaluated with in vitro binding assays. Three of the N-fluoroalkyl compounds were prepared with the positron-emitting radionuclide {sup 18}F (1a, 2a, 5a), and their biodistribution was determined in rats. Compounds 2a and 5a were made by using a two-step labeling procedure, ({sup 18}F)fluoride displacement of an iodoalkyl triflate followed by N-alkylation, that required 2 h and proceeded in 4-6% overall radiochemical yield at the end of synthesis. The effective specific activity of compounds 2a and 5a, determined by competitive receptor binding assay, was 840-1820 Ci/mmol. Compound 1a was made by the same two-step procedure, with the bromoalkyl triflate, in 0.3-0.6% radiochemical yield at an effective specific activity of 106-264 Ci/mmol. Specificity of binding in vivo was measured as the percent injected dose/gram of striatal tissue divided by the percent injected dose/gram of cerebellar tissue. The best striatum to cerebellum ratio (3.32 +/- 0.74 at 30 min) was achieved with N-(3-({sup 18}F)-fluoropropyl)-N-nordiprenorphine (2a, ({sup 18}F)FPND). The high specific binding demonstrated by this compound indicates that it may be useful for in vivo imaging of opioid receptors with positron emission tomography.

  15. 4-alkyl-L-(Dehydro)proline biosynthesis in actinobacteria involves N-terminal nucleophile-hydrolase activity of γ-glutamyltranspeptidase homolog for C-C bond cleavage

    Science.gov (United States)

    Zhong, Guannan; Zhao, Qunfei; Zhang, Qinglin; Liu, Wen

    2017-07-01

    γ-Glutamyltranspeptidases (γ-GTs), ubiquitous in glutathione metabolism for γ-glutamyl transfer/hydrolysis, are N-terminal nucleophile (Ntn)-hydrolase fold proteins that share an autoproteolytic process for self-activation. γ-GT homologues are widely present in Gram-positive actinobacteria where their Ntn-hydrolase activities, however, are not involved in glutathione metabolism. Herein, we demonstrate that the formation of 4-Alkyl-L-(dehydro)proline (ALDP) residues, the non-proteinogenic α-amino acids that serve as vital components of many bioactive metabolites found in actinobacteria, involves unprecedented Ntn-hydrolase activity of γ-GT homologue for C-C bond cleavage. The related enzymes share a key Thr residue, which acts as an internal nucleophile for protein hydrolysis and then as a newly released N-terminal nucleophile for carboxylate side-chain processing likely through the generation of an oxalyl-Thr enzyme intermediate. These findings provide mechanistic insights into the biosynthesis of various ALDP residues/associated natural products, highlight the versatile functions of Ntn-hydrolase fold proteins, and particularly generate interest in thus far less-appreciated γ-GT homologues in actinobacteria.

  16. Complementarily addressed modification and cleavage of a single-stranded fragment of DNA with the aid of alkylating derivatives of oligonucleotides

    International Nuclear Information System (INIS)

    Brosalina, E.B.; Vlasov, V.V.; Kutyavin, I.V.; Mamaev, S.V.; Pletnev, A.G.; Podyminogin, M.A.

    1986-01-01

    The chemical modification of a 303-nucleotide single-stranded fragment of DNA by alkylating oligonucleotide derivatives bearing 4-[N-methyl-N-(2-chloroethyl)amino]benzyl groups in the 5'-terminal phosphate of the 3'-terminal ribose residue has been investigated. It has been shown that under the conditions of the formation of a complex with the DNA fragment both types of derivatives specifically alkylate nucleotides of the DNA fragments that are located directly adjacent to the sections complementary to the oligonucleotides bearing the reactive groups. Alkylation takes place with a high efficiency, and the DNA fragment can be cleaved specifically at the position of the alkylated nucleotides

  17. The influence of tannin, pectin and polyethylene glycol on attachment of {sup 15}N-labelled rumen microorganisms to cellulose

    Energy Technology Data Exchange (ETDEWEB)

    Bento, M.H.L. [Avian Science Research Centre, Animal Health Group, SAC, Edinburgh, Scotland (United Kingdom) and FAO/IAEA Division of Nuclear Techniques in Food and Agriculture, International Atomic Energy Agency, Vienna (Austria)]. E-mail: helena.bento@sac.ac.uk; Acamovic, T. [Avian Science Research Centre, Animal Health Group, SAC, Edinburgh, Scotland (United Kingdom); Makkar, H.P.S. [FAO/IAEA Division of Nuclear Techniques in Food and Agriculture, International Atomic Energy Agency, Vienna (Austria)

    2005-08-19

    The microbial attachment to and gas production from {alpha}-cellulose (Sigma; C-8002) without and with mimosa tannin (MT), pectin (P), polyethylene glycol (PEG), MT + P or MT + PEG, were investigated using the in vitro gas production system. Microbial attachment based on {sup 15}N-labelled rumen microorganisms in the residual pellet after 24 h incubation was estimated, which varied from 113.7 to 161.3 {mu}g {sup 15}N per g residual pellet. C + MT had the lowest microbial attachment (P < 0.05) of all treatments and C + P the highest (P < 0.05). Both pectin and PEG improved microbial attachment when added to C + MT (P < 0.001). Gas production was measured at 2, 4, 6, and 24 h. Mimosa tannin drastically reduced gas production only at 24 h (P < 0.001). Pectin increased gas production throughout the incubation period (P < 0.001). Both pectin and PEG increased gas production at 24 h, when added to C + MT (P < 0.05), however, for C + MT + P, the gas production was only half (P < 0.05) of the gas produced in the control (when only C incubated). A rapid degradation of pectin early in the incubation could have reduced the interaction of pectin with the MT. Microbial attachment agreed well with gas production at 24 h (R{sup 2} = 0.84, P < 0.001). However, the inclusion of MT and pectin may have resulted in differences in microbial profiles, thereby altering the capability of the adhered microbes to degrade cellulose. This assertion is supported by the lower gas production (ml per {mu}g of {sup 15}N) in the residual pellet measured for C + MT (0.054) and C + MT + P (0.159), compared with the other treatments (0.32 for C; 0.34 for C + P; 0.33 for C + PEG; and 0.33 for C + MT + PEG). A MT concentration of 194 g/kg diet reduced microbial attachment and activity of rumen microorganisms in vitro. Polyethylene glycol counteracted the effect of MT on microbial attachment and activity. Pectin exerted a beneficial effect on attachment and fermentation in the initial hours of incubation

  18. Charge properties and bacterial contact-killing of hyperbranched polyurea-polyethyleneimine coatings with various degrees of alkylation

    International Nuclear Information System (INIS)

    Roest, Steven; Mei, Henny C. van der; Loontjens, Ton J.A.; Busscher, Henk J.

    2015-01-01

    Highlights: • Cationic charge density does not reflect bacterial contact-killing by QUAT coatings. • Charge carrier and density reflect bacterial killing by QUAT coatings. • Fluorescein staining cannot distinguish charge carriers in cationic coatings. • Charge carrier and density of QUAT coatings are reflected in the N401.3 eV XPS peak. • The at.% N401.3 eV should be more than 0.45% for effective bacterial contact-killing. - Abstract: Coatings of immobilized-quaternary-ammonium-ions (QUAT) uniquely kill adhering bacteria upon contact. QUAT-coatings require a minimal cationic-charge surface density for effective contact-killing of adhering bacteria of around 10 14 cm −2 . Quaternization of nitrogen is generally achieved through alkylation. Here, we investigate the contribution of additional alkylation with methyl-iodide to the cationic-charge density of hexyl-bromide alkylated, hyperbranched polyurea-polyethyleneimine coatings measuring charge density with fluorescein staining. X-ray-photoelectron-spectroscopy was used to determine the at.% alkylated-nitrogen. Also streaming potentials, water contact-angles and bacterial contact-killing were measured. Cationic-charge density increased with methyl-iodide alkylation times up to 18 h, accompanied by an increase in the at.% alkylated-nitrogen. Zeta-potentials became more negative upon alkylation as a result of shielding of cationiccharges by hydrophobic alkyl-chains. Contact-killing of Gram-positive Staphylococci only occurred when the cationic-charge density exceeded 10 16 cm −2 and was carried by alkylated-nitrogen (electron-binding energy 401.3 eV). Gram-negative Escherichia coli was not killed upon contact with the coatings. There with this study reveals that cationic-charge density is neither appropriate nor sufficient to determine the ability of QUAT-coatings to kill adhering bacteria. Alternatively, the at.% of alkylated-nitrogen at 401.3 eV is proposed, as it reflects both cationic-charge and its

  19. Charge properties and bacterial contact-killing of hyperbranched polyurea-polyethyleneimine coatings with various degrees of alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Roest, Steven [University of Groningen, University Medical Center Groningen, Department of Biomedical Engineering, AntoniusDeusinglaan 1, 9713 AV Groningen (Netherlands); Mei, Henny C. van der, E-mail: h.c.van.der.mei@umcg.nl [University of Groningen, University Medical Center Groningen, Department of Biomedical Engineering, AntoniusDeusinglaan 1, 9713 AV Groningen (Netherlands); Loontjens, Ton J.A. [University of Groningen, Zernike Institute for Advanced Materials, Department of Polymer Chemistry, Nijenborgh 4, 9747 AG Groningen (Netherlands); Busscher, Henk J. [University of Groningen, University Medical Center Groningen, Department of Biomedical Engineering, AntoniusDeusinglaan 1, 9713 AV Groningen (Netherlands)

    2015-11-30

    Highlights: • Cationic charge density does not reflect bacterial contact-killing by QUAT coatings. • Charge carrier and density reflect bacterial killing by QUAT coatings. • Fluorescein staining cannot distinguish charge carriers in cationic coatings. • Charge carrier and density of QUAT coatings are reflected in the N401.3 eV XPS peak. • The at.% N401.3 eV should be more than 0.45% for effective bacterial contact-killing. - Abstract: Coatings of immobilized-quaternary-ammonium-ions (QUAT) uniquely kill adhering bacteria upon contact. QUAT-coatings require a minimal cationic-charge surface density for effective contact-killing of adhering bacteria of around 10{sup 14} cm{sup −2}. Quaternization of nitrogen is generally achieved through alkylation. Here, we investigate the contribution of additional alkylation with methyl-iodide to the cationic-charge density of hexyl-bromide alkylated, hyperbranched polyurea-polyethyleneimine coatings measuring charge density with fluorescein staining. X-ray-photoelectron-spectroscopy was used to determine the at.% alkylated-nitrogen. Also streaming potentials, water contact-angles and bacterial contact-killing were measured. Cationic-charge density increased with methyl-iodide alkylation times up to 18 h, accompanied by an increase in the at.% alkylated-nitrogen. Zeta-potentials became more negative upon alkylation as a result of shielding of cationiccharges by hydrophobic alkyl-chains. Contact-killing of Gram-positive Staphylococci only occurred when the cationic-charge density exceeded 10{sup 16} cm{sup −2} and was carried by alkylated-nitrogen (electron-binding energy 401.3 eV). Gram-negative Escherichia coli was not killed upon contact with the coatings. There with this study reveals that cationic-charge density is neither appropriate nor sufficient to determine the ability of QUAT-coatings to kill adhering bacteria. Alternatively, the at.% of alkylated-nitrogen at 401.3 eV is proposed, as it reflects both

  20. The Tobacco Smoke Component, Acrolein, Suppresses Innate Macrophage Responses by Direct Alkylation of c-Jun N-Terminal Kinase

    Science.gov (United States)

    Hristova, Milena; Spiess, Page C.; Kasahara, David I.; Randall, Matthew J.; Deng, Bin

    2012-01-01

    The respiratory innate immune system is often compromised by tobacco smoke exposure, and previous studies have indicated that acrolein, a reactive electrophile in tobacco smoke, may contribute to the immunosuppressive effects of smoking. Exposure of mice to acrolein at concentrations similar to those in cigarette smoke (5 ppm, 4 h) significantly suppressed alveolar macrophage responses to bacterial LPS, indicated by reduced induction of nitric oxide synthase 2, TNF-α, and IL-12p40. Mechanistic studies with bone marrow–derived macrophages or MH-S macrophages demonstrated that acrolein (1–30 μM) attenuated these LPS-mediated innate responses in association with depletion of cellular glutathione, although glutathione depletion itself was not fully responsible for these immunosuppressive effects. Inhibitory actions of acrolein were most prominent after acute exposure (acrolein with critical signaling pathways. Among the key signaling pathways involved in innate macrophage responses, acrolein marginally affected LPS-mediated activation of nuclear factor (NF)-κB, and significantly suppressed phosphorylation of c-Jun N-terminal kinase (JNK) and activation of c-Jun. Using biotin hydrazide labeling, NF-κB RelA and p50, as well as JNK2, a critical mediator of innate macrophage responses, were revealed as direct targets for alkylation by acrolein. Mass spectrometry analysis of acrolein-modified recombinant JNK2 indicated adduction to Cys41 and Cys177, putative important sites involved in mitogen-activated protein kinase (MAPK) kinase (MEK) binding and JNK2 phosphorylation. Our findings indicate that direct alkylation of JNK2 by electrophiles, such as acrolein, may be a prominent and hitherto unrecognized mechanism in their immunosuppressive effects, and may be a major factor in smoking-induced effects on the immune system. PMID:21778411

  1. Antimutagenic components in Glycyrrhiza against N-methyl-N-nitrosourea in the Ames assay.

    Science.gov (United States)

    Inami, Keiko; Mine, Yusuke; Kojo, Yukiko; Tanaka, Satomi; Ishikawa, Satoko; Mochizuki, Masataka

    2017-03-01

    Antimutagenesis against N-nitroso compounds contribute to prevention of human cancer. We have found that Glycyrrhiza aspera ethanolic extract exhibits antimutagenic activity against N-methyl-N-nitrosourea (MNU) using the Ames assay with Salmonella typhimurium TA1535. In the present study, eight purified components from Glycyrrhiza, namely glabridin, glycyrrhetinic acid, glycyrrhizin, licochalcone A, licoricesaponin H2, licoricesaponin G2, liquiritigenin and liquiritin were evaluated for their antimutagenicity against MNU in the Ames assay with S. typhimurium TA1535. Glycyrrhetinic acid, glycyrrhizin, licoricesaponin G2, licoricesaponin H2 and liquiritin did not show the antimutagenicity against MNU in S. typhimurium TA1535. Glabridin, licochalcone A and liquiritigenin reduced revertant colonies derived from MNU in S. typhimurium TA1535 without showing cytotoxic effects, indicating that these compounds possess antimutagenic activity against MNU. The inhibitory activity of glabridin and licochalcone A was more effective than that of liquiritigenin. Thus, Glycyrrhiza contains antimutagenic components against DNA alkylating, direct-acting carcinogens.

  2. Spectroscopic investigation (FT-IR, FT-Raman), HOMO-LUMO, NBO, and molecular docking analysis of N-ethyl-N-nitrosourea, a potential anticancer agent

    Science.gov (United States)

    Singh, Priyanka; Islam, S. S.; Ahmad, Hilal; Prabaharan, A.

    2018-02-01

    Nitrosourea plays an important role in the treatment of cancer. N-ethyl-N-nitrosourea, also known as ENU, (chemical formula C3H7N3O2), is a highly potent mutagen. The chemical is an alkylating agent and acts by transferring the ethyl group of ENU to nucleobases (usually thymine) in nucleic acids. The molecular structure of N-ethyl-N-nitrosourea has been elucidated using experimental (FT-IR and FT-Raman) and theoretical (DFT) techniques. APT charges, Mulliken atomic charges, Natural bond orbital, Electrostatic potential, HOMO-LUMO and AIM analysis were performed to identify the reactive sites and charge transfer interactions. Furthermore, to evaluate the anticancer activity of ENU molecular docking studies were carried out against 2JIU protein.

  3. Alkylation damage in DNA and RNA--repair mechanisms and medical significance

    DEFF Research Database (Denmark)

    Drabløs, Finn; Feyzi, Emadoldin; Aas, Per Arne

    2004-01-01

    Alkylation lesions in DNA and RNA result from endogenous compounds, environmental agents and alkylating drugs. Simple methylating agents, e.g. methylnitrosourea, tobacco-specific nitrosamines and drugs like temozolomide or streptozotocin, form adducts at N- and O-atoms in DNA bases. These lesions...... are mainly repaired by direct base repair, base excision repair, and to some extent by nucleotide excision repair (NER). The identified carcinogenicity of O(6)-methylguanine (O(6)-meG) is largely caused by its miscoding properties. Mutations from this lesion are prevented by O(6)-alkylG-DNA alkyltransferase......, inactivation of the MMR system in an AGT-defective background causes resistance to the killing effects of O(6)-alkylating agents, but not to the mutagenic effect. Bifunctional alkylating agents, such as chlorambucil or carmustine (BCNU), are commonly used anti-cancer drugs. DNA lesions caused by these agents...

  4. New iodocuprates(I) with N-heterocyclic molecules as the cations

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Jin-Jing [College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, Jilin 130023 (China); Zhang, Xiao [State Key Lab of Urban Water Resource and Environment (SKLUWRE) and Academy of Fundamental and Interdisciplinary Science, Harbin Institute of Technology, Harbin, Heilongjiang 150080 (China); Wang, Yan-Ning; Jia, Hong-Li [College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, Jilin 130023 (China); Yu, Jie-Hui, E-mail: jhyu@jlu.edu.cn [College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, Jilin 130023 (China); Xu, Ji-Qing, E-mail: xjq@mail.jlu.edu.cn [College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, Jilin 130023 (China)

    2013-11-15

    Under the hydrothermal conditions, the reactions between CuI, KI and bp/bpp (bp=4,4′-bipiperidine, bpp=1,3-bis(4-piperidyl)propane) in an acidic alcohol solution produced three new organically templated iodocuprates(I) as [H{sub 2}bp]{sub 2}[Cu{sub 2}I{sub 6}] 1, [tmbp][Cu{sub 2}I{sub 4}] 2 and [tmbpp] 2 [Cu{sub 4}I{sub 8}]·2H{sub 2}O 3 (tmbp{sup 2+}=N,N,N′,N′-tetramethyl-4,4′-bipiperidinium; tmbpp{sup 2+}=N,N,N′,N′-tetramethyl-1,3-bis(4-piperidyl)propane dication). X-ray analysis revealed that (i) tmbp{sup 2+} and tmbpp{sup 2+} in compounds 2 and 3 originated from the complete N-alklation of bp/bpp with CH{sub 3}OH; (ii) templated by H{sub 2}bp{sup 2+}, the inorganic anion [Cu{sub 2}I{sub 6}]{sup 2−} of 1 possesses a dinuclear structure, whereas templated by tmbp{sup 2+}, the inorganic anion [Cu{sub 2}I{sub 4}]{sup 2−} of 2 exhibits a one-dimensional (1D) chain structure; (iii) templated by tmbpp{sup 2+}, the inorganic anion [Cu{sub 4}I{sub 8}]{sup 4−} of 3 shows a cubane-like structure modified by four terminal I{sup −} ions. The photoluminescence analysis indicates that compounds 1 and 2 emit blue light, while compound 3 emits green light. - Graphical abstract: By employing hydrothermal in situ N-alkylation of bp/bpp with CH{sub 3}OH, three new organically templated iodocuprates(I) were obtained. Display Omitted - Highlights: • Three new organically templated iodocuprates(I) were reported. • Cations tmbp{sup 2+} and tmbpp{sup 2+} originated from in situ alkylation of bp/bpp with CH{sub 3}OH. • H{sup +} and I{sup −} play a key role in alkylation of bp/bpp with CH{sub 3}OH. • Photoluminescence emission for iodocuprates(I) is related to Cu···Cu interaction.

  5. One-pot and one-step novel N-methylation of 2,6-diaminopyridine

    Directory of Open Access Journals (Sweden)

    Mehdi Nabati

    2014-07-01

    Full Text Available 2,6-Diaminopyridine is extensively used as a pharmaceutical intermediate and a hair dye coupler. It is soluble in protic solvents. Primary and secondary amines are N-methylated by various me-thods such as direct alkylation of amines with Hofmann mechanism, but in many of these me-thods due to over-alkylations, we earn a mixture of amino products. Consequently, they aren't selective in the case of secondary amines preparation. Also, the synthesis of secondary amines is a problematic field in organic chemistry. In this research, 2,6-diaminopyridine N-methylated-selictivity was done from reaction with sodium azide and orthoformic ester in low time with good yields.

  6. Análisis inferencial de las potencialidades de promoción de absorción de una familia de 1-O-alquil gliceroles Inferable analysis related to promotion of the absorption potentialities from 1-O-alkyl glycerol family

    Directory of Open Access Journals (Sweden)

    Miguel Francisco Bilbao Díaz

    2009-12-01

    Full Text Available La interrelación entre las propiedades físico-químicas y la biodisponibilidad de una familia de 1-O-alquil gliceroles son discutidas, se han utilizado como compuestos de referencia, moléculas que presentan una analogía estructural-funcional con estos compuestos, los cuales han sido reconocidos como agentes promotores clase I, de alta capacidad. El enfoque TOPS-MODE (ModesLab fue utilizado para estimar los momentos espectrales, con diferentes ponderaciones, como descriptores de las propiedades físico-químicas más relevantes utilizadas en los modelos predictivos de permeabilidad intestinal obtenidos, e interpretar estos en términos de contribución de grupos funcionales de los 1-O-alquil gliceroles. A partir de este análisis se establecieron interpretaciones de tipo inferencial sobre las reales potencialidades teóricas de esta familia para su evaluación perspectiva como agentes promotores de absorción clase I. Este enfoque de tamizaje in sílico asistido por computadora permitió postular que los 1-O-alquil gliceroles, en particular el 1-O-hexadecil glicerol y 1-O-octadecil glicerol, son excelentes candidatos para demostrar su elevada capacidad promotora en estudios in vivo, los que han alcanzado altos niveles porcentuales de biodisponibilidad (> 90 %. Se concluye, según análisis por discriminante, que todos los miembros de la familia presentaron potencialidades para la absorción gastrointestinal.The interrelation among the physical-chemical properties and the bioavailability of a 1-O-alkyl glycerol family is discussed. As reference compounds we used molecules presenting a structural-functional similarity with these compounds, which have been recognized as class I high quality promoting agents. TOPS-MODE approach (ModesLab was used to estimate spectral moments with different weighing as descriptors of the more relevant physical-chemical properties used in the achieved predictive models of intestinal permeability, and its

  7. Nucleotide excision repair modulates the cytotoxic and mutagenic effects of N-n-butyl-N-nitrosourea in cultured mammalian cells as well as in mouse splenocytes in vivo.

    Science.gov (United States)

    Bol, S A; van Steeg, H; van Oostrom, C T; Tates, A D; Vrieling, H; de Groot, A J; Mullenders, L H; van Zeeland, A A; Jansen, J G

    1999-05-01

    The butylating agent N-n-butyl-N-nitrosourea (BNU) was employed to study the role of nucleotide excision repair (NER) in protecting mammalian cells against the genotoxic effects of monofunctional alkylating agents. The direct acting agent BNU was found to be mutagenic in normal and XPA mouse splenocytes after a single i.p. treatment in vivo. After 25 and 35 mg/kg BNU, but not after 75 mg/ kg, 2- to 3-fold more hprt mutants were detected in splenocytes from XPA mice than from normal mice. Using O6-alkylguanine-DNA alkyltransferase (AGT)-deficient hamster cells, it was found that NER-deficient CHO UV5 cells carrying a mutation in the ERCC-2 gene were 40% more mutable towards lesions induced by BNU when compared with parental NER-proficient CHO AA8 cells. UV5 cells were 1.4-fold more sensitive to the cytotoxic effects of BNU compared with AA8 cells. To investigate whether this increased sensitivity of NER-deficient cells is modulated by AGT activity, cell survival studies were performed in human and mouse primary fibroblasts as well. BNU was 2.7-fold more toxic for mouse XPA fibroblasts compared with normal mouse fibroblasts. Comparable results were found for human fibroblasts. Taken together these data indicate that the role of NER in protecting rodent cells against the mutagenic and cytotoxic effects of the alkylating agent BNU depends on AGT.

  8. Photoluminescence decay lifetime measurements of hemicyanine derivatives of different alkyl chain lengths

    International Nuclear Information System (INIS)

    Shim, Taekyu; Lee, Myounghee; Kim, Sungho; Sung, Jaeho; Rhee, Bum Ku; Kim, Doseok; Kim, Hyunsung; Yoon, Kyung Byung

    2004-01-01

    The fluorescence upconversion setup for the detection of photoluminescence (PL) decay lifetime with subpicosecond time resolution was constructed, and the photoluminescence phenomena of several hemicyanine dyes with alkyl chains of different chain lengths tethered to the N atom of the pyridine moiety (HC-n, n=6, 15, 22) in methanol were investigated. The average decay lifetimes of the solutions determined from the measured data by multi-order exponential decay curve fitting were ∼27 ps at the PL peak wavelength. It was found that the PL decay properties did not depend on the alkyl chain length in the molecule, implying that the twist of the alkylpyridinium ring of the molecule is not possible as a nonfluorescing relaxation pathway. The time-dependent PL spectra constructed from the PL lifetime data showed the dynamic Stokes shift of ∼1000 cm -1

  9. Ethylene glycol and propylene glycol ethers – Reproductive and developmental toxicity

    Directory of Open Access Journals (Sweden)

    Beata Starek-Świechowicz

    2015-10-01

    Full Text Available Both ethylene and propylene glycol alkyl ethers (EGAEs and PGAEs, respectively are widely used, mainly as solvents, in industrial and household products. Some EGAEs demonstrate gonadotoxic, embriotoxic, fetotoxic and teratogenic effects in both humans and experimental animals. Due to the noxious impact of these ethers on reproduction and development of organisms EGAEs are replaced for considerably less toxic PGAEs. The data on the mechanisms of testicular, embriotoxic, fetotoxic and teratogenic effects of EGAEs are presented in this paper. Our particular attention was focused on the metabolism of some EGAEs and their organ-specific toxicities, apoptosis of spermatocytes associated with changes in the expression of various genes that code for oxidative stress factors, protein kinases and nuclear hormone receptors. Med Pr 2015;66(5:725–737

  10. Antibiotic Potency against E. coli Is Enhanced by Channel-Forming Alkyl Lariat Ethers.

    Science.gov (United States)

    Negin, Saeedeh; Patel, Mohit B; Gokel, Michael R; Meisel, Joseph W; Gokel, George W

    2016-11-17

    Several N,N'-bis(n-alkyl-4,13-diaza[18]crown-6) lariat ethers were found to significantly enhance the potency of rifampicin and tetracycline, but not erythromycin and kanamycin, against the non-pathogenic DH5α and K-12 strains of Escherichia coli when administered at levels below their minimum inhibitory concentrations (MICs). The enhancements in antibiotic potency observed for the lariat ethers ranged from three- to 20-fold, depending on the strain of E. coli, the antibiotic, and the lengths of the alkyl chains attached at the macroring nitrogen atoms. The dialkyl lariat ethers, previously thought to only be cation carriers, formed well-behaved, ion-conducting pores in soybean asolectin membranes, as judged by planar bilayer conductance measurements. The ability of lariat ethers to form stable pores, which appeared to be aggregated, depended in part on alkyl chain length and in part on the composition of the bilayer membrane in which they were studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Tailored reforming of n-dodecane in an aqueous discharge reactor

    KAUST Repository

    Zhang, Xuming; Cha, Min

    2016-01-01

    permittivity of the mixture facilitates electrical discharges that cause the electron impact dissociation of n-dodecane into alkyl and hydrogen radicals, while the addition of water also provides a steam-reforming environment inside the discharged bubbles. We

  12. Synthesis of [methyl-[sup 14]C]-N-methylputrescine

    Energy Technology Data Exchange (ETDEWEB)

    Secor, H.V.; Izac, R.R.; Hassam, S.B.; Frisch, A.F. (Philip Morris Research Center, Richmond, VA (United States))

    1994-05-01

    [Methyl-[sup 14]C]-N-methylputrescine was prepared from [[sup 14]C]methylamine hydrochloride in five steps. Reaction of benzaldehyde and [[sup 14]C]methylamine (10 mCi) followed by catalytic hydrogenation yielded [methyl-[sup 14]C]-N-methylbenzylamine. The key step in this process is the alkylation of [methyl-[sup 14]C]-N-methylbenzylamine in aqueous medium with 4-bromobutyronitrile. The radiochemical purity of the final product after two successive catalytic hydrogenations was in excess of 97%. The radiochemical yields in two successive runs were 26 and 38%, based on starting [[sup 14]C]methylamine, with specific activities of 22 and 23 mCi/mmol, respectively. This sequence provides a convenient and efficient regioselective radiosynthesis of [methyl-[sup 14]C]-N-methylputrescine. (author).

  13. 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

  14. Large area, soft crystalline thin films of N,N' ,N'' -trialkyltriazatriangulenium salts with homeotropic alignment of the discotic cores in a lamellar lattice

    DEFF Research Database (Denmark)

    Just Sørensen, Thomas; Hildebrandt, Christoffer B.; Elm, Jonas

    2012-01-01

    techniques confirm that the 15–30 nm thick films maintain the lamellar structure of the bulk crystals, are flat on macroscopic length scales, and are completely ordered relative to the substrate. The triazatriangulenium molecules are electroactive dyes, and in the highly anisotropic polycrystalline thin film......N,N' ,N'' -Trialkyltriazatriangulenium (R-TATA+) tetrafluoroborate (BF4) salts form highly ordered thin films directly when spin-cast onto rotating substrates. The homogeneous and crystalline thin films show macroscopic order over centimetres. The crystal structures of the R-TATA$BF4 salts...... are investigated and compared for the propyl, 3-methylpentyl and octyl derivatives. In all cases the molecules pack in hexagonally ordered bilayers, with segregation of the ionic groups and the alkyl chains. This is a rare packing motif with the rigid discotic TATA+ cores organized co-planarly in sheets separated...

  15. Thermodynamic and optical studies of some ethylene glycol ethers in aqueous solutions at T = 298.15 K

    International Nuclear Information System (INIS)

    Dhondge, Sudhakar S.; Pandhurnekar, Chandrashekhar P.; Parwate, Dilip V.

    2009-01-01

    Experimental results of density (ρ), speed of sound (u), and refractive index (n D ) have been obtained for aqueous solutions of ethylene glycol monomethyl ether (EGMME), ethylene glycol monoethyl ether (EGMEE), diethylene glycol monomethyl ether (DEGMME), and diethylene glycol monoethyl ether (DEGMEE) over the entire concentration range at T = 298.15 K. From these measurements, the derived parameters, apparent molar volume of solute (φ V ), excess molar volume (V E ), isentropic compressibility of solution (β S ), apparent molar isentropic compressibility of solute (φ KS ), deviation in isentropic compressibility (Δβ S ), molar refraction [R] 1,2 and deviation in refractive index of solution (Δn D ) have been calculated. The Redlich-Kister equation has been fitted to the calculated values of V E , Δβ S and Δn D for the solution. The results obtained are interpreted in terms of hydrogen bonding and various interactions among solute and solvent molecules

  16. Two new barium-copper-ethylene glycol complexes: Synthesis and structure of BaCu(C2H6O2)n(C2H4O2)2 (N = 3, 6)

    International Nuclear Information System (INIS)

    Love, C.P.; Page, C.J.; Torardi, C.C.

    1992-01-01

    Two crystalline barium-copper-ethylene glycol complexes have been isolated and structurally characterized by single-crystal x-ray diffraction. The solution-phase complex has also been investigated as a molecular precursor for use in sol-gel synthesis of high-temperature superconductors. The first crystalline form has the formula BaCu(C 2 H 6 O 2 ) 6 (C 2 H 4 O 2 ) 2 (1) and has been isolated directly from ethylene glycol solutions of the barium-copper salt. In this molecule, copper is coordinated to the four xygens of two ethylene glycolate ligands in a nearly square planar geometry. Barium is coordinated by three bidentate ethylene glycol molecules and three monodentate ethylene glycol molecules; the 9-fold coordination resembles a trigonal prism with each rectangular face capped. Copper and barium moieties do not share any ethylene glycol or glycolate oxygens; they are found by hydrogen bonding to form linear chains. The second crystal type has formula BaCu(C 2 H 6 O 2 ) 3 (C 2 H 4 O 2 ) 2 (2). It was prepared via crystallization of the mixed-metal alkoxide from an ethylene glycol/methyl ethyl ketone solution. As for 1, the copper is coordinated to four oxygen atoms of two ethylene glycolate ligands in a nearly square planar arrangement. Barium is 8-coordinate in a distorted cubic geometry. It is coordinated to three bidentate ethylene glycol molecules and shares two of the oxygen atoms bound to the copper (one from each coordinated ethylene glycol) to form a discrete molecular barium-copper complex

  17. Biomonitoring of N-ethyl-2-pyrrolidone in automobile varnishers.

    Science.gov (United States)

    Koslitz, Stephan; Meier, Swetlana; Schindler, Birgit Karin; Weiss, Tobias; Koch, Holger Martin; Brüning, Thomas; Käfferlein, Heiko Udo

    2014-12-01

    N-alkyl-2-pyrrolidones are important organic solvents for varnishes in industry. This study investigates exposure to N-ethyl-2-pyrrolidone (NEP) in varnishing of hard plastic components in an automobile plant. Two specific biomarkers of exposure, 5-hydroxy-N-ethyl-2-pyrrolidone (5-HNEP) and 2-hydroxy-N-ethylsuccinimide (2-HESI), were analyzed in urine samples of 14 workers. For this purpose, pre-shift, post-shift and next day pre-shift urine samples were collected midweek. Twelve workers performed regular work tasks (loading, wiping and packing), whereas two workers performed special work tasks including cleaning the sprayer system with organic solvents containing N-alkyl-2-pyrrolidones. Spot urine samples of nine non-exposed persons of the same plant served as controls. Median post-shift urinary levels of workers with regular work tasks (5-HNEP: 0.15 mg/L; 2-HESI: 0.19 mg/L) were ∼5-fold higher compared to the controls (0.03 mg/L each). Continuously increasing metabolite levels, from pre-shift via post-shift to pre-shift samples of the following day, were observed in particular for the two workers with the special working tasks. Maximum levels were 31.01 mg/L (5-HNEP) and 8.45 mg/L (2-HESI). No clear trend was evident for workers with regular working tasks. In summary, we were able to show that workers can be exposed to NEP during varnishing tasks in the automobile industry. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  18. Chemical carcinogenesis in the nervous system. Preferential accumulation of O6-methylguanine in rat brain deoxyribonucleic acid during repetitive administration of N-methyl-N-nitrosourea.

    Science.gov (United States)

    Margison, G P; Kleihues, P

    1975-01-01

    The alkylation of purine bases in DNA of several rat tissues was determined during weekly injections (10 mg/kg) of N-[3H]methyl-N-nitrosourea, a dose schedule known to selectively induce tumours of the nervous system. Each group of animals was killed 1 week after the final injection, and the DNA hydrolysates were analysed by chromatography on Sephadex G-10. After five weekly applications, O6-methylguanine had accumulated in brain DNA to an extent which greatly exceeded that in kidney, spleen and intestine. In the liver, the final O6-methylguanine concentration was less than 1% of that in brain. Between the first and the fifth injection, the O6-methylguanine/7-methylguanine ratio in cerebral DNA increased from 0.28 to 0.68. In addition, 3-methylguanine was found to accumulate in brain DNA whereas in the other organs no significant quantities of this base were detectable. The results are compatible with the hypothesis that O6-alkylation of guanine in DNA plays a major role in the induction of tumours by N-methyl-N-nitrosourea and related carcinogens. The kinetics of the increase of O6-methylguanine in cerebral DNA suggest that there is no major cell fraction in the brain which is capable of excising chemically methylated bases from DNA. This repair deficiency could be a determining factor in the selective induction of nervous-system tumours by N-methyl-N-nitrosourea and other neuro-oncogenic compounds. PMID:1200992

  19. 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.

  20. [Quantitative analysis of urinary ethylene glycol in rats exposed to ethylene oxide].

    Science.gov (United States)

    Koga, M; Hori, H; Tanaka, I; Akiyama, T; Inoue, N

    1985-03-01

    A gas chromatographic method was used for determining ethylene glycol in urine. The analytical procedure is based on an azeotropic distillation and on esterification with n-butyl boronic acid. The linear calibration curve was obtained up to 500 micrograms/ml of ethylene glycol. The detection limit was estimated to be 10 micrograms/ml and relative standard deviation was 3.5% for 100 micrograms/ml of ethylene glycol. This method was applied to determine the urinary excretion of ethylene glycol in rats exposed to ethylene oxide at various concentrations (from 50 to 500 ppm). The excretion amounts of ethylene glycol were observed to be dependent on the concentration of ethylene oxide exposed.

  1. Assessing the toxic effects of ethylene glycol ethers using Quantitative Structure Toxicity Relationship models

    International Nuclear Information System (INIS)

    Ruiz, Patricia; Mumtaz, Moiz; Gombar, Vijay

    2011-01-01

    Experimental determination of toxicity profiles consumes a great deal of time, money, and other resources. Consequently, businesses, societies, and regulators strive for reliable alternatives such as Quantitative Structure Toxicity Relationship (QSTR) models to fill gaps in toxicity profiles of compounds of concern to human health. The use of glycol ethers and their health effects have recently attracted the attention of international organizations such as the World Health Organization (WHO). The board members of Concise International Chemical Assessment Documents (CICAD) recently identified inadequate testing as well as gaps in toxicity profiles of ethylene glycol mono-n-alkyl ethers (EGEs). The CICAD board requested the ATSDR Computational Toxicology and Methods Development Laboratory to conduct QSTR assessments of certain specific toxicity endpoints for these chemicals. In order to evaluate the potential health effects of EGEs, CICAD proposed a critical QSTR analysis of the mutagenicity, carcinogenicity, and developmental effects of EGEs and other selected chemicals. We report here results of the application of QSTRs to assess rodent carcinogenicity, mutagenicity, and developmental toxicity of four EGEs: 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, and 2-butoxyethanol and their metabolites. Neither mutagenicity nor carcinogenicity is indicated for the parent compounds, but these compounds are predicted to be developmental toxicants. The predicted toxicity effects were subjected to reverse QSTR (rQSTR) analysis to identify structural attributes that may be the main drivers of the developmental toxicity potential of these compounds.

  2. Bifunctional rhodium intercalator conjugates as mismatch-directing DNA alkylating agents.

    Science.gov (United States)

    Schatzschneider, Ulrich; Barton, Jacqueline K

    2004-07-21

    A conjugate of a DNA mismatch-specific rhodium intercalator, containing the bulky chrysenediimine ligand, and an aniline mustard has been prepared, and targeting of mismatches in DNA by this conjugate has been examined. The preferential alkylation of mismatched over fully matched DNA is found by a mobility shift assay at concentrations where untethered organic mustards show little reaction. The binding site of the Rh intercalator was determined by DNA photocleavage, and the position of covalent modification was established on the basis of the enhanced depurination associated with N-alkylation. The site-selective alkylation at mismatched DNA renders these conjugates useful tools for the covalent tagging of DNA base pair mismatches and new chemotherapeutic design.

  3. A straightforward and efficient method for the synthesis of diversely substituted {beta}-aminoketones and {gamma}-aminoalcohols from 3-(N,N-dimethylamino)propiophenones as starting materials

    Energy Technology Data Exchange (ETDEWEB)

    Abonia, Rodrigo; Arteaga, Danny; Castillo, Juan; Insuasty, Braulio; Quiroga, Jairo; Ortiz, Alejandro, E-mail: rodrigo.abonia@correounivalle.edu.co [Universidad del Valle, Cali (Colombia). Department of Chemistry. Research Group of Heterocyclic Compounds

    2013-09-15

    Libraries of novel {beta}-aminoketones and {gamma}-aminoalcohols showing a wide structural diversity were easily obtained from a simple approach, using 3-(N,N-dimethylamino)propiophenone derivatives as key starting material. The procedure involved initially an N-alkylation of secondary benzylamines with propiophenone salts yielding the desired {beta}-aminoketones. Chemical or catalytic reduction of their carbonyl groups provided the final {gamma}-aminoalcohols in good yields. This protocol proved to be convenient as an alternative route for the synthesis of the local anesthetic Falicain Registered-Sign and for the topic antifungal drug Naftifine Registered-Sign . (author)

  4. Sequence-specific DNA alkylation targeting for Kras codon 13 mutation by pyrrole-imidazole polyamide seco-CBI conjugates.

    Science.gov (United States)

    Taylor, Rhys Dylan; Asamitsu, Sefan; Takenaka, Tomohiro; Yamamoto, Makoto; Hashiya, Kaori; Kawamoto, Yusuke; Bando, Toshikazu; Nagase, Hiroki; Sugiyama, Hiroshi

    2014-01-27

    Hairpin N-methylpyrrole-N-methylimidazole polyamide seco-CBI conjugates 2-6 were designed for synthesis by Fmoc solid-phase synthesis, and their DNA-alkylating activities against the Kras codon 13 mutation were compared by high-resolution denaturing gel electrophoresis with 225 base pair (bp) DNA fragments. Conjugate 5 had high reactivity towards the Kras codon 13 mutation site, with alkylation occurring at the A of the sequence 5'-ACGTCACCA-3' (site 2), including minor 1 bp-mismatch alkylation against wild type 5'-ACGCCACCA-3' (site 3). Conjugate 6, which differs from conjugate 5 by exchanging one Py unit with a β unit, showed high selectivity but only weakly alkylated the A of 5'-ACGTCACCA-3' (site 2). The hairpin polyamide seco-CBI conjugate 5 thus alkylates according to Dervan's pairing rule with the pairing recognition which β/β pair targets T-A and A-T pairs. SPR and a computer-minimized model suggest that 5 binds to the target sequence with high affinity in a hairpin conformation, allowing for efficient DNA alkylation. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. C-N Bond Activation and Ring Opening of a Saturated N-Heterocyclic Carbene by Lateral Alkali-Metal-Mediated Metalation.

    Science.gov (United States)

    Hernán-Gómez, Alberto; Kennedy, Alan R; Hevia, Eva

    2017-06-01

    Combining alkali-metal-mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes=[:C{N(2,4,6-Me 3 C 6 H 2 )CH 2 } 2 ]) with Group 1 alkyl bases suggest this destructive process is triggered by lateral metalation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH 2 SiMe 3 ) 2 and Al(TMP)iBu 2 ), key intermediates in this process have been isolated and structurally defined. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Time-resolved fluorescence sensing of N-acetyl amino acids, nucleobases, nucleotides and DNA by the luminescent Tb (III) - 8-alkyl-2-oxo-2H-chromene-3-carbaldehyde probe

    Energy Technology Data Exchange (ETDEWEB)

    Azab, Hassan A. [Chemistry Department, Faculty of Science, Suez Canal University, 41522 Ismailia (Egypt); Khairy, Gasser M., E-mail: gasser_chemist@yahoo.com [Chemistry Department, Faculty of Science and Arts, Aljouf University, P.O. Box # 2014, Skaka 41421 (Saudi Arabia); Chemistry Department, Faculty of Science, Suez Canal University, 41522 Ismailia (Egypt); Abd El-Ghany, N.; Ahmed, Marwa A. [Chemistry Department, Faculty of Science, Suez Canal University, El-Arish (Egypt)

    2016-08-15

    A time-resolved (gated) luminescence-based method for the detection of some of N-acetyl amino acids, nucleobases, nucleotides, and DNA using terbium- 8-alkyl-2-oxo-2H-chromene-3-carbaldehyde (AOCC) complex in 1:2 metal: ligand ratio in microtiterplate format has been evolved. The linear range for determination of the selected biomolecules is 0.1–1.0 µM. The detection limit was in the range of 0.0371–0.106 µM. The thermodynamic parameters, and binding constants (K) of N-acetyl amino acids, nucleobases, nucleotides with Tb (III) –(AOCC) {sub 2} complex were calculated. Positive and negative values of entropy (ΔS) and enthalpy (ΔH) changes for Tb (III) –(AOCC){sub 2}– N-acetyl amino acids, nucleobases or nucleotides ternary complexes were evaluated. Selectivity of Tb (III) -complex towards different biomolecules has been studied using ratiometric methods of analysis by comparison of biomolecules binding affinities for Tb (III) -complex. Interaction of Tb (III) complex with DNA has been studied.

  7. Time-resolved fluorescence sensing of N-acetyl amino acids, nucleobases, nucleotides and DNA by the luminescent Tb (III) - 8-alkyl-2-oxo-2H-chromene-3-carbaldehyde probe

    International Nuclear Information System (INIS)

    Azab, Hassan A.; Khairy, Gasser M.; Abd El-Ghany, N.; Ahmed, Marwa A.

    2016-01-01

    A time-resolved (gated) luminescence-based method for the detection of some of N-acetyl amino acids, nucleobases, nucleotides, and DNA using terbium- 8-alkyl-2-oxo-2H-chromene-3-carbaldehyde (AOCC) complex in 1:2 metal: ligand ratio in microtiterplate format has been evolved. The linear range for determination of the selected biomolecules is 0.1–1.0 µM. The detection limit was in the range of 0.0371–0.106 µM. The thermodynamic parameters, and binding constants (K) of N-acetyl amino acids, nucleobases, nucleotides with Tb (III) –(AOCC) 2 complex were calculated. Positive and negative values of entropy (ΔS) and enthalpy (ΔH) changes for Tb (III) –(AOCC) 2 – N-acetyl amino acids, nucleobases or nucleotides ternary complexes were evaluated. Selectivity of Tb (III) -complex towards different biomolecules has been studied using ratiometric methods of analysis by comparison of biomolecules binding affinities for Tb (III) -complex. Interaction of Tb (III) complex with DNA has been studied.

  8. The effect of the alkyl chain length on physicochemical features of (ionic liquids + γ-butyrolactone) binary mixtures

    International Nuclear Information System (INIS)

    Papović, Snežana; Bešter-Rogač, Marija; Vraneš, Milan; Gadžurić, Slobodan

    2016-01-01

    Highlights: • Influence of alkyl substituent length on IL properties was studied. • Nature of interactions between studied [C_nC_1im][NTf_2] and GBL were discussed. • Angell strength parameter indicates [C_nC_1im][NTf_2] are fragile liquids. • ILs properties regularly change with increase of the alkyl chain length. • Absence of GBL self-association upon addition of IL is observed. - Abstract: Densities and viscosities were determined and analysed for γ-butyrolactone (GBL) binary mixtures with 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids (where alkyl = ethyl, hexyl, octyl) as a function of temperature at atmospheric pressure (p = 0.1 MPa) and over the whole composition range. Excess molar volumes have been calculated from the experimental densities and were fitted using Redlich–Kister’s polynomial equation. Other volumetric parameters have been also calculated in order to obtain information about interactions between GBL and imidazolium based ionic liquids with different alkyl chain length. From the viscosity measurements, the Angell strength parameter was calculated for pure ionic liquids indicating that all investigated electrolytes are “fragile” liquids.

  9. Studies of Hydrogen Bonding Between N, N-Dimethylacetamide and Primary Alcohols

    Directory of Open Access Journals (Sweden)

    M. S. Manjunath

    2009-01-01

    Full Text Available Hydrogen bonding between N, N-dimethylacetamide (DMA and alcohols has been studied in carbon tetrachloride solution by an X-band Microwave bench at 936GHz. The dielectric relaxation time (τ of the binary system are obtained by both Higasi's method and Gopalakrishna method. The most likely association complex between alcohol and DMA is 1:1 stoichiometric complex through the hydroxyl group of the alcohol and the carbonyl group of amide. The results show that the interaction between alcohols and amides is 1:1 complex through the free hydroxyl group of the alcohol and the carbonyl group of amide and the alkyl chain-length of both the alcohols and amide plays an important role in the determination of the strength of hydrogen bond (O-H: C=O formed and suggests that the proton donating ability of alcohols is in the order: 1-propanol < 1-butanol < 1-pentanol and the accepting ability of DMA.

  10. The Impact of Commonly Used Alkylating Agents on Artifactual Peptide Modification.

    Science.gov (United States)

    Hains, Peter G; Robinson, Phillip J

    2017-09-01

    Iodoacetamide is by far the most commonly used agent for alkylation of cysteine during sample preparation for proteomics. An alternative, 2-chloroacetamide, has recently been suggested to reduce the alkylation of residues other than cysteine, such as the N-terminus, Asp, Glu, Lys, Ser, Thr, and Tyr. Here we show that although 2-chloroacetamide reduces the level of off-target alkylation, it exhibits a range of adverse effects. The most significant of these is methionine oxidation, which increases to a maximum of 40% of all Met-containing peptides, compared with 2-5% with iodoacetamide. Increases were also observed for mono- and dioxidized tryptophan. No additional differences between the alkylating reagents were observed for a range of other post-translational modifications and digestion parameters. The deleterious effects were observed for 2-chloroacetamide from three separate suppliers. The adverse impact of 2-chloroacetamide on methionine oxidation suggests that it is not the ideal alkylating reagent for proteomics.

  11. 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.

  12. 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...

  13. Rituximab, alkylating agents or combination therapy for gastric mucosa-associated lymphoid tissue lymphoma: a monocentric non-randomised observational study.

    Science.gov (United States)

    Amiot, A; Lévy, M; Copie-Bergman, C; Dupuis, J; Szablewski, V; Le Baleur, Y; Baia, M; Belhadj, K; Sobhani, I; Leroy, K; Haioun, C; Delchier, J-C

    2014-03-01

    There is no consensus on the standard treatment of gastric mucosa-associated lymphoid tissue (MALT) lymphoma for Helicobacter pylori-negative patients and for patients with persistent disease despite H. pylori eradication. To evaluate the comparative efficacy and safety of alkylating agents and rituximab alone or in combination. In this monocentric retrospective study, which included 106 patients who had not been previously treated with anti-cancer agents, we evaluated the efficacy and safety of oral alkylating agents monotherapy (n = 48), rituximab monotherapy (n = 28) and the therapy combining both drugs (n = 30). Evaluations were performed at weeks 6 (W6), 25 (W25), and 52 (W52) and after 2 years (W104). After a median follow-up period of 4.9 years (range 0.4-17.2 years), complete remission and overall response were significantly higher in patients in the combination therapy group at W104 (92% and 100% respectively) compared with patients treated with alkylating agents alone (66% and 68%) and rituximab alone (64% and 73%). The 5-year progression-free survival probabilities were 68%, 70% and 89% in patients treated with alkylating agents alone, rituximab alone and combination therapy respectively. Haematological adverse events were reported in 32 (30%) patients (mostly grade 1) and were more frequent in the two groups receiving alkylating agents (P = 0.05 and P alkylating agents alone. Rituximab has a better safety profile than regimens containing alkylating agents. © 2014 John Wiley & Sons Ltd.

  14. Isobutane as a probe of the structure of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids

    International Nuclear Information System (INIS)

    Pison, Laure; Bernales, Varinia; Fuentealba, Patricio; Padua, Agilio A.H.

    2015-01-01

    Highlights: • The solubility of isobutane was determined in [C n C 1 Im][NTf 2 ] (n = 2, 4, 6, 8 and 10). • Iso-C 4 H 10 solubility decreases with T and increases with n to reach x = 0.1 (n = 10, T = 303 K). • Isobutane is, on average, 1.6 times less soluble than n-butane in this family of ionic liquids. • Solubility increase with n is due to a more negative enthalpy of dissolution (n ⩾ 6). - Abstract: An experimental study of the solubility and of the thermodynamic properties of solvation, between temperatures (303 and 343) K and at pressures close to atmospheric, of 2-methylpropane (isobutane) in several ionic liquids based on the bis(trifluoromethylsulfonyl)imide anion and on 1-alkyl-3-methylimidazolium cations, [C n C 1 Im][NTf 2 ], with alkyl side-chains varying from two to ten carbon atoms is presented. The isobutane solubility increases with increasing size of the alkyl side-chain of the cation in the ionic liquid and decreases with increasing temperature (as typical of an exothermal dissolution process). The mole fraction solubility of isobutane varies from 0.904 · 10 −2 in [C 2 C 1 Im][NTf 2 ] at T = 343 K to 1.002 · 10 −1 in [C 10 C 1 Im][NTf 2 ] at T = 303 K. The values measured in this work are compared to the behaviour of n-butane in the same ionic liquids published in a previous study (Costa Gomes et al., 2012). Isobutane was found to be significantly less soluble than n-butane in all the ionic liquids. The differences found are interpreted in relation to the molecular structures obtained by molecular dynamics simulations for the solutions of n-butane and isobutane in the studied [C n C 1 Im][NTf 2 ] ionic liquids

  15. DNA alkylation and tumor induction in regenerating rat liver after cell cycle-related continuous N-nitrosodimethylamine infusion

    Energy Technology Data Exchange (ETDEWEB)

    Rabes, H.M.; Kerler, R.; Wilhelm, R.

    1983-01-01

    Synchronized regenerating rat liver after partial hepatectomy was used to study cell cycle-related DNA base alkylation and liver carcinogenesis. A continuous iv infusion of (/sup 14/C)N-nitrosodimethylamine (DMN) at a dose of 0.5 mg/kg/hour was given to inbred male Wistar Af/Han rats over a period of 8 hours either during the G1 phase, hydroxyurea-synchronized DNA synthesis, or the G2+M-phase of regenerating liver or to untreated rats (G0-phase liver--carcinogen dose, 1.5 mg/kg/hour). Two hours after the end of the infusion, the amount of 7-methylguanine was highest in the G0-phase liver, with a decrease in the G1 phase, the S-phase, and the G2+M-phase. After continuous DMN exposure, the O/sub 6/-methylguanine:7-methylguanine ratio was lower in the S-phase and G2+M-phase livers than in the G0-phase and G1-phase livers, indicating an increased O/sub 6/-methylguanine repair during DNA synthesis and the G2+M-phase. Liver tumors in rats treated by continuous DMN infusion either during the G0 phase or the S-phase developed only after carcinogen exposure during DNA synthesis.

  16. Influence of alkyl chain length and temperature on thermophysical properties of ammonium-based ionic liquids with molecular solvent.

    Science.gov (United States)

    Kavitha, T; Attri, Pankaj; Venkatesu, Pannuru; Devi, R S Rama; Hofman, T

    2012-04-19

    Mixing of ionic liquids (ILs) with molecular solvent can expand the range of structural properties and the scope of molecular interactions between the molecules of the solvents. Exploiting of these phenomena essentially require a basic fundamental understanding of mixing behavior of ILs with molecular solvents. In this context, a series of protic ILs possessing tetra-alkyl ammonium cation [R(4)N](+) with commonly used anion hydroxide [OH](-) were synthesized and characterized by temperature dependent thermophysical properties. The ILs [R(4)N](+)[OH](-) are varying only in the length of alkyl chain (R is methyl, ethyl, propyl, or butyl) of tetra-alkyl ammonium on the cationic part. The ILs used for the present study included tetramethyl ammonium hydroxide [(CH(3))(4)N](+)[OH](-) (TMAH), tetraethyl ammonium hydroxide [(C(2)H(5))(4)N](+)[OH](-) (TEAH), tetrapropyl ammonium hydroxide [(C(3)H(7))(4)N](+)[OH](-) (TPAH) and tetrabutyl ammonium hydroxide [(C(4)H(9))(4)N](+)[OH](-) (TBAH). The alkyl chain length effect has been analyzed by precise measurements such as densities (ρ), ultrasonic sound velocity (u), and viscosity (η) of these ILs with polar solvent, N-methyl-2-pyrrolidone (NMP), over the full composition range as a function of temperature. The excess molar volume (V(E)), the deviation in isentropic compressibility (Δκ(s)) and deviation in viscosity (Δη) were predicted using these properties as a function of the concentration of ILs. Redlich-Kister polynomial was used to correlate the results. A qualitative analysis of the results is discussed in terms of the ion-dipole, ion-pair interactions, and hydrogen bonding between ILs and NMP molecules. Later, the hydrogen bonding features between ILs and NMP were also analyzed using a molecular modeling program with the help of HyperChem 7.

  17. Selective Alkylation of C-Rich Bulge Motifs in Nucleic Acids by Quinone Methide Derivatives.

    Science.gov (United States)

    Lönnberg, Tuomas; Hutchinson, Mark; Rokita, Steven

    2015-09-07

    A quinone methide precursor featuring a bis-cyclen anchoring moiety has been synthesized and its capacity to alkylate oligonucleotide targets quantified in the presence and absence of divalent metal ions (Zn(2+) , Ni(2+) and Cd(2+) ). The oligonucleotides were designed for testing the sequence and secondary structure specificity of the reaction. Gel electrophoretic analysis revealed predominant alkylation of C-rich bulges, regardless of the presence of divalent metal ions or even the bis-cyclen anchor. This C-selectivity appears to be an intrinsic property of the quinone methide electrophile as reflected by its reaction with an equimolar mixture of the 2'-deoxynucleosides. Only dA-N1 and dC-N3 alkylation products were detected initially and only the dC adduct persisted for detection under conditions of the gel electrophoretic analysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Charge transport across metal/molecular (alkyl) monolayer-Si junctions is dominated by the LUMO level

    NARCIS (Netherlands)

    Yaffe, O.; Qi, Y.; Scheres, L.M.W.; Puniredd, S.R.; Segev, L.; Ely, T.; Haick, H.; Zuilhof, H.; Vilan, A.; Kronik, L.; Kahn, A.; Cahen, D.

    2012-01-01

    We compare the charge transport characteristics of heavy-doped p(++)- and n(++)-Si-alkyl chain/Hg junctions. Based on negative differential resistance in an analogous semiconductor-inorganic insulator/metal junction we suggest that for both p(++)- and n(++)-type junctions, the energy difference

  19. Gold recovery from acidic leach solutions using as extractants trialkylamines of N,N'-di-alkyl-aliphatic amides

    Energy Technology Data Exchange (ETDEWEB)

    Baroncelli, F.; Carlini, D.; Gasparini, G.M.; Simonetti, E.

    1988-07-01

    TriOctylAmine (TOA) and a di-substituted aliphatic amide, N,N-Di-N-ButylOctanamide (DBOA), were examined in batch and in mini mixer-settler experiments using leachates of Peruvian and Bolivian concentrates. With these minerals, very rich in sulfur (pyrites, stybine), 90-95% gold recovery in 12-24 hours was reached by leaching with 4M aqua regia (HCl 3M nitric acid 1M) at room temperature and with 1/3 solid/liquid ratio. With these leachate solutions (2-3M total acidity, 10-60 ppm ao Au), the two processes with TOA (GAMEX PROCESS) and with DBOA (AUMIDEX PROCESS) were tested and compared. Experimental results strongly support the possibility of using TOA and DBOA on an industrial scale.

  20. 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

  1. Deuterium isotope effect on metabolism of N-nitrosodimethylamine in vivo in rat

    International Nuclear Information System (INIS)

    Swann, P.F.; Mace, R.; Angeles, R.M.; Keefer, L.K.

    1983-01-01

    The maximal rates of metabolic oxidation of N-nitrosodimethylamine (NDMA) and N-nitrosodimethylamine-d6 (NDMA-d6) in vivo (VH and VD, respectively) have been measured by following 14CO2 exhalation in rats after intraperitoneal injection of the two 14C-labelled carcinogens at high doses (20 or 40 mg/kg). Complete deuteration of NDMA reduced only slightly the maximal rate of metabolism when the two substrates were administered separately (VH/VD approximately 1.2). However, much larger (approximately 4-fold) deuterium isotope effects were observed when mixtures of NDMA with NDMA-d6 were injected. These results are tentatively interpreted as evidence that C-H bond cleavage is not a rate limiting feature of overall metabolism, but that the complex between NDMA and the principal enzyme(s) metabolizing it in vivo freely equilibrates with unbound substrate. Single, large, intraperitoneal doses of NDMA and NDMA-d6 produced a similar alkylation of rat liver DNA and also of kidney DNA. However, a small oral dose (54 micrograms/kg) of NDMA-d6 produced 1/3 less alkylation of liver DNA and 3 times as much alkylation of kidney DNA as did an equimolar dose of NDMA. The reduction in alkylation of liver DNA correlates well with, and possibly explains, the decreased ability of NDMA-d6 to induce liver tumors in rats. The associated increase in the alkylation of kidney DNA suggests that this change is due to a decrease in the amount of nitrosamine removed from the portal blood on the first pass through the liver

  2. Repercussion of Solid state vs. Liquid state synthesized p-n heterojunction RGO-copper phosphate on proton reduction potential in water.

    Science.gov (United States)

    Samal, Alaka; Das, Dipti P; Madras, Giridhar

    2018-02-13

    The same copper phosphate catalysts were synthesized by obtaining the methods involving solid state as well as liquid state reactions in this work. And then the optimised p-n hybrid junction photocatalysts have been synthesized following the same solid/liquid reaction pathways. The synthesized copper phosphate photocatalyst has unique rod, flower, caramel-treat-like morphology. The Mott-Schottky behavior is in accordance with the expected behavior of n-type semiconductor and the carrier concentration was calculated using the M-S analysis for the photocatalyst. And for the p-n hybrid junction of 8RGO-Cu 3 (PO 4 ) 2 -PA (PA abbreviated for photoassisted synthesis method), 8RGO-Cu 3 (PO 4 ) 2 -EG(EG abbreviated for Ethylene Glycol based synthesis method), 8RGO-Cu 3 (PO 4 ) 2 -PEG (PEG abbreviated for Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol based synthesis method)the amount of H 2 synthesized was 7500, 6500 and 4500 µmol/h/g, respectively. The excited electrons resulting after the irradiation of visible light on the CB of p-type reduced graphene oxide (RGO) migrate easily to n-type Cu 3 (PO 4 ) 2 via. the p-n junction interfaces and hence great charge carrier separation was achieved.

  3. Enhanced n-Doping Efficiency of a Naphthalenediimide-Based Copolymer through Polar Side Chains for Organic Thermoelectrics

    KAUST Repository

    Kiefer, David; Giovannitti, Alexander; Sun, Hengda; Biskup, Till; Hofmann, Anna; Koopmans, Marten; Cendra, Camila; Weber, Stefan; Anton Koster, L. Jan; Olsson, Eva; Rivnay, Jonathan; Fabiano, Simone; McCulloch, Iain; Mü ller, Christian

    2018-01-01

    (gNDI-gT2) that carries oligoethylene glycol-based side chains and show that the polymer displays superior miscibility with the benzimidazole–dimethylbenzenamine-based n-dopant N-DMBI. The good compatibility of p(gNDI-gT2) and N-DMBI results in a relatively

  4. Experimental and theoretical study of pyrazole N-alkylation catalyzed by basic modified molecular sieves

    Czech Academy of Sciences Publication Activity Database

    Matos, I.; Pérez-Mayoral, E.; Soriano, E.; Zukal, Arnošt; Martín-Aranda, R. M.; López-Peinado, A. J.; Fonseca, I.; Čejka, Jiří

    2010-01-01

    Roč. 161, č. 3 (2010), s. 377-383 ISSN 1385-8947 R&D Projects: GA AV ČR 1QS400400560 Institutional research plan: CEZ:AV0Z40400503 Keywords : pyrazole alkylation * basic mesoporous materials * reaction mechanism Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.074, year: 2010

  5. 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.

  6. NMR study of 1,4-dihydropyridine derivatives endowed with long alkyl and functionalized chains

    Energy Technology Data Exchange (ETDEWEB)

    Suarez, Margarita; Salfran, Esperanza; Rodriguez, Hortensia; Coro, Julieta, E-mail: msuarez@fq.uh.c [Universidad de La Habana (Cuba). Facultad de Quimica. Lab. de Sintesis Organica; Molero, Dolores; Saez, Elena [Universidad Complutense, Madrid (Spain). CAI-RMN; Martinez-Alvarez, Roberto; Martin, Nazario [Universidad Complutense, Madrid (Spain). Facultad de Quimica. Dept. de Quimica Organica I

    2011-07-01

    The {sup 1}H , {sup 13}C and {sup 15}N NMR spectroscopic data for 1,4-dihydropyridine endowed with long alkyl and functionalized chain on C-3 and C-5, have been fully assigned by combination of one- and two dimensional experiments (DEPT, HMBC, HMQC, COSY, nOe). (author)

  7. The implications of water extractable organic matter (WEOM) on the sorption of typical parent, alkyl and N/O/S-containing polycyclic aromatic hydrocarbons (PAHs) by microplastics.

    Science.gov (United States)

    Li, Ruilong; Tan, Huadong; Zhang, Linlin; Wang, Shaopeng; Wang, Yinghui; Yu, Kefu

    2018-07-30

    Microplastics sorption of persistent organic pollutants (POPs) was the core processes that cause negative effects to biota, and their influencing factors and related mechanisms are poorly understood. In this study, we explored the impacts of water extractable organic matter (WEOM), an important source of endogenous dissolved organic matter in mangrove sediment, on the sorption coefficients of typical parent, alkyl and N/O/S-containing polycyclic aromatic hydrocarbons (PAHs) by microplastics. The presence of L-WEOM (D) impeded the PAHs sorption as the coefficients (K f ) decreased to 10.17 (μg/kg)/(μg/L) n and to 8.39 (μg/kg)/(μg/L) n for fluorene (Flu) and 1-methyl-fluorene (1-M-Flu), respectively. The K f exhibited good linear relationships with the aliphaticity of L-WEOM (p  0.05). Under the presences of L-WEOM (D), (S) and (K), the lone pair electrons of N/O/S-containing PAHs was the dominant factor contributing to the obvious difference of the K f values from the other groups. Moreover, the largest impact of L-WEOM (D) on the Flu sorption was in the case of PVC microplastics, while almost no effect was in the case of PS microplastics. The findings of our work may be helpful in improving our understanding of the role of WEOM on the sorption of PAHs to microplastics in the field mangrove sediment. Copyright © 2018 Elsevier Inc. All rights reserved.

  8. Critical role of alkyl chain branching of organic semiconductors in enabling solution-processed N-channel organic thin-film transistors with mobility of up to 3.50 cm² V(-1) s(-1).

    Science.gov (United States)

    Zhang, Fengjiao; Hu, Yunbin; Schuettfort, Torben; Di, Chong-an; Gao, Xike; McNeill, Christopher R; Thomsen, Lars; Mannsfeld, Stefan C B; Yuan, Wei; Sirringhaus, Henning; Zhu, Daoben

    2013-02-13

    Substituted side chains are fundamental units in solution processable organic semiconductors in order to achieve a balance of close intermolecular stacking, high crystallinity, and good compatibility with different wet techniques. Based on four air-stable solution-processed naphthalene diimides fused with 2-(1,3-dithiol-2-ylidene)malononitrile groups (NDI-DTYM2) that bear branched alkyl chains with varied side-chain length and different branching position, we have carried out systematic studies on the relationship between film microstructure and charge transport in their organic thin-film transistors (OTFTs). In particular synchrotron measurements (grazing incidence X-ray diffraction and near-edge X-ray absorption fine structure) are combined with device optimization studies to probe the interplay between molecular structure, molecular packing, and OTFT mobility. It is found that the side-chain length has a moderate influence on thin-film microstructure but leads to only limited changes in OTFT performance. In contrast, the position of branching point results in subtle, yet critical changes in molecular packing and leads to dramatic differences in electron mobility ranging from ~0.001 to >3.0 cm(2) V(-1) s(-1). Incorporating a NDI-DTYM2 core with three-branched N-alkyl substituents of C(11,6) results in a dense in-plane molecular packing with an unit cell area of 127 Å(2), larger domain sizes of up to 1000 × 3000 nm(2), and an electron mobility of up to 3.50 cm(2) V(-1) s(-1), which is an unprecedented value for ambient stable n-channel solution-processed OTFTs reported to date. These results demonstrate that variation of the alkyl chain branching point is a powerful strategy for tuning of molecular packing to enable high charge transport mobilities.

  9. Nucleation, growth and habit modification of n-alkanes and homologous mixtures in the absence and presence of flow improving additives

    International Nuclear Information System (INIS)

    Taggart, Audrey M.

    1996-01-01

    A detailed study has been performed on the nucleation, growth and habit modification of n-alkanes and homologous mixtures in the absence and presence of flow improving additives in an attempt to gain a clearer appreciation of the interaction mechanisms behind wax / additive crystallisation. Kinetic and structural assessment of melt phase n-alkanes illustrate the different crystallographic forms present within the homologous series. Studies demonstrate the alternating behaviour of the even and odd numbered homologues which converges as a function of increasing molecular weight. Greater crystal lattice stabilities were found for those n-alkanes which have an even carbon number and which crystallise into the triclinic crystal structure. Solid state phase behaviour of the n-alkanes was found to vary depending on the number and parity of n. Nucleation kinetic studies of n-alkanes and homologous mixtures from model diesel fuel solvents (dodecane, m-xylene, decalin, pristane and a dewaxed fuel) are assessed using turbidity as the method of crystallite detection. Saturation temperatures are found to be related to both alkane structure and molecular chain length for all solvent systems. N-alkane solubilities are lower for n-alkane like solvents. The width of the meta stable zone varies as a function of solvent in order of dodecane ≅ pristane 19 H 40 and solvent m-xylene. Wax precipitation from distillate fuels in the presence of flow improving additives (di-alkyl di-amino xylene, phthalic acid and sulphobenzene acid derivatives and high molecular weight polymers) reveal responsive wax crystal nucleator and growth inhibitor additives. The crystal morphology of heptacosane, C 27 H 56 to simulate a model wax crystal is assessed in addition to its response to blocker 'tailor made' additives: methyl substituted C 27 H 56 and di-alkyl substituted phenyl additives [additive (A) and (B)]. Pure C 27 H 56 reveals a thin lozenge shaped platelet. All additives studied induce growth

  10. Grafting C8-C16 alkyl groups altered the self-assembly and curcumin –loading properties of sodium caseinate in water

    Directory of Open Access Journals (Sweden)

    Yaqiong Zhang

    2018-02-01

    Full Text Available The data presented here are related to the research article entitled “Synthesis and characterization of alkylated caseinate, and its structure-curcumin loading property relationship in water” (Zhang et al., 2018 [1]. This data article reports the detailed spectra information for 1H NMR, 13C NMR and UPLC-Q-TOF MS of the N-succinimidyl fatty acid esters with various alkyl chain lengths (Cn-NHSs, n = 8, 12, 14 and 16. 1H NMR, 13C NMR and UPLC-Q-TOF MS spectra for C16-NHS are shown as an example. Then the stacked 1H NMR spectra of the obtained alkylated caseinates (Cn-caseinates, n = 8, 12, 14 and 16 are provided. The surface hydrophobicity index (S0 of Cn-caseinates with different substitution degrees (SD of alkyl groups is shown. Additionally, Visual appearances for the formed aqueous dispersions of curcumin-loaded native caseinate (NaCas and Cn-caseinates self-assemblies are shown. X-ray diffraction patterns of curcumin, C16-caseinate, its physical mixture and curcumin-loaded C16-caseinate self-assemblies are examined. The re-dispersibility and short-term storage stability of the curcumin-loaded NaCas and C16-caseinate self-assemblies are also studied. Keywords: Caseinate, Alkylated caseinate, Self-assembly, Curcumin-loading property

  11. DNA Polymerases ImuC and DinB Are Involved in DNA Alkylation Damage Tolerance in Pseudomonas aeruginosa and Pseudomonas putida.

    Science.gov (United States)

    Jatsenko, Tatjana; Sidorenko, Julia; Saumaa, Signe; Kivisaar, Maia

    2017-01-01

    Translesion DNA synthesis (TLS), facilitated by low-fidelity polymerases, is an important DNA damage tolerance mechanism. Here, we investigated the role and biological function of TLS polymerase ImuC (former DnaE2), generally present in bacteria lacking DNA polymerase V, and TLS polymerase DinB in response to DNA alkylation damage in Pseudomonas aeruginosa and P. putida. We found that TLS DNA polymerases ImuC and DinB ensured a protective role against N- and O-methylation induced by N-methyl-N'-nitro-N-nitrosoguanidine (MNNG) in both P. aeruginosa and P. putida. DinB also appeared to be important for the survival of P. aeruginosa and rapidly growing P. putida cells in the presence of methyl methanesulfonate (MMS). The role of ImuC in protection against MMS-induced damage was uncovered under DinB-deficient conditions. Apart from this, both ImuC and DinB were critical for the survival of bacteria with impaired base excision repair (BER) functions upon alkylation damage, lacking DNA glycosylases AlkA and/or Tag. Here, the increased sensitivity of imuCdinB double deficient strains in comparison to single mutants suggested that the specificity of alkylated DNA lesion bypass of DinB and ImuC might also be different. Moreover, our results demonstrated that mutagenesis induced by MMS in pseudomonads was largely ImuC-dependent. Unexpectedly, we discovered that the growth temperature of bacteria affected the efficiency of DinB and ImuC in ensuring cell survival upon alkylation damage. Taken together, the results of our study disclosed the involvement of ImuC in DNA alkylation damage tolerance, especially at low temperatures, and its possible contribution to the adaptation of pseudomonads upon DNA alkylation damage via increased mutagenesis.

  12. Solvent-free sample preparation by headspace solid-phase microextraction applied to the tracing of n-butyl nitrite abuse.

    Science.gov (United States)

    Tytgat, J; Daenens, P

    1996-01-01

    The most common alkyl nitrites encountered in forensic toxicology are iso-butyl, n-butyl and iso-pentyl(amyl) nitrites. All have become popular as an aphrodisiac, especially among the homosexual population. Alkyl nitrites are a volatile and unstable group of compounds, which hydrolyse in aqueous matrices to the alcohol and nitrite ion. Here we describe a fast, clean and sensitive procedure for the detection of hydrolysed n-butyl nitrite in whole human blood using a new, solvent-free sampling technique, the headspace solid-phase micro-extraction (HSPME), combined with GC/FID analysis. Sample preparation was investigated using two different stationary phases (100 microns polydimethylsiloxane and 85 microns polyacrylate), coating a fused silica fibre. The effect of different sampling times at fixed temperatures was also studied. Our results demonstrate that the HSPME/GC/FID procedure allows tracing of n-butyl nitrite abuse and detects hydrolysed n-butyl nitrite, i.e., released n-butanol, in whole blood at the 1 ng/mL level.

  13. Overexpressed human metallothionein IIA gene protects Chinese hamster ovary cells from killing by alkylating agents

    International Nuclear Information System (INIS)

    Kaina, B.; Lohrer, H.; Karin, M.; Herrlich, P.

    1990-01-01

    Experiments were designed to detect survival advantages that cells gain by overexpressing metallothionein (MT). Chinese hamster ovary K1-2 cells and an x-ray-sensitive derivative were transfected with a bovine papillomavirus (BPV)-linked construct carrying the human metallothionein IIA (hMT-IIA) gene. Transfectants survived 40-fold higher levels of cadmium chloride, harbored at least 30 copies of hMT-IIA, and contained 25- to 166-fold more MT than the parent cells. Even under conditions of reduced glutathione synthesis, the transfectants were not more resistant to the lethal effects of ionizing radiation and bleomycin than the parent cells. Thus free radicals generated by these agents cannot be scavenged efficiently by MT in vivo. The hMT-IIA transfectants, however, but not control transfectants harboring a BPV-MT promoter-neo construct, tolerated significantly higher doses of the alkylating agents N-methyl-N-nitrosourea and N-methyl-N'-nitro-N-nitrosoguanidine. Resistance and MT overexpression occurred irrespective of selection and cultivation in cadmium and zinc. There was no increase in resistance to methyl methanesulfonate and N-hydroxyethyl-N-chloroethylnitrosourea. MT did not affect the degree of overall DNA methylation after N-methyl-N-nitrosourea treatment nor the level of O6-methylguanine-DNA methyltransferase. The results suggest that MT participates as a cofactor or regulatory element in repair or tolerance of toxic alkylation lesions

  14. Overexpressed human metallothionein IIA gene protects Chinese hamster ovary cells from killing by alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Kaina, B.; Lohrer, H.; Karin, M.; Herrlich, P. (Kernforschungszentrum Karlsruhe, Karlsruhe (Germany, F.R.))

    1990-04-01

    Experiments were designed to detect survival advantages that cells gain by overexpressing metallothionein (MT). Chinese hamster ovary K1-2 cells and an x-ray-sensitive derivative were transfected with a bovine papillomavirus (BPV)-linked construct carrying the human metallothionein IIA (hMT-IIA) gene. Transfectants survived 40-fold higher levels of cadmium chloride, harbored at least 30 copies of hMT-IIA, and contained 25- to 166-fold more MT than the parent cells. Even under conditions of reduced glutathione synthesis, the transfectants were not more resistant to the lethal effects of ionizing radiation and bleomycin than the parent cells. Thus free radicals generated by these agents cannot be scavenged efficiently by MT in vivo. The hMT-IIA transfectants, however, but not control transfectants harboring a BPV-MT promoter-neo construct, tolerated significantly higher doses of the alkylating agents N-methyl-N-nitrosourea and N-methyl-N'-nitro-N-nitrosoguanidine. Resistance and MT overexpression occurred irrespective of selection and cultivation in cadmium and zinc. There was no increase in resistance to methyl methanesulfonate and N-hydroxyethyl-N-chloroethylnitrosourea. MT did not affect the degree of overall DNA methylation after N-methyl-N-nitrosourea treatment nor the level of O6-methylguanine-DNA methyltransferase. The results suggest that MT participates as a cofactor or regulatory element in repair or tolerance of toxic alkylation lesions.

  15. Overexpressed human metallothionein IIA gene protects Chinese hamster ovary cells from killing by alkylating agents.

    Science.gov (United States)

    Kaina, B; Lohrer, H; Karin, M; Herrlich, P

    1990-01-01

    Experiments were designed to detect survival advantages that cells gain by overexpressing metallothionein (MT). Chinese hamster ovary K1-2 cells and an x-ray-sensitive derivative were transfected with a bovine papillomavirus (BPV)-linked construct carrying the human metallothionein IIA (hMT-IIA) gene. Transfectants survived 40-fold higher levels of cadmium chloride, harbored at least 30 copies of hMT-IIA, and contained 25- to 166-fold more MT than the parent cells. Even under conditions of reduced glutathione synthesis, the transfectants were not more resistant to the lethal effects of ionizing radiation and bleomycin than the parent cells. Thus free radicals generated by these agents cannot be scavenged efficiently by MT in vivo. The hMT-IIA transfectants, however, but not control transfectants harboring a BPV-MT promoter-neo construct, tolerated significantly higher doses of the alkylating agents N-methyl-N-nitrosourea and N-methyl-N'-nitro-N-nitrosoguanidine. Resistance and MT overexpression occurred irrespective of selection and cultivation in cadmium and zinc. There was no increase in resistance to methyl methanesulfonate and N-hydroxyethyl-N-chloroethylnitrosourea. MT did not affect the degree of overall DNA methylation after N-methyl-N-nitrosourea treatment nor the level of O6-methylguanine-DNA methyltransferase. The results suggest that MT participates as a cofactor or regulatory element in repair or tolerance of toxic alkylation lesions. Images PMID:2320583

  16. Reactions of 4-nitro-1,2,3-triazole with alkylating agents and compounds with activated multiple bonds

    Energy Technology Data Exchange (ETDEWEB)

    Vereshchagin, L.I.; Kuznetsova, N.I.; Kirillova, L.P.; Shcherbakov, V.V.; Sukhanov, G.T.; Gareev, G.A.

    1987-01-01

    When 4-nitro-1,2,3-triazole is alkylated, a mixture of N1- and N2-isomers is formed, with the latter usually predominating. The same behavior is also observed in addition reactions of 4-nitrotriazole to activated multiple bonds.

  17. Application of polyacrylic acid-poly-N,N-dimethyldiallylammonium chloride polyelectrolyte complexes for structuring of polluted soil of Semipalatinsk nuclear test site

    International Nuclear Information System (INIS)

    Sabantseva, T.; Bashenova, A.; Orazzhanova, L.K.; Yashkarova, M.G.; Bimendina, L.A.

    2002-01-01

    The present communication is devoted to investigation of structuring efficiency of polyacrylic acid-poly-N,N-dimethyldiallylammonium chloride (PAA-PDMDAACI) polyelectrolyte complexes. The granulometric analysis of selected soil samples before and after the treatment of aqueous solution of PAA, PDMDAACI and PAA-PDMDAACI complexes at different molar ratio of polymer components and polymer concentrations was carried out. Analysis shows that nonstoichiometric polyelectrolyte complex [PAA]:[PDMDAACI]=3:1 possesses the best structuring effect. But this result is worse than in the case using of [PAA]:[polyethylene glycol]=1:1 inter-polymer complex

  18. Cu(ll) mediated ATRP of MMA by using a novel tetradentate amine ligand with oligo(ethylene glycol) pendant groups

    NARCIS (Netherlands)

    Becer, C.R.; Hoogenboom, R.; Founier, D.; Schubert, U.S.

    2007-01-01

    A novel tetradentate amine ligand namely N,N,N,N,N;,N;-hexaoligo(ethylene glycol) triethylenetetramine (HOEGTETA) was employed in the homogenous ATRP of MMA in anisole using CuBr and CuBr2 as the catalyst and ethyl 2-bromoisobutyrate (EBiB) as an initiator. The effect of the polymerization

  19. Cascade alkylarylation of substituted N-allylbenzamides for the construction of dihydroisoquinolin-1(2H-ones and isoquinoline-1,3(2H,4H-diones

    Directory of Open Access Journals (Sweden)

    Ping Qian

    2016-02-01

    Full Text Available An oxidative reaction for the synthesis of 4-alkyl-substituted dihydroisoquinolin-1(2H-ones with N-allylbenzamide derivatives as starting materials has been developed. The radical alkylarylation reaction proceeds through a sequence of alkylation and intramolecular cyclization. The substituent on the C–C double bond was found to play a key role for the progress of the reaction to give the expected products with good chemical yields. Additionally, N-methacryloylbenzamides were also suitable substrates for the current reaction and provided the alkyl-substituted isoquinoline-1,3(2H,4H-diones in good yield.

  20. Thermal aromatic Claisen rearrangement and Strecker reaction of alkyl(allyl-aryl ethers under green reaction conditions: Efficient and clean preparation of ortho-allyl phenols (naphthols and alkyl(allyloxyarene-based γ-amino nitriles

    Directory of Open Access Journals (Sweden)

    Kheila N. Silgado-Gómez

    2017-11-01

    Full Text Available Chemical transformations of 13 diverse allyl(alkyl-aryl ethers, easily prepared using Williamson reaction of different hydroxyarenes and allyl bromide and alkyl (n-butyl, n-octyl bromides, were studied. Thermal aromatic Claisen rearrangement of allyl-aryl ethers to obtain ortho-allyl phenols (naphthols employing propylene carbonate as a nontoxic and biodegradable solvent was described for the first time. The use of this green solvent allowed to enhance notably product yields and reduce significantly the reaction time comparing with the use of 1,2-dichlorobenzene, toxic solvent, which is traditionally employed in this type of Claisen rearrangement. Three-component Strecker reaction of selected alkyl(allyl-aryl ethers with formyl function on aryl fragment and, piperidine and potassium cyanide in the presence of sulfuric acid supported on silica gel (SSA, SiO2-O-SO3H under mild reaction conditions was used in the preparation of new γ-amino nitriles, analogues of alkaloid girgensohnine [2-(4-hydroxyphenyl-2-(piperidin-1-ylacetonitrile], a perspective biological model in the search for new insecticidal agrochemicals against Aedes aegypti. The use of SSA, an inexpensive and reusable solid catalyst, allowed to obtain new series of 2-[4-alkyl(allyloxyphenyl]-2-(piperidin-1-ylacetonitriles in short time at room temperature with good yields.

  1. Tailored reforming of n-dodecane in an aqueous discharge reactor

    KAUST Repository

    Zhang, Xuming

    2016-03-24

    Here, we present an original technical approach to simultaneously produce a tailored synthetic liquid fuel and a syngas. In an aqueous discharge reactor with gaseous bubbles, we reformed an emulsified n-dodecane/water mixture. The higher dielectric permittivity of the mixture facilitates electrical discharges that cause the electron impact dissociation of n-dodecane into alkyl and hydrogen radicals, while the addition of water also provides a steam-reforming environment inside the discharged bubbles. We added methane and carbon dioxide to the system because they dissociate into methyl and oxygen radicals, respectively, which prevent the alkyl-alkyl recombinations that result in the formation of long-chain hydrocarbons (HCs). Thus, we were able to control product selectivity by adding methane to increase the production of short-chain HCs and hydrogen gas or by adding carbon dioxide to increase the production of oxygenated fuels, such as 1-dodecanol. Using gas chromatography and gas chromatography-mass spectrometry we detail the compositions of both the synthetic liquid and the syngas, and we provide conceptual chemical mechanisms to selectively increase the production of oxygenates and that of HCs that are shorter or longer than the base fuel. The basis of this in-liquid discharge for the purpose of fuel reforming has potential applications to advanced engines to control ignition delay time, a continuing focus of study in our lab. © 2016 IOP Publishing Ltd.

  2. The beneficial effect of cynodon dactylon fractions on ethylene glycol-induced kidney calculi in rats.

    Science.gov (United States)

    Khajavi Rad, Abolfazl; Hadjzadeh, Mousa-Al-Reza; Rajaei, Ziba; Mohammadian, Nema; Valiollahi, Saleh; Sonei, Mehdi

    2011-01-01

    To assess the beneficial effect of different fractions of Cynodon dactylon (C. dactylon) on ethylene glycol-induced kidney calculi in rats. Male Wistar rats were randomly divided into control, ethylene glycol, curative, and preventive groups. The control group received tap drinking water for 35 days. Ethylene glycol, curative, and preventive groups received 1% ethylene glycol for induction of calcium oxalate (CaOx) calculus formation. Preventive and curative subjects also received different fractions of C. dactylon extract in drinking water at 12.8 mg/kg, since day 0 and day 14, respectively. After 35 days, the kidneys were removed and examined for histopathological findings and counting the CaOx deposits in 50 microscopic fields. In curative protocol, treatment of rats with C. dactylon N-butanol fraction and N-butanol phase remnant significantly reduced the number of the kidney CaOx deposits compared to ethylene glycol group. In preventive protocol, treatment of rats with C. dactylon ethyl acetate fraction significantly decreased the number of CaOx deposits compared to ethylene glycol group. Fractions of C. dactylon showed a beneficial effect on preventing and eliminating CaOx deposition in the rat kidney. These results provide a scientific rational for preventive and treatment roles of C. dactylon in human kidney stone disease.

  3. Density functional theory with van der waals corrections study of the adsorption of alkyl, alkylthiol, alkoxyl, and amino-alkyl chains on the H:Si(111) surface.

    Science.gov (United States)

    Arefi, Hadi H; Nolan, Michael; Fagas, Giorgos

    2014-11-11

    Surface modification of silicon with organic monolayers tethered to the surface by different linkers is an important process in realizing future miniaturized electronic and sensor devices. Understanding the roles played by the nature of the linking group and the chain length on the adsorption structures and stabilities of these assemblies is vital to advance this technology. This paper presents a density functional theory (DFT) study of the hydrogen passivated Si(111) surface modified with alkyl chains of the general formula H:Si-(CH2)n-CH2 and H:Si-X-(CH2)n-CH3, where X = NH, O, S and n = (0, 1, 3, 5, 7, 9, 11), at half coverage. For (X)-hexane and (X)-dodecane functionalization, we also examined various coverages up to full monolayer grafting in order to validate the result of half covered surface and the linker effect on the coverage. We find that it is necessary to take into account the van der Waals interaction between the alkyl chains. The strongest binding is for the oxygen linker, followed by S, N, and C, irrespective of chain length. The result revealed that the sequence of the stability is independent of coverage; however, linkers other than carbon can shift the optimum coverage considerably and allow further packing density. For all linkers apart from sulfur, structural properties, in particular, surface-linker-chain angles, saturate to a single value once n > 3. For sulfur, we identify three regimes, namely, n = 0-3, n = 5-7, and n = 9-11, each with its own characteristic adsorption structures. Where possible, our computational results are shown to be consistent with the available experimental data and show how the fundamental structural properties of modified Si surfaces can be controlled by the choice of linking group and chain length.

  4. The synthesis of 1-11C-labelled ethyl, propyl, butyl and isobutyl iodides and examples of alkylation reactions

    International Nuclear Information System (INIS)

    Laangstroem, B.; Antoni, G.; Gullberg, P.; Halldin, C.; Naagren, K.; Rimland, A.; Svaerd, H.

    1986-01-01

    New 11 C-labelled precursors [1- 11 C]ethyl,[1- 11 C]propyl, [1- 11 C]butyl, and [1- 11 C]isobutyl iodides have been prepared by a 3-step reaction route using a one-pot system. The labelled iodides were obtained in 20-55#percent# radiochemical yields and 65-95#percent# radiochemical purities, with a total time for synthesis of the order of 10-14 min. The labelled iodides have been used in alkylation reactions with nitrogen, oxygen and carbon nucleophiles. The nitrogen alkylation reactions are exemplified by the synthesis of the analgetics N-[1- 11 C-ethyl]iodocaine and N-[1- 11 C-butyl] bupivacaine. The synthesis of 3-nitrophenyl[1- 11 C]propyl ether is also presented in this paper as an example of an oxygen alkylation. (author)

  5. ANIONIC POLYMERIZATION OF ALKYL METHACRYLATES INITIATED BY nBuCu(NCy2)Li

    Institute of Scientific and Technical Information of China (English)

    Bing-yong Han; Jian-guo Liang; Jian-min Lu; Feng An; Wan-tai Yang

    2009-01-01

    Anionic polymerization of methyl methacrylate (MMA), n-butyl methacrylate (nBMA) and glycidyl methacrylate (GMA) initiated by nBuCu(NCy2)Li (1) in tetrahydrofuran (THF) at -50℃ to -10℃ was investigated. It was found that the polymerization of MMA and nBMA initiated by 1 proceeded quantitatively in THF to afford PMMA and PBMA with polydispersity index 1.15-1.30 and nearly 100% initiator efficiencies at -10℃. The molecular weights increased linearly with the ratio of [monomer]/[1]. However, a post-polymerization experiment carried out on this system revealed a double polymer peak by GPC when fresh monomer was added after an interval of 10 rain. Polymerization of styrene could be initiated by 1, but the initiator efficiency was low.

  6. Synthesis and antibacterial activities of 1-N [(S)-omega-amino-2-hydroxyalkyl] kanamycin A derivatives.

    Science.gov (United States)

    Richardson, K; Jevons, S; Moore, J W; Ross, B C; Wright, J R

    1977-10-01

    Four 1-N-aminohydroxy-alkyl derivatives of kanamycin A were prepared and their in vitro activities against aminoglycoside-sensitive and aminoglycoside-resistant organisms were compared with amikacin. 1-N-[(S)-4-Amino-2-hydroxybutyl] kanamycin A (Fig. 1, compound 2, code no. UK-18,892) was equipotent to amikacin in all these tests and in mouse protection studies.

  7. DNA-Directed alkylating agents. 7. Synthesis, DNA interaction, and antitumor activity of bis(hydroxymethyl)- and bis(carbamate)-substituted pyrrolizines and imidazoles.

    Science.gov (United States)

    Atwell, G J; Fan, J Y; Tan, K; Denny, W A

    1998-11-19

    A series of bis(hydroxymethyl)-substituted imidazoles, thioimidazoles, and pyrrolizines and related bis(carbamates), linked to either 9-anilinoacridine (intercalating) or 4-(4-quinolinylamino)benzamide (minor groove binding) carriers, were synthesized and evaluated for sequence-specific DNA alkylation and cytotoxicity. The imidazole and thioimidazole analogues were prepared by initial synthesis of [(4-aminophenyl)alkyl]imidazole-, thioimidazole-, or pyrrolizine dicarboxylates, coupling of these with the desired carrier, and reduction to give the required bis(hydroxymethyl) alkylating moiety. The pyrrolizines were the most reactive alkylators, followed by the thioimidazoles, while the imidazoles were unreactive. The pyrrolizines and some of the thioimidazoles cross-linked DNA, as measured by agarose gel electrophoresis. Strand cleavage assays showed that none of the compounds reacted at purine N7 or N3 sites in the gpt region of the plasmid gpt2Eco, but the polymerase stop assay showed patterns of G-alkylation in C-rich regions. The corresponding thioimidazole bis(carbamates) were more selective than the bis(hydroxymethyl) pyrrolizines, with high-intensity bands at 5'-NCCN, 5'-NGCN and 5'-NCGN sequences in the PCR stopping assay ( indicates block sites). The data suggest that these targeted compounds, like the known thioimidazole bis(carbamate) carmethizole, alkylate exclusively at guanine residues via the 2-amino group, with little or no alkylation at N3 and N7 guanine or adenine sites. The cytotoxicities of the compounds correlated broadly with their reactivities, with the bis(hydroxymethyl)imidazoles being the least cytotoxic (IC50s >1 microM; P388 leukemia) and with the intercalator-linked analogues being more cytotoxic than the corresponding minor-groove-targeted ones. This was true also for the more reactive thioimidazole bis(carbamates) (IC50s 0.8 and 11 microM, respectively), but both were more active than the analogous "untargeted" carmethizole (IC50 20

  8. Newly designed PdRuBi/N-Graphene catalysts with synergistic effects for enhanced ethylene glycol electro-oxidation

    International Nuclear Information System (INIS)

    Li, Tengfei; Huang, Yiyin; Ding, Kui; Wu, Peng; Abbas, Syed Comail; Ghausi, Muhammad Arsalan; Zhang, Teng; Wang, Yaobing

    2016-01-01

    Graphical abstract: We rationally design and synthesize a ternary PdRuBi/NG catalyst with significantly enhanced catalytic activity with synergetic effect of Ru and Bi towards ethylene glycol electro-oxidation. - Abstract: Palladium (Pd)-based catalysts are appealing electro-catalysts for alcohol oxidation reaction in fuel cell, but still not efficient as the complicated oxidation process and sluggish kinetic. Here we rationally design and synthesize a PdRuBi/NG tri-metallic catalyst with space synergetic effect for enhanced ethylene glycol electro-oxidation, in which both Ru and Bi in the catalyst are synergistic effective in promoting catalytic activity of Pd catalytic interlayer by electronic effect and surface modification mechanism respectively. It shows 4.2 times higher peak current density towards ethylene glycol electro-oxidation than commercial Pd/C catalyst, and the catalytic durability is also greatly improved.

  9. 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.

  10. Using ethane and butane as probes to the molecular structure of 1-alkyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] imide ionic liquids.

    Science.gov (United States)

    Costa Gomes, Margarida F; Pison, Laure; Pensado, Alfonso S; Pádua, Agilio A H

    2012-01-01

    In this work, we have studied the solubility and the thermodynamic properties of solvation, between 298 and 343 K and at pressures close to atmospheric, of ethane and n-butane in several ionic liquids based on the bis[(trifluoromethyl) sulfonyl]imide anion and on 1-alkyl-3-methylimidazolium cations, [CnC1Im] [NTf2], with alkyl side-chains varying from two to ten carbon atoms. The solubility of butane is circa one order of magnitude larger than that of ethane with mole fractions as high as 0.15 in [C10C1Im][NTf2] at 300 K. The solubilities of both n-butane and ethane gases are higher for ionic liquids with longer alkyl chains. The behaviour encountered is explained by the preferential solvation of the gases in the non-polar domains of the solvents, the larger solubility of n-butane being attributed to the dispersive contributions to the interaction energy. The rise in solubility with increasing size of the alkyl-side chain is explained by a more favourable entropy of solvation in the ionic liquids with larger cations. These conclusions are corroborated by molecular dynamics simulation studies.

  11. Spray-dried mucoadhesives for intravesical drug delivery using N-acetylcysteine- and glutathione-glycol chitosan conjugates.

    Science.gov (United States)

    Denora, Nunzio; Lopedota, Angela; Perrone, Mara; Laquintana, Valentino; Iacobazzi, Rosa M; Milella, Antonella; Fanizza, Elisabetta; Depalo, Nicoletta; Cutrignelli, Annalisa; Lopalco, Antonio; Franco, Massimo

    2016-10-01

    This work describes N-acetylcysteine (NAC)- and glutathione (GSH)-glycol chitosan (GC) polymer conjugates engineered as potential platform useful to formulate micro-(MP) and nano-(NP) particles via spray-drying techniques. These conjugates are mucoadhesive over the range of urine pH, 5.0-7.0, which makes them advantageous for intravesical drug delivery and treatment of local bladder diseases. NAC- and GSH-GC conjugates were generated with a synthetic approach optimizing reaction times and purification in order to minimize the oxidation of thiol groups. In this way, the resulting amount of free thiol groups immobilized per gram of NAC- and GSH-GC conjugates was 6.3 and 3.6mmol, respectively. These polymers were completely characterized by molecular weight, surface sulfur content, solubility at different pH values, substitution and swelling degree. Mucoadhesion properties were evaluated in artificial urine by turbidimetric and zeta (ζ)-potential measurements demonstrating good mucoadhesion properties, in particular for NAC-GC at pH 5.0. Starting from the thiolated polymers, MP and NP were prepared using both the Büchi B-191 and Nano Büchi B-90 spray dryers, respectively. The resulting two formulations were evaluated for yield, size, oxidation of thiol groups and ex-vivo mucoadhesion. The new spray drying technique provided NP of suitable size (polymers, avoiding thiolic oxidation during the formulation. MP with acceptable size produced by spray-dryer Büchi B-191 were compared with NP made with the apparatus Nano Büchi B-90. Copyright © 2016 Acta Materialia Inc. All rights reserved.

  12. Effect of the alkyl chain length of the ionic liquid anion on polymer electrolytes properties

    International Nuclear Information System (INIS)

    Leones, Rita; Sentanin, Franciani; Nunes, Sílvia Cristina; Esperança, José M.S.S.; Gonçalves, Maria Cristina

    2015-01-01

    New polymer electrolytes (PEs) based on chitosan and three ionic liquid (IL) families ([C 2 mim][C n SO 3 ], [C 2 mim][C n SO 4 ] and [C 2 mim][diC n PO 4 ]) were synthesized by the solvent casting method. The effect of the length of the alkyl chain of the IL anion on the thermal, morphological and electrochemical properties of the PEs was studied. The solid polymer electrolytes SPE membranes were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), polarized optical microscopy (POM), atomic force microscopy (AFM), complex impedance spectroscopy (ionic conductivity) and cyclic voltammetry (CV). The obtained results evidenced an influence of the alkyl chain length of the IL anion on the temperature of degradation, birefringence, surface roughness and ionic conductivity of the membranes. The DSC, XRD and CV results showed independency from the length of the IL-anion-alkyl chain. The PEs displayed an predominantly amorphous morphology, a minimum temperature of degradation of 135 °C, a room temperature (T = 25 °C) ionic conductivity of 7.78 × 10 −4 S cm −1 and a wide electrochemical window of ∼ 4.0 V.

  13. N-(2-chloroethyl)-N-nitrosoureas covalently bound to nonionic and monocationic lexitropsin dipeptides. Synthesis, DNA affinity binding characteristics, and reactions with 32P-end-labeled DNA

    International Nuclear Information System (INIS)

    Church, K.M.; Wurdeman, R.L.; Zhang, Yi; Chen, Faxian; Gold, B.

    1990-01-01

    The synthesis and characterization of a series of compounds that contain an N-alkyl-N-nitrosourea functionality linked to DNA minor groove binding bi- and tripeptides (lexitropsins or information-reading peptides) based on methylpyrrole-2-carboxamide subunits are described. The lexitropsins (lex) synthesized have either a 3-(dimethylamino)propyl or propyl substituent on the carboxyl terminus. The preferred DNA affinity binding sequences of these compounds were footprinted in 32 P-end-labeled restriction fragments with methidiumpropyl-EDTA·Fe(II), and in common with other structural analogues, e.g., distamycin and netropsin, these nitrosoureas recognize A-T-rich runs. The affinity binding of the compound with the dimethylamino terminus, which is ionized at near-neutral pH, appeared stronger than that observed for the neutral dipeptide. The sequence specificity for DNA alkylation by (2-chloroethyl)nitrosourea-lex dipeptides (Cl-ENU-lex), with neutral and charged carboxyl termini, using 32 P-end-labeled restriction fragments, was determined by the conversion of the adducted sites into single-strand breaks by sequential heating at neutral pH and exposure to base. The DNA cleavage sites were visualized by polyacrylamide gel electrophoresis and autoradiography. Linking the Cl-ENU moiety to minor groove binders is a viable strategy to qualitatively and quantitatively control the delivery and release of the ultimate DNA alkylating agent in a sequence-dependent fashion

  14. Synthesis of N-methyl-N-nitrosourea linked to a methidium chloride analogue and its reactions with 32P-end-labeled DNA

    International Nuclear Information System (INIS)

    Konakahara, T.; Wurdeman, R.L.; Gold, B.

    1988-01-01

    The synthesis and characterization of an N-methyl-N-nitrosourea (MNU) analogue that is covalently linked to methidium nucleus (9) is described. At 37/degrees/C in pH 8.0 buffer 9 hydrolyzes via pseudo-first-order kinetics, with a calculated t/sub 1/2/ = 77 min. By use of polyacrylamide sequencing gels the formation of piperidine-labile N 7 -methylguanine adducts from the reaction of 9 and MNU with 5'- 32 P-end-labeled DNA restriction fragments is reported. DNA methylation by 9 in 10 mM Tris buffer is enhanced with increasing ionic strength (50-200 mM NaCl), which contrasts to the inhibition of MNU-induced cleavage with increasing salt. In addition, 9 methylates all G sites equally, while MNU shows a clear preference for d(G)/sub n/ (n ≥ 3) runs and an asymmetrical methylation pattern within these G-rich regions. The results are discussed in terms of the delivery of the MNU moiety to the DNA target by a non-sequence-specific intercalation process and the subsequent hydrolytic generation of a nondiffusible alkylating intermediate

  15. Synthesis of 1-/sup 11/C-labelled ethyl, propyl, butyl and isobutyl iodides and examples of alkylation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Laangstroem, B.; Antoni, G.; Gullberg, P.; Halldin, C.; Naagren, K.; Rimland, A.; Svaerd, H.

    1986-01-01

    New /sup 11/C-labelled precursors (1-/sup 11/C)ethyl,(1-/sup 11/C)propyl, (1-/sup 11/C)butyl, and (1-/sup 11/C)isobutyl iodides have been prepared by a 3-step reaction route using a one-pot system. The labelled iodides were obtained in 20-55% radiochemical yields and 65-95% radiochemical purities, with a total time for synthesis of the order of 10-14 min. The labelled iodides have been used in alkylation reactions with nitrogen, oxygen and carbon nucleophiles. The nitrogen alkylation reactions are exemplified by the synthesis of the analgetics N-(1-/sup 11/C-ethyl)iodocaine and N-(1-/sup 11/C-butyl) bupivacaine. The synthesis of 3-nitrophenyl(1-/sup 11/C)propyl ether is also presented in this paper as an example of an oxygen alkylation.

  16. Mass spectral analysis of N-oxides of Chemical Weapons Convention related aminoethanols under electrospray ionization conditions.

    Science.gov (United States)

    Sridhar, L; Karthikraj, R; Murty, M R V S; Raju, N Prasada; Vairamani, M; Prabhakar, S

    2011-02-28

    N,N'-Dialkylaminoethanols are the hydrolyzed products or precursors of chemical warfare agents such as V-agents and nitrogen mustards, and they are prone to undergo oxidation in environmental matrices or during decontamination processes. Consequently, screening of the oxidized products of aminoethanols in aqueous samples is an important task in the verification of chemical weapons convention-related chemicals. Here we report the successful characterization of the N-oxides of N,N'-dialkylaminoethanols, alkyl diethanolamines, and triethanolamine using positive ion electrospray ionization mass spectrometry. The collision-induced dissociation (CID) spectra of the [M+H](+) and [M+Na](+) ions show diagnostic product ions that enable the unambiguous identification of the studied N-oxides, including those of isomeric compounds. The proposed fragmentation pathways are supported by high-resolution mass spectrometry data and product/precursor ion spectra. The CID spectra of [M+H](+) ions included [MH-CH(4)O(2)](+) as the key product ion, in addition to a distinctive alkene loss that allowed us to recognize the alkyl group attached to the nitrogen. The [M+Na](+) ions show characteristic product ions due to the loss of groups (R) attached to nitrogen either as a radical (R) or as a molecule [R+H or (R-H)] after hydrogen migration. Copyright © 2011 John Wiley & Sons, Ltd.

  17. Novel poly (arylene-ether-ether-ketone)s containing preformed imide unit and pendant long chain alkyl group

    International Nuclear Information System (INIS)

    Sayyed, Maheboob M.; Maldar, Noormahmad N.

    2010-01-01

    The studies were carried out to get preformed imide unit containing PEEKs and Co-PEEKs with pendant long chain alkyl group. Thus two new bisphenols; N,N'-bis (4-hydroxy 2-pentadecyl phenyl) pyromellitimide (HPI) (I) and N,N'-bis (4-hydroxy 2-pentadecyl phenyl 3,3',4,4'-benzophenone tetracarboxylic imide (HBI) (II) containing imide unit, pendant C-15 alkyl substituents were synthesized, characterized by spectral data and polycondensed with 4,4'-difluorobenzophenone (DFB) to yield several PEEK and Co-PEEKs. The polymers were characterized by FTIR, inherent viscosity, solubility, and XRD. The polymers were obtained in good yields and had inherent viscosities up to 0.65 dL/g in NMP. Polymerization of mixture of two bisphenols; [(I) and BPA]; and [(II) and BPA] in various mol%, with DFB gave number of the copolymers viz. Co-PEEK-BPAPI and Co-PEEK-BPABI. Many of the Co-PEEKs had good solubility in polar solvents. The solubility of PEEK containing bulky pendant alkyl substituents did not much improve probably due to simultaneous presence of rigid imide structures. XRD analysis indicated that PEEK and Co-PEEKs were partially crystalline or amorphous depending on the nature and % content of imide-bisphenol. These new PEEK materials can be used as high performance films, coatings, gas separation membranes, in aerospace and nuclear industries.

  18. Grafting C8-C16 alkyl groups altered the self-assembly and curcumin -loading properties of sodium caseinate in water.

    Science.gov (United States)

    Zhang, Yaqiong; Yang, Puyu; Yao, Fangyi; Liu, Jie; Yu, Liangli Lucy

    2018-02-01

    The data presented here are related to the research article entitled "Synthesis and characterization of alkylated caseinate, and its structure-curcumin loading property relationship in water" (Zhang et al., 2018) [1]. This data article reports the detailed spectra information for 1 H NMR, 13 C NMR and UPLC-Q-TOF MS of the N-succinimidyl fatty acid esters with various alkyl chain lengths (Cn-NHSs, n = 8, 12, 14 and 16). 1 H NMR, 13 C NMR and UPLC-Q-TOF MS spectra for C16-NHS are shown as an example. Then the stacked 1 H NMR spectra of the obtained alkylated caseinates (Cn-caseinates, n = 8, 12, 14 and 16) are provided. The surface hydrophobicity index (S 0 ) of Cn-caseinates with different substitution degrees (SD) of alkyl groups is shown. Additionally, Visual appearances for the formed aqueous dispersions of curcumin-loaded native caseinate (NaCas) and Cn-caseinates self-assemblies are shown. X-ray diffraction patterns of curcumin, C16-caseinate, its physical mixture and curcumin-loaded C16-caseinate self-assemblies are examined. The re-dispersibility and short-term storage stability of the curcumin-loaded NaCas and C16-caseinate self-assemblies are also studied.

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

    KAUST Repository

    Manoj Kumar Reddy, P.

    2016-08-23

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

  20. Collision induced dissociation of protonated N-nitrosodimethylamine by ion trap mass spectrometry: Ultimate carcinogens in gas phase

    Science.gov (United States)

    Kulikova, Natalia; Baker, Michael; Gabryelski, Wojciech

    2009-12-01

    Collision induced dissociation of protonated N-nitrosodimethylamine (NDMA) and isotopically labeled N-nitrosodimethyl-d6-amine (NDMA-d6) was investigated by sequential ion trap mass spectrometry to establish mechanisms of gas phase reactions leading to intriguing products of this potent carcinogen. The fragmentation of (NDMA + H+) occurs via two dissociation pathways. In the alkylation pathway, homolytic cleavage of the N-O bond of N-dimethyl, N'-hydroxydiazenium ion generates N-dimethyldiazenium distonic ion which reacts further by a CH3 radical loss to form methanediazonium ion. Both methanediazonium ion and its precursor are involved in ion/molecule reactions. Methanediazonium ion showed to be capable of methylating water and methanol molecules in the gas phase of the ion trap and N-dimethyldiazenium distonic ion showed to abstract a hydrogen atom from a solvent molecule. In the denitrosation pathway, a tautomerization of N-dimethyl, N'-hydroxydiazenium ion to N-nitrosodimethylammonium intermediate ion results in radical cleavage of the N-N bond of the intermediate ion to form N-dimethylaminium radical cation which reacts further through [alpha]-cleavage to generate N-methylmethylenimmonium ion. Although the reactions of NDMA in the gas phase are different to those for enzymatic conversion of NDMA in biological systems, each activation method generates the same products. We will show that collision induced dissociation of N-nitrosodiethylamine (NDEA) and N-nitrosodipropylamine (NDPA) is also a feasible approach to gain information on formation, stability, and reactivity of alkylating agents originating from NDEA and NDPA. Investigating such biologically relevant, but highly reactive intermediates in the condensed phase is hampered by the short life-times of these transient species.

  1. Self-Assembly, Surface Activity and Structure of n-Octyl-β-D-thioglucopyranoside in Ethylene Glycol-Water Mixtures

    Directory of Open Access Journals (Sweden)

    Cristóbal Carnero Ruiz

    2013-02-01

    Full Text Available The effect of the addition of ethylene glycol (EG on the interfacial adsorption and micellar properties of the alkylglucoside surfactant n-octyl-β-D-thioglucopyranoside (OTG has been investigated. Critical micelle concentrations (cmc upon EG addition were obtained by both surface tension measurements and the pyrene 1:3 ratio method. A systematic increase in the cmc induced by the presence of the co-solvent was observed. This behavior was attributed to a reduction in the cohesive energy of the mixed solvent with respect to pure water, which favors an increase in the solubility of the surfactant with EG content. Static light scattering measurements revealed a decrease in the mean aggregation number of the OTG micelles with EG addition. Moreover, dynamic light scattering data showed that the effect of the surfactant concentration on micellar size is also controlled by the content of the co-solvent in the system. Finally, the effect of EG addition on the microstructure of OTG micelles was investigated using the hydrophobic probe Coumarin 153 (C153. Time-resolved fluorescence anisotropy decay curves of the probe solubilized in micelles were analyzed using the two-step model. The results indicate a slight reduction of the average reorientation time of the probe molecule with increasing EG in the mixed solvent system, thereby suggesting a lesser compactness induced by the presence of the co-solvent.

  2. Cell-permeable and plasma-stable peptidomimetic inhibitors of the postsynaptic density-95/N-methyl-D-aspartate receptor interaction

    DEFF Research Database (Denmark)

    Bach, Anders*; Eildal, Jonas Nii Nortey*; Stuhr-Hansen, Nicolai

    2011-01-01

    of this interaction, and here, this template is exploited for the development of blood plasma-stable and cell-permeable inhibitors. Initially, we explored both the amino acid sequence of the tetrapeptide and the nature of the N-alkyl groups, which consolidated N-cyclohexylethyl-ETAV (1) as the most potent...

  3. Concerted bis-alkylating reactivity of clerocidin towards unpaired cytosine residues in DNA

    Science.gov (United States)

    Richter, Sara N.; Menegazzo, Ileana; Fabris, Daniele; Palumbo, Manlio

    2004-01-01

    Clerocidin (CL) is a topoisomerase II poison, which cleaves DNA irreversibly at guanines (G) and reversibly at cytosines (C). Furthermore, the drug can induce enzyme-independent strand breaks at the G and C level. It has been previously shown that G-damage is induced by alkylation of the guanine N7, followed by spontaneous depurination and nucleic acid cleavage, whereas scission at C is obtained only after treatment with hot alkali, and no information is available to explain the nature of this damage. We present here a systematic study on the reactivity of CL towards C both in the DNA environment and in solution. Selected synthetic derivatives were employed to evaluate the role of each chemical group of the drug. The structure of CL–dC adduct was then characterized by tandem mass spectrometry and NMR: the adduct is a stable condensed ring system resulting from a concerted electrophilic attack of the adjacent carbonyl and epoxide groups of CL towards the exposed NH2 and N3, respectively. This reaction mechanism, shown here for the first time, is characterized by faster kinetic rates than alkylation at G, due to the fact that the rate-determining step, alkylation at the epoxide, is an intramolecular process, provided a Schiff base linking CL and C can rapidly form, whereas the corresponding reaction of G N7 is intermolecular. These results provide helpful hints to explain the reversible/irreversible nature of topoisomerase II mediated DNA damage produced by CL at C/G steps. PMID:15494453

  4. 15N-Labelling and structure determination of adamantylated azolo-azines in solution

    Directory of Open Access Journals (Sweden)

    Sergey L. Deev

    2017-11-01

    Full Text Available Determining the accurate chemical structures of synthesized compounds is essential for biomedical studies and computer-assisted drug design. The unequivocal determination of N-adamantylation or N-arylation site(s in nitrogen-rich heterocycles, characterized by a low density of hydrogen atoms, using NMR methods at natural isotopic abundance is difficult. In these compounds, the heterocyclic moiety is covalently attached to the carbon atom of the substituent group that has no bound hydrogen atoms, and the connection between the two moieties of the compound cannot always be established via conventional 1H-1H and 1H-13C NMR correlation experiments (COSY and HMBC, respectively or nuclear Overhauser effect spectroscopy (NOESY or ROESY. The selective incorporation of 15N-labelled atoms in different positions of the heterocyclic core allowed for the use of 1H-15N (JHN and 13C-15N (JCN coupling constants for the structure determinations of N-alkylated nitrogen-containing heterocycles in solution. This method was tested on the N-adamantylated products in a series of azolo-1,2,4-triazines and 1,2,4-triazolo[1,5-a]pyrimidine. The syntheses of adamantylated azolo-azines were based on the interactions of azolo-azines and 1-adamatanol in TFA solution. For azolo-1,2,4-triazinones, the formation of mixtures of N-adamantyl derivatives was observed. The JHN and JCN values were measured using amplitude-modulated 1D 1H spin-echo experiments with the selective inversion of the 15N nuclei and line-shape analysis in the 1D 13С spectra acquired with selective 15N decoupling, respectively. Additional spin–spin interactions were detected in the 15N-HMBC spectra. NMR data and DFT (density functional theory calculations permitted to suggest a possible mechanism of isomerization for the adamantylated products of the azolo-1,2,4-triazines. The combined analysis of the JHN and JCN couplings in 15N-labelled compounds provides an efficient method for the structure

  5. Alkylation of Staurosporine to Derive a Kinase Probe for Fluorescence Applications.

    Science.gov (United States)

    Disney, Alexander J M; Kellam, Barrie; Dekker, Lodewijk V

    2016-05-06

    The natural product staurosporine is a high-affinity inhibitor of nearly all mammalian protein kinases. The labelling of staurosporine has proven effective as a means of generating protein kinase research tools. Most tools have been generated by acylation of the 4'-methylamine of the sugar moiety of staurosporine. Herein we describe the alkylation of this group as a first step to generate a fluorescently labelled staurosporine. Following alkylation, a polyethylene glycol linker was installed, allowing subsequent attachment of fluorescein. We report that this fluorescein-staurosporine conjugate binds to cAMP-dependent protein kinase in the nanomolar range. Furthermore, its binding can be antagonised with unmodified staurosporine as well as ATP, indicating it targets the ATP binding site in a similar fashion to native staurosporine. This reagent has potential application as a screening tool for protein kinases of interest. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  6. Characterizing Frothers through Critical Coalescence Concentration (CCC95-Hydrophile-Lipophile Balance (HLB Relationship

    Directory of Open Access Journals (Sweden)

    Wei Zhang

    2012-08-01

    Full Text Available Frothers are surfactants commonly used to reduce bubble size in mineral flotation. This paper describes a methodology to characterize frothers by relating impact on bubble size reduction represented by CCC (critical coalescence concentration to frother structure represented by HLB (hydrophile-lipophile balance. Thirty-six surfactants were tested from three frother families: Aliphatic Alcohols, Polypropylene Glycol Alkyl Ethers and Polypropylene Glycols, covering a range in alkyl groups (represented by n, the number of carbon atoms and number of Propylene Oxide groups (represented by m. The Sauter mean size (D32 was derived from bubble size distribution measured in a 0.8 m3 mechanical flotation cell. The D32 vs. concentration data were fitted to a 3-parameter model to determine CCC95, the concentration giving 95% reduction in bubble size compared to water only. It was shown that each family exhibits a unique CCC95-HLB relationship dependent on n and m. Empirical models were developed to predict CCC95 either from HLB or directly from n and m. Commercial frothers of known family were shown to fit the relationships. Use of the model to predict D32 is illustrated.

  7. 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

  8. n-Octyl gallate as inhibitor of pyruvate carboxylation and lactate gluconeogenesis.

    Science.gov (United States)

    Eler, Gabrielle Jacklin; Santos, Israel Souza; de Moraes, Amarilis Giaretta; Comar, Jurandir Fernando; Peralta, Rosane Marina; Bracht, Adelar

    2015-04-01

    The alkyl gallates are found in several natural and industrial products. In the latter products, these compounds are added mainly for preventing oxidation. In the present work, the potencies of methyl gallate, n-propyl gallate, n-pentyl gallate, and n-octyl gallate as inhibitors of pyruvate carboxylation and lactate gluconeogenesis were evaluated. Experiments were done with isolated mitochondria and the isolated perfused rat liver. The potency of the gallic acid esters as inhibitors of pyruvate carboxylation in isolated mitochondria obeyed the following decreasing sequence: n-octyl gallate > n-pentyl gallate > n-propyl gallate > methyl gallate. A similar sequence of decreasing potency for lactate gluconeogenesis inhibition in the perfused liver was found in terms of the portal venous concentration. Both actions correlate with the lipophilicity of the compounds. The effects are harmful at high concentrations. At appropriate concentrations, however, octyl gallate should act therapeutically because its inhibitory action on gluconeogenesis will contribute further to its proposed antihyperglycemic effects. © 2014 Wiley Periodicals, Inc.

  9. Histone H2AX is a critical factor for cellular protection against DNA alkylating agents.

    Science.gov (United States)

    Meador, J A; Zhao, M; Su, Y; Narayan, G; Geard, C R; Balajee, A S

    2008-09-25

    Histone H2A variant H2AX is a dose-dependent suppressor of oncogenic chromosome translocations. H2AX participates in DNA double-strand break repair, but its role in other DNA repair pathways is not known. In this study, role of H2AX in cellular response to alkylation DNA damage was investigated. Cellular sensitivity to two monofunctional alkylating agents (methyl methane sulfonate and N-methyl-N'-nitro-N-nitrosoguanidine (MNNG)) was dependent on H2AX dosage, and H2AX null cells were more sensitive than heterozygous cells. In contrast to wild-type cells, H2AX-deficient cells displayed extensive apoptotic death due to a lack of cell-cycle arrest at G(2)/M phase. Lack of G(2)/M checkpoint in H2AX null cells correlated well with increased mitotic irregularities involving anaphase bridges and gross chromosomal instability. Observation of elevated poly(ADP) ribose polymerase 1 (PARP-1) cleavage suggests that MNNG-induced apoptosis occurs by PARP-1-dependent manner in H2AX-deficient cells. Consistent with this, increased activities of PARP and poly(ADP) ribose (PAR) polymer synthesis were detected in both H2AX heterozygous and null cells. Further, we demonstrate that the increased PAR synthesis and apoptotic death induced by MNNG in H2AX-deficient cells are due to impaired activation of mitogen-activated protein kinase pathway. Collectively, our novel study demonstrates that H2AX, similar to PARP-1, confers cellular protection against alkylation-induced DNA damage. Therefore, targeting either PARP-1 or histone H2AX may provide an effective way of maximizing the chemotherapeutic value of alkylating agents for cancer treatment.

  10. Metal-free, mild, nonepimerizing, chemo- and enantio- or diastereoselective N-alkylation of amines by alcohols via oxidation/imine-iminium formation/reductive amination: a pragmatic synthesis of octahydropyrazinopyridoindoles and higher ring analogues.

    Science.gov (United States)

    Khan, Imran A; Saxena, Anil K

    2013-12-06

    A mild step and atom-economical nonepimerizing chemo- and enantioselective N-alkylating procedure has been developed via oxidation/imine-iminium formation/reduction cascade using TEMPO-BAIB-HEH-Brønsted acid catalysis in DMPU as solvent and a stoichiometric amount of amine. The optimized conditions were further extended for the nonenzymatic kinetic resolution of the chiral amine thus formed under nonenzymatic in situ hydrogen-transfer conditions using VAPOL-derived phosphoric acid (VAPOL-PA) as the Brønsted acid catalyst. The enantioselective cascade of the presented reaction was successfully utilized in the synthesis of octahydropyrazinopyridoindole and its higher ring analogues.

  11. Grafting C8-C16 alkyl groups altered the self-assembly and curcumin –loading properties of sodium caseinate in water

    OpenAIRE

    Yaqiong Zhang; Puyu Yang; Fangyi Yao; Jie Liu; Liangli (Lucy) Yu

    2018-01-01

    The data presented here are related to the research article entitled “Synthesis and characterization of alkylated caseinate, and its structure-curcumin loading property relationship in water” (Zhang et al., 2018) [1]. This data article reports the detailed spectra information for 1H NMR, 13C NMR and UPLC-Q-TOF MS of the N-succinimidyl fatty acid esters with various alkyl chain lengths (Cn-NHSs, n = 8, 12, 14 and 16). 1H NMR, 13C NMR and UPLC-Q-TOF MS spectra for C16-NHS are shown as an exampl...

  12. Thermal Studies of Zn(II, Cd(II and Hg(II Complexes of Some N-Alkyl-N-Phenyl-Dithiocarbamates

    Directory of Open Access Journals (Sweden)

    Peter A. Ajibade

    2012-07-01

    Full Text Available The thermal decomposition of Zn(II, Cd(II and Hg(II complexes of N-ethyl-N-phenyl and N-butyl-N-phenyl dithiocarbamates have been studied using thermogravimetric analysis (TGA and differential scanning calorimetry (DSC. The products of the decomposition, at two different temperatures, were further characterized by scanning electron microscopy (SEM and energy-dispersive X-ray spectroscopy (EDX. The results show that while the zinc and cadmium complexes undergo decomposition to form metal sulphides, and further undergo oxidation forming metal oxides as final products, the mercury complexes gave unstable volatiles as the final product.

  13. Crystal structure and thermal property of polyethylene glycol octadecyl ether

    International Nuclear Information System (INIS)

    Meng, Jie-yun; Tang, Xiao-fen; Li, Wei; Shi, Hai-feng; Zhang, Xing-xiang

    2013-01-01

    Highlights: ► The crystal structure of C18En for n ≥ 20 is a monoclinic system. ► Polyethylene glycol octadecyl ether crystallizes perfectly. ► The number of repeat units has significant effect on the melting, crystallizing temperature and enthalpy. ► The thermal stable temperature increases rapidly with increasing the number of repeat unit. - Abstract: The crystal structure, phase change property and thermal stable temperature (T d ) of polyethylene glycol octadecyl ether [HO(CH 2 CH 2 O) n C 18 H 37 , C18En] with various numbers of repeat units (n = 2, 10, 20 and 100) as phase change materials (PCMs) were investigated using temperature variable Fourier transformed infrared spectroscopy (FTIR), wide-angle X-ray diffraction (XRD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TG). C18En crystallizes perfectly at 0 °C; and the crystal structure for n ≥ 20 is a monoclinic system. The number of repeat units has great effect on the phase change properties of C18En. The thermal stable temperature increases rapidly with increasing the number of repeat units. They approach to that of PEG-2000 as the number of repeat units is more than 10. T d increases rapidly with increasing the number of repeat units. C18En are a series of promising polymeric PCMs

  14. Lithium alkyl anions of uranium(IV) and uranium(V)

    International Nuclear Information System (INIS)

    Sigurdson, E.R.; Wilkinson, G.

    1977-01-01

    Organouranium compounds with six or eight uranium-to-carbon sigma-bonds have been synthesized for the first time. The interaction of uranium tetrachloride with lithium alkyls in diethyl ether leads to the isolation of unstable lithium alkyluranate(IV) compounds of stoicheiometry Li 2 UR 6 .8Et 2 0 (R = Me, CH 2 SiMe 3 . Ph, and o-Me 2 NCH 2 C 6 H 4 ). These lithium salts can also be obtained with other donor solvents, such as tetrahydrofuran or NNN'N'-tetramethylethylenediamine. From uranium pentaethoxide similar lithium salts of stoicheiometry Li 3 UR 8 .3 dioxan (R = Me, CH 2 CMe 3 , and CH 2 SiMe 3 ) can be obtained. The interaction of uranium(VI) hexaisopropoxide with lithium, magnesium, or aluminium alkyls does not give compounds containing U-C bonds, but green oils, e.g. U(OPrsup(i)) 6 (MgMe 2 ) 3 , that appear to be adducts in which the oxygen atom of the isopropoxide group bound to uranium is acting as a donor. I.r. and n.m.r. spectroscopy and analytical data for the new compounds are presented. (author)

  15. Density and surface tension of ionic liquids.

    Science.gov (United States)

    Kolbeck, C; Lehmann, J; Lovelock, K R J; Cremer, T; Paape, N; Wasserscheid, P; Fröba, A P; Maier, F; Steinrück, H-P

    2010-12-30

    We measured the density and surface tension of 9 bis[(trifluoromethyl)sulfonyl]imide ([Tf(2)N](-))-based and 12 1-methyl-3-octylimidazolium ([C(8)C(1)Im](+))-based ionic liquids (ILs) with the vibrating tube and the pendant drop method, respectively. This comprehensive set of ILs was chosen to probe the influence of the cations and anions on density and surface tension. When the alkyl chain length in the [C(n)C(1)Im][Tf(2)N] series (n = 1, 2, 4, 6, 8, 10, 12) is increased, a decrease in density is observed. The surface tension initially also decreases but reaches a plateau for alkyl chain lengths greater than n = 8. Functionalizing the alkyl chains with ethylene glycol groups results in a higher density as well as a higher surface tension. For the dependence of density and surface tension on the chemical nature of the anion, relations are only found for subgroups of the studied ILs. Density and surface tension values are discussed with respect to intermolecular interactions and surface composition as determined by angle-resolved X-ray photoelectron spectroscopy (ARXPS). The absence of nonvolatile surface-active contaminants was proven by ARXPS.

  16. Reactions of N,N'-bis(2-hydroxyethyl)oxalamide with Ethylene Carbonate and Use of the Obtained Products as Components of Polyurethanes Foams

    International Nuclear Information System (INIS)

    Niemiec, I.Z.

    2010-01-01

    N,N'-bis(2-hydroxyethyl)oxalamide (BHEOA) was subject to hydroxy alkylation with ethylene carbonate (EC). By means of instrumental methods (IR, 1H-NMR, MALDI ToF, GC, and GC-MS), an influence of the reaction conditions on structure and compositions of the obtained products was investigated. The hydroxyalkyl and hydroxy alkoxy derivatives of oxalamide (OA) were obtained by reaction of BHEOA with 210-molar excess of ethylene carbonate (EC, 1,3-dioxolane-2-one). The products have a good thermal stability and possess suitable physical properties as substrates for foamed polyurethanes. The obtained products were used in manufacturing the rigid polyurethane foams which possess enhanced thermal stability and good mechanical properties.

  17. N,N-Dihexyl-4-[2-(4-nitrophenylvinyl]aniline

    Directory of Open Access Journals (Sweden)

    Dieter Schollmeyer

    2011-06-01

    Full Text Available The title compound, C26H36N2O2, was prepared by Horner olefination of p-dihexylaminobenzaldehyde and diethyl p-nitrobenzylphosphonate. It crystallizes with two independent molecules in the asymmetric unit. Both have similar geometries of the π-systems but the conformations of all hexyl chains are different. Whereas one hexyl chain of the first molecule shows the typical all-anti conformation, the second is arranged in a gauche-anti-gauche-anti conformation with N—C—C—C, C—C—C—C, C—C—C—C and C—C—C—C torsion angles of −65.1 (4, 167.3 (3, 63.3 (4, and 179.4 (3°. One of the hexyl chains in the other molecule has an anti-anti-gauche-anti conformation [N—C—C—C, C—C—C—C, C—C—C—C and C—C—C—C torsion angles = 179.6 (3, −179.8 (3, −68.7 (5 and −178.8 (4°], the other starts with an anti-gauche-gauche sequence. Molecules A and B are composed of five planar subunits. The angle sums around the N atoms are in the range 356 (2–360.0 (2°. Torsion angles between these segments do not exceed 4.9 (4°, except for one of the alkyl chains each [molecule A = 26.2 (4°; molecule B = −6.0 (4°]. The high planarity of the molecules and the short aniline C—N bonds [1.385 (3 Å in molecule A and 1.378 (3 Å in molecule B] indicate a strong electronic coupling through the stilbene unit. One methylene group is disordered over two positions with an occupancy ratio of 0.72:0.28.

  18. A poly(alkyl methacrylate-divinylbenzene-vinylbenzyl trimethylammonium chloride) monolithic column for solid-phase microextraction.

    Science.gov (United States)

    Liu, Wan-Ling; Lirio, Stephen; Yang, Yicong; Wu, Lin-Tai; Hsiao, Shu-Ying; Huang, Hsi-Ya

    2015-05-22

    In this study, an organic polymer monolithic columns, which were prepared via in situ polymerization of alkyl methacrylate-ester (AMA), divinylbenzene (DVB) and vinylbenzyl trimethylammonium chloride (VBTA, charged monomer), were developed as adsorbent for solid-phase microextraction (SPME). Different parameters affecting the extraction efficiency for nine (9) non-steroidal anti-inflammatory drugs (NSAIDs) such as the ratio of the stearyl methacrylate (SMA) to DVB monomer, column length, sample pH, extraction flow rate and desorption solvent were investigated to obtain the optimal SPME condition. Also, the permeability for each poly(AMA-DVB-VBTA) monolithic column was investigated by adding porogenic solvent (poly(ethylene glycol), PEG). Using the optimized condition, a series of AMA-based poly(AMA-DVB-VBTA) monolith columns were developed to determine the effect the extraction efficiency of NSAIDs by varying the alkyl chain length of the methacrylate ester (methyl-, butyl-, octyl-, or lauryl-methacrylate; (MMA, BMA, OMA, LMA)). Results showed that decreasing the AMA chain length increases the extraction efficiency of some NSAIDs (i.e. sulindac (sul), naproxen (nap), ketoprofen (ket) and indomethacin (idm)). Among the poly(AMA-DVB-VBTA) monolithic columns, poly(BMA-DVB-VBTA) showed a highly repeatable extraction efficiency for NSAIDs with recoveries ranging from 85.0 to 100.2% with relative standard deviation (RSD) less than 6.8% (n=3). The poly(BMA-DVB-VBTA) can also be reused for at least 50 times without any significant effect in extraction efficiency for NSAIDs. Finally, using the established conditions, the poly(BMA-DVB-VBTA) was used to extract trace-level NSAIDs (100μgL(-1)) in river water with good recoveries ranging from 75.8 to 90.8% (RSD<14.9%). Copyright © 2015 Elsevier B.V. All rights reserved.

  19. The ada operon of Mycobacterium tuberculosis encodes two DNA methyltransferases for inducible repair of DNA alkylation damage.

    Science.gov (United States)

    Yang, Mingyi; Aamodt, Randi M; Dalhus, Bjørn; Balasingham, Seetha; Helle, Ina; Andersen, Pernille; Tønjum, Tone; Alseth, Ingrun; Rognes, Torbjørn; Bjørås, Magnar

    2011-06-10

    The ada operon of Mycobacterium tuberculosis, which encodes a composite protein of AdaA and AlkA and a separate AdaB/Ogt protein, was characterized. M. tuberculosis treated with N-methyl-N'-nitro-N-nitrosoguanidine induced transcription of the adaA-alkA and adaB genes, suggesting that M. tuberculosis mount an inducible response to methylating agents. Survival assays of the methyltransferase defective Escherichia coli mutant KT233 (ada ogt), showed that expression of the adaB gene rescued the alkylation sensitivity. Further, adaB but not adaA-alkA complemented the hypermutator phenotype of KT233. Purified AdaA-AlkA and AdaB possessed methyltransferase activity. These data suggested that AdaB counteract the cytotoxic and mutagenic effect of O(6)-methylguanine, while AdaA-AlkA most likely transfers methyl groups from innocuous methylphosphotriesters. AdaA-AlkA did not possess alkylbase DNA glycosylase activity nor rescue the alkylation sensitivity of the E. coli mutant BK2118 (tag alkA). We propose that AdaA-AlkA is a positive regulator of the adaptive response in M. tuberculosis. It thus appears that the ada operon of M. tuberculosis suppresses the mutagenic effect of alkylation but not the cytotoxic effect of lesions such as 3-methylpurines. Collectively, these data indicate that M. tuberculosis hypermutator strains with defective adaptive response genes might sustain robustness to cytotoxic alkylation DNA damage and confer a selective advantage contributing to host adaptation. Copyright © 2011 Elsevier B.V. All rights reserved.

  20. Synthesis, crystal structure determination, biological screening and docking studies of N1-substituted derivatives of 2,3-dihydroquinazolin-4(1H)-one as inhibitors of cholinesterases.

    Science.gov (United States)

    Sultana, Nargis; Sarfraz, Muhammad; Tanoli, Saba Tahir; Akram, Muhammad Safwan; Sadiq, Abdul; Rashid, Umer; Tariq, Muhammad Ilyas

    2017-06-01

    Pursuing the strategy of developing potent AChE inhibitors, we attempted to carry out the N 1 -substitution of 2,3-dihydroquinazolin-4(1H)-one core. A set of 32 N-alkylated/benzylated quinazoline derivatives were synthesized, characterized and evaluated for their inhibition against cholinesterases. N-alkylation of the series of the compounds reported previously (N-unsubstituted) resulted in improved activity. All the compounds showed inhibition of both enzymes in the micromolar to submicromolar range. Structure activity relationship (SAR) of the 32 derivatives showed that N-benzylated compounds possess good activity than N-alkylated compounds. N-benzylated compounds 2ad and 2af were found very active with their IC 50 values toward AChE in submicromolar range (0.8µM and 0.6µM respectively). Binding modes of the synthesized compounds were explored by using GOLD (Genetic Optimization for Ligand Docking) suit v5.4.1. Computational predictions of ADMET studies reveal that all the compounds have good pharmacokinetic properties with no AMES toxicity and carcinogenicity. Moreover, all the compounds are predicted to be absorbed in human intestine and also have the ability to cross blood brain barrier. Overall, the synthesized compounds have established a structural foundation for the design of new inhibitors of cholinesterase. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Cellular response to alkylating agent MNNG is impaired in STAT1-deficients cells.

    Science.gov (United States)

    Ah-Koon, Laurent; Lesage, Denis; Lemadre, Elodie; Souissi, Inès; Fagard, Remi; Varin-Blank, Nadine; Fabre, Emmanuelle E; Schischmanoff, Olivier

    2016-10-01

    The SN 1 alkylating agents activate the mismatch repair system leading to delayed G2 /M cell cycle arrest and DNA repair with subsequent survival or cell death. STAT1, an anti-proliferative and pro-apoptotic transcription factor is known to potentiate p53 and to affect DNA-damage cellular response. We studied whether STAT1 may modulate cell fate following activation of the mismatch repair system upon exposure to the alkylating agent N-methyl-N'-nitro-N-nitrosoguanidine (MNNG). Using STAT1-proficient or -deficient cell lines, we found that STAT1 is required for: (i) reduction in the extent of DNA lesions, (ii) rapid phosphorylation of T68-CHK2 and of S15-p53, (iii) progression through the G2 /M checkpoint and (iv) long-term survival following treatment with MNNG. Presence of STAT1 is critical for the formation of a p53-DNA complex comprising: STAT1, c-Abl and MLH1 following exposure to MNNG. Importantly, presence of STAT1 allows recruitment of c-Abl to p53-DNA complex and links c-Abl tyrosine kinase activity to MNNG-toxicity. Thus, our data highlight the important modulatory role of STAT1 in the signalling pathway activated by the mismatch repair system. This ability of STAT1 to favour resistance to MNNG indicates the targeting of STAT1 pathway as a therapeutic option for enhancing the efficacy of SN1 alkylating agent-based chemotherapy. © 2016 The Authors. Journal of Cellular and Molecular Medicine published by John Wiley & Sons Ltd and Foundation for Cellular and Molecular Medicine.

  2. In situ forming poly(ethylene glycol)- Poly(L -lactide) hydrogels via michael addition: Mechanical properties, degradation, and protein release

    NARCIS (Netherlands)

    Buwalda, S.J.; Dijkstra, Pieter J.; Feijen, Jan

    2012-01-01

    Chemically crosslinked hydrogels are prepared at remarkably low macromonomer concentrations from 8-arm poly(ethylene glycol)-poly(L-lactide) star block copolymers bearing acrylate end groups (PEG-(PLLAn)8-AC, n = 4 or 12) and multifunctional PEG thiols (PEG-(SH)n, n = 2, 4, or 8) through a

  3. Base free N-alkylation of anilines with ArCH2OH and transfer hydrogenation of aldehydes/ketones catalyzed by the complexes of η5-Cp*Ir(iii) with chalcogenated Schiff bases of anthracene-9-carbaldehyde.

    Science.gov (United States)

    Dubey, Pooja; Gupta, Sonu; Singh, Ajai K

    2018-03-12

    The condensation of anthracene-9-carbaldehyde with 2-(phenylthio/seleno)ethylamine results in Schiff bases [PhS(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ](L1) and [PhSe(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ] (L2). On their reaction with [(η 5 -Cp*)IrCl(μ-Cl)] 2 and CH 3 COONa at 50 °C followed by treatment with NH 4 PF 6 , iridacycles, [(η 5 -Cp*)Ir(L-H)][PF 6 ] (1: L = L1; 2: L = L2), result. The same reaction in the absence of CH 3 COONa gives complexes [(η 5 -Cp*)Ir(L)Cl][PF 6 ] (3-4) in which L = L1(3)/L2(4) ligates in a bidentate mode. The ligands and complexes were authenticated with HR-MS and NMR spectra [ 1 H, 13 C{ 1 H} and 77 Se{ 1 H} (in the case of L2 and its complexes only)]. Single crystal structures of L2 and half sandwich complexes 1-4 were established with X-ray crystallography. Three coordination sites of Ir in each complex are covered with η 5 -Cp* and on the remaining three, donor atoms present are: N, S/Se and C - /Cl - , resulting in a piano-stool structure. The moisture and air insensitive 1-4 act as efficient catalysts under mild conditions for base free N-alkylation of amines with benzyl alcohols and transfer hydrogenation (TH) of aldehydes/ketones. The optimum loading of 1-4 as a catalyst is 0.1-0.5 mol% for both the activations. The best reaction temperature is 80 °C for transfer hydrogenation and 100 °C for N-alkylation. The mercury poisoning test supports a homogeneous pathway for both the reactions catalyzed by 1-4. The two catalytic processes are most efficient with 3 followed by 4 > 1 > 2. The mechanism proposed on the basis of HR-MS of the reaction mixtures of the two catalytic processes taken after 1-2 h involves the formation of an alkoxy and hydrido species. The real catalytic species proposed in the case of iridacycles results due to the loss of the Cp* ring.

  4. On the effect of N-GaN/P-GaN/N-GaN/P-GaN/N-GaN built-in junctions in the n-GaN layer for InGaN/GaN light-emitting diodes.

    Science.gov (United States)

    Kyaw, Zabu; Zhang, Zi-Hui; Liu, Wei; Tan, Swee Tiam; Ju, Zhen Gang; Zhang, Xue Liang; Ji, Yun; Hasanov, Namig; Zhu, Binbin; Lu, Shunpeng; Zhang, Yiping; Sun, Xiao Wei; Demir, Hilmi Volkan

    2014-01-13

    N-GaN/P-GaN/N-GaN/P-GaN/N-GaN (NPNPN-GaN) junctions embedded between the n-GaN region and multiple quantum wells (MQWs) are systematically studied both experimentally and theoretically to increase the performance of InGaN/GaN light emitting diodes (LEDs) in this work. In the proposed architecture, each thin P-GaN layer sandwiched in the NPNPN-GaN structure is completely depleted due to the built-in electric field in the NPNPN-GaN junctions, and the ionized acceptors in these P-GaN layers serve as the energy barriers for electrons from the n-GaN region, resulting in a reduced electron over flow and enhanced the current spreading horizontally in the n- GaN region. These lead to increased optical output power and external quantum efficiency (EQE) from the proposed device.

  5. Evaluation of N,N-dialkylamides as promising process extractants

    International Nuclear Information System (INIS)

    Pathak, P N; Prabhu, D R; Kanekar, A S; Manchanda, V K

    2010-01-01

    Studies carried out at BARC, India on the development of new extractants for reprocessing of spent fuel suggested that while straight chain N,N-dihexyloctanamide (DHOA) is promising alternative to TBP for the reprocessing of irradiated uranium based fuels, branched chain N,N-di(2-ethylhexyl)isobutyramide (D2EHIBA) is suitable for the selective recovery of 233 U from irradiated Th. In advanced fuel cycle scenarios, the coprocessing of U/Pu stream appears attractive particularly with respect to development of proliferation resistant technologies. DHOA extracted Pu(IV) more efficiently than TBP, both at trace-level concentration as well as under uranium/plutonium loading conditions. Uranium extraction behavior of DHOA was however, similar to that of TBP during the extraction cycle. Stripping behavior of U and Pu (without any reductant) was better for DHOA than that of TBP. It was observed during batch studies that whereas 99% Pu is stripped in four stages in case of DHOA, only 89% Pu is stripped in case of TBP under identical experimental conditions. DHOA offered better fission product decontamination than that of TBP. GANEX (Group ActiNide EXtraction) and ARTIST (Amide-based Radio-resources Treatment with Interim Storage of Transuranics) processes proposed for actinide partitioning use branched chain amides for the selective extraction of uranium from spent fuel feed solutions. The branched-alkyl monoamide (BAMA) proposed to be used in ARTIST process is N,N-di-(2-ethylhexyl)butyramide (D2EHBA). In this context, the extraction behavior of U(VI) and Pu(IV) were compared using D2EHIBA, TBP, and D2EHBA under similar concentration of nitric acid (0.5 - 6M) and of uranium (0-50g/L). These studies suggested that D2EHIBA is a promising extractant for selective extraction of uranium over plutonium in process streams. Similarly, D2EHIBA offered distinctly better decontamination of 233 U over Th and fission products under THOREX feed conditions. The possibility of simultaneous

  6. Evaluation of N,N-dialkylamides as promising process extractants

    Science.gov (United States)

    Pathak, P. N.; Prabhu, D. R.; Kanekar, A. S.; Manchanda, V. K.

    2010-03-01

    Studies carried out at BARC, India on the development of new extractants for reprocessing of spent fuel suggested that while straight chain N,N-dihexyloctanamide (DHOA) is promising alternative to TBP for the reprocessing of irradiated uranium based fuels, branched chain N,N-di(2-ethylhexyl)isobutyramide (D2EHIBA) is suitable for the selective recovery of 233U from irradiated Th. In advanced fuel cycle scenarios, the coprocessing of U/Pu stream appears attractive particularly with respect to development of proliferation resistant technologies. DHOA extracted Pu(IV) more efficiently than TBP, both at trace-level concentration as well as under uranium/plutonium loading conditions. Uranium extraction behavior of DHOA was however, similar to that of TBP during the extraction cycle. Stripping behavior of U and Pu (without any reductant) was better for DHOA than that of TBP. It was observed during batch studies that whereas 99% Pu is stripped in four stages in case of DHOA, only 89% Pu is stripped in case of TBP under identical experimental conditions. DHOA offered better fission product decontamination than that of TBP. GANEX (Group ActiNide EXtraction) and ARTIST (Amide-based Radio-resources Treatment with Interim Storage of Transuranics) processes proposed for actinide partitioning use branched chain amides for the selective extraction of uranium from spent fuel feed solutions. The branched-alkyl monoamide (BAMA) proposed to be used in ARTIST process is N,N-di-(2-ethylhexyl)butyramide (D2EHBA). In this context, the extraction behavior of U(VI) and Pu(IV) were compared using D2EHIBA, TBP, and D2EHBA under similar concentration of nitric acid (0.5 — 6M) and of uranium (0-50g/L). These studies suggested that D2EHIBA is a promising extractant for selective extraction of uranium over plutonium in process streams. Similarly, D2EHIBA offered distinctly better decontamination of 233U over Th and fission products under THOREX feed conditions. The possibility of simultaneous

  7. The Effect of n vs. iso Isomerization on the Thermophysical Properties of Aromatic and Non-aromatic Ionic Liquids.

    Science.gov (United States)

    Rodrigues, Ana S M C; Almeida, Hugo F D; Freire, Mara G; Lopes-da-Silva, José A; Coutinho, João A P; Santos, Luís M N B F

    2016-09-15

    This work explores the n vs. iso isomerization effects on the physicochemical properties of different families of ionic liquids (ILs) with variable aromaticity and ring size. This study comprises the experimental measurements, in a wide temperature range, of the ILs' thermal behavior, heat capacities, densities, refractive indices, surface tensions, and viscosities. The results here reported show that the presence of the iso -alkyl group leads to an increase of the temperature of the glass transition, T g . The iso- pyrrolidinium (5 atoms ring cation core) and iso -piperidinium (6 atoms ring cation core) ILs present a strong differentiation in the enthalpy and entropy of melting. Non-aromatic ILs have higher molar heat capacities due to the increase of the atomic contribution, whereas it was not found any significant differentiation between the n and iso -alkyl isomers. A small increase of the surface tension was observed for the non-aromatic ILs, which could be related to their higher cohesive energy of the bulk, while the lower surface entropy observed for the iso isomers indicates a structural resemblance between the IL bulk and surface. The significant differentiation between ILs with a 5 and 6 atoms ring cation in the n -alkyl series (where 5 atoms ring cations have higher surface entropy) is an indication of a more efficient arrangement of the non-polar region at the surface in ILs with smaller cation cores. The ILs constituted by non-aromatic piperidinium cation, and iso -alkyl isomers were found to be the most viscous among the studied ILs due to their higher energy barriers for shear stress.

  8. Synthesis of benzimidazoles by PIDA-promoted direct C(sp2)-H imidation of N-arylamidines.

    Science.gov (United States)

    Huang, Jinbo; He, Yimiao; Wang, Yong; Zhu, Qiang

    2012-10-29

    A metal-free synthesis of diversified benzimidazoles from N-arylamidines through a phenyliodine(III) diacetate (PIDA) promoted intramolecular direct C(sp(2))-H imidation has been developed. The reaction proceeds smoothly at 0 °C or ambient temperature to provide the desired products in good to excellent yields. The synthesis of 2-alkyl- or 2-alkyl-fused benzimidazoles, which are generally inaccessible by similar Pd- or Cu-catalyzed approaches, can also be achieved. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Rhodium(III)- and iridium(III)-catalyzed C7 alkylation of indolines with diazo compounds.

    Science.gov (United States)

    Ai, Wen; Yang, Xueyan; Wu, Yunxiang; Wang, Xuan; Li, Yuanchao; Yang, Yaxi; Zhou, Bing

    2014-12-22

    A Rh(III)-catalyzed procedure for the C7-selective C-H alkylation of various indolines with α-diazo compounds at room temperature is reported. The advantages of this process are: 1) simple, mild, and pH-neutral reaction conditions, 2) broad substrate scope, 3) complete regioselectivity, 4) no need for an external oxidant, and 5) N2 as the sole byproduct. Furthermore, alkylation and bis-alkylation of carbazoles at the C1 and C8 positions have also been developed. More significantly, for the first time, a successful Ir(III)-catalyzed intermolecular insertion of arene C-H bonds into α-diazo compounds is reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Glycol porphyrin derivatives and temoporfin elicit resistance to photodynamic therapy by different mechanisms

    Czech Academy of Sciences Publication Activity Database

    Králová, Jarmila; Kolář, Michal; Kahle, Michal; Truksa, Jaroslav; Lettlová, Sandra; Balusiková, K.; Bartůněk, Petr

    2017-01-01

    Roč. 7, Mar 15 (2017), č. článku 44497. ISSN 2045-2322 R&D Projects: GA MŠk LO1220 Institutional support: RVO:68378050 ; RVO:86652036 Keywords : Glycol porphyrin derivates * chemotherapy * cancer * multidrug resistance Subject RIV: EB - Genetics ; Molecular Biology; EB - Genetics ; Molecular Biology (BTO-N) OBOR OECD: Biochemistry and molecular biology; Biochemistry and molecular biology (BTO-N) Impact factor: 4.259, year: 2016

  11. Improved Morphology and Efficiency of n-i-p Planar Perovskite Solar Cells by Processing with Glycol Ether Additives

    KAUST Repository

    Ugur, Esma

    2017-07-31

    Planar perovskite solar cells can be prepared without high temperature processing steps typically associated with mesoporous device architectures; however, their efficiency has been lower and producing high quality perovskite films in planar devices has been challenging. Here, we report a modified two-step interdiffusion protocol suitable to prepare pin-hole free perovskite films with greatly improved morphology. This is achieved by simple addition of small amounts of glycol ethers to the preparation protocol. We unravel the impact the glycol ethers have on the perovskite film formation using in-situ UV-Vis absorbance and GIWAXS experiments. From these experiments we conclude: addition of glycol ethers changes the lead iodide to perovskite conversion dynamics and enhances the conversion efficiency, resulting in more compact polycrystalline films, and it creates micrometer-sized perovskite crystals vertically-aligned across the photoactive layer. Consequently, the average photovoltaic performance increases from 13.5% to 15.9% and reproduciability is enhanced, specifically when 2-methoxyethanol is used as additive.

  12. Improved Morphology and Efficiency of n-i-p Planar Perovskite Solar Cells by Processing with Glycol Ether Additives

    KAUST Repository

    Ugur, Esma; Sheikh, Arif D.; Munir, Rahim; Khan, Jafar Iqbal; Barrit, Dounya; Amassian, Aram; Laquai, Fré dé ric

    2017-01-01

    Planar perovskite solar cells can be prepared without high temperature processing steps typically associated with mesoporous device architectures; however, their efficiency has been lower and producing high quality perovskite films in planar devices has been challenging. Here, we report a modified two-step interdiffusion protocol suitable to prepare pin-hole free perovskite films with greatly improved morphology. This is achieved by simple addition of small amounts of glycol ethers to the preparation protocol. We unravel the impact the glycol ethers have on the perovskite film formation using in-situ UV-Vis absorbance and GIWAXS experiments. From these experiments we conclude: addition of glycol ethers changes the lead iodide to perovskite conversion dynamics and enhances the conversion efficiency, resulting in more compact polycrystalline films, and it creates micrometer-sized perovskite crystals vertically-aligned across the photoactive layer. Consequently, the average photovoltaic performance increases from 13.5% to 15.9% and reproduciability is enhanced, specifically when 2-methoxyethanol is used as additive.

  13. Activity coefficients at infinite dilution of hydrocarbons in glycols: Experimental data and thermodynamic modeling with the GCA-EoS

    International Nuclear Information System (INIS)

    González Prieto, Mariana; Williams-Wynn, Mark D.; Bahadur, Indra; Sánchez, Francisco A.; Mohammadi, Amir H.

    2017-01-01

    Highlights: • Experimental infinite dilution activity coefficients of hydrocarbons in glycols. • Inverse gas-liquid chromatography technique. • Solutes investigated include n-alkanes, 1-alkenes, and cycloalkanes. • Highly non-ideal systems are modeled with the GCA-EoS. - Abstract: The infinite dilution activity coefficients for 12 non-polar hydrocarbon solutes in the solvents, monoethylene and diethylene glycol, were measured using the gas-liquid chromatography technique. Pre-saturation of the carrier gas was required to avoid solvent loss from the chromatographic column during the measurements that were carried out at T = (303.15, 313.15 and 323.15) K for monoethylene glycol and at T = (304.15, 313.15 and 323.15) K for diethylene glycol. The solutes investigated include n-alkanes, 1-alkenes, and cycloalkanes. The new data are compared with the highly scattered data that is available in the open literature. Finally, these highly non-ideal systems are modeled with the GCA-EoS.

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

    International Nuclear Information System (INIS)

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

    1995-01-01

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

  15. Thermodynamics of micellization of cationic surfactants based on O-alkyl and O-perfluoro-N,N'-diisopropylisourea: Effect of the counter ion nature

    International Nuclear Information System (INIS)

    Lehanine, Zineb; Badache, Leila

    2011-01-01

    Graphical abstract: The pseudo phase thermodynamic model was applied to study the process of micellization of O-dodecyl- and O-tridecafluorooctyl-N,N'-diisopropylisourea hydrohalogenides. Free energy of micellization is weakly temperature dependent and decreased slightly with the size of the counterion, indicating a more favored micellization. Enthalpies and entropies of micellization decrease strongly with increasing temperature. The enthalpy-entropy compensation phenomenon was observed for all the surfactants studied. Highlights: → The pseudo phase thermodynamic model was applied to study the process of micellization of O-dodecyl- and O-tridecafluorooctyl-N,N'-diisopropylisourea hydrohalogenides. → Free energy of micellization is weakly temperature dependent and decreased slightly with the size of the counterion, indicating a more favored micellization. → Enthalpies and entropies of micellization decrease strongly with increasing temperature. → The enthalpy-entropy compensation phenomenon was observed for all the surfactants studied. - Abstract: A thermodynamic study on the micellization process of two series of cationic surfactants, viz. the O-dodecyl-N,N'-diisopropylisourea hydrochloride, hydrobromide, and hydroiodide and the O-tridecafluorooctyl-N,N'-diisopropylisourea hydrochloride, and hydrobromide, is reported. In order to explain the effect of the counter ion nature in the micellization process, thermodynamic parameters to include the standard free energy (ΔG mic 0 ), enthalpy (ΔH mic 0 ), entropy (ΔS mic 0 ), and heat capacity (ΔC p,mic 0 ) of micellization have been discussed. These parameters are evaluated from the variation of the critical micelle concentration (CMC) with temperature by fitting these values to expressions derived on the basis of a micellization thermodynamic model. The heat capacities of micellization (ΔC p,mic 0 ) were determined from the temperature dependence of ΔH mic 0 . For both surfactant series, the free energy of

  16. Alkyne- and alkyl-tris(cyclopentadienyl) complexes of uranium(III)

    International Nuclear Information System (INIS)

    Foyentin, M.; Folcher, G.; Ephritkhine, M.

    1987-01-01

    Treatment of cp 3 U(THF) (1) (cp=eta-C 5 H 5 , THF=tetrahydrofuran) with diphenylacetylene affords the alkyne complex cp 3 U(Ph-C identical to C-Ph); (1) reacts with RLi (R = Me, Busup(n)) to give the alkyl compounds cp 3 URLi (3); hydrogenolysis of (3) in the presence of a terminal alkene R'(-H) leads to the formation of cp 3 UR'Li. (author)

  17. Comparison of conventional freezing and vitrification with dimethylformamide and ethylene glycol for cryopreservation of ovine embryos.

    Science.gov (United States)

    Varago, F C; Moutacas, V S; Carvalho, B C; Serapião, R V; Vieira, F; Chiarini-Garcia, H; Brandão, F Z; Camargo, L S; Henry, M; Lagares, M A

    2014-10-01

    The aim of this work was to evaluate the efficiency of the cryoprotectants dimethylformamide and ethylene glycol for cryopreservation of ovine embryos using vitrification and conventional freezing. The recovered embryos were distributed randomly in three treatment groups: Gr. 1: conventional freezing (n = 44), Gr. 2: vitrification with ethylene glycol (n = 39) and Gr. 3: vitrification with dimethylformamide (n = 38). Quality of fresh embryos in control group as well as of frozen and vitrified embryos was examined by three methodologies: staining with propidium iodide and Hoechst 33258 and evaluation under fluorescent microscopy, evaluation of re-expansion and hatching rates after culture, and determination of apoptotic index with TUNEL technique. It was established that re-expansion rate in all treatment groups was similar. In the same time, hatching rates were higher in Gr. 1 (40.5%) and Gr. 2 (35.3%) in comparison with Gr. 3 (15.5%, p conventional freezing, 10.1 ± 8.5, p conventional freezing) and fresh embryos. In conclusion, the dimethylformamide and ethylene glycol used as cryoprotectant to vitrify ovine embryos, in the concentrations and exposition time tested in this work, were not as efficient as the conventional freezing for cryopreservation of ovine embryos Thus, the conventional freezing with ethylene glycol was the most efficient method to cryopreserve ovine embryos in comparison with vitrification. © 2014 Blackwell Verlag GmbH.

  18. Bacillus subtilis mutants deficient in the adaptive response to simple alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Morohoshi, F.; Munakata, N.

    1985-03-01

    Three mutant strains exhibiting hyper-sensitivity to N-methyl-N'-nitro-N-nitrosoguanidine, but not to methyl methanesulfonate, were selected by a replica method from mutagenized spores of Bacillus subtilis. All three were totally deficient in the adaptive response to N-methyl-N'-nitro-N-nitrosoguanidine with regard to both lethality and mutagenesis. The activity to destroy O/sup 6/-methylguanine residues in the methylated DNA was not elevated in the mutant cells by the pretreatment with sublethal concentrations of N-methyl-N-nitro-N-nitrosoguanidine. This deficiency corresponded to the persistance of O/sup 6/-methylguanine residues in the DNA of both control and pretreated mutant cells challenged with the drug. The lethal and mutagenic sensitivity of the mutant strains were observed only for methyl- or ethyl-nitroso compounds that are thought to be active as inducers and are also active in O-alkylation. Except for the insensitivity to methyl methanesulfonate, the phenotypes of these mutants look very similar to those of ada mutants isolated previously in Escherichia coli.

  19. Radiation grafting from binary mixtures of vinyl ether of mono ethanol amine with N-vinylpyrrolidone and vinyl ether of ethylene glycol onto polyolefins films and metallization of obtained films

    International Nuclear Information System (INIS)

    Al'-Saed Abdel' Aal'; Nurkeeva, Z.; Khutoryanskij, V.; Mun, G.; Sangajlo, M.

    2003-01-01

    Radiation grafting from binary mixtures of vinyl ether of mono ethanol amine with N-vinylpyrrolidone and vinyl ether of ethylene glycol onto polyolefins films using γ-radiation and accelerated electrons has been studied. IR-spectroscopy is used to confirm the structure of grafted films. A combination of and metallization of obtained films. A combination of gravimetric and potentiometric techniques is applied to determine the fraction of each monomer in graft copolymer. Water uptake and contact angle measurements confirmed that the grafting process improve the hydrophilic properties of obtained films. The obtained materials are metallized by electroless copper plating. The metallized films have good electro conductive properties. (author)

  20. 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.

  1. Maltose neopentyl glycol-3 (MNG-3) analogues for membrane protein study

    DEFF Research Database (Denmark)

    Cho, Kyung Ho; Husri, Mohd; Amin, Anowarul

    2015-01-01

    characteristics is necessary to advance MP research. Maltose neopentyl glycol-3 (MNG-3) has contributed to >10 crystal structures including G-protein coupled receptors. Here, we prepared MNG-3 analogues and characterised their properties using selected MPs. Most MNGs were superior to a conventional detergent, n...

  2. N-alylated mercaptoacetyl glycine derivatives as multipurpose ligands in radio tracer design. Pt. 2

    International Nuclear Information System (INIS)

    Noll, B.; Semmler, W.

    1994-01-01

    N 1 -alkylated mercaptoacetyl glycine ligands were labelled with technetium-99m and the formed products analyzed by chromatographic methods. Biodistribution patterns of the resulting species were determined in Wistar rats. The compounds were tested with regard to their ability to be accumulated in arterioclerotic plaques. (orig.)

  3. Charge properties and bacterial contact-killing of hyperbranched polyurea-polyethyleneimine coatings with various degrees of alkylation

    Science.gov (United States)

    Roest, Steven; van der Mei, Henny C.; Loontjens, Ton J. A.; Busscher, Henk J.

    2015-11-01

    Coatings of immobilized-quaternary-ammonium-ions (QUAT) uniquely kill adhering bacteria upon contact. QUAT-coatings require a minimal cationic-charge surface density for effective contact-killing of adhering bacteria of around 1014 cm-2. Quaternization of nitrogen is generally achieved through alkylation. Here, we investigate the contribution of additional alkylation with methyl-iodide to the cationic-charge density of hexyl-bromide alkylated, hyperbranched polyurea-polyethyleneimine coatings measuring charge density with fluorescein staining. X-ray-photoelectron-spectroscopy was used to determine the at.% alkylated-nitrogen. Also streaming potentials, water contact-angles and bacterial contact-killing were measured. Cationic-charge density increased with methyl-iodide alkylation times up to 18 h, accompanied by an increase in the at.% alkylated-nitrogen. Zeta-potentials became more negative upon alkylation as a result of shielding of cationiccharges by hydrophobic alkyl-chains. Contact-killing of Gram-positive Staphylococci only occurred when the cationic-charge density exceeded 1016 cm-2 and was carried by alkylated-nitrogen (electron-binding energy 401.3 eV). Gram-negative Escherichia coli was not killed upon contact with the coatings. There with this study reveals that cationic-charge density is neither appropriate nor sufficient to determine the ability of QUAT-coatings to kill adhering bacteria. Alternatively, the at.% of alkylated-nitrogen at 401.3 eV is proposed, as it reflects both cationic-charge and its carrier. The at.% N401.3 eV should be above 0.45 at.% for Gram-positive bacterial contact-killing.

  4. From Leaf Synthesis to Senescence: n-Alkyl Lipid Abundance and D/H Composition Among Plant Species in a Temperate Deciduous Forest at Brown's Lake Bog, Ohio, USA

    Science.gov (United States)

    Freimuth, E. J.; Diefendorf, A. F.; Lowell, T. V.

    2014-12-01

    The hydrogen isotope composition (D/H, δD) of terrestrial plant leaf waxes is a promising paleohydrology proxy because meteoric water (e.g., precipitation) is the primary hydrogen source for wax synthesis. However, secondary environmental and biological factors modify the net apparent fractionation between precipitation δD and leaf wax δD, limiting quantitative reconstruction of paleohydrology. These secondary factors include soil evaporation, leaf transpiration, biosynthetic fractionation, and the seasonal timing of lipid synthesis. Here, we investigate the influence of each of these factors on n-alkyl lipid δD in five dominant deciduous angiosperm tree species as well as shrubs, ferns and grasses in the watershed surrounding Brown's Lake Bog, Ohio, USA. We quantified n-alkane and n-alkanoic acid concentrations and δD in replicate individuals of each species at weekly to monthly intervals from March to October 2014 to assess inter- and intraspecific isotope variability throughout the growing season. We present soil, xylem and leaf water δD from each individual, and precipitation and atmospheric water vapor δD throughout the season to directly examine the relationship between source water and lipid isotope composition. These data allow us to assess the relative influence of soil evaporation and leaf transpiration among plant types, within species, and along a soil moisture gradient throughout the catchment. We use leaf water δD to approximate biosynthetic fractionation for each individual and test whether this is a species-specific and seasonal constant, and to evaluate variation among plant types with identical growth conditions. Our high frequency sampling approach provides new insights into the seasonal timing of n-alkane and n-alkanoic acid synthesis and subsequent fluctuations in concentration and δD in a temperate deciduous forest. These results will advance understanding of the magnitude and timing of secondary influences on the modern leaf wax

  5. Sensitization of human carcinoma cells to alkylating agents by small interfering RNA suppression of 3-alkyladenine-DNA glycosylase.

    Science.gov (United States)

    Paik, Johanna; Duncan, Tod; Lindahl, Tomas; Sedgwick, Barbara

    2005-11-15

    One of the major cytotoxic lesions generated by alkylating agents is DNA 3-alkyladenine, which can be excised by 3-alkyladenine DNA glycosylase (AAG). Inhibition of AAG may therefore result in increased cellular sensitivity to chemotherapeutic alkylating agents. To investigate this possibility, we have examined the role of AAG in protecting human tumor cells against such agents. Plasmids that express small interfering RNAs targeted to two different regions of AAG mRNA were transfected into HeLa cervical carcinoma cells and A2780-SCA ovarian carcinoma cells. Stable derivatives of both cell types with low AAG protein levels were sensitized to alkylating agents. Two HeLa cell lines with AAG protein levels reduced by at least 80% to 90% displayed a 5- to 10-fold increase in sensitivity to methyl methanesulfonate, N-methyl-N-nitrosourea, and the chemotherapeutic drugs temozolomide and 1,3-bis(2-chloroethyl)-1-nitrosourea. These cells showed no increase in sensitivity to UV light or ionizing radiation. After treatment with methyl methanesulfonate, AAG knockdown HeLa cells were delayed in S phase but accumulated in G2-M. Our data support the hypothesis that ablation of AAG activity in human tumor cells may provide a useful strategy to enhance the efficacy of current chemotherapeutic regimens that include alkylating agents.

  6. The acute toxic effects of 1-alkyl-3-methylimidazolium nitrate ionic liquids on Chlorella vulgaris and Daphnia magna.

    Science.gov (United States)

    Zhang, Cheng; Zhang, Shuai; Zhu, Lusheng; Wang, Jinhua; Wang, Jun; Zhou, Tongtong

    2017-10-01

    Given their increasingly widespread application, the toxic effects of ionic liquids (ILs) have become the subject of significant attention in recent years. Therefore, the present study assessed the acute toxic effects of 1-alkyl-3-methylimidazolium nitrate ([C n mim]NO 3 (n = 2, 4, 6, 8, 10, 12)) on Chlorella vulgaris and Daphnia magna. The sensitivity of the tested organism Daphnia magna and the investigated IL concentrations in water using high-performance liquid chromatography (HPLC) were also evaluated to demonstrate the reliability of the present study. The results illustrated that Daphnia magna is indeed sensitive to the reference toxicant and the investigated ILs were stable in the aquatic environment. The 50% effect concentration (EC 50 ) was used to represent the acute toxic effects on Chlorella vulgaris and Daphnia magna. With the increasing alkyl-chain lengths, the toxicity of the investigated ILs increased in both the test organisms. Accordingly, the alkyl-chain lengths can cause significantly toxic effects on aquatic organisms, and Daphnia magna are much more sensitive than Chlorella vulgaris to the imidazolium-based ILs used in the present study. Furthermore, the present study provides more information on the acute toxic effects of 1-alkyl-3-methylimidazolium nitrate. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. A facile preparation of alkyl α-glycosides of the methyl ester of N-acetyl-D-neuraminic acid

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Vleugel, D.J.M. van der; Heeswijk, W.A.R. van

    1982-01-01

    The reaction of methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-2-chloro-2,3,5-trideoxy-β-D-glycero-D-galacto-2-nonulopyranosonate with primary and secondary alcohols in the presence of silver salicylate affords, after O-deacetylation, stereo-specifically the corresponding methyl (alkyl

  8. 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.

  9. Aggregation behavior of gemini pyrrolidine-based ionic liquids 1,1'-(butane-1,4-diyl)bis(1-alkylpyrrolidinium) bromide ([C(n)py-4-C(n)py][Br2]) in aqueous solution.

    Science.gov (United States)

    Zhang, Shaohua; Yan, Han; Zhao, Mingwei; Zheng, Liqiang

    2012-04-15

    Three gemini pyrrolidine-based ionic liquids, 1,1'-(butane-1,4-diyl)bis(1-alkylpyrrolidinium) bromide ([C(n)py-4-C(n)py][Br(2)], n=10, 12, 14), were synthesized. Their aggregation behavior in aqueous solution was systematically investigated by surface tension, electrical conductivity, and steady-state fluorescence. Compared with their corresponding monomers, N-alkyl-N-methylpyrrolidinium bromide (C(n)MPB), [C(n)py-4-C(n)py][Br(2)], have higher surface activity. The special structure of [C(n)py-4-C(n)py][Br(2)] that has a spacer in their hydrophilic head groups results in a lower surface excess concentration (Γ(max)) and a larger molecular cross-sectional area (A(min)). Electrical conductivity studies show a lower degree of counter-ion binding to the aggregates. A smaller aggregation number (N(agg)) is observed by the pyrene fluorescence quenching method. A series of thermodynamic parameters (ΔG(agg)(0),ΔH(agg)(0),-TΔS(agg)(0)) of aggregation derived from electrical conductivity indicate that the aggregation of [C(n)py-4-C(n)py][Br(2)] is enthalpy-driven, while aggregation of C(n)MPB is entropy-driven at low temperatures but enthalpy-driven at high temperatures. Copyright © 2012 Elsevier Inc. All rights reserved.

  10. 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)

  11. The gas-liquid chromatography of carboxylic acid esters of the urinary 11-deoxy-17-oxo steroids. Determination as n-butyrates.

    Science.gov (United States)

    Sadler, P A; Kellie, A E

    1967-06-01

    1. The gas-liquid-chromatographic separations of the acetate, propionate, n-butyrate, isobutyrate and n-valerate esters of androsterone, aetiocholanolone and dehydroepiandrosterone were studied on a 1% neopentyl glycol sebacate column. The n-butyrate, isobutyrate and n-valerate esters were well resolved. 2. The three steroids derived from hydrolysed urinary 17-oxo steroid conjugate extracts were analysed by gas-liquid chromatography after conversion into their n-butyrate esters. The results were compared with independent determinations involving chromatography on alumina.

  12. Iridium- and Ruthenium-Catalyzed N-alkylation of Amines with Alcohols and Amines

    DEFF Research Database (Denmark)

    Lorentz-Petersen, Linda Luise Reeh

    -helical propensity. Hereby, it was believed that more stable proteins would be obtained. Folding of the mutants was studied in terms of thermodynamics and kinetics by guanidine hydrochloride denaturation monitored by fluorescence. The results were unfortunately unreliable due to errors in the spectrofluorometer....... in the reaction, as ethyleneglycol and 1,2-ethylenediamine failed to produce piperazine. Introduction of a C-substituent on one or both of the starting materials gave Csubstituted piperazines in high yields. Synthesis of N-benzylpiperazine from ethyleneglycol and N-benzylethylenediamine was also successful. Self...... experiments were conducted and emphasized the importance of the Voigt reaction in the formation of the product. Protein folding During an external stay at The Scripps Research Institute, San Diego, California, USA, folding of the well-known protein CI2 was studied. Several mutants were synthetically prepared...

  13. 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.

  14. elementary mechanistic steps and the influence of process variables in isobutane alkylation over H-BEA

    NARCIS (Netherlands)

    Nivarthy, G.S.; He, Y.; Seshan, Kulathuiyer; Lercher, J.A.

    1998-01-01

    Liquid phase conversion of n-butene in excess iso-butane was investigated over zeolite BEA as catalyst in a continuously operated slurry reactor. Single and multiple alkylation and cracking were the main reaction pathways. Only saturated products were observed indicating that hydride transfer

  15. Acetylcholinesterase-Inhibiting Activity of Salicylanilide N-Alkylcarbamates and Their Molecular Docking

    Directory of Open Access Journals (Sweden)

    Josef Jampilek

    2012-08-01

    Full Text Available A series of twenty-five novel salicylanilide N-alkylcarbamates were investigated as potential acetylcholinesterase inhibitors. The compounds were tested for their ability to inhibit acetylcholinesterase (AChE from electric eel (Electrophorus electricus L.. Experimental lipophilicity was determined, and the structure-activity relationships are discussed. The mode of binding in the active site of AChE was investigated by molecular docking. All the discussed compounds expressed significantly higher AChE inhibitory activity than rivastigmine and slightly lower than galanthamine. Disubstitution by chlorine in C'(3,4 of the aniline ring and the optimal length of hexyl-undecyl alkyl chains in the carbamate moiety provided the most active AChE inhibitors. Monochlorination in C'(4 exhibited slightly more effective AChE inhibitors than in C'(3. Generally it can be stated that compounds with higher lipophilicity showed higher inhibition, and the activity of the compounds is strongly dependent on the length of the N-alkyl chain.

  16. Viscosity-dependent drain current noise of AlGaN/GaN high electron mobility transistor in polar liquids

    International Nuclear Information System (INIS)

    Fang, J. Y.; Hsu, C. P.; Kang, Y. W.; Fang, K. C.; Kao, W. L.; Yao, D. J.; Chen, C. C.; Li, S. S.; Yeh, J. A.; Wang, Y. L.; Lee, G. Y.; Chyi, J. I.; Hsu, C. H.; Huang, Y. F.; Ren, F.

    2013-01-01

    The drain current fluctuation of ungated AlGaN/GaN high electron mobility transistors (HEMTs) measured in different fluids at a drain-source voltage of 0.5 V was investigated. The HEMTs with metal on the gate region showed good current stability in deionized water, while a large fluctuation in drain current was observed for HEMTs without gate metal. The fluctuation in drain current for the HEMTs without gate metal was observed and calculated as standard deviation from a real-time measurement in air, deionized water, ethanol, dimethyl sulfoxide, ethylene glycol, 1,2-butanediol, and glycerol. At room temperature, the fluctuation in drain current for the HEMTs without gate metal was found to be relevant to the dipole moment and the viscosity of the liquids. A liquid with a larger viscosity showed a smaller fluctuation in drain current. The viscosity-dependent fluctuation of the drain current was ascribed to the Brownian motions of the liquid molecules, which induced a variation in the surface dipole of the gate region. This study uncovers the causes of the fluctuation in drain current of HEMTs in fluids. The results show that the AlGaN/GaN HEMTs may be used as sensors to measure the viscosity of liquids within a certain range of viscosity

  17. One-pot Synthesis of Substituted Pyrroles with N,N,N',N'

    African Journals Online (AJOL)

    In this research, N,N,N'N'-tetrachlorobenzene-1,3-disulphonamide as novel catalytic reagent and N,N'-diiodo-N,N'-1,2-ethanediylbis(p-toluenesulphonamide) as new catalyst were used for the synthesis of N-substituted pyrroles in good to excellent yields under mild conditions. These reusable reagents were compared with ...

  18. Temperature dependence of the volumetric properties of some alkoxypropanols + n-alkanol mixtures

    International Nuclear Information System (INIS)

    Pal, Amalendu; Kumar, Harsh

    2004-01-01

    The excess molar volumes V m E for binary liquid mixtures containing dipropylene glycol monomethyl ether or dipropylene glycol monobutyl ether and methanol, 1-propanol, 1-pentanol and 1-heptanol have been measured as a function of composition using a continuous dilution dilatometer at T=(288.15, 298.15, and 308.15) K and atmospheric pressure over the whole concentration range. The excess volume results allowed the following mixing quantities to be reported in all range of concentrations or at equimolar concentrations: α, volume expansivity; (∂V m E /∂T) p ; (∂H E /∂P) T at T=298.15 K. The obtained results have been compared at T=298.15 K with the calculated values by using the Flory theory of liquid mixtures. The theory predicts the α, and α E values rather well, while the calculated values of (∂V m E /∂T) p and (∂H E /∂P) T show general variation with the alkyl chain length of the alkoxypropanols. The results are discussed in terms of order or disorder creation

  19. O-alkylation of disodium salt of diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate with 1,2-dichloroethane catalyzed by ionic type phase transfer catalyst and potassium iodide

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Huasheng; Yin, Hengbo; Wang, Aili; Shen, Jun; Yan, Xiaobo; Liu, Yumin; Zhang, Changhua [Jiangsu University, Zhenjiang (China)

    2014-01-15

    Diethyl 3,4-ethylenedioxy thiophene-2,5-dicarboxylate was efficiently synthesized via the O-alkylation of disodium salt of diethyl 3,4-dihydroxy thiophene-2,5-dicarboxylate with 1,2-dichloroethane over ionic type phase transfer catalysts, such as tetrabutyl ammonium bromide and benzyl triethyl ammonium chloride. The ionic type phase transfer catalysts showed higher catalytic activities than the nonionic type phase transfer catalysts, such as triethylamine, pyridine, 18-crown-6, and polyethylene glycol 400/600, in the O-alkylation reaction. The conversion of the disodium salt of more than 97% and the selectivity of diethyl 3,4-ethylenedioxy thiophene-2,5-dicarboxylate of more than 98% were achieved when the O-alkylation reaction was synergistically catalyzed by tetrabutyl ammonium bromide and potassium iodide.

  20. Formaldehyde-free and thermal resistant microcapsules containing n-octadecane

    International Nuclear Information System (INIS)

    Shan, X.L.; Wang, J.P.; Zhang, X.X.; Wang, X.C.

    2009-01-01

    Microcapsules containing n-octadecane were synthesized using methacrylic acid (MAA), methyl methacrylate (MMA) and 1,4-butylene glycol diacrylate (BDDA) as shell. The surface morphology, thermal physical properties, thermal stabilities and diameter distributions of the microcapsules were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and particle size distribution analysis, respectively. The experimental results show that, the core material is well encapsulated in the presence of emulsifier-sodium salt of styrene-maleic anhydride co-polymer. The average diameter of the microcapsules is 18 μm. The enthalpy of microencapsulated n-octadecane (MC 18 ) with MAA-MMA co-polymeric shell is 155 J g -1 which corresponds to 70 wt.% core content. The thermal resistant temperature of MC 18 is 238 o C, which is affected by n-octadecane/monomers mass ratios and the content of cross-linking agent-BDDA.

  1. Coal anion structure and chemistry of coal alkylation. Fourth quarterly progress report, December 1, 1977--February 28, 1978. [Carbon atoms in butyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.

    1978-01-01

    Three research problems are in progress. First, work is progressing well concerning the methods appropriate for the reductive alkylation of Illinois No. 6 coal samples. We have investigated the influence of the leaving group on the conversion of the Illinois coal to a soluble material. We find that the n-butyl iodide is more effective than other n-butyl halides. Second, preliminary results have been obtained concerning the distribution of hydrogen and deuterium atoms in the reaction of Illinois No. 6 coal samples with perdeuteriotetralin at 400/sup 0/C. Third, the nuclear magnetic resonance spectra of appropriate model compounds with n-butyl groups have been tabulated for comparison with the spectroscopic results obtained from coal alkylation products. Fourth, the chromatographic procedures necessary for the separation of the coal samples are being developed.

  2. Mutagenic activity of N-nitrosoethylene urea in higher plants. [C. cappilaris L

    Energy Technology Data Exchange (ETDEWEB)

    Sal' nikova, T.V.; Grigorova, N.V.; Laputin, D.L.; Shustova, L.L., Zazimko, V.V.; Shustov, G.V.; Kostyanovskiy, R.G.

    1984-04-01

    Cytopathogenetic effect of N-nitrosoethylene urea (NETM) on common wheat and C. cappilaris L. are studied. Air-dried wheat seeds were treated with 1 of 5 concentrations (0.1-0.01%) of NETM for 18 hours at pH 5.7 or 7.0. Treatment of seeds with NETM reduced the germinating power significantly at pH 5.7, especially at high concentrations of NETM. NETM is also a highly effective chemical mutagen. Maximum mutagenic effect appears at pH 7.0. NETM greatly reduced mitotic activity of wheat and C. cappilaris L. which is typical for alkylating type mutagens. The aberration rate is rather high for both objects studied. In both the anaphase and metaphase method of calculating chromosomal injuries, a great percentage of the total number of aberrations are chromatid type reconstructions which indicates predominance of the alkylating action of NETM. Wheat affected by NETM has a large number of anaphase cells with lagging chromosome which is atypical for alkylating type mutagens. This may be explained by the effect of NETM on centromeric and precentromeric parts of chromosomes and spindle filaments. NETM is an alkylating agent rather than a carbamoylating agent. It is a highly active and slightly toxic mutagen. 25 references, 1 figure.

  3. Effect of leaf litter degradation and seasonality on D/H isotope ratios of n-alkane biomarkers

    NARCIS (Netherlands)

    Zech, M.; Pedentchouk, N.; Buggle, B.; Leiber, K.; Kalbitz, K.; Markovic, S.B.; Glaser, B.

    2011-01-01

    During the last decade, compound-specific hydrogen isotope analysis of plant leaf-wax and sedimentary n-alkyl lipids has become a promising tool for paleohydrological reconstructions. However, with the exception of several previous studies, there is a lack of knowledge regarding possible effects of

  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. Comparative NMR study of nPrBTP and iPrBTP

    Energy Technology Data Exchange (ETDEWEB)

    Adam, C.; Muellich, U.; Geist, A.; Geckeis, H. [Karlsruhe Institute of Technology - KIT, Institute for Nuclear Waste Disposal - INE, Herrmann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Rohde, V. [Fraunhofer Institute for Chemical Technology - ICT, Environmental Engineering, Joseph-von-Fraunhofer-Str. 7, 76327 Pfinztal (Germany); Kaden, P. [Helmholtz-Zentrum Dresden - Rossendorf e. V., Institute of Resource Ecology, Bautzner Landstrasse 400, 01328 Dresden (Germany); Panak, P.J. [Karlsruhe Institute of Technology - KIT, Institute for Nuclear Waste Disposal - INE, Herrmann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); University of Heidelberg, Department of Physical Chemistry, Im Neuenheimer Feld 253, 69120 Heidelberg (Germany)

    2016-07-01

    Bis-triazinyl-pyridine type ligands are important extracting agents for separating trivalent actinide ions from trivalent lanthanides. The alkyl substituents on the lateral triazine rings have a significant effect on the stability of the ligand against hydrolysis and radiolysis. Furthermore they influence solubility, extraction behaviour and selectivity. TRLFS and extraction studies suggest differences in complexation and extraction behaviour of BTP ligands bearing iso-propyl or n-propyl substituents, respectively. As NMR studies allow insight into the metal-ligand bonding, we conducted NMR studies on a range of {sup 15}N-labelled nPrBTP and iPrBTP Ln(III) and Am(III) complexes. Our results show that no strong change in the metal-ligand bonding occurs, thus excluding electronic reasons for differences in complexation behaviour, extraction kinetics and selectivity. This supports mechanistic reasons for the observed differences. (authors)

  6. Alkylation of isobutane with butenes in the presence of HNaY zeolite modified by cations of nickel, calcium and rare-earth elements

    Energy Technology Data Exchange (ETDEWEB)

    Kuznetsov, O.I.; Panchenkov, G.M.; Plakhotnik, V.A.; Razali, B.; Tolkacheva, Y.I.

    1981-01-01

    A study was made of alkylation of isobutane with n-butenes in the presence of ion-exchange forms of zeolites, containing ions of Ni/sup 2 +/ and rare-earth elements. It was established that the addition to HCaY zeolite of Ni/sup 2 +/ ions reduces alkylate yield and increases the content of intermediate products. The use in the reaction studied of HCaY zeolite containing La/sup 3 +/ or Gd/sup 3 +/ ions increases the content of iso-octane hydrocarbons in the alkylate and reduces the content of fractions C/sub 9/ and higher.

  7. Métodos de obtención de microesferas biodegradables

    Directory of Open Access Journals (Sweden)

    Diana Ramos Picos

    2001-08-01

    Full Text Available La liberación controlada de agentes terapéuticos desde microesferas biodegradables poliméricas ha sido extensamente estudiada. El ácido poliláctico y sus copolímeros con el ácido glicólico se han utilizado en la preparación de microesferas debido a su biodegradabilidad y biocompatibilidad. Estas microesferas han sido preparadas por varios métodos de obtención, los que son revisados en este trabajo. Se plantean las ventajas y desventajas de algunos de los métodos de obtención. En el caso del método de evaporación/extracción del solvente, que es el más usado, se plantean las variables que pueden influir en este y se discuten algunas de ellas.The controlled release of therapeutic agents from polymeric biodegradable microspheres has been widely studied. Polylactic acid and its copolymers with glycolic acid have been used in the preparation of microspheres because of their biodegradability and biocompatibility. These microspheres have been prepared by various methods which are reviewed in this paper. As to their most used solvent evaporation-extraction method. The variables that might affect it are set forth here and some of them are also discussed.

  8. Reduction of friction stress of ethylene glycol by attached hydrogen ions

    Science.gov (United States)

    Li, Jinjin; Zhang, Chenhui; Deng, Mingming; Luo, Jianbin

    2014-01-01

    In the present work, it is shown that the friction stress of ethylene glycol can decrease by an order of magnitude to achieve superlubricity if there are hydrogen ions attached on the friction surfaces. An ultra-low friction coefficient (μ = 0.004) of ethylene glycol between Si3N4 and SiO2 can be obtained with the effect of hydrogen ions. Experimental result indicates that the hydrogen ions adsorbed on the friction surfaces forming a hydration layer and the ethylene glycol in the contact region forming an elastohydrodynamic film are the two indispensable factors for the reduction of friction stress. The mechanism of superlubricity is attributed to the extremely low shear strength of formation of elastohydrodynamic film on the hydration layer. This finding may introduce a new approach to reduce friction coefficient of liquid by attaching hydrogen ions on friction surfaces. PMID:25428584

  9. Radiosynthesis and in vitro evaluation of 2-(N-alkyl-N-1'-11C-propyl)amino-5-hydroxytetralin analogs as high affinity agonists for dopamine D-2 receptors

    International Nuclear Information System (INIS)

    Shi Bingzhi; Narayanan, Tanjore K.; Yang, Z.-Y.; Christian, Bradley T.; Mukherjee, Jogeshwar

    1999-01-01

    We have developed radiotracers based on agonists that may potentially allow the in vivo assessment of the high affinity (HA) state of the dopamine D-2 receptors. The population of HA state, which is likely the functional state of the receptor, may be altered in certain diseases. We carried out radiosyntheses and evaluated the binding affinities, lipophilicity, and in vitro autoradiographic binding characteristics of three dopamine D-2 receptor agonists: (±)-2-(N,N-dipropyl)amino-5-hydroxytetralin (5-OH-DPAT), (±)-2-(N-phenethyl-N-propyl)amino-5-hydroxytetralin (PPHT), and (±)-2-(N-cyclohexylethyl-N-propyl)amino-5-hydroxytetralin (ZYY-339). In 3 H-spiperone assays using rat striata, ZYY-339 exhibited subnanomolar affinity for D-2 receptor sites ( IC 50 =0.010 nM), PPHT was somewhat weaker ( IC 50 =0.65 nM), and 5-OH-DPAT exhibited the weakest affinity ( IC 50 =2.5 nM) of the three compounds. Radiosynthesis of these derivatives, 2-(N-propyl-N-1'- 11 C-propyl)amino-5-hydroxytetralin ( 11 C-5-OH-DPAT), 2-(N-phenethyl-N-1'- 11 C-propyl)amino-5-hydroxytetralin ( 11 C-PPHT), and 2-(N-cyclohexylethyl-N-1'- 11 C-propyl)amino-5-hydroxytetralin ( 11 C-ZYY-339) was achieved by first synthesizing 11 C-1-propionyl chloride and subsequent coupling with the appropriate secondary amine precursor to form the respective amide, which was then reduced to provide the desired tertiary amine products. The final products were obtained by reverse-phase high performance liquid chromatography (HPLC) purification in radiochemical yields of 5-10% after 60-75 min from the end of 11 CO 2 trapping and with specific activities in the range of 250-1,000 Ci/mmol. In vitro autoradiographs in rat brain slices with 11 C-5-OH-DPAT, 11 C-PPHT, and 11 C-ZYY-339 revealed selective binding of the three radiotracers to the dopamine D-2 receptors in the striata

  10. Synthesis of α-alkyl ω-trimethoxysilane polyoxazolines and their application as coatings on glass fibres

    NARCIS (Netherlands)

    Loontjens, Ton; Rique-Lurbet, Laurence

    1999-01-01

    A novel class of telechelic α-alkyl ω-trimethoxysilane poly(N-propionylethylene imine)s (TMS-PPEIs) has been synthesized by living cationic ring-opening polymerization of 2-oxazolines. A new route for the termination reaction of the living polyoxazoline is dcscribed. These block copolymers have been

  11. One-step formation of bifunctionnal aryl/alkyl grafted films on conducting surfaces by the reduction of diazonium salts in the presence of alkyl iodides.

    Science.gov (United States)

    Hetemi, Dardan; Hazimeh, Hassan; Decorse, Philippe; Galtayries, Anouk; Combellas, Catherine; Kanoufi, Frédéric; Pinson, Jean; Podvorica, Fetah I

    2015-05-19

    The formation of partial perfluoroalkyl or alkyl radicals from partial perfluoroalkyl or alkyl iodides (ICH2CH2C6F13 and IC6H13) and their reaction with surfaces takes place at low driving force (∼-0.5 V/SCE) when the electrochemical reaction is performed in acetonitrile in the presence of diazonium salts (ArN2(+)), at a potential where the latter is reduced. By comparison to the direct grafting of ICH2CH2C6F13, this corresponds to a gain of ∼2.1 V in the case of 4-nitrobenzenediazonium. Such electrochemical reaction permits the modification of gold surfaces (and also carbon, iron, and copper) with mixed aryl-alkyl groups (Ar = 3-CH3-C6H4, 4-NO2-C6H4, and 4-Br-C6H4, R = C6H13 or (CH2)2-C6F13). These strongly bonded mixed layers are characterized by IRRAS, XPS, ToF-SIMS, ellipsometry, water contact angles, and cyclic voltammetry. The relative proportions of grafted aryl and alkyl groups can be varied along with the relative concentrations of diazonium and iodide components in the grafting solution. The formation of the films is assigned to the reaction of aryl and alkyl radicals on the surface and on the first grafted layer. The former is obtained from the electrochemical reduction of the diazonium salt; the latter results from the abstraction of an iodine atom by the aryl radical. The mechanism involved in the growth of the film provides an example of complex surface radical chemistry.

  12. Development of Cy5.5-Labeled Hydrophobically Modified Glycol Chitosan Nanoparticles for Protein Delivery

    Science.gov (United States)

    Chin, Amanda

    Therapeutic proteins are often highly susceptible to enzymatic degradation, thus restricting their in vivo stability. To overcome this limitation, delivery systems designed to promote uptake and reduce degradation kinetics have undergone a rapid shift from macro-scale systems to nanomaterial based carriers. Many of these nanomaterials, however, elicit immune responses and may have cytotoxic effects both in vitro and in vivo. The naturally derived polysaccharide chitosan has emerged as a promising biodegradable material and has been utilized for many biomedical applications; nevertheless, its function is often constrained by poor solubility. Glycol chitosan, a derivative of chitosan, can be hydrophobically modified to impart amphiphilic properties that enable the self-assembly into nanoparticles in aqueous media at neutral pH. This nanoparticle system has shown initial success as a therapeutic agent in several model cell culture systems, but little is known about its stability against enzymatic degradation. Therefore, the goal of this research was to investigate the resistance of hydrophobically modified glycol chitosan against enzyme-catalyzed degradation using an in vivo simulated system containing lysozyme. To synthesize the nanoparticles, hydrophobic cholanic acid was first covalently conjugated to glycol chitosan using of N-(3-Dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS). Conjugates were purified by dialysis, lyophilized, and ultra-sonicated to form nanoparticles. Fourier transform infrared (FT-IR) spectroscopy confirmed the binding of 5beta-cholanic acid to the glycol chitosan. Particle size and stability over time were determined with dynamic light scattering (DLS), and particle morphology was evaluated by transmission electron microscopy (TEM). The average diameter of the nanoparticles was approximately 200 nm, which remained stable at 4°C for up to 10 days. Additionally, a near infrared fluorescent (NIRF) dye

  13. Mechanism of n-butane hydrogenolysis promoted by Ta-hydrides supported on silica

    KAUST Repository

    Pasha, Farhan Ahmad

    2014-06-06

    The mechanism of hydrogenolysis of alkanes, promoted by Ta-hydrides supported on silica via 2 ≡ Si-O- bonds, has been studied with a density functional theory (DFT) approach. Our study suggests that the initial monohydride (≡ Si-O-)2Ta(III)H is rapidly trapped by molecular hydrogen to form the more stable tris-hydride (≡ Si-O-) 2Ta(V)H3. Loading of n-butane to the Ta-center occurs through C-H activation concerted with elimination of molecular hydrogen (σ-bond metathesis). Once the Ta-alkyl species is formed, the C-C activation step corresponds to a β-alkyl transfer to the metal with elimination of an olefin. According to these calculations, an α-alkyl transfer to the metal to form a Ta-carbene species is of higher energy. The olefins formed during the C-C activation step can be rapidly hydrogenated by both mono- and tris-Ta-hydride species, making the overall process of alkane cracking thermodynamically favored. © 2014 American Chemical Society.

  14. Ultrasonic promoted catalyst-free N-formylation of amines in neutral ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate

    Directory of Open Access Journals (Sweden)

    Vinod T. Kamble

    2017-05-01

    Full Text Available A catalyst-free, simple and efficient protocol for N-formylation of alkyl, aryl, and heteroaryl amines with formic acid under ultrasonic irradiation at room temperature using 1-butyl-3-methylimidazolium tetrafluoroborate [Bmim]BF4 as a neutral medium is described.

  15. Synthesis and characterisation of new Schiff base monomers containing N-(alkyl and phenyl) pyrrole moieties

    Science.gov (United States)

    Amer, Ahcene Ait; Ilikti, Hocine; Maschke, Ulrich

    2017-11-01

    This article deals with the synthesis and characterisation of seven new functional Schiff base monomers, such as: M1: 1-(3-Pyrrole-1-yl-propylimino-methyl)-naphtalen-2-ol; M2: 2-(3-Pyrrole-1-yl-phenylimino-methyl)-phenol; M3: 1-(3-Pyrrole-1-yl-phenylimino-methyl)-naphtalen-2-ol; M4: N-(pyridin-2-yl-methylene)-2-(pyrrol-1-yl)-benzenamine; M5: N-(pyridin-2-yl-methylene)-3-(pyrrol-1-yl)-propan-1-amine; M6: 2-(3-pyrrol-1-yl-propylimino-methyl)-quinolin-8-ol; M7: 2-(3-pyrrol-1-yl-phenylimino-methyl)-quinolin-8-ol. Two series of compounds emerged from this study, N-propyl pyrrole derivatives (M1, M5, M6) and N-phenyl pyrrole compounds (M2, M3, M4, M7). All monomers were elaborated by condensation reactions between appropriate amines and aldehydes, and their molecular structures were confirmed by spectroscopic analysis methods like FT-IR, 1H NMR, 13C NMR, and GC-MS.

  16. Characterization of reaction conditions providing rapid and specific cysteine alkylation for peptide-based mass spectrometry.

    Science.gov (United States)

    Paulech, Jana; Solis, Nestor; Cordwell, Stuart J

    2013-01-01

    Alkylation converts Cys thiols to thioethers and prevents unwanted side reactions, thus facilitating mass spectrometric identification of Cys-containing peptides. Alkylation occurs preferentially at Cys due to its high nucleophilicity, however reactions at other such sites are possible. N-ethylmaleimide (NEM) shows rapid reaction kinetics with Cys and careful definition of reaction conditions results in little reactivity at other sites. Analysis of a protein standard alkylated under differing reaction conditions (pH, NEM concentrations and reaction times) was performed using liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) and selected reaction monitoring (SRM) of NEM-modified and unmodified peptide pairs. Mis-alkylation sites at primary and secondary amines were identified and limited to one equivalent of NEM. No evidence for hydroxyl or thioether alkylation was observed. Improved specificity was achieved by restricting the pH below neutral, NEM concentration below 10mM and/or reaction time to below 5min. Maximal removal of Cys activity was observed in tissue homogenates at 40mM NEM within 1min, dependent upon efficient protein denaturation. SRM assays identified peptide-specific levels of mis-alkylation, indicating that NEM-modified to unmodified ratios did not exceed 10%, with the exception of Cys alkylation that proceeded to 100%, and some Lys residues that resulted in tryptic missed cleavages. High reactivity was observed for His residues considering their relatively low abundance. These data indicate that rapid and specific Cys alkylation is possible with NEM under relatively mild conditions, with more abrasive conditions leading to increased non-specific alkylation without appreciable benefit for MS-based proteomics. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. Diphenylphosphino Styrene-Containing Homopolymers: Influence of Alkylation and Mobile Anions on Physical Properties.

    Science.gov (United States)

    Jangu, Chainika; Schultz, Alison R; Wall, Candace E; Esker, Alan R; Long, Timothy E

    2016-07-01

    Conventional free radical polymerization and post-alkylation of 4-diphenylphosphino styrene (DPPS) generate a new class of high-molecular-weight phosphonium-containing homopolymers with tunable thermal, viscoelastic, and wetting properties. Post-alkylation and subsequent anion exchange provide an effective method for tuning Tg values and thermal stability as a function of alkyl chain length and counteranion selection (X(-) , BF4 (-) , TfO(-) , and Tf2 N(-) ). Rheological characterization facilitates the generation of time-temperature-superposition (TTS) pseudomaster curves and subsequent analysis of frequency sweeps at various temperatures reveals two relaxation modes corresponding to long-range segmental motion and the onset of viscous flow. Contact angle measurements reveal the influence of counteranion selection on wetting properties, revealing increased contact angles for homopolymers containing nucleophilic counteranions. These investigations provide fundamental insight into phosphonium-containing polymers, aiming to guide future research and applications involving electro-active polymeric devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Effects of 1-Alkyl-3-Methylimidazolium Nitrate on Soil Physical and Chemical Properties and Microbial Biomass.

    Science.gov (United States)

    Zhou, Tongtong; Wang, Jun; Ma, Zhiqiang; Du, Zhongkun; Zhang, Cheng; Zhu, Lusheng; Wang, Jinhua

    2018-05-01

    Ionic liquids (ILs), also called room temperature ILs, are widely applied in many fields on the basis of their unique physical and chemical properties. However, numerous ILs may be released into and gradually accumulate in the environment due to their extensive use and absolute solubility. The effects of 1-alkyl-3-methylimidazolium nitrate ([C n mim]NO 3 , n = 4, 6, 8) on soil pH, conductivity, cation exchange capacity, microbial biomass carbon, and microbial biomass nitrogen were examined at the doses of 1, 10, and 100 mg/kg on days 10, 20, 30, and 40. The results demonstrated that the soil pH decreased and the conductivity increased with increasing IL doses. No significant differences were observed in the soil cation-exchange capacity. All three of the tested ILs decreased the soil microbial biomass carbon and nitrogen. Additionally, there were few differences among the ILs with different alkyl chain lengths on the tested indicators except for the microbial biomass nitrogen. The present study addressed a gap in the literature regarding the effects of the aforementioned ILs with different alkyl side chains on the physicochemical properties of soil, and the results could provide the basic data for future studies on their toxicity to soil organisms, such as earthworms and soil microbes.

  19. The retention and distribution of parent, alkylated, and N/O/S-containing polycyclic aromatic hydrocarbons on the epidermal tissue of mangrove seedlings.

    Science.gov (United States)

    Li, Ruilong; Tan, Huadong; Zhu, Yaxian; Zhang, Yong

    2017-07-01

    The polycyclic aromatic hydrocarbons (PAHs) located on the epidermal tissues showed distinctive toxic effects to root, while the retention and distribution of PAHs on mangrove seedlings poorly understood. Our results confirmed that the partition coefficients (K f ) of the PAHs retained on the epidermal tissue of mangrove roots, such as Kandelia obovata, Avicennia marina and Aegiceras corniculatum, were much higher than the Poaceae plants roots, for example wheat and maize (Wild et al., 2005). Moreover, to the parent and alkyl PAHs, a well negative correlation was observed between the surface polarity of these three species of mangrove root and the K f values (p mangrove root epidermal tissues formed larger clusters than that of on Poaceae plants, such as wheat and maize (Wild et al., 2005) due to the limitation of the suberization of the root exodermis and endodermis. After exposure of 30 d, rhizo- and endophytic bacteria degraded parts of the N/O/S-containing PAHs to medium-lifetime fluorescence substances. To our knowledge, this is the first time to assess the retention of PAHs on the epidermal tissue of mangrove root, which will improve our understanding of the root uptake PAHs process. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. 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.

  1. Combined high-performance liquid chromatography/32P-postlabeling assay of N7-methyldeoxyguanosine

    International Nuclear Information System (INIS)

    Shields, P.G.; Povey, A.C.; Wilson, V.L.; Weston, A.; Harris, C.C.

    1990-01-01

    A highly sensitive and specific assay for the detection of N7-methyl-2'-deoxyguanosine (N7methyldG) has been developed by combining high-performance liquid chromatography, 32 P-postlabeling, and nucleotide chromatography. Separation of normal nucleotides and adducts by high-performance liquid chromatography and then combining a portion of 2'-deoxyguanosine to the N7methyldG allows for quantitation using an internal standard. The directly determined molar ratio is not subject to errors in digestion, variable ATP-specific activity, or assumptions in relative adduct-labeling efficiency. The detection limit was one N7methyldG adduct in 10(7) unmodified 2'-deoxyguanosine bases. N7methyldG adducts have been detected in 5 human lung samples in which O6-methyl-2'-deoxyguanosine adducts had been previously determined. The mean ratio of N7methyldG to O6-methyl-2'-deoxyguanosine was determined to be approximately 10. The current assay complements the high-performance liquid chromatography/ 32 P-postlabeling assay for O6-methyl-2'-deoxyguanosine and increases the detection sensitivity of DNA methylated by exogenous alkylating agents

  2. Site selectivity in the addition of ketoximes to activated allenes and alkynes; N- versus O-alkylation

    OpenAIRE

    Heaney, Frances; Kelly, Bronwyn M.; Bourke, Sharon; Rooney, Oliver; Cunningham, Desmond; McArdle, Patrick

    1999-01-01

    Reaction of ketoximes with methyl propiolate afforded geometrical isomers of the methyl 3-(hydroxyimino)propanoates 4 and of the O-vinyl oximes 5 as well as the 2-isoxazoline 6. With dimethyl penta-2,3-diendioate 8c reaction progressed via an O-alkylation to give the O-oxime ethers 9, only in the case of cyclopentanone oxime was the spirocyclic dihydroazepinol 11 also obtained, its identity has been confirmed by an X-ray structure determination.

  3. Role of alkyl alcohol on viscosity of silica-based chemical gels for decontamination of highly radioactive nuclear facilities

    International Nuclear Information System (INIS)

    Choi, B. S.; Yoon, S. B.; Jung, C. H.; Lee, K. W.; Moon, J. K.

    2012-01-01

    Silica-based chemical gel for the decontamination of nuclear facilities was prepared by using fumed silica as a viscosifier, a 0.5 M Ce (IV) solution dissolved in concentrated nitric acid as a chemical decontamination agent, and tripropylene glycol butyl ether (TPGBE) as a co-viscosifier. A new effective strategy for the preparation of the chemical gel was investigated by introducing the alkyl alcohols as organic solvents to effectively dissolve the co-viscosifier. The mixture solution of the co-viscosifier and alkyl alcohols was more effective in the control of viscosity than that of the co-viscosifier only in gel. Here, the alkyl alcohols played a key role as an effective dissolution solvent for the co-viscosifier in the preparation of the chemical gel, resulting in a reducing of the amount of the co-viscosifier and gel time compared with that of the chemical gel prepared without the alkyl alcohols. It was considered that the alkyl alcohols contributed to the effective dissolution of the co-viscosifier as well as the homogeneous mixing in the formation of the gel, while the co-viscosifier in an aqueous media of the chemical decontamination agent solution showed a lower solubility. The decontamination efficiency of the chemical gels prepared in this work using a multi-channel analyzer (MCA) showed a high decontamination efficiency of over ca. 94% and ca. 92% for Co-60 and Cs-137 contaminated on surface of the stainless steel 304, respectively. (authors)

  4. Influence of process variables on the continuous alkylation of isobutane with 2-butene on superacid sulfated zirconia catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Corma, A.; Martinez, A.; Martinez, C. [Instituto de Tecnologia Quimica, Valencia (Spain)

    1994-09-01

    Two sulfated zirconia catalysts have been prepared by impregnation of zirconium hydroxide with H{sub 2}SO{sub 4} 0.3 N and 1 N. Both samples showed superacid sites as shown by a desorption temperature peak in the NH{sub 3} TPD at ca. 813 K. The activity and selectivity of these catalysts have been studied for the alkylation of isobutane with trans-2 butene in a computer-controlled continuous fixed bed reactor coupled with a sampling system which allows to make differential analysis of the products from very short reaction times. In this way, the influence of the main process variables, i.e, time on stream, reaction temperature, olefin WHSV, and isoparaffin/olefin ratio, on the 2-butene conversation and product distribution has been investigated. Cracking of larger carbocations and alkylation of isobutane with 2-butene to give trimethylpentanes were the predominant reactions occurring on the superacid catalyst in the initial stages of the reaction. The alkylation/cracking ratio increased when decreasing reaction temperature. A fast catalyst decay with time on stream was also observed, and this was accompanied by an increase in the oligomerization of butene. 23 refs., 5 figs., 4 tabs.

  5. [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.

  6. 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.

  7. Quantum mechanics/molecular mechanics modeling of covalent addition between EGFR-cysteine 797 and N-(4-anilinoquinazolin-6-yl) acrylamide.

    Science.gov (United States)

    Capoferri, Luigi; Lodola, Alessio; Rivara, Silvia; Mor, Marco

    2015-03-23

    Irreversible epidermal growth factor receptor (EGFR) inhibitors can circumvent resistance to first-generation ATP-competitive inhibitors in the treatment of nonsmall-cell lung cancer. They covalently bind a noncatalytic cysteine (Cys797) at the surface of EGFR active site by an acrylamide warhead. Herein, we used a hybrid quantum mechanics/molecular mechanics (QM/MM) potential in combination with umbrella sampling in the path-collective variable space to investigate the mechanism of alkylation of Cys797 by the prototypical covalent inhibitor N-(4-anilinoquinazolin-6-yl) acrylamide. Calculations show that Cys797 reacts with the acrylamide group of the inhibitor through a direct addition mechanism, with Asp800 acting as a general base/general acid in distinct steps of the reaction. The obtained reaction free energy is negative (ΔA = -12 kcal/mol) consistent with the spontaneous and irreversible alkylation of Cys797 by N-(4-anilinoquinazolin-6-yl) acrylamide. Our calculations identify desolvation of Cys797 thiolate anion as a key step of the alkylation process, indicating that changes in the intrinsic reactivity of the acrylamide would have only a minor impact on the inhibitor potency.

  8. Rh-Catalyzed Annulations of N-Methoxybenzamides and Ketenimines: Sterically and Electronically Controlled Synthesis of Isoquinolinones and Isoindolinones.

    Science.gov (United States)

    Zhou, Xiaorong; Zhang, Zhiyin; Zhao, Hongyang; Lu, Ping; Wang, Yanguang

    2017-04-07

    Rhodium-catalyzed C-H activation/annulation reactions of ketenimines with N-methoxybenzamides are reported. The outcome of reactions is dependent on the structure of ketenimines. The β-alkyl-substituted ketenimines furnish 3-iminoisoquinolin-1(2H)-ones in a formal [4 + 2] annulation manner, while the β-ester substituted ketenimines afford 3-aminoisoindolin-1-ones in a formal [4 + 1] annulation manner. The synthesized [4 + 2] products undergo an intramolecular Cu-catalyzed C-N coupling to be converted to benzo[4,5]imidazo[1,2-b]isoquinolin-11-ones, which can be directly prepared from ketenimines and N-methoxybenzamides by a one-pot Rh-catalyzed annulation/Cu-catalyzed C-N coupling sequence.

  9. 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.

  10. Synthesis and stereochemical assignments of diastereomeric Ni(II complexes of glycine Schiff base with (R-2-(N-{2-[N-alkyl-N-(1-phenylethylamino]acetyl}aminobenzophenone; a case of configurationally stable stereogenic nitrogen

    Directory of Open Access Journals (Sweden)

    Hiroki Moriwaki

    2014-02-01

    Full Text Available A family of chiral ligands derived from α-phenylethylamine and 2-aminobenzophenone were prepared by alkylation of the nitrogen atom. Upon reaction with glycine and a Ni(II salt, these ligands were transformed into diastereomeric complexes, as a result of the configurational stability of the stereogenic nitrogen atom. Different diastereomeric ratios were observed depending on the substituent R introduced in the starting ligand, and stereochemical assignments were based on X-ray analysis, along with NMR studies and optical rotation measurements.

  11. Activation of protein kinase A and clustering of cell surface receptors by N-methyl-N'-nitro-N-nitrosoguanidine are independent of genomic DNA damage

    Energy Technology Data Exchange (ETDEWEB)

    Wang Zheng; Wang Guliang; Yang Jun; Guo Lei; Yu Yingnian

    2003-07-25

    Alkylating agent N-methyl-N'-nitro-N-nitrosoguanidine (MNNG) induces cellular stress leading to chromosomal aberrations, mutations and cell death. Previous reports from our laboratory have shown that low concentration of MNNG induces untargeted mutation (UTM), which occurs on intact DNA in mammalian cells through changes in gene expression profile. It also causes the activation of cAMP-protein kinase A (PKA) and up-regulation of POL-{beta}, which is demonstrated to play a role in DNA repair system. In order to find out the possible initial signal involved in UTM, we try to investigate whether the activation of PKA-CREB signal pathway is closely related to DNA damage. Our data shows that the treatment of low concentration MNNG (0.2 {mu}M) activates PKA-CREB pathway in a comparable level both in a nuclear and enucleated cell system. And similar to the cell response caused by UV, the clustering of cell surface receptors of epidermal growth factor (EGF) and tumor necrosis factor {alpha} (TNF{alpha}) was also observed in cells exposed to MNNG. It was further demonstrated that the clustering of the surface receptors is independent of the genomic DNA damage, as this phenomenon was also observed in enucleated cells. These observations indicate that the initiation of signal cascades induced by low concentration of MNNG might be associated with its interaction with cell surface receptors and/or direct activation of related signal proteins but not its DNA damaging property.

  12. Enzymatic removal of O6-ethylguanine from mitochondrial DNA in rat tissues exposed to N-ethyl-N-nitrosourea in vivo

    International Nuclear Information System (INIS)

    Satoh, M.S.; Huh, N.; Rajewsky, M.F.; Kuroki, T.

    1988-01-01

    DNA repair is essential for maintaining the integrity of the genetic material, and a number of DNA repair mechanisms have been fairly well characterized for the nuclear DNA of eukaryotic cells as well as prokaryotes. However, little is know about DNA repair in mitochondria. Using highly sensitive immunoanalytical methods to detect specific DNA alkylation products, the authors found active removal of O 6 -ethyl-2'-deoxyguanosine (O 6 -EtdGuo) from rat liver mitochondrial DNA after pulse-exposure to N-ethyl-N-nitrosourea in vivo. In the kidney, O 6 -EtdGuo was removed from mitochondrial DNA with moderate efficiency, but nearly no removal was observed from the DNA of brain mitochondria. Among the rat tissues examined, the kinetics of O 6 -EtdGuo elimination from mitochondrial DNA was very similar to the kinetics of removal from nuclear DNA. O 4 -Ethyl-2'-deoxythymidine, another premutagenic DNA ethylation product, was stable in both mitochondrial and nuclear DNA of rat liver

  13. N,N'-Diethyl-N,N'-diphenylpyridine-2,6-dicarboxamide

    Czech Academy of Sciences Publication Activity Database

    Klepetářová, Blanka; Makrlík, E.; Babain, V.A.; Kašička, Václav

    2012-01-01

    Roč. 68, č. 4 (2012), o1099-o1100 ISSN 1600-5368 Grant - others:GA ČZU(CZ) 42900/1312/3114 Institutional research plan: CEZ:AV0Z40550506 Keywords : N,N'-Diethyl-N,N'-diphenylpyridine-2,6-dicarboxamide * crystal structure * amide nitrogen Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 0.347, year: 2011

  14. Synthesis and DNA cleavage activity of Bis-3-chloropiperidines as alkylating agents.

    Science.gov (United States)

    Zuravka, Ivonne; Roesmann, Rolf; Sosic, Alice; Wende, Wolfgang; Pingoud, Alfred; Gatto, Barbara; Göttlich, Richard

    2014-09-01

    Nitrogen mustards are an important class of bifunctional alkylating agents routinely used in chemotherapy. They react with DNA as electrophiles through the formation of highly reactive aziridinium ion intermediates. The antibiotic 593A, with potential antitumor activity, can be considered a naturally occurring piperidine mustard containing a unique 3-chloropiperidine ring. However, the total synthesis of this antibiotic proved to be rather challenging. With the aim of designing simplified analogues of this natural product, we developed an efficient bidirectional synthetic route to bis-3-chloropiperidines joined by flexible, conformationally restricted, or rigid diamine linkers. The key step involves an iodide-catalyzed double cyclization of unsaturated bis-N-chloroamines to simultaneously generate both piperidine rings. Herein we describe the synthesis and subsequent evaluation of a series of novel nitrogen-bridged bis-3-chloropiperidines, enabling the study of the impact of the linker structure on DNA alkylation properties. Our studies reveal that the synthesized compounds possess DNA alkylating abilities and induce strand cleavage, with a strong preference for guanine residues. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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...

  16. Highly Selective Separation of Carbon Dioxide from Nitrogen and Methane by Nitrile/Glycol-Difunctionalized Ionic Liquids in Supported Ionic Liquid Membranes (SILMs)

    OpenAIRE

    Hojniak, Sandra D.; Silverwood, Ian P.; Laeeq Khan, Asim; Vankelecom, Ivo F.J.; Dehaen, Wim; Kazarian, Sergei G.; Binnemans, Koen

    2014-01-01

    Novel difunctionalized ionic liquids (ILs) containing a triethylene glycol monomethyl ether chain and a nitrile group on a pyrrolidinium or imidazolium cation have been synthesized and incorporated into supported ionic liquid membranes (SILMs). These ILs exhibit ca. 2.3 times higher CO2/N2 and CO2/CH4 gas separation selectivities than analogous ILs functionalized only with a glycol chain. Although the glycol moiety ensures room temperature liquidity of the pyrrolidinium and imidazolium ILs, t...

  17. CC-1065 and the duocarmycins: unraveling the keys to a new class of naturally derived DNA alkylating agents.

    Science.gov (United States)

    Boger, D L; Johnson, D S

    1995-01-01

    Key studies defining the DNA alkylation properties and selectivity of a new class of exceptionally potent, naturally occurring antitumor antibiotics including CC-1065, duocarmycin A, and duocarmycin SA are reviewed. Recent studies conducted with synthetic agents containing deep-seated structural changes and the unnatural enantiomers of the natural products and related analogs have defined the structural basis for the sequence-selective alkylation of duplex DNA and fundamental relationships between chemical structure, functional reactivity, and biological properties. The agents undergo a reversible, stereoelectronically controlled adenine-N3 addition to the least substituted carbon of the activated cyclopropane within selected AT-rich sites. The preferential AT-rich non-covalent binding selectivity of the agents within the narrower, deeper AT-rich minor groove and the steric accessibility to the alkylation site that accompanies deep AT-rich minor groove penetration control the sequence-selective DNA alkylation reaction and stabilize the resulting adduct. For the agents that possess sufficient reactivity to alkylate DNA, a direct relationship between chemical or functional stability and biological potency has been defined. Images Fig. 1 Fig. 2 PMID:7731958

  18. Molecular characterization of an adaptive response to alkylating agents in the opportunistic pathogen Aspergillus fumigatus.

    Science.gov (United States)

    O'Hanlon, Karen A; Margison, Geoffrey P; Hatch, Amy; Fitzpatrick, David A; Owens, Rebecca A; Doyle, Sean; Jones, Gary W

    2012-09-01

    An adaptive response to alkylating agents based upon the conformational change of a methylphosphotriester (MPT) DNA repair protein to a transcriptional activator has been demonstrated in a number of bacterial species, but this mechanism appears largely absent from eukaryotes. Here, we demonstrate that the human pathogen Aspergillus fumigatus elicits an adaptive response to sub-lethal doses of the mono-functional alkylating agent N-methyl-N'-nitro-N-nitrosoguanidine (MNNG). We have identified genes that encode MPT and O(6)-alkylguanine DNA alkyltransferase (AGT) DNA repair proteins; deletions of either of these genes abolish the adaptive response and sensitize the organism to MNNG. In vitro DNA repair assays confirm the ability of MPT and AGT to repair methylphosphotriester and O(6)-methylguanine lesions respectively. In eukaryotes, the MPT protein is confined to a select group of fungal species, some of which are major mammalian and plant pathogens. The evolutionary origin of the adaptive response is bacterial and rooted within the Firmicutes phylum. Inter-kingdom horizontal gene transfer between Firmicutes and Ascomycete ancestors introduced the adaptive response into the Fungal kingdom. Our data constitute the first detailed characterization of the molecular mechanism of the adaptive response in a lower eukaryote and has applications for development of novel fungal therapeutics targeting this DNA repair system.

  19. Optical absorption and photoconductivity in iodine-excess ionic liquids: the case of 1-alkyl-3-methyl imidazolium iodides.

    Science.gov (United States)

    Aono, Masami; Miyazaki, Hisashi; Takekiyo, Takahiro; Tsuzuki, Seiji; Abe, Hiroshi

    2018-02-21

    We investigated the optical absorption and photoconductivity of iodine-excess ionic liquids (ILs) based on 1-alkyl-3-methyl imidazolium iodide ([C n mim][I]; n = 3, 4, and 6). The iodide concentration m was 2 ≦ m ≦ 8, which was determined by the molar fraction [C n mim] +  : [I m ] - = 1 : m. By adding iodine, an absorption edge shifted from 282 nm in the UV region to around 600 nm in the visible-light region. The optical bandgaps E o decreased gradually from 2.3 eV to 1.9 eV with increasing m from 2 to 8. The alkyl-side chain lengths of the cations have little effect on the E o . This experimental result was confirmed by ab initio molecular orbital calculations. The effects were reflected in the photoconductivity of the ILs, as expected. [C 4 mim][I m ] exhibited greater photo-induced electron generation compared with [C 3 mim][I m ] and [C 6 mim][I m ]. The photoconductivity in both [C 3 mim][I m ] and [C 6 mim][I m ] increased slightly with increasing m. The trend of photoconductivity in [C 4 mim][I m ] exhibited an N-shaped form. The highest photoconductivity 1.6 was observed in [C 4 mim][I 8 ].

  20. Identification in the mu-opioid receptor of cysteine residues responsible for inactivation of ligand binding by thiol alkylating and reducing agents.

    Science.gov (United States)

    Gaibelet, G; Capeyrou, R; Dietrich, G; Emorine, L J

    1997-05-19

    Inactivation by thiol reducing and alkylating agents of ligand binding to the human mu-opioid receptor was examined. Dithiothreitol reduced the number of [3H]diprenorphine binding sites. Replacement by seryl residues of either C142 or C219 in extracellular loops 1 and 2 of the mu receptor resulted in a complete loss of opioid binding. A disulfide bound linking C142 to C219 may thus be essential to maintain a functional conformation of the receptor. We also demonstrated that inactivation of ligand binding upon alkylation by N-ethylmaleimide occurred at two sites. Alteration of the more sensitive (IC50 = 20 microM) did not modify antagonists binding but decreased agonist affinity almost 10-fold. Modification of the less reactive site (IC50 = 2 mM) decreased the number of both agonist and antagonist binding sites. The alkylation site of higher sensitivity to N-ethylmaleimide was shown by mutagenesis experiments to be constituted of both C81 and C332 in transmembrane domains 1 and 7 of the mu-opioid receptor.

  1. Spectral and thermodynamic properties for the exciplexes of N-alkyl carbazoles with dicyanobenzenes in THF

    Science.gov (United States)

    Asim, Sadia; Mansha, Asim; Landgraf, Stephan; Grampp, Günter; Zahid, Muhammad; Bhatti, Haq Nawaz

    2014-01-01

    The exciplex emission spectra of N-ethylcarbazole with 1,2-dicyanobenzene (NEC/1,2-DCB), N-methylcarbazole with 1,2-dicyanobenzene (NMC/1,2-DCB), 1,3-dicyanobenzene (NMC/1,3-DCB), and 1,4-dicyanobenzene (NMC/1,4-DCB) are studied in tetrahydrofuran (THF) for the temperature range starting from 253 K to 334 K. Thermochromic shifts along with the spectral properties including change in peak intensities and the ratio of exciplex peak intensity to fluorophore peak intensity are studied. Effect of temperature on the energy of zero-zero transitions hνo‧, Huang-Rhys factor (S), Gauss broadening of vibronic level (σ) and the dominant high-frequency vibration (hνν) are also part of investigation. Enthalpy of exciplex formation (ΔHEX∗) calculated by the model proposed by A. Weller and the Gibb's energy of electron transfer (ΔGet∗) for all exciplex systems are also discussed in the present paper. All the exciplexes under study were observed to be dipolar in nature. The exciplex of the N-methylcarbazole/1,4-dicyanobenzene was found to be the most stable and the N-methylcarbazole/1,3-dicyanobenzene was the weakest exciplex system.

  2. Photogeneration and reactivity of naphthoquinone methides as purine selective DNA alkylating agents.

    Science.gov (United States)

    Verga, Daniela; Nadai, Matteo; Doria, Filippo; Percivalle, Claudia; Di Antonio, Marco; Palumbo, Manlio; Richter, Sara N; Freccero, Mauro

    2010-10-20

    A one-step protecting-group-free synthesis of both 6-hydroxy-naphthalene-2-carbaldehyde and the bifunctional binaphthalenyl derivative afforded 6-hydroxymethylnaphthalen-2-ol, 6-methylaminomethyl-naphthalen-2-ol, [(2-hydroxy-3-naphthyl)methyl]trimethyl ammonium iodide, and a small library of bifunctional binol analogues in good yields. Irradiation of naphthol quaternary ammonium salt and binol-derivatives (X = OH, NHR, NMe(3)(+), OCOCH(3), and L-proline) at 310 and 360 nm resulted in the photogeneration of the 2,6-naphthoquinone-6-methide (NQM) and binol quinone methide analogues (BQMs) by a water-mediated excited-state proton transfer (ESPT). The hydration, the mono- and bis-alkylation reactions of morpholine and 2-ethanethiol, as N and S prototype nucleophiles, by the transient NQM (λ(max) 310, 330 nm) and BQMs (λ(max) 360 nm) were investigated in water by product distribution analysis and laser flash photolysis (LFP). Both the photogeneration and the reactivity of NQM and BQMs exhibited striking differences. BQMs were at least 2 orders of magnitude more reactive than NQM, and they were generated much more efficiently from a greater variety of photoprecursors including the hydroxymethyl, quaternary ammonium salt and several binol-amino acids. On the contrary, the only efficient precursor of NQM was the quaternary ammonium salt. All water-soluble BQM precursors were further investigated for their ability to alkylate and cross-link plasmid DNA and oligonucleotides by gel electrophoresis: the BQMs were more efficient than the isomeric o-BQM (binol quinone methide analogue of 2,3-naphthoquinone-3-methide). Sequence analysis by gel electrophoresis, HPLC, and MS showed that the alkylation occurred at purines, with a preference for guanine. In particular, a BQM was able to alkylate N7 of guanines resulting in depurination at the oligonucleotide level, and ribose loss at the nucleotide level. The photoreactivity of BQM precursors translated into photocytotoxic and

  3. Alkylarylnitrosoureas--stability in aqueous solution, partition coefficient, alkylating activity and its relationship to SCE induction in Chinese hamster V 79-E cells.

    Science.gov (United States)

    Mendel, J; Thust, R; Schwarz, H

    1982-01-01

    The alkylating activity, chemical stability in aqueous solution (pH 7.0; 37 degrees C), and partition coefficient (octanol/water) of the following compounds were determined: 1-methyl-3-phenyl-1-nitrosourea (MPNU), 1-ethyl-3-phenyl-1-nitrosourea (EPNU), 1-isopropyl-3-phenyl-1-nitrosourea (i-PrPNU), 1-methyl-3-(p-fluorophenyl)-1-nitrosourea (F-MPNU), 1-methyl-3-(p-chlorophenyl)-1-nitrosourea (Cl-MPNU), 1-methyl-3-(p-bromophenyl)-1-nitrosourea (Br-MPNU), 1,3-dimethyl-3-phenyl-1-nitrosourea (DMPNU), and 1-methyl-3-naphthyl-1-nitrosocarbamate (NCA). 1-Methyl-1-nitrosourea (MNU) and 1-ethyl-1-nitrosourea (ENU) were used for the comparison. THe rate of decomposition in aqueous solution is discussed concerning the influences of the substituents at the 1- and 3-N-atom. The mono- and disubstituted N-nitrosoureas showed a coarse correlation between alkylating activity and SCE induction in Chinese hamster V 79-E cells. On the other hand, this correlation is missing in the case of NCA, which is a potent SCE inducer despite relatively low alkylating activity. DMPNU is the strongest SCE inducer, but this compound shows a high stability in aqueous solution and, consequently, we were not able to detect an alkylating activity.

  4. 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.

  5. Ascorbic Acid-Initiated Tandem Radical Cyclization of N-Arylacrylamides to Give 3,3-Disubstituted Oxindoles

    Directory of Open Access Journals (Sweden)

    Sheng Liu

    2015-08-01

    Full Text Available An ascorbic acid-promoted and metal-free tandem room temperature cyclization of N-arylacrylamides with 4-nitrobenzenediazonium generated in situ was developed. This reaction proceeds smoothly through a radical mechanism and provides an environmentally friendly alternative approach to biologically active 3-alkyl-3-benzyloxindoles, avoiding the use of excess oxidants and light irradiation.

  6. Release of the cyano moiety in the crystal structure of N-cyanomethyl-N-(2-methoxyethyl)-daunomycin complexed with d(CGATCG).

    Science.gov (United States)

    Saminadin, P; Dautant, A; Mondon, M; Langlois D'estaintot, B; Courseille, C; Précigoux, G

    2000-01-01

    Doxorubicin is among the most widely used anthracycline in cancer chemotherapy. In an attempt to avoid the cardiotoxicity and drug resistance of doxorubicin therapy, several analogues were synthesized. The cyanomorpholinyl derivative is the most cytotoxic. They differ greatly from their parent compound in their biological and pharmacological properties, inducing cross-links in drug DNA complexes. The present study concerns N-cyanomethyl-N-(2-methoxyethyl)-daunomycin (CMDa), a synthetic analogue of cyanomorpholino-daunomycin. Compared to doxorubicin, CMDa displays a cytotoxic activity on L1210 leukemia cells at higher concentration but is effective on doxorubicin resistant cells. The results of fluorescence quenching experiments as well as the melting temperature (DeltaTm = 7.5 degrees C) studies are consistent with a drug molecule which intercalates between the DNA base pairs and stabilizes the DNA double helix. The crystal structure of CMDa complexed to the hexanucleotide d(CGATCG) has been determined at 1.5 A resolution. The complex crystallizes in the space group P41212 and is similar to other anthracycline-hexanucleotide complexes. In the crystal state, the observed densities indicate the formation of N-hydroxymethyl-N-(2-methoxyethyl)-daunomycin (HMDa) with the release of the cyano moiety without DNA alkylation. The formation of this degradation compound is discussed in relation with other drug modifications when binding to DNA. Comparison with two other drug-DNA crystal structures suggests a correlation between a slight change in DNA conformation and the nature of the amino sugar substituents at the N3' position located in the minor groove.

  7. Abnormal sensitivity of skin fibroblasts from familial polyposis patients to DNA alkylating agents

    International Nuclear Information System (INIS)

    Barfknecht, T.R.; Little, J.B.

    1982-01-01

    Fibroblast cell strains derived from different patients all afflicted with genetic predisposing to the development of intestinal polyposis and cancer were tested for their sensitivity to the lethal effects of the DNA alkylating agents methylmethanesulfonate (MMS), ethyl methanesulfonate, N-methyl-N'-nitro-N-nitrosoguanidine, and 4-nitroquinoline 1-oxide. The genetic syndromes studied were: (a) adenomatosis of the colon and rectum only, an autosomal dominant trait; (b) Turcot's syndrome, a rare autosomal recessive polyposis syndrome also characterized by central nervous system tumors; and (c) Gardner's syndrome, an autosomal dominant syndrome which, in addition to intestinal polyposis, is also clinically characterized by osteomas and soft tissue tumors. Fibroblasts from a patient with Turcot's syndrome were hypersensitive to MMS, having a D0 value of 0.24 mM (p less than 0.01) versus the normal average D0 of 0.36 mM and a D10 value of 0.95 mM (p less than 0.01) compared with the normal average value of 1.3 mM. Fibroblasts from the Gardner's syndrome proband were moderately sensitive to MMS, ethyl methanesulfonate, and N-methyl-N'-nitro-N-nitrosoguanidine due to significant differences of D10 values of 0.60 mM (p less than 0.01), 15 mM (p less than 0.01), and 4.8 microM (p less than 0.025), respectively, versus the normal average values of 1.3 mM, 28 mM, and 9.4 microM. Fibroblasts from the clinically affected Gardner's syndrome daughter of the proband were significantly more sensitive to MMS treatment, D0 of 0.22 mM (p less than 0.01) versus the normal average D0 of 0.36 mM and a D10 of 0.97 mM (p less than 0.01) versus the normal average. This differential sensitivity to the several DNA alkylating agents suggests that different mechanisms of hypersensitivity to these chemicals may be associated with fibroblasts from the various forms of familial polyposis

  8. Cell Fate of Müller Cells During Photoreceptor Regeneration in an N-Methyl-N-nitrosourea-Induced Retinal Degeneration Model of Zebrafish.

    Science.gov (United States)

    Ogai, Kazuhiro; Hisano, Suguru; Sugitani, Kayo; Koriyama, Yoshiki; Kato, Satoru

    2016-01-01

    Zebrafish can regenerate several organs such as the tail fin, heart, central nervous system, and photoreceptors. Very recently, a study has demonstrated the photoreceptor regeneration in the alkylating agent N-methyl-N-nitrosourea (MNU)-induced retinal degeneration (RD) zebrafish model, in which whole photoreceptors are lost within a week after MNU treatment and then regenerated within a month. The research has also shown massive proliferation of Müller cells within a week. To address the question of whether proliferating Müller cells are the source of regenerating photoreceptors, which remains unknown in the MNU-induced zebrafish RD model, we employed a BrdU pulse-chase technique to label the proliferating cells within a week after MNU treatment. As a result of the BrdU pulse-chase technique, a number of BrdU(+) cells were observed in the outer nuclear layer as well as the inner nuclear layer. This implies that regenerating photoreceptors are derived from proliferating Müller cells in the zebrafish MNU-induced RD model.

  9. Reichardt's dye and its reactions with the alkylating agents 4-chloro-1-butanol, ethyl methanesulfonate, 1-bromobutane and Fast Red B - a potentially useful reagent for the detection of genotoxic impurities in pharmaceuticals.

    Science.gov (United States)

    Corrigan, Damion K; Whitcombe, Michael J; McCrossen, Sean; Piletsky, Sergey

    2009-04-01

    Alkylating agents are potentially genotoxic impurities that may be present in drug products. These impurities occur in pharmaceuticals as by-products from the synthetic steps involved in drug production, as impurities in starting materials or from in-situ reactions that take place in the final drug product. Currently, analysis for genotoxic impurities is typically carried out using either HPLC/MS or GC/MS. These techniques require specialist expertise, have long analysis times and often use sample clean-up procedures. Reichardt's dye is well known for its solvatochromic properties. In this paper the dye's ability to undergo alkylation is reported. The reaction between Reichardt's dye and alkylating agents such as 4-chloro-1-butanol and ethyl methanesulfonate was monitored spectrophotometrically at 618 nm in acetonitrile and 624 nm in N,N-dimethylformamide. Changes in absorption were observed using low levels of alkylating agent (5-10 parts per million). Alkylation of the dye with 4-chloro-1-butanol and ethyl methanesulfonate was confirmed. Reichardt's dye, and its changing UV absorption, was examined in the presence of paracetamol (10 and 100 mg/ml). Whilst the alkylation-induced changes in UV absorption were not as pronounced as with standard solutions, detection of alkylation was still possible. Using standard solutions and in the presence of a drug matrix, Reichardt's dye shows promise as a reagent for detection of low levels of industrially important alkylating agents.

  10. Analysis of products of thymine irradiated by 18O8+ ion beam in N2O saturated aqueous solution

    International Nuclear Information System (INIS)

    Cai Xichen; Wei Zengquan; Li Wenjian; Liang Jianping; Li Qiang

    1999-01-01

    Some methods of capillary gas chromatography, such as GC, GC-MS GC-FT-IR, are used to analyze the products of thymine irradiated by 18 O 8+ ion beam in N 2 O saturated aqueous solution. From the results of GC-MS the molecular weight of products can be determined, and from the results of GC-FT-IR some molecular structure information of products can be obtained. By this way the products, 5,6-Dihydro-thymine, 5-Hydroxyl-5-Methylhydantoin, 5-Hydroxyl-6-Hydro-thymine, 5-Hydro-6-Hydroxyl thymine, 5-Hydroxymethyluracil, Trans-Thymine glycol, Cis-Thymine glycol and dimers are determined without separation of them from samples. Though these products are as same as those products of thymine irradiated by γ rays in N 2 O saturated aqueous solution, the mechanism of thymine irradiated by heavy ion beam in aqueous solution is different from that by γ rays. The main products of thymine irradiated by 18 O 8+ ion beam in N 2 O saturated aqueous solution are hydroxyl adducts at 5-6 band of thymine, while the main products of thymine irradiated by γ ray in N 2 O saturated aqueous solution are dimers of thymine

  11. 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.

  12. Mutagenic effects of alkylating agents on prophage lambda

    Energy Technology Data Exchange (ETDEWEB)

    Bresler, S.; Kalinin, V.L.; Kuznetsova, L.V.

    1984-06-01

    An evaluation was made of the relative contribution of repair and reparative mechanisms to the mutagenic potency of several alkylating agents on thermoinducible prophage lambdacI857 ind/sup -/ in several stains of E. coli. Following treatment of lysogenic E. coli with the mutagens and heat induction, 0.02 N-nitroso-N-methylurea (NMU) induced c mutations with a high frequency (ca. 10%) in both wild type E. coli and cells with repair mutations (recA13, lexA102, uvrA6, umuC36, xthA9, recF143, polA1, uvrD3, uvrD502). It appears that NUM-induced mutations are stabilized as replicative errors due to mismatched, altered bases. Delay in induction following exposure to NMU improves prophage survival and diminishes c mutant formation, regardless of the E. coli genotype. Evidently, carbamoylation is not involved in NMU mutagenicity since 0.02 M KNCO is nonmutagenic and is virtually without effect on prophage viability. Replicative mechanisms are also involved in N-methyl-N'-nitro-N-nitrosoguanidine (15%) and ethyl methanesulfonate (2%) induced mutations, since the maximum yield of mutants was independent of recA/sup +/ genotype. However, the mutagenicity of methyl methanesulfonate was abolished by the recA mutation, indicating that the mutagenicity of this agent is repair-dependent. Mitomycin C (0.1%) and acridine mustard (0.3%) induce c mutations regardless of recA/sup +/ and, therefore, appear to do so by intercalation. 26 references, 6 figures.

  13. Anticancer activity of botanical alkyl hydroquinones attributed to topoisomerase II poisoning

    International Nuclear Information System (INIS)

    Huang, C.-P.; Fang, W.-H.; Lin, L.-I.; Chiou, Robin Y.; Kan, L.-S.; Chi, N.-H.; Chen, Y.-R.; Lin, T.-Y.; Lin, S.-B.

    2008-01-01

    Cytotoxic alkyl hydroquinone compounds have been isolated from many plants. We previously isolated 3 structurally similar cytotoxic alkyl hydroquinone compounds from the sap of the lacquer tree Rhus succedanea L. belonging to the sumac family, which have a long history of medicinal use in Asia. Each has an unsaturated alkyl chain attached to the 2-position of a hydroquinone ring. One of these isolates, 10'(Z),13'(E),15'(E)-heptadecatrienylhydroquinone [HQ17(3)], being the most cytotoxic, was chosen for studying the anticancer mechanism of these compounds. We found that HQ17(3) was a topoisomerase (Topo) II poison. It irreversibly inhibited Topo IIα activity through the accumulation of Topo II-DNA cleavable complexes. A cell-based assay showed that HQ17(3) inhibited the growth of leukemia HL-60 cells with an EC 50 of 0.9 μM, inhibited the topoisomerase-II-deficient cells HL-60/MX2 with an EC 50 of 9.6 μM, and exerted no effect on peripheral blood mononuclear cells at concentrations up to 50 μM. These results suggest that Topo II is the cellular drug target. In HL-60 cells, HQ17(3) promptly inhibited DNA synthesis, induced chromosomal breakage, and led to cell death with an EC 50 about one-tenth that of hydroquinone. Pretreatment of the cells with N-acetylcysteine could not attenuate the cytotoxicity and DNA damage induced by HQ17(3). However, N-acetylcysteine did significantly reduce the cytotoxicity of hydroquinone. In F344 rats, intraperitoneal injection of HQ17(3) for 28 days induced no clinical signs of toxicity. These results indicated that HQ17(3) is a potential anticancer agent, and its structural features could be a model for anticancer drug design

  14. Manipulating the morphology and textural property of γ-AlOOH by modulating the alkyl chain length of cation in ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Zhe, E-mail: tangzhe1983@163.com; Hu, Xiaofu, E-mail: hjj19850922@126.cn; Liang, Jilei, E-mail: liang.jilei_ttplan@126.com; Zhao, Jinchong, E-mail: Dr.zhaojc@gmail.com; Liu, Yunqi, E-mail: liuyq@upc.edu.cn; Liu, Chenguang, E-mail: cgliu@upc.edu.cn

    2013-06-01

    Graphical abstract: - Highlights: • γ-AlOOH was the only product in all experiments. • Different morphology of γ-AlOOH was obtained according to the alkyl chain length. • The textural property of γ-AlOOH was changed according to the alkyl chain length. • The possible formation mechanisms for hollow sphere and microflower were proposed. - Abstract: We demonstrated that the morphology and textural property of γ-AlOOH can be tuned by modulating the alkyl chain length of cation in [C{sub n}mim]{sup +}Cl{sup −} (n = 4, 8, 16). Using the short alkyl chain length-based [C{sub 4}mim]{sup +}Cl{sup −} as the structure-directed reagent, the morphology of γ-AlOOH was not changed and preserved as the hollow sphere structure in all experiments. The specific area and the number of small meso-pores of γ-AlOOH increased with the increase of [C{sub 4}mim]{sup +}Cl{sup −} dosage. While, using the larger alkyl chain length-based ionic liquids as the soft-template, such as [C{sub 8}mim]{sup +}Cl{sup −} and [C{sub 16}mim]{sup +}Cl{sup −}, the morphologies of γ-AlOOH were changed from initiative hollow spheres into the final microflowers. The specific areas of γ-AlOOH firstly increased then decreased with the increase of their dosage. The samples were characterized by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscope (SEM) and Transmission Electron Microscopy (TEM). Furthermore, the possible formation mechanisms of γ-AlOOH have been proposed.

  15. Summertime C1-C5 alkyl nitrates over Beijing, northern China: Spatial distribution, regional transport, and formation mechanisms

    Science.gov (United States)

    Sun, Jingjing; Li, Zeyuan; Xue, Likun; Wang, Tao; Wang, Xinfeng; Gao, Jian; Nie, Wei; Simpson, Isobel J.; Gao, Rui; Blake, Donald R.; Chai, Fahe; Wang, Wenxing

    2018-05-01

    Alkyl nitrates (RONO2) are an important class of nitrogen oxides reservoirs in the atmosphere and play a key role in tropospheric photochemistry. Despite the increasing concern for photochemical air pollution over China, the knowledge of characteristics and formation mechanisms of alkyl nitrates in this region is limited. We analyzed C1-C5 alkyl nitrates measured in Beijing at a polluted urban site in summer 2008 and at a downwind rural site in summers of both 2005 and 2008. Although the abundances of NOx and hydrocarbons were much lower at the rural site, the mixing ratios of RONO2 were comparable between both sites, emphasizing the regional nature of alkyl nitrate pollution. Regional transport of urban plumes governed the elevated RONO2 levels at the rural site. The concentrations of C1-C2 RONO2 were significantly higher at the rural site in 2008 compared to 2005 despite a decline in NOx and anthropogenic VOCs, mainly owing to enhanced contributions from biogenic VOCs. The photochemical formation regimes of RONO2 were evaluated by both a simplified sequential reaction model and a detailed master chemical mechanism box model. The observed C4-C5 RONO2 levels can be well explained by the photochemical degradation of n-butane and n-pentane, while the sources of C1-C3 RONO2 were rather complex. In addition to the C1-C3 alkanes, biogenic VOCs and reactive aromatics were also important precursors of methyl nitrate, and alkenes and long-chain alkanes contributed to the formation of C2-C3 RONO2. This study provides insights into the spatial distribution, inter-annual variation and photochemical formation mechanisms of alkyl nitrate pollution over the Beijing area.

  16. New validated LC-MS/MS method for the determination of three alkylated adenines in human urine and its application to the monitoring of alkylating agents in cigarette smoke.

    Science.gov (United States)

    Tian, Yongfeng; Hou, Hongwei; Zhang, Xiaotao; Wang, An; Liu, Yong; Hu, Qingyuan

    2014-09-01

    A highly specific liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for simultaneous determination of urinary N(3)-methyladenine (N(3)-MeA), N(3)-ethyladenine (N(3)-EtA), and N(3)-(2-hydroxyethyl)adenine (N(3)-HOEtA). Chromatographic separation was achieved on a hydrophilic interaction liquid chromatography column, with a mobile phase gradient prepared from aqueous 10 mM ammonium formate-acetonitrile (5:95 v/v, pH 4.0). Quantification of the analytes was done by multiple reaction monitoring using a triple-quadrupole mass spectrometer in positive-ionization mode. The limits of quantification were 0.13, 0.02, and 0.03 ng/mL for N(3)-MeA, N(3)-EtA, and N(3)-HOEtA, respectively. Intraday and interday variations (relative standard deviations) ranged from 0.6 to 1.3 % and from 3.7 to 7.5 %. The recovery ranges of N(3)-MeA, N(3)-EtA, and N(3)-HOEtA in urine were 80.1-97.3 %, 83.3-90.0 %, and 100.0-110.0 %, respectively. The proposed method was successfully applied to urine samples from 251 volunteers including 193 regular smokers and 58 nonsmokers. The results showed that the levels of urinary N(3)-MeA, N(3)-EtA, and N(3)-HOEtA in smokers were significantly higher than those in nonsmokers. Furthermore, the level of urinary N(3)-MeA in smokers was found to be positively correlated with the level of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (r = 0.48, P alkylating agent exposure.

  17. OXIDATIVE ALKYLATION OF (ETA-5-C5ME5)2TIR (R=CL, ME, ET, CH=CH2, PH, OME, N=C(H)TERT-BU) TO (ETA-5-C5ME5)2TI(ME)R BY GROUP-12 ORGANOMETALLIC COMPOUNDS MME2

    NARCIS (Netherlands)

    LUINSTRA, GA; TEUBEN, JH

    1991-01-01

    Oxidative alkylation of Cp*2TiX (Cp*: eta-5-C5Me5; X = OMe, Cl, N = C(H)tBu) and Cp*2TiMe by CdMe2 or ZnMe2 gives diamagnetic Cp*2Ti(Me)X and Cp*2TiMe2 respectively, and cadmium or zinc. The reactions of Cp*2TiR (R = Et, CH = CH2, Ph) with MMe2 (M = Cd, Zn) give statistical mixtures of Cp*2Ti(Me)R,

  18. N-nitrosamines induced infertility and hepatotoxicity in male rabbits.

    Science.gov (United States)

    Sheweita, S A; El Banna, Y Y; Balbaa, M; Abdullah, I A; Hassan, H E

    2017-09-01

    N-nitrosamines are widely spread environmental pollutants of well-known toxicity and carcinogenicity in various animal species. These compounds are metabolically activated by cytochrome P450 system predominantly in the liver and in other tissues into more active metabolites leading to generation of both alkylating agents that alkylate DNA and reactive oxygen species. In the current study, we investigated the influence of four types of N-nitrosamines that are commonly present in the environment [methyethylnitrosamine, (MEN), diethylnitrosamine (DEN), diphenylnitroasamine (DPN) and dimethylnitrosamine (DMN)] on both livers and testes of male rabbits through assessment of 17 β-hydroxysteroid dehydrogenase (17 β-HSD) activity. The protein expression of the three cytochrome P450s (CYP11A1, CYP19A1, and CYP21A2) is involved in the steroidogenesis. The levels of testosterone (T) and estradiol (E2) were also determined in the plasma of N-nitrosamines-treated rabbits after one, four-, eight- and twelve weeks of treatment of male New Zealand rabbits with an oral dose of 0.5 mg/kg B.W/day of each compound. In addition, activities of glutathione reductase (GR), superoxide dismutase (SOD), catalase (CAT) and levels of free radicals measured as thiobarbituric acid reactive substances (TBARS), and reduced glutathione (GSH) level were quantified in both livers and testes. The present study showed that levels of free radicals (TBARS) were markedly increased, whereas GSH levels were depleted in the tissues of both livers and testes after treatment of rabbits with any of N-nitrosamines. In addition, all tested N-nitrosamines inhibited the activities of antioxidant enzyme activities (GR, GST, SOD, and CAT) in hepatic and testicular tissues of rabbits after 12 weeks of treatment. Histopathological examination showed that N-nitrosamines caused lymphocytic infiltration with vascular degeneration and necrosis, congestion of central vein with RBCs hemolysis, dilated sinusoids, as well as

  19. Systematic Evaluation of Protein Reduction and Alkylation Reveals Massive Unspecific Side Effects by Iodine-containing Reagents.

    Science.gov (United States)

    Müller, Torsten; Winter, Dominic

    2017-07-01

    Reduction and alkylation of cysteine residues is part of virtually any proteomics workflow. Despite its frequent use, up to date no systematic investigation of the impact of different conditions on the outcome of proteomics studies has been performed. In this study, we compared common reduction reagents (dithiothreitol, tris-(2-carboxyethyl)-phosphine, and β-mercaptoethanol) and alkylation reagents (iodoacetamide, iodoacetic acid, acrylamide, and chloroacetamide). Using in-gel digests as well as SAX fractionated in-solution digests of cytosolic fractions of HeLa cells, we evaluated 13 different reduction and alkylation conditions resulting in considerably varying identification rates. We observed strong differences in offsite alkylation reactions at 7 amino acids as well as at the peptide N terminus, identifying single and double adducts of all reagents. Using dimethyl labeling, mass tolerant searches, and synthetic peptide experiments, we identified alkylation of methionine residues by iodine-containing alkylation reagents as one of the major factors for the differences. We observed differences of more than 9-fold in numbers of identified methionine-containing peptide spectral matches for in-gel digested samples between iodine- and noniodine-containing alkylation reagents. This was because of formation of carbamidomethylated and carboxymethylated methionine side chains and a resulting prominent neutral loss during ESI ionization or in MS/MS fragmentation, strongly decreasing identification rates of methionine-containing peptides. We achieved best results with acrylamide as alkylation reagent, whereas the highest numbers of peptide spectral matches were obtained when reducing with dithiothreitol and β-mercaptoethanol for the in-solution and the in-gel digested samples, respectively. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  20. [Carcinogenic activity of ethylene oxide and its reaction products 2-chloroethanol, 2-bromoethanol, ethylene glycol and diethylene glycol. III. Research on ethylene glycol and diethylene glycol for carcinogenic effects].

    Science.gov (United States)

    Dunkelberg, H

    1987-03-01

    Ethylene glycol and diethylene glycol were each administered once weekly subcutaneously to groups of 100 female NMRI mice at 3 dosages (30; 10 und 3 mg single dose per mouse). Tricaprylin was used as solvent. The mean total dosage per mouse was 2110.5; 707.0 and 196.2 mg for ethylene glycol and 2029.8; 671.7 and 213.3 mg for diethylene glycol. Neither ethylene glycol nor diethylene glycol induced tumors at the injection site or away from the point of administration.

  1. Effects of alkyl chain length and substituent pattern of fullerene bis-adducts on film structures and photovoltaic properties of bulk heterojunction solar cells.

    Science.gov (United States)

    Tao, Ran; Umeyama, Tomokazu; Kurotobi, Kei; Imahori, Hiroshi

    2014-10-08

    A series of alkoxycarbonyl-substituted dihydronaphthyl-based [60]fullerene bis-adduct derivatives (denoted as C2BA, C4BA, and C6BA with the alkyl chain of ethyl, n-butyl, and n-hexyl, respectively) have been synthesized to investigate the effects of alkyl chain length and substituent pattern of fullerene bis-adducts on the film structures and photovoltaic properties of bulk heterojunction polymer solar cells. The shorter alkyl chain length caused lower solubility of the fullerene bis-adducts (C6BA > C4BA > C2BA), thereby resulting in the increased separation difficulty of respective bis-adduct isomers. The device performance based on poly(3-hexylthiophene) (P3HT) and the fullerene bis-adduct regioisomer mixtures was enhanced by shortening the alkyl chain length. When using the regioisomerically separated fullerene bis-adducts, the devices based on trans-2 and a mixture of trans-4 and e of C4BA exhibited the highest power conversion efficiencies of ca. 2.4%, which are considerably higher than those of the C6BA counterparts (ca. 1.4%) and the C4BA regioisomer mixture (1.10%). The film morphologies as well as electron mobilities of the P3HT:bis-adduct blend films were found to affect the photovoltaic properties considerably. These results reveal that the alkyl chain length and substituent pattern of fullerene bis-adducts significantly influence the photovoltaic properties as well as the film structures of bulk heterojunction solar cells.

  2. Impact of gate engineering in enhancement mode n++GaN/InAlN/AlN/GaN HEMTs

    Science.gov (United States)

    Adak, Sarosij; Swain, Sanjit Kumar; Rahaman, Hafizur; Sarkar, Chandan Kumar

    2016-12-01

    This paper illustrate the effect of gate material engineering on the performance of enhancement mode n++GaN/InAlN/AlN/GaN high electron mobility transistors (HEMTs). A comparative analysis of key device parameters is discussed for the Triple Material Gate (TMG), Dual Material Gate (DMG) and the Single Material Gate (SMG) structure HEMTs by considering the same device dimensions. The simulation results shows that an significant improvement is noticed in the key analysis parameters such as drain current (Id), transconductance (gm), cut off frequency (fT), RF current gain, maximum cut off frequency (fmax) and RF power gain of the gate material engineered devices with respect to SMG normally off n++GaN/InAlN/AlN/GaN HEMTs. This improvement is due to the existence of the perceivable step in the surface potential along the channel which successfully screens the drain potential variation in the source side of the channel for the gate engineering devices. The analysis suggested that the proposed TMG and DMG engineered structure enhancement mode n++GaN/InAlN/AlN/GaN HEMTs can be considered as a potential device for future high speed, microwave and digital application.

  3. Formation of 2-alkyl-(2H)-thiapyrans and 2-alkylthiophenes in cooked beef and lamb.

    Science.gov (United States)

    Elmore, J S; Mottram, D S

    2000-06-01

    2-Alkyl-(2H)-thiapyrans and 2-alkylthiophenes have been identified in the volatiles of cooked beef and lamb. The quantities of both groups of compounds were higher in the meat of animals fed lipid supplements high in n-3 polyunsaturated fatty acids. 2-Alkyl-(2H)-thiapyrans were formed when (E,E)-2,4-dienals (C(6)-C(11)) and hydrogen sulfide were heated at 140 degrees C for 30 min. This confirmed their proposed route of formation in cooked meat from lipid-derived aldehydes and hydrogen sulfide; the latter was produced from the degradation of cysteine, via the Maillard reaction. The mass spectra and NMR spectra of these thiapyrans are reported for the first time. Although 2-alkyl-(2H)-thiapyrans were found to have only low odor potency, the reactions by which they are formed may have important implications for meat flavor. These reactions may remove potent aroma compounds and their intermediates from meat, thus modifying the overall aroma profile.

  4. N,N,N-Tris(diphenylphosphorylmethylamine

    Directory of Open Access Journals (Sweden)

    Olaf Walter

    2017-10-01

    Full Text Available The structure of N,N,N-tris(diphenylphosphorylmethylamine, C39H36NO3P3, at 103 K has monoclinic (P21/c symmetry. Two molecules, each with pseudo-threefold rotation symmetry, crystallize in the asymmetric unit of the monoclinic unit cell. The compound acts as ligand for the stabilization of metal ions with flexible coordination enabling three- or fourfold coordination.

  5. Eficacia de una solución de polietilenglicol en la preparación del colon: Estudio preliminar

    Directory of Open Access Journals (Sweden)

    Marta Amarilys Vasallo Sellek

    2002-04-01

    Full Text Available Se realizó un estudio preliminar con 50 pacientes que acudieron a la Consulta de Coloproctología del Hospital Universitario "General Calixto García" para cirugía electiva de colon por diversos motivos. La muestra se dividió en 2 grupos: uno se preparó con solución de manitol 0,1 % y el otro con solución de polietilenglicol (PEG. Se compararon ambos grupos según la edad y el sexo, sin que se encontraran diferencias significativas entre ellos. Fue estadísticamente significativo el número de pacientes normales en el preoperatorio y bien preparados en el transoperatorio para el grupo que se preparó con solución de PEG (pA preliminary study was conducted with 50 patients that were seen at the Coloproctology Consulting Room of "General Calixto García" Teaching Hospital to undergo selective colon surgery due to different reasons. The sample was divided into 2 groups: one was prepared with mannitol solution 0.1 % and the other with polyethylene glycol (PEG solution. Both groups were compared as regards age and sex and no significant differences were found between them. The number of normal patients in the preoperative and of well prepared in the transoperative was statistically significant in the group that received PEG solution (p<0.05. The adverse effects and the complications predominated in the group prepared with mannitol solution 0.1 %. The intestinal transit was reestablished faster in the group that was administered PEG. The use of PEG solution is recommended for colon preparation.

  6. Nickel(II) and copper(II) complexes of N,N-dialkyl-N‧-3-chlorobenzoylthiourea: Synthesis, characterization, crystal structures, Hirshfeld surfaces and antimicrobial activity

    Science.gov (United States)

    Binzet, Gun; Gumus, Ilkay; Dogen, Aylin; Flörke, Ulrich; Kulcu, Nevzat; Arslan, Hakan

    2018-06-01

    We synthesized four new N,N-dialkyl-N‧-3-chlorobenzoylthiourea ligands (Alkyl: Dimethyl, diethyl, di-n-propyl and di-n-butyl) and their metal complexes with copper and nickel atoms. The structure of all synthesized compounds was fully characterized by physicochemical, spectroscopic and single crystal X-ray diffraction analysis techniques. The physical, spectral and analytical data of the newly synthesized metal complexes have shown the formation of 1:2 (metal:ligand) ratio. The benzoylthiourea ligands coordinate with metal atoms through oxygen and sulphur atoms. The metal atoms are in slightly distorted square-planar coordination geometry in Ni(II) or Cu(II) complex. Two oxygen and two sulphur atoms are mutually cis to each other in Ni(II) or Cu(II) complex. The intermolecular contacts in the compounds, which are HL1 and HL3, were examined by Hirshfeld surfaces and fingerprint plots using the data obtained from X-ray single crystal diffraction measurement. Besides these, their antimicrobial activities against Gram-positive bacteria (Bacillus subtilis, Staphylococcus aureus, Streptococcus pyogenes and Enterococcus faecalis) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and anti-yeast activity (Candida glabrata, Candida parapsilosis and Candida albicans) were investigated. This exhibited some promising results towards testing organism. Among all the compounds, Ni(L1)2 complex showed high activity against Bacillus subtilis with MIC values at 7.81 μg/mL.

  7. Evaluation of Some (n,n'), (n,γ), (n,p), (n,2n) and (n,3n) Reaction Excitation Functions for Fission and Fusion Reactor Dosimetry Applications; Evaluation of the Excitation Functions for the 54Fe(n,p)54Mn, 58Ni(n,2n)57Ni, 67Zn(n,p)67Cu, 92Mo(n,p)92mNb, 93Nb(n,γ)94Nb, 113In(n,n')113mIn, 115In(n,γ) 116mIn, and 169Tm(n,3n)167Tm Reactions. Progress Report on Research Contract No 16242

    International Nuclear Information System (INIS)

    Zolotarev, K.I.; Zolotarev, P.K.

    2013-12-01

    Cross section data for the 54 Fe(n,p) 54 Mn, 58 Ni(n,2n) 57 Ni, 67 Zn(n,p) 67 Cu, 92 Mo(n,p) 92m Nb, 93 Nb(n,γ) 94 Nb, 113 In(n,n') 113m In, 115 In(n,γ) 116m In, 169 Tm(n,3n) 167 Tm reactions are needed to solve a wide spectrum of scientific and technical tasks. Activation detectors based on these reactions may be used in the field of reactor dosimetry. Furthermore, the 54 Fe(n,p) 54 Mn reaction is often used in experimental nuclear physics as a monitor reaction for measurements of unknown cross sections by means of the activation method over the neutron energy range from 5 to 15 MeV. The 93 Nb(n,γ) 94 Nb reaction is also very promising for using in retrospective neutron dosimetry for determination of total neutron fluence during a campaign of a reactor. In the existing version of the International Reactor Dosimetry File and the new extended version named as IRDFF data for excitation functions of 67 Zn(n,p) 67 Cu, 92 Mo(n,p) 92m Nb, 113 In(n,n') 113m In, and 169 Tm(n,3n) 167 Tm reactions are absent. Data for these reactions are also absent in the JENDL/D-99 dosimetry file. Excitation functions of 67 Zn(n,p) 67 Cu and 169 Tm(n,3n) 167 Tm are presented in the TENDL-2012, EAF-2010, JENDL-4.0, JEFF-3.1/A, MENDL-2 libraries. Cross section data for the 67 Zn(n,p) 67 Cu reaction up to 20 MeV are given also in the JENDL/HE-2007 library. Excitation functions of the 92 Mo(n,p) 92m Nb and 113 In(n,n') 113m In reactions are evaluated in the EAF-2010 and JEFF-3.1/A libraries. Cross section data for the 113 In(n,n') 113m In reaction are given also in the TENDL-2010 library. It is necessary to note that neutron data in the JEFF-3.1/A and JENDL-4.0 libraries were evaluated up to 20 MeV. Neutron data in the TENDL-2012, EAF-2010, MENDL-2 and TENDL-2010 libraries had been evaluated up to 30 MeV, 60 MeV, 100 MeV and 200 MeV, respectively. Neutron cross sections in the MENDL-2, TENDL-2010 and TENDL-2012 libraries had been obtained on the basis of pure theoretical model calculations

  8. Structure, conformations, vibrations, and ideal-gas properties of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic pairs and constituent ions.

    Science.gov (United States)

    Paulechka, Yauheni U; Kabo, Gennady J; Emel'yanenko, Vladimir N

    2008-12-11

    Energies, geometries, and frequencies of normal vibrations have been calculated by quantum-chemical methods for different conformers of a bis(trifluoromethylsulfonyl)imide anion (NTf2-), 1-alkyl-3-methylimidazolium cations ([C(n)mim]+, n = 2, 4, 6, 8), and [C(n)mim]NTf2 ionic pairs. The assignment of frequencies for NTf2-, [C2mim]+, and [C4mim]+ in the vibrational spectra of ionic liquids have been performed. Thermodynamic properties of [C(n)mim]NTf2, [C(n)mim]+, and NTf2- in the gas state have been calculated by the statistical thermodynamic methods. The resulting entropies are in satisfactory agreement with the values obtained from the experimental data previously reported in literature.

  9. Ohmic contacts to n+-GaN capped AlGaN/AlN/GaN high electron mobility transistors

    International Nuclear Information System (INIS)

    Wang Liang; Mohammed, Fitih M.; Ofuonye, Benedict; Adesida, Ilesanmi

    2007-01-01

    Investigations of Ti/Al/Mo/Au Ohmic contact formation, premetallization plasma treatment effects, and interfacial reactions for n + -GaN capped AlGaN/AlN/GaN heterostructures are presented. Ti thickness played an important role in determining contact performance. Transmission electron microscopy studies confirmed that thick Ti layer was necessary to fully consume the GaN cap and the top of AlGaN to enable a higher tunneling current flow. A direct correlation of plasma treatment conditions with I-V linearity, current level, and contact performance was established. The plasma-affected region is believed to extend over 20 nm into the AlGaN and GaN

  10. Standard specification for Nickel-Chromium-Iron alloys (UNS N06600, N06601, N06603, N06690, N06693, N06025, N06045, and N06696), Nikel-Chromium-Cobalt-Molybdenum alloy (UNS N06617), and Nickel-Iron-Chromium-Tungsten alloy (UNS N06674) seamless pipe and tube

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2011-01-01

    Standard specification for Nickel-Chromium-Iron alloys (UNS N06600, N06601, N06603, N06690, N06693, N06025, N06045, and N06696), Nikel-Chromium-Cobalt-Molybdenum alloy (UNS N06617), and Nickel-Iron-Chromium-Tungsten alloy (UNS N06674) seamless pipe and tube

  11. Standard specification for Nickel-Chromium-Iron alloys (UNS N06600, N06601, N06603, N06690, N06693, N06025, N06045 and N06696), Nickel-Chromium-Cobalt-Molybdenum alloy (UNS N06617), and Nickel-Iron-Chromium-Tungsten alloy (UNS N06674) plate, sheet and strip

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2011-01-01

    Standard specification for Nickel-Chromium-Iron alloys (UNS N06600, N06601, N06603, N06690, N06693, N06025, N06045 and N06696), Nickel-Chromium-Cobalt-Molybdenum alloy (UNS N06617), and Nickel-Iron-Chromium-Tungsten alloy (UNS N06674) plate, sheet and strip

  12. Standard specification for Nickel-Chromium-Iron alloys (UNS N06600, N06601, N06603, N06690, N06693, N06025, N06045, and N06696), Nickel-Chromium-Cobalt-Molybdenum alloy (UNS N06617), and Nickel-Iron-Chromium-Tungsten alloy (UNS N06674) rod, bar, and wire

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2011-01-01

    Standard specification for Nickel-Chromium-Iron alloys (UNS N06600, N06601, N06603, N06690, N06693, N06025, N06045, and N06696), Nickel-Chromium-Cobalt-Molybdenum alloy (UNS N06617), and Nickel-Iron-Chromium-Tungsten alloy (UNS N06674) rod, bar, and wire

  13. 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.

  14. Characterization of newly isolated Pseudonocardia sp. N23 with high 1,4-dioxane-degrading ability.

    Science.gov (United States)

    Yamamoto, Norifumi; Saito, Yuji; Inoue, Daisuke; Sei, Kazunari; Ike, Michihiko

    2018-01-02

    This study was conducted to elucidate the 1,4-dioxane degradation characteristics of a newly isolated 1,4-dioxane-degrading bacterial strain and evaluate the applicability of the strain to biological 1,4-dioxane removal from wastewater. A bacterial strain (designated strain N23) capable of degrading 1,4-dioxane as the sole carbon and energy source was isolated from an enrichment culture prepared from 1,4-dioxane-contaminated groundwater. Strain N23 was phylogenetically identified as belonging to the genus Pseudonocardia, based on 16S rRNA gene sequencing. 1,4-Dioxane degradation experiments revealed that strain N23 is capable of constitutive 1,4-dioxane degradation. Further, this strain exhibited the highest specific 1,4-dioxane degradation rate of 0.230 mg-1,4-dioxane (mg-protein) -1  h -1 among 1,4-dioxane-degrading bacteria with constitutively expressed degrading enzymes reported to date. In addition, strain N23 was shown to degrade up to 1100 mg L -1 of 1,4-dioxane without significant inhibition, and to maintain a high level of 1,4-dioxane degradation activity under a wide pH (pH 3.8-8.2) and temperature (20-35 °C) range. In particular, the specific 1,4-dioxane degradation rate, even at pH 3.8, was 83% of the highest rate at pH 7.0. In addition, strain N23 was capable of utilizing ethylene glycol and diethylene glycol, which are both considered to be present in 1,4-dioxane-containing industrial wastewater, as the sole carbon source. The present results indicate that strain N23 exhibits the potential for 1,4-dioxane removal from industrial wastewater. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  15. Thermodynamic activity of saturated solutions of CsClO4 in ethylene glycol and its analogs of the HOCH2(CH2CH2O)nCH2OH series

    International Nuclear Information System (INIS)

    Krasnoperova, A.P.; Ivanova, E.F.; Kijko, S.M.; Yukhno, G.D.

    1997-01-01

    Solubility of CsClO 4 in ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with molar mass 300 and 400 in the temperature range of 273.15-318.15 K has been ascertained by the method of radioactive indicators. Dependence of saturated solutions activity on temperature, dielectric permittivity and the number of (CH 2 CH 2 O) ether groups in glycols is discussed

  16. THE EFFECTS OF ORAL ADMINISTRATION OF PROPYLENE GLYCOL AND CALCIUM PROPIONATE IN DAIRY COWS

    Directory of Open Access Journals (Sweden)

    C. GAVAN

    2009-10-01

    Full Text Available This study was designed to determine the effects of the oral administration of propylene glycol and calcium propionate on performance of dairy cows. Treatments were 10 l water (control, 10 l water+300 ml propylene glycol (GP and 10 l water+500 g calcium propionate (CP. Animals were mainly of Holstein breeds and were fed and managed in a commercial setting. The cows were divided randomly into an experimental group, n=24 (n=12 with PG and n=12 with CP and a control group, n=11. Cows received the assigned treatment within 10 hours of calving and 24 hours after calving. Health events were recorded during calving and for the first 21 days in milk (DIM. Health examinations were performed on cows that appeared not well. The cows were milked three times daily and milk production was recorded electronically. Milk solid content and somatic cell score were determinate from three consecutive milking weekly till 20 DIM and than monthly till 110 DIM. Retained placenta, hypocalcaemia, displaced abomasums, ketosis and metritis were low in treatment groups (with PG and CP. The cows receiving PG had 2.8 Kg/day grater milk production than control group. The cows receiving CP had 1.7 kg/day grater milk production than control group. Prophylactic administration of PG and CP drenches to Holstein cows may be justified by potentially higher milk yields and reduced health complications.

  17. Palladium(II) complexes with R(2)edda derived ligands. Part IV. O,O'-dialkyl esters of (S,S)-ethylenediamine-N,N'-di-2-(4-methyl)-pentanoic acid dihydrochloride and their palladium(II) complexes: synthesis, characterization and in vitro antitumoral activity against chronic lymphocytic leukemia (CLL) cells.

    Science.gov (United States)

    Vujić, Jelena M; Cvijović, Milica; Kaluderović, Goran N; Milovanović, Marija; Zmejkovski, Bojana B; Volarević, Vladislav; Arsenijević, Nebojsa; Sabo, Tibor J; Trifunović, Srećko R

    2010-09-01

    Four novel bidentate N,N'-ligand precursors, including O,O'-dialkyl esters (alkyl = ethyl, n-propyl, n-butyl and n-pentyl), L1 x 2 HCl-L4 x 2 HCl, of (S,S)-ethylenediamine-N,N'-di-2-(4-methyl)-pentanoic acid dihydrochloride [(S,S)-H(4)eddl]Cl(2) and the corresponding palladium(II) complexes 1-4, were prepared and characterized by IR, (1)H NMR and (13)C NMR spectroscopy and elemental analysis. In vitro cytotoxicity of all compounds was determined against chronic lymphocytic leukemia cells (CLL). The compounds were found to exhibit higher antitumoral activity than cisplatin. The most active compound 2, [PdCl(2){(S,S)-nPr(2)eddl}], was found to be 13.6 times more active than cisplatin on CLL cells. 2010 Elsevier Masson SAS. All rights reserved.

  18. Metabolism and elimination of methyl, iso- and n-butyl paraben in human urine after single oral dosage.

    Science.gov (United States)

    Moos, Rebecca K; Angerer, Jürgen; Dierkes, Georg; Brüning, Thomas; Koch, Holger M

    2016-11-01

    Parabens are used as preservatives in personal care and consumer products, food and pharmaceuticals. Their use is controversial because of possible endocrine disrupting properties. In this study, we investigated metabolism and urinary excretion of methyl paraben (MeP), iso-butyl paraben (iso-BuP) and n-butyl paraben (n-BuP) after oral dosage of deuterium-labeled analogs (10 mg). Each volunteer received one dosage per investigated paraben separately and at least 2 weeks apart. Consecutive urine samples were collected over 48 h. In addition to the parent parabens (free and conjugated) which are already used as biomarkers of internal exposure and the known but non-specific metabolites, p-hydroxybenzoic acid (PHBA) and p-hydroxyhippuric acid (PHHA), we identified new, oxidized metabolites with hydroxy groups on the alkyl side chain (3OH-n-BuP and 2OH-iso-BuP) and species with oxidative modifications on the aromatic ring. MeP represented 17.4 % of the dose excreted in urine, while iso-BuP represented only 6.8 % and n-BuP 5.6 %. Additionally, for iso-BuP, about 16 % was excreted as 2OH-iso-BuP and for n-BuP about 6 % as 3OH-n-BuP. Less than 1 % was excreted as ring-hydroxylated metabolites. In all cases, PHHA was identified as the major but non-specific metabolite (57.2-63.8 %). PHBA represented 3.0-7.2 %. For all parabens, the majority of the oral dose captured by the above metabolites was excreted in the first 24 h (80.5-85.3 %). Complementary to the parent parabens excreted in urine, alkyl-chain-oxidized metabolites of the butyl parabens are introduced as valuable and contamination-free biomarkers of exposure.

  19. Synthesis of a Pseudodisaccharide α-C-Glycosidically Linked to an 8-Alkylated Guanine

    Directory of Open Access Journals (Sweden)

    Jan Duchek

    2013-04-01

    Full Text Available The synthesis of stable guanofosfocin analogues has attracted considerable attention in the past 15 years. Several guanofosfocin analogues mimicking the three constitutional elements of mannose, ribose, and guanine were designed and synthesized. Interest in ether-linked pseudodisaccharides and 8-alkylated guanines is increasing, due to their potential applications in life science. In this article, a novel guanofosfocin analogue 6, an ether-linked pseudodisaccharide connected α-C-glycosidically to an 8-alkylated guanine, was synthesized in a 10-longest linear step sequence from known diol 13, resulting in an overall yield of 26%. The key steps involve the ring-opening of cyclic sulfate 8 by alkoxide generated from 7 and a reductive cyclization of 4-N-acyl-2,4-diamino-5-nitrosopyrimidine 19 to form compound 6.

  20. Automated synthesis of n.c.a. [18F]FDOPA via nucleophilic aromatic substitution with [18F]fluoride

    International Nuclear Information System (INIS)

    Shen, B.; Ehrlichmann, W.; Uebele, M.; Machulla, H.-J.; Reischl, G.

    2009-01-01

    An improved, automated synthesis of [ 18 F]FDOPA including four synthetic steps (fluorination, reductive iodination, alkylation and hydrolysis) is reported with each step optimized individually. In a home-made automatic synthesizer, 9064±3076 MBq of [ 18 F]FDOPA were produced within 120 min from EOB (n=5). Radiochemical purity and enantiomeric excess were both ≥95%. Specific activity was ca. 50 GBq/μmol at EOS. This automatically operable synthesis is well suited for the multi-patient-dose routine production of n.c.a. [ 18 F]FDOPA.