Sample records for alkyl alkenyl cycloalkyl

  1. Redox shuttle additives for lithium-ion batteries

    DOEpatents

    Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

    2017-03-21

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

  2. Non-aqueous electrolyte for lithium-ion battery

    DOEpatents

    Amine, Khalil; Zhang, Lu; Zhang, Zhengcheng

    2016-01-26

    A substantially non-aqueous electrolyte solution includes an alkali metal salt, a polar aprotic solvent, and an organophosphorus compound of Formula IA, IB, or IC: ##STR00001## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkoxy, alkenoxy, alkynoxy, cycloalkoxy, aryloxy, heterocyclyloxy, heteroaryloxy, siloxyl, silyl, or organophosphatyl; R.sup.5 and R.sup.6 are each independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; R.sup.7 is ##STR00002## and R.sup.8, R.sup.9 and R.sup.10 are each independently alkyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; provided that if the organophosphorus compound is of Formula IB, then at least one of R.sup.5, and R.sup.6 are other than hydrogen, alkyl, or alkenyl; and if the organophosphorus compound is of Formula IC, then the electrolyte solution does not include 4-methylene-1,3-dioxolan-2-one or 4,5-dimethylene-1,3-dioxolan-2-one.

  3. Engaging Alkenyl Halides with Alkylsilicates via Photoredox Dual Catalysis.

    PubMed

    Patel, Niki R; Kelly, Christopher B; Jouffroy, Matthieu; Molander, Gary A

    2016-02-19

    Single-electron transmetalation via photoredox/nickel dual catalysis provides the opportunity for the construction of Csp(3)-Csp(2) bonds through the transfer of alkyl radicals under very mild reaction conditions. A general procedure for the cross-coupling of primary and secondary (bis-catecholato)alkylsilicates with alkenyl halides is presented. The developed method allows not only alkenyl bromides and iodides but also previously underexplored alkenyl chlorides to be employed.

  4. Diacyl, alkenyl, and alkyl ether phospholipids in ejaculated, in utero-, and in vitro-incubated porcine spermatozoa.

    PubMed

    Evans, R W; Weaver, D E; Clegg, E D

    1980-02-01

    The phospholipids of porcine spermatozoa were analyzed by a hydrolytic procedure directly after ejaculation, and after incubation for 120 min in vitro or in ligated uterine segments of females with induced estrus. Total phospholipid content of ejaculated sperm was 65.7 micro g lipid P per 10(9) sperm, of which 41% was alkyl ether and 23% was alkenyl ether glycerophospholipid. All of the ether phospholipids were choline and ethanolamine glycerophospholipids. In order of decreasing amount (% of total phospholipid), the phospholipids were choline and ethanolamine glycerophospholipids (49.9 and 28.2), sphingolipid (10.6), cardiolipin (5.5), phosphatidylinositol (2.3), phosphatidic acid (1.5), phosphatidylserine (1.2), and phosphatidylglycerol (0.8). Phosphorus-containing sphingolipid separated into two components during thin-layer chromatography. Sphingosine was the only long-chain base identified in either band. Major fatty acids in the band with lower R(f) were 16:0 (56%), 20:0 (23%), and 18:0 (11%) plus smaller amounts of 14:0, 18:1, and 22:0, while those in the band with higher R(f) were 14:0 (30%), 16:0 (45%), and 18:1 (12%) plus smaller amounts of 18:0, 20:0, and 22:0. Choline was the only water-soluble base present in the lower R(f) sphingomyelin while ethanolamine was prevalent in the higher R(f) component. Incubation of washed spermatozoa in Ca(2+)-free Ringer-fructose at 37 degrees C for 2 hr produced no significant change in the level of any of the phospholipids. Incubation of washed sperm in the uterus for 2 hr, in the presence of oviductal secretions, produced an increase in phosphatidylcholine from 7.2 to 10.2 micro g lipid P per 10(9) sperm.-Evans, R. W., D. E. Weaver, and E. D. Clegg. Diacyl, alkenyl, and alkyl ether phospholipids in ejaculated, in utero-, and in vitro-incubated porcine spermatozoa.

  5. Engaging unactivated alkyl, alkenyl and aryl iodides in visible-light-mediated free radical reactions

    NASA Astrophysics Data System (ADS)

    Nguyen, John D.; D'Amato, Erica M.; Narayanam, Jagan M. R.; Stephenson, Corey R. J.

    2012-10-01

    Radical reactions are a powerful class of chemical transformations. However, the formation of radical species to initiate these reactions has often required the use of stoichiometric amounts of toxic reagents, such as tributyltin hydride. Recently, the use of visible-light-mediated photoredox catalysis to generate radical species has become popular, but the scope of these radical precursors has been limited. Here, we describe the identification of reaction conditions under which photocatalysts such as fac-Ir(ppy)3 can be utilized to form radicals from unactivated alkyl, alkenyl and aryl iodides. The generated radicals undergo reduction via hydrogen atom abstraction or reductive cyclization. The reaction protocol utilizes only inexpensive reagents, occurs under mild reaction conditions, and shows exceptional functional group tolerance. Reaction efficiency is maintained upon scale-up and decreased catalyst loading, and the reaction time can be significantly shortened when the reaction is performed in a flow reactor.

  6. Arylation, alkenylation, and alkylation of 2-halopyridine N-oxides with grignard reagents: a solution to the problem of C2/C6 regioselective functionalization of pyridine derivatives.

    PubMed

    Zhang, Song; Liao, Lian-Yan; Zhang, Fang; Duan, Xin-Fang

    2013-03-15

    A facile arylation, alkenylation, and alkylation of functionalized 2-halopyridine N-oxides with various Grignard reagents was developed. It represented a highly efficient and selective C-H bond functionalization of pyridine derivatives in the presence of reactive C-Cl or C-Br bonds. Using Cl or Br as a blocking group, C2/C6 site-controllable functionalization of pyridine derivatives has been achieved. Various pyridine compounds can be prepared as illustrated in the total syntheses of Onychine, dielsine, and PARP-1 inhibitor GPI 16539.

  7. Cross-coupling of alkenyl/aryl carboxylates with Grignard reagent via Fe-catalyzed C-O bond activation.

    PubMed

    Li, Bi-Jie; Xu, Li; Wu, Zhen-Hua; Guan, Bing-Tao; Sun, Chang-Liang; Wang, Bi-Qin; Shi, Zhang-Jie

    2009-10-21

    Iron-catalyzed cross-coupling of alkenyl/aryl carboxylates with primary alkyl Grignard reagent was described. This reaction brought a new family of electrophiles to iron catalysis. The combination of an inexpensive carboxylate electrophile and an iron catalyst would generate ample advantages.

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

    PubMed

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

    2014-12-03

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

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

    PubMed

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

    2017-07-18

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

  10. General Synthesis of Alkenyl Sulfides by Palladium-Catalyzed Thioetherification of Alkenyl Halides and Tosylates.

    PubMed

    Velasco, Noelia; Virumbrales, Cintia; Sanz, Roberto; Suárez-Pantiga, Samuel; Fernández-Rodríguez, Manuel A

    2018-05-08

    The cross-coupling reaction of alkenyl bromides with thiols catalyzed by palladium complexes derived from inexpensive dppf ligand is reported. These reactions occur under low catalyst loading and in high yields and display wide scope, including the coupling of bulky thiols and trisubstituted bromoolefins, and functional group tolerance. In addition, the thioetherification of less reactive chloroalkenes and, for the first time, alkenyl tosylates was accomplished using a catalyst generated from CyPF tBu alkylbisphosphine ligand.

  11. 40 CFR 721.2093 - Alkenyl carboxylate, metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkenyl carboxylate, metal salt... Specific Chemical Substances § 721.2093 Alkenyl carboxylate, metal salt (generic). (a) Chemical substance... alkenyl carboxylate, metal salt (PMN P-99-0848) is subject to reporting under this section for the...

  12. Synthesis of enyne and aryl vinyl sulfoxides: functionalization via Pummerer rearrangement.

    PubMed

    Souza, Frederico B; Shamim, Anwar; Argomedo, Luiz M Z; Pimenta, Daniel C; Stefani, Hélio A

    2015-11-01

    An efficient methodology for the synthesis of aryl-substituted vinyl sulfoxides through direct substitution of aryl-substituted alkynyl grignard reagents on menthyl-p-toluenesulfinate followed by Suzuki-Miyaura cross-coupling reaction has been developed. It has also been described that the reaction of alkyl-substituted and cycloalkyl-substituted alkynyl grignard reagents with menthyl-p-toluenesulfinate led to two products, i.e., alkynyl sulfoxide derivatives, as a result of substitution, and enyne sulfoxide derivatives, which resulted from substitution followed by Michael type addition. It was possible to selectively synthesize the enyne sulfoxide derivatives by changing the concentration of the grignard reagent. These alkenyl sulfoxides were transformed into the corresponding [Formula: see text]-thio aldehydes in high yields via additive Pummerer rearrangement.

  13. Process for alkane group dehydrogenation with organometallic catalyst

    DOEpatents

    Kaska, W.C.; Jensen, C.M.

    1998-07-14

    An improved process is described for the catalytic dehydrogenation of organic molecules having a ##STR1## group to produce a ##STR2## group. The organic molecules are: ##STR3## wherein: A.sup.1, A.sup.2, A.sup.3, and A.sup.4 are each independently P, As or N: E.sup.2 is independently C or N; E.sup.3 is independently C, Si or Ge; E.sup.4 is independently C, Si, or Ge; and E.sup.5 is independently C, Si or Ge; M.sup.1, M.sup.2, M.sup.3, and M.sup.4 each is a metal atom independently selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum; Q.sup.1, Q.sup.2, Q.sup.3, and Q.sup.4 are each independently a direct bond, --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, or CH.dbd.CH--; in structure I, structure II or structure IV, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.1 and R.sup.2 together and R.sup.3 and R.sup.4 together form a ring structure having from 4 to 10 carbon atoms, or in structure III, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.5 and R.sup.6 together and R.sup.7 and R.sup.8 together form a ring structure having from 4 to 10 carbon atoms, at a temperature of between about 100.degree. and 250.degree. C. for between about 1 hr and 300 days in the absence of N.sub.2. The surprisingly stable catalyst is a complex of an organic ligand comprising H, C, Si, N, P atoms, and a platinum group metal. The dehydrogenation is performed between about 100 to 200.degree. C., and has increased turnover.

  14. Process for alkane group dehydrogenation with organometallic catalyst

    DOEpatents

    Kaska, William C.; Jensen, Craig M.

    1998-01-01

    An improved process is described for the catalytic dehydrogenation of organic molecules having a ##STR1## group to produce a ##STR2## group. The organic molecules are: ##STR3## wherein: A.sup.1, A.sup.2, A.sup.3, and A.sup.4 are each independently P, As or N: E.sup.2 is independently C or N; E.sup.3 is independently C, Si or Ge; E.sup.4 is independently C, Si, or Ge; and E.sup.5 is independently C, Si or Ge; M.sup.1, M.sup.2, M.sup.3, and M.sup.4 each is a metal atom independently selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum; Q.sup.1, Q.sup.2, Q.sup.3, and Q.sup.4 are each independently a direct bond, --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, or CH.dbd.CH--; in structure I, structure II or structure IV, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.1 and R.sup.2 together and R.sup.3 and R.sup.4 together form a ring structure having from 4 to 10 carbon atoms, or in structure III, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.5 and R.sup.6 together and R.sup.7 and R.sup.8 together form a ring structure having from 4 to 10 carbon atoms, at a temperature of between about 100.degree. and 250.degree. C. for between about 1 hr and 300 days in the absence of N.sub.2. The surprisingly stable catalyst is a complex of an organic ligand comprising H, C, Si, N, P atoms, and a platinum group metal. The dehydrogenation is performed between about 100 to 200.degree. C., and has increased turnover.

  15. 40 CFR 721.10127 - Alkenyl dimethyl betaine (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkenyl dimethyl betaine (generic... Specific Chemical Substances § 721.10127 Alkenyl dimethyl betaine (generic). (a) Chemical substance and... dimethyl betaine (PMN P-06-693) is subject to reporting under this section for the significant new uses...

  16. 40 CFR 721.10127 - Alkenyl dimethyl betaine (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkenyl dimethyl betaine (generic... Specific Chemical Substances § 721.10127 Alkenyl dimethyl betaine (generic). (a) Chemical substance and... dimethyl betaine (PMN P-06-693) is subject to reporting under this section for the significant new uses...

  17. 40 CFR 721.10127 - Alkenyl dimethyl betaine (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkenyl dimethyl betaine (generic... Specific Chemical Substances § 721.10127 Alkenyl dimethyl betaine (generic). (a) Chemical substance and... dimethyl betaine (PMN P-06-693) is subject to reporting under this section for the significant new uses...

  18. 40 CFR 721.10127 - Alkenyl dimethyl betaine (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkenyl dimethyl betaine (generic... Specific Chemical Substances § 721.10127 Alkenyl dimethyl betaine (generic). (a) Chemical substance and... dimethyl betaine (PMN P-06-693) is subject to reporting under this section for the significant new uses...

  19. 40 CFR 721.10127 - Alkenyl dimethyl betaine (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkenyl dimethyl betaine (generic... Specific Chemical Substances § 721.10127 Alkenyl dimethyl betaine (generic). (a) Chemical substance and... dimethyl betaine (PMN P-06-693) is subject to reporting under this section for the significant new uses...

  20. Stereospecific Ni-Catalyzed Cross-Coupling of Potassium Alkenyltrifluoroborates with Alkyl Halides

    PubMed Central

    2015-01-01

    A general method for the alkenylation of alkyl electrophiles using nearly stoichiometric amounts of the air- and moisture-stable potassium organotrifluoroborates has been developed. Various functional groups were tolerated on both the nucleophilic and electrophilic partner. Reactions of highly substituted E- and Z-alkenyltrifluoroborates, as well as vinyl- and propenyltrifluoroborates, were successful, and no loss of stereochemistry or regiochemistry was observed. PMID:24666316

  1. Lubricants or lubricant additives composed of ionic liquids containing ammonium cations

    DOEpatents

    Qu, Jun [Knoxville, TN; Truhan, Jr; John, J [Cookeville, TN; Dai, Sheng [Knoxville, TN; Luo, Huimin [Knoxville, TN; Blau, Peter J [Knoxville, TN

    2010-07-13

    A lubricant or lubricant additive is an ionic liquid alkylammonium salt. The alkylammonium salt has the structure R.sub.xNH.sub.(4-x).sup.+,[F.sub.3C(CF.sub.2).sub.yS(O).sub.2].sub.2N.sup- .- where x is 1 to 3, R is independently C.sub.1 to C.sub.12 straight chain alkyl, branched chain alkyl, cycloalkyl, alkyl substituted cycloalkyl, cycloalkyl substituted alkyl, or, optionally, when x is greater than 1, two R groups comprise a cyclic structure including the nitrogen atom and 4 to 12 carbon atoms, and y is independently 0 to 11. The lubricant is effective for the lubrication of many surfaces including aluminum and ceramics surfaces.

  2. Multipotent MAO and cholinesterase inhibitors for the treatment of Alzheimer's disease: synthesis, pharmacological analysis and molecular modeling of heterocyclic substituted alkyl and cycloalkyl propargyl amine.

    PubMed

    Samadi, Abdelouahid; de los Ríos, Cristóbal; Bolea, Irene; Chioua, Mourad; Iriepa, Isabel; Moraleda, Ignacio; Bartolini, Manuela; Andrisano, Vincenza; Gálvez, Enrique; Valderas, Carolina; Unzeta, Mercedes; Marco-Contelles, José

    2012-06-01

    The synthesis, pharmacological evaluation and molecular modeling of heterocyclic substituted alkyl and cycloalkyl propargyl amines 1-7 of type I, and 9-12 of type II, designed as multipotent inhibitors able to simultaneously inhibit monoamine oxidases (MAO-A/B) as well as cholinesterase (AChE/BuChE) enzymes, as potential drugs for the treatment of Alzheimer's disease, are described. Indole derivatives 1-7 of type I are well known MAO inhibitors whose capacity to inhibit AChE and BuChE was here investigated for the first time. As a result, compound 7 was identified as a MAO-B inhibitor (IC(50) = 31 ± 2 nM) and a moderately selective eqBuChE inhibitor (IC(50) = 4.7 ± 0.2 μM). Conversely, the new and readily available 5-amino-7-(prop-2-yn-1-yl)-6,7,8,9-tetrahydropyrido[2,3-b][1,6]naphthyridine derivatives 9-13 of type II are poor MAO inhibitors, but showed AChE selective inhibition, compound 12 being the most attractive as it acts as a non-competitive inhibitor on EeAChE (IC(50) = 25 ± 3 nM, K(i) = 65 nM). The ability of this compound to interact with the AChE peripheral binding site was confirmed by kinetic studies and by molecular modeling investigation. Studies on human ChEs confirmed that 12 is a selective AChE inhibitor with inhibitory potency in the submicromolar range. Moreover, in agreement with its mode of action, 12 was shown to be able to inhibit Aβ aggregation induced by hAChE by 30.6%. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  3. Anti-cancer agents based on N-acyl-2, 3-dihydro-1H-pyrrolo[2,3-b] quinoline derivatives and a method of making

    DOEpatents

    Gakh, Andrei; Krasavin, Mikhail; Karapetian, Ruben; Rufanov, Konstantin A; Konstantinov, Igor; Godovykh, Elena; Soldatkina, Olga; Sosnov, Andrey V

    2013-04-16

    The present disclosure relates to novel compounds that can be used as anti-cancer agents in the prostate cancer therapy. In particular, the invention relates to N-acyl derivatives of 2,3-dihydro-1H-pyrrolo[2,3-b]quinolines having the structural Formula (I), ##STR00001## stereoisomers, tautomers, racemics, prodrugs, metabolites thereof, or pharmaceutically acceptable salt and/or solvate thereof. The meaning of R1 is independently selected from H; C1-C6 Alkyl, cyclo-Alkyl or iso-Alkyl substituents; R2 is selected from C1-C6 Alkyl, cyclo-Alkyl or iso-Alkyl; substituted or non-substituted, fused or non-fused to substituted or non-substituted aromatic ring, aryl or heteroaryl groups. The invention also relates to methods for preparing said compounds, and to pharmaceutical compositions comprising said compounds.

  4. Synthesis and properties of alkoxy- and alkenyl-substituted peralkylated imidazolium ionic liquids.

    PubMed

    Maton, Cedric; Brooks, Neil R; Van Meervelt, Luc; Binnemans, Koen; Schaltin, Stijn; Fransaer, Jan; Stevens, Christian V

    2013-10-21

    Novel peralkylated imidazolium ionic liquids bearing alkoxy and/or alkenyl side chains have been synthesized and studied. Different synthetic routes towards the imidazoles and the ionic liquids comprising bromide, iodide, methanesulfonate, bis(trifluoromethylsulfonyl)imide ([NTf2](-)), and dicyanamide {[N(CN)2](-)} as the anion were evaluated, and this led to a library of analogues, for which the melting points, viscosities, and electrochemical windows were determined. Incorporation of alkenyl moieties hindered solidification, except for cations with high symmetry. The alkoxy-derivatized ionic liquids are often crystalline; however, room-temperature ionic liquids (RTILs) were obtained with the weakly coordinating anions [NTf2](-) and [N(CN)2](-). For the viscosities of the peralkylated RTILs, an opposite trend was found, that is, the alkoxy derivatives are less viscous than their alkenyl-substituted analogues. Of the crystalline compounds, X-ray diffraction data were recorded and related to their molecular properties. Upon alkoxy substitution, the electrochemical cathodic limit potential was found to be more positive, whereas the complete electrochemical window of the alkenyl-substituted imidazolium salts was shifted to somewhat more positive potentials. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis

    PubMed Central

    Koh, Ming Joo; Nguyen, Thach T.; Zhang, Hanmo; Schrock, Richard R.; Hoveyda, Amir H.

    2016-01-01

    Olefin metathesis has made a significant impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is very limited. In this manuscript, we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of an in situ-generated catalyst with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents and proceed to high conversion at ambient temperature within four hours. Many alkenyl chlorides, bromides and fluorides can be obtained in up to 91 percent yield and complete Z selectivity. This method can be used to easily synthesize biologically active compounds and to perform the site- and stereoselective fluorination of other organic compounds. PMID:27008965

  6. Synthesis and Tuberculostatic Activity Evaluation of Novel Benzazoles with Alkyl, Cycloalkyl or Pyridine Moiety.

    PubMed

    Krause, Malwina; Foks, Henryk; Augustynowicz-Kopeć, Ewa; Napiórkowska, Agnieszka; Szczesio, Małgorzata; Gobis, Katarzyna

    2018-04-23

    Compounds possessing benzimidazole system exhibit significant antituberculous activity. In order to examine how structure modifications affect tuberculostatic activity, a series of benzazole derivatives were synthesized and screened for their antitubercular activity. The compounds 1 ⁻ 20 were obtained by the reaction between o -diamine, o -aminophenol, or o -aminothiophenol with carboxylic acids or thioamides. The newly synthesized compounds were characterized by IR, ¹H-NMR, 13 C-NMR spectra, and elemental analysis. Synthesized benzazoles were evaluated for their tuberculostatic activity toward Mycobacterium tuberculosis strains. Quantum chemical calculations were performed to study the molecular geometry and the electronic structure of benzimidazoles GK-151B, 4 , 6 , and benzoxazole 11 , using the Gaussian 03W software (Gaussian, Inc., Wallingford, CT, USA). Three-dimensional structure of benzimidazoles 1 ⁻ 3 , MC-9, and GK-151B was determined by ab initio calculation using Gamess-US software. The activity of the received benzimidazoles was moderate or good. All of the benzoxazoles and benzothiazoles demonstrated much lower activity. Benzoxazoles were less active by about 50 times, and benzothiazole by 100 times than the benzimidazole analogs. Quantum chemical calculations showed differences in the distribution of electrostatic potential in the benzazole system of benzimidazoles and benzoxazoles. Three-dimensional structure calculations revealed how the parity of the alkyl substituent at the C2 position impacts the activity. Benzimidazole system is essential for the antituberculosis activity that is associated with the presence of the imine nitrogen atom in N-1 position. Its replacement by an oxygen or sulfur atom results in a decrease of the activity. The parity of the alkyl substituent at the C-2 position also modifies the activity.

  7. Direct synthesis of alkenyl iodides via indium-catalyzed iodoalkylation of alkynes with alcohols and aqueous HI.

    PubMed

    Wu, Chao; Wang, Zheng; Hu, Zhan; Zeng, Fei; Zhang, Xing-Yu; Cao, Zhong; Tang, Zilong; He, Wei-Min; Xu, Xin-Hua

    2018-05-02

    A convenient and efficient indium-catalyzed approach to synthesize alkenyl iodides has been developed through direct iodoalkylation of alkynes with alcohols and aqueous HI under mild conditions. This catalytic protocol offers an attractive approach for the synthesis of a diverse range of alkenyl iodides in good to excellent yields.

  8. 40 CFR 721.2093 - Alkenyl carboxylate, metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.2093 Alkenyl carboxylate, metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

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

    PubMed

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

    2014-04-09

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

  10. Alkenyl Carboxylic Acid: Engineering the Nanomorphology in Polymer-Polymer Solar Cells as Solvent Additive.

    PubMed

    Zhang, Yannan; Yuan, Jianyu; Sun, Jianxia; Ding, Guanqun; Han, Lu; Ling, Xufeng; Ma, Wanli

    2017-04-19

    We have investigated a series of commercially available alkenyl carboxylic acids with different alkenyl chain lengths (trans-2-hexenoic acid (CA-6), trans-2-decenoic acid (CA-10), 9-tetradecenoic acid (CA-14)) for use as solvent additives in polymer-polymer non-fullerene solar cells. We systematically investigated their effect on the film absorption, morphology, carrier generation, transport, and recombination in all-polymer solar cells. We revealed that these additives have a significant impact on the aggregation of polymer acceptor, leading to improved phase segregation in the blend film. This in-depth understanding of the additives effect on the nanomorphology in all-polymer solar cell can help further boost the device performance. By using CA-10 with the optimal alkenyl chain length, we achieved fine phase separation, balanced charge transport, and suppressed recombination in all-polymer solar cells. As a result, an optimal power conversion efficiency (PCE) of 5.71% was demonstrated which is over 50% higher than that of the as-cast device (PCE = 3.71%) and slightly higher than that of devices with DIO treatment (PCE = 5.68%). Compared with widely used DIO, these halogen-free alkenyl carboxylic acids have a more sustainable processing as well as better performance, which may make them more promising candidates for use as processing additives in organic non-fullerene solar cells.

  11. Imidazoline conditioner for the flotation of oxidized coal

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hefner, R.E. Jr.

    1984-05-22

    Froth flotation of oxidized coal in the presence of certain imidazoline or imidazolinium salts improves both the selectivity and recovery attained. Imidazolines found particularly efficacious are those bearing a fatty alkyl group in the 2- position and an N-aminoethyl or N-hydroxyethyl group. Preferred imidazolinium salts are those corresponding to the following formula: 1-((-)OOC-CH/sub 2/-),1-(C/sub 11/ to C/sub 17/ alkyl or alkenyl-COO-CH/sub 2/-),2-R-2-imidazoline(+) wherein R is a C/sub 6/ to C/sub 22/ alkyl or alkenyl group.

  12. Copper-catalyzed aerobic decarboxylative sulfonylation of cinnamic acids with sodium sulfinates: stereospecific synthesis of (E)-alkenyl sulfones.

    PubMed

    Jiang, Qing; Xu, Bin; Jia, Jing; Zhao, An; Zhao, Yu-Rou; Li, Ying-Ying; He, Na-Na; Guo, Can-Cheng

    2014-08-15

    A copper-catalyzed aerobic decarboxylative sulfonylation of alkenyl carboxylic acids with sodium sulfinates is developed. This study offers a new and expedient strategy for stereoselective synthesis of (E)-alkenyl sulfones that are widely present in biologically active natural products and therapeutic agents. Moreover, the transformation is proposed to proceed via a radical process and exhibits a broad substrate scope and good functional group tolerance.

  13. Boron-containing organosilane polymers and ceramic materials thereof

    NASA Technical Reports Server (NTRS)

    Riccitiello, Salvatore R. (Inventor); Hsu, Ming-Ta S. (Inventor); Chen, Timothy S. (Inventor)

    1989-01-01

    The present invention relates to a polyorgano borosilane ceramic precursor polymer comprising a plurality of repeating units of the formula: (R(sup 1) single bond B)(sub p) being linked together at B by second units of the formula: single bond (R sup 2) single bond (Si single bond R sup 3) single bond (sub q), where R(sup 1) is a lower alkyl, cycloalkyl, phenyl, or (R(sup 2)R(sup 3) single bond Si single bond B single bond)(sub n) and R(sup 2) and R(sup 3) are each independently selected from hydrogen, lower alkyl, vinyl, cycloalkyl, or aryl, n is an integer between 1 and 100; p is an integer between 1 and 100; and q is an integer between 1 and 100. These materials are prepared by combining an organo borohalide of the formula R(sup 4) single bond B single bond (X sup 1) (sub 2) where R(sup 4) is selected from halogen, lower alkyl, cycloalkyl, or aryl, and an organo halosilane of the formula: R(sup 2)(R sup 3)Si(X sup 2)(sub 2) where R(sup 2) and R (sup 3) are each independently selected from lower alkyl, cycloalkyl, or aryl, and X(sup 1) and X(sup 2) are each independently selected from halogen, in an anhydrous aprotic solvent having a boiling point at ambient pressure of not greater than 160 C with in excess of four equivalents of an alkali metal, heating the reaction mixture and recovering the polyorgano borosilane. These silicon boron polymers are useful to generate high-temperature ceramic materials, such as SiC, SiB4, and B4C, upon thermal degradation above 600 C.

  14. Inhibitors of glycogen synthase 3 kinase

    DOEpatents

    Schultz, Peter; Ring, David B.; Harrison, Stephen D.; Bray, Andrew M.

    2000-01-01

    Compounds of formula 1: ##STR1## wherein R.sub.1 is alkyl, cycloalkyl, aryl, aralkyl, heteroaryl, or heteroaralkyl, substituted with 0-3 substituents selected from lower alkyl, halo, hydroxy, lower alkoxy, amino, lower alkyl-amino, and nitro; R.sub.2 is hydroxy, amino, or lower alkoxy; R.sub.3 is H, lower alkyl, lower acyl, lower alkoxy-acyl, or amnino-acyl; R.sub.4 is H or lower alkyl; and pharmaceutically acceptable salts and esters thereof; are effective inhibitors of GSK3.

  15. Inhibitors of glycogen synthase 3 kinase

    DOEpatents

    Schultz, Peter; Ring, David B.; Harrison, Stephen D.; Bray, Andrew M.

    2006-05-30

    Compounds of formula 1: ##STR00001## wherein R.sub.1 is alkyl, cycloalkyl, aryl, aralkyl, heteroaryl, or heteroaralkyl, substituted with 0 3 substituents selected from lower alkyl, halo, hydroxy, lower alkoxy, amino, lower alkyl-amino, and nitro; R.sub.2 is hydroxy, amino, or lower alkoxy; R.sub.3 is H, lower alkyl, lower acyl, lower alkoxy-acyl, or amino-acyl; R.sub.4 is H or lower alkyl; and pharmaceutically acceptable salts and esters thereof; are effective inhibitors of GSK3.

  16. 78 FR 50147 - 2012 Liquid Chemical Categorization Updates

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-08-16

    ..., Alkenyl(C12+) acid ester mixture... Alkyl acrylate-Vinylpyridine copolymer in toluene *.... Y Alkylbenzene...) phenylamine in aromatic solvents Y Alkyl(C9+) benzenes Y Alkyl(C11-C17) benzene sulfonic acid Y Alkylbenzene sulfonic acid (4% or less) Alkyl dithiocarbamate (C19-C35) Y Alkyl dithiothiadiazole (C6-C24) Y Alkyl ester...

  17. Nickel-Catalyzed Addition-Type Alkenylation of Unactivated, Aliphatic C-H Bonds with Alkynes: A Concise Route to Polysubstituted γ-Butyrolactones.

    PubMed

    Li, Mingliang; Yang, Yudong; Zhou, Danni; Wan, Danyang; You, Jingsong

    2015-05-15

    Through the nickel-catalyzed chelation-assisted C-H bond activation strategy, the addition-type alkenylation of unreactive β-C(sp(3))-H bonds of aliphatic amides with internal alkynes is developed for the first time to produce γ,δ-unsaturated carboxylic amide derivatives. The resulting alkenylated products can further be transformed into polysubstituted γ-butyrolactones with pyridinium chlorochromate (PCC).

  18. 15 CFR Supplement No. 1 to Part 745 - Schedules of Chemicals

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 15 Commerce and Foreign Trade 2 2014-01-01 2014-01-01 false Schedules of Chemicals No. Supplement... CHEMICAL WEAPONS CONVENTION REQUIREMENTS Pt. 745, Supp. 1 Supplement No. 1 to Part 745—Schedules of Chemicals C.A.S. Registry No. Schedule 1 A. Toxic chemicals: (1) O-Alkyl (≤C10, incl. cycloalkyl) alkyl (Me...

  19. 15 CFR Supplement No. 1 to Part 745 - Schedules of Chemicals

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 15 Commerce and Foreign Trade 2 2012-01-01 2012-01-01 false Schedules of Chemicals No. Supplement... CHEMICAL WEAPONS CONVENTION REQUIREMENTS Pt. 745, Supp. 1 Supplement No. 1 to Part 745—Schedules of Chemicals C.A.S. Registry No. Schedule 1 A. Toxic chemicals: (1) O-Alkyl (≤C10, incl. cycloalkyl) alkyl (Me...

  20. 15 CFR Supplement No. 1 to Part 745 - Schedules of Chemicals

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 15 Commerce and Foreign Trade 2 2013-01-01 2013-01-01 false Schedules of Chemicals No. Supplement... CHEMICAL WEAPONS CONVENTION REQUIREMENTS Pt. 745, Supp. 1 Supplement No. 1 to Part 745—Schedules of Chemicals C.A.S. Registry No. Schedule 1 A. Toxic chemicals: (1) O-Alkyl (≤C10, incl. cycloalkyl) alkyl (Me...

  1. Boron-based dual imaging probes, compositions and methods for rapid aqueous F-18 labeling, and imaging methods using same

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Zibo; Gabbai, Francois P.; Conti, Peter S.

    A composition useful as a PET and/or fluorescence imaging probe a compound a compound of Formula I, including salts, hydrates and solvates thereof: ##STR00001## wherein R.sub.1-R.sub.7 may be independently selected from hydrogen, halogen, hydroxy, alkoxy, nitro, substituted and unsubstituted amino, cycloalkyl, carboxy, carboxylic acids and esters thereof, cyano, haloalkyl, aryl, X is selected from the group consisting of C and N; and A is selected of hydrogen, halogen, hydroxy, alkoxy, nitro, substituted and unsubstituted amino, alkyl, cycloalkyl, carboxy, carboxylic acids and esters thereof, cyano, haloalkyl, aryl, including phenyl and aminophenyl, and heteroaryl.

  2. Selective thermal oxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    2000-01-01

    A process for selective thermal oxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls is carried out in solvent free zeolites under dark thermal conditions. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  3. Robust, self-assembled, biocompatible films

    DOEpatents

    Swanson, Basil I; Anderson, Aaron S.; Dattelbaum, Andrew M.; Schmidt, Jurgen G.

    2014-06-24

    The present invention provides a composite material including a substrate having an oxide surface, and, a continuous monolayer on the oxide surface, the monolayer including a silicon atom from a trifunctional alkyl/alkenyl/alkynyl silane group that attaches to the oxide surface, an alkyl/alkenyl/alkynyl portion of at least three carbon atoms, a polyalkylene glycol spacer group, and either a reactive site (e.g., a recognition ligand) or a site resistant to non-specific binding (e.g., a methoxy or the like) at the terminus of each modified SAM. The present invention further provides a sensor element, a sensor array and a method of sensing, each employing the composite material. Patterning is also provided together with backfilling to minimize non-specific binding.

  4. Method of using polysilane positive photoresist materials

    DOEpatents

    Harrah, L.A.; Zeigler, J.M.

    1986-05-06

    New polysilane copolymers comprise recurring units of --Si(X)(Y)-- and Si(A)(B)--, Si(X)(Y) being different from Si(A)(B), wherein X and Y together have 1-13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl, with the proviso that only one of X and Y contains a phenyl moiety, or together X and Y are an alkylene group forming a ring with the adjoining Si atom, and wherein A and B together have 3-13 carbon atoms, and A and B each independently is alkyl or cycloalkyl, with the proviso (a) that when one of A and B is ethyl, the other is not methyl or ethyl, and (b) that when one of A ad B is n-propyl and the other is methyl, X and Y are not both methyl. Corresponding homopolysilanes are also provided. Upon ultraviolet irradiation, they photodepolymerize to form volatile products. As a result, they represent a new class of photoresists which enable direct formation of a positive image eliminating the heretofore required development step.

  5. Polysilane positive photoresist materials and methods for their use

    DOEpatents

    Harrah, L.A.; Zeigler, J.M.

    1984-04-05

    New polysilane copolymers comprise recurring units of -Si(X)(Y)- and Si(A)(B)-, Si(X)(Y) being different from Si(A)(B). X and Y together have 1 to 13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl, with the proviso that only one of X and Y contains a phenyl moiety, or together X and Y are an alkylene group forming a ring with the adjoining Si atom. A and B together have 3 to 13 carbon atoms, and A and B each independently is alkyl or cycloalkyl, with the proviso that when one of A and B is ethyl, the other is not methyl or ethyl, and that when one of A and B is n-propyl and the other is methyl, X and Y are not both methyl. Corresponding homopolysilanes are also provided. Upon ultraviolet irradiation, they photodepolymerize to form volatile products. As a result, they represent a new class of photoresists which enable direct formation of a positive image eliminating the heretofore required development step.

  6. Method of using polysilane positive photoresist materials

    DOEpatents

    Harrah, Larry A.; Zeigler, John M.

    1986-01-01

    New polysilane copolymers comprise recurring units of --Si(X)(Y)-- and Si(A)(B)--, Si(X)(Y) being different from Si(A)(B), wherein X and Y together have 1-13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl, with the proviso that only one of X and Y contains a phenyl moiety, or together X and Y are an alkylene group forming a ring with the adjoining Si atom, and wherein A and B together have 3-13 carbon atoms, and A and B each independently is alkyl or cycloalkyl, with the proviso (a) that when one of A and B is ethyl, the other is not methyl or ethyl, and (b) that when one of A ad B is n-propyl and the other is methyl, X and Y are not both methyl. Corresponding homopolysilanes are also provided. Upon ultraviolet irradiation, they photodepolymerize to form volatile products. As a result, they represent a new class of photoresists which enable direct formation of a positive image eliminating the heretofore required development step.

  7. Polysilane positive photoresist materials and methods for their use

    DOEpatents

    Harrah, Larry A.; Zeigler, John M.

    1986-01-01

    New polysilane copolymers comprise recurring units of --Si(X)(Y)-- and Si(A)(B)--, Si(X)(Y) being different from Si(A)(B), wherein X and Y together have 1-13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl, with the proviso that only one of X and Y contains a phenyl moiety, or together X and Y are an alkylene group forming a ring with the adjoining Si atom, and wherein A and B together have 3-13 carbon atoms, and A and B each independently is alkyl or cycloalkyl, with the proviso (a) that when one of A and B is ethyl, the other is not methyl or ethyl, and (b) that when one of A and B is n-propyl and the other is methyl, X and Y are not both methyl. Corresponding homopolysilanes are also provided. Upon ultraviolet irradiation, they photodepolymerize to form volatile products. As a result, they represent a new class of photoresists which enable direct formation of a positive image eliminating the heretofore required development step.

  8. Novel one-pot synthesis of 5-alkenyl-15-alkynylporphyrins and their derivatisation to a butadiyne-linked benzoporphyrin dimer.

    PubMed

    Yamada, Hiroko; Kushibe, Kayo; Okujuma, Tetsuo; Uno, Hidemitsu; Ono, Noboru

    2006-01-28

    5-Alkenyl-15-alkynylporphyrins have been obtained unexpectedly by [2 + 2] acid-catalyzed condensation of dipyrrylmethane and TMS propynal in addition to 5,15-dialkynylporphyrin, and the unsymmetrical porphyrin can be converted to a butadiyne-linked dimer by selective desilylation of the alkynyl TMS.

  9. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    1999-01-01

    A process for selective thermal oxidation or photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  10. Decarboxylative alkenylation

    NASA Astrophysics Data System (ADS)

    Edwards, Jacob T.; Merchant, Rohan R.; McClymont, Kyle S.; Knouse, Kyle W.; Qin, Tian; Malins, Lara R.; Vokits, Benjamin; Shaw, Scott A.; Bao, Deng-Hui; Wei, Fu-Liang; Zhou, Ting; Eastgate, Martin D.; Baran, Phil S.

    2017-04-01

    Olefin chemistry, through pericyclic reactions, polymerizations, oxidations, or reductions, has an essential role in the manipulation of organic matter. Despite its importance, olefin synthesis still relies largely on chemistry introduced more than three decades ago, with metathesis being the most recent addition. Here we describe a simple method of accessing olefins with any substitution pattern or geometry from one of the most ubiquitous and variegated building blocks of chemistry: alkyl carboxylic acids. The activating principles used in amide-bond synthesis can therefore be used, with nickel- or iron-based catalysis, to extract carbon dioxide from a carboxylic acid and economically replace it with an organozinc-derived olefin on a molar scale. We prepare more than 60 olefins across a range of substrate classes, and the ability to simplify retrosynthetic analysis is exemplified with the preparation of 16 different natural products across 10 different families.

  11. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, H.; Blatter, F.; Sun, H.

    1999-06-22

    A process is described for selective thermal oxidation or photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts. 19 figs.

  12. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    2001-01-01

    A process for a combined selective thermal oxidation and photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly combined selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  13. 1,2-Dicyclopropylethyne and (Cyclopropylethynyl)cyclobutane from an Efficient Synthesis of 1,2-(omega-Haloalkyl)ethynes and 1-Cycloalkyl-2-(omega-haloalkyl)ethynes (Pre Print)

    DTIC Science & Technology

    2012-02-09

    Efficient Synthesis of 1,2-(ω-Haloalkyl0ethynes and 1 -Cycloalkyl-2-(ω-haloalkyl)ethynes 5b. GRANT NUMBER (Pre Print) 5c. PROGRAM ELEMENT NUMBER...suffers from low yield as is evi- dent from the reported synthesis of 5-chloropent- 1 -yne (5, 57%)9 and 1,8-dichlorooct- 1 -yne (9, 36%).8 The synthesis ... chloropropane / 1 -bromo-4-chlorobutane is very sluggish and incomplete in THF. However, the reaction in the presence of 10 mol % Bu4NI results in an

  14. Preliminary antifungal and cytotoxic evaluation of synthetic cycloalkyl[b]thiophene derivatives with PLS-DA analysis.

    PubMed

    Souza, Beatriz C C; De Oliveira, Tiago B; Aquino, Thiago M; de Lima, Maria C A; Pitta, Ivan R; Galdino, Suely L; Lima, Edeltrudes O; Gonçalves-Silva, Teresinha; Militão, Gardênia C G; Scotti, Luciana; Scotti, Marcus T; Mendonça, Francisco J B

    2012-06-01

    A series of 2-[(arylidene)amino]-cycloalkyl[b]thiophene-3-carbonitriles (2a-x) was synthesized by incorporation of substituted aromatic aldehydes in Gewald adducts (1a-c). The title compounds were screened for their antifungal activity against Candida krusei and Criptococcus neoformans and for their antiproliferative activity against a panel of 3 human cancer cell lines (HT29, NCI H-292 and HEP). For antiproliferative activity, the partial least squares (PLS) methodology was applied. Some of the prepared compounds exhibited promising antifungal and proliferative properties. The most active compounds for antifungal activity were cyclohexyl[b]thiophene derivatives, and for antiproliferative activity cycloheptyl[b]thiophene derivatives, especially 2-[(1H-indol-2-yl-methylidene)amino]- 5,6,7,8-tetrahydro-4H-cyclohepta[b]thiophene-3-carbonitrile (2r), which inhibited more than 97 % growth of the three cell lines. The PLS discriminant analysis (PLS-DA) applied generated good exploratory and predictive results and showed that the descriptors having shape characteristics were strongly correlated with the biological data.

  15. Stereospecific olefin polymerization catalysts

    DOEpatents

    Bercaw, John E.; Herzog, Timothy A.

    1998-01-01

    A metallocene catalyst system for the polymerization of .alpha.-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula ##STR1## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ; R.sup.5 is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E.sup.1, E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; and the ligand may have C.sub.S or C.sub.1 -symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from .alpha.-olefin monomers.

  16. Stereospecific olefin polymerization catalysts

    DOEpatents

    Bercaw, J.E.; Herzog, T.A.

    1998-01-13

    A metallocene catalyst system is described for the polymerization of {alpha}-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula shown wherein: R{sup 1}, R{sup 2}, and R{sup 3} are independently selected from the group consisting of hydrogen, C{sub 1} to C{sub 10} alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C{sub 1} to C{sub 10} alkyls as a substituent, C{sub 6} to C{sub 15} aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R{sup 8}){sub 3} where R{sup 8} is selected from the group consisting of C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; R{sup 4} and R{sup 6} are substituents both having van der Waals radii larger than the van der Waals radii of groups R{sup 1} and R{sup 3}; R{sup 5} is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E{sup 1}, E{sup 2} are independently selected from the group consisting of Si(R{sup 9}){sub 2}, Si(R{sup 9}){sub 2}--Si(R{sup 9}){sub 2}, Ge(R{sup 9}){sub 2}, Sn(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}--C(R{sup 9}){sub 2}, where R{sup 9} is C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; and the ligand may have C{sub S} or C{sub 1}-symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from {alpha}-olefin monomers.

  17. Tricyclic [1,2,4]triazine 1,4-dioxides as hypoxia selective cytotoxins.

    PubMed

    Hay, Michael P; Hicks, Kevin O; Pchalek, Karin; Lee, Ho H; Blaser, Adrian; Pruijn, Frederik B; Anderson, Robert F; Shinde, Sujata S; Wilson, William R; Denny, William A

    2008-11-13

    A series of novel tricyclic triazine-di- N-oxides (TTOs) related to tirapazamine have been designed and prepared. A wide range of structural arrangements with cycloalkyl, oxygen-, and nitrogen-containing saturated rings fused to the triazine core, coupled with various side chains linked to either hemisphere, resulted in TTO analogues that displayed hypoxia-selective cytotoxicity in vitro. Optimal rates of hypoxic metabolism and tissue diffusion coefficients were achieved with fused cycloalkyl rings in combination with both the 3-aminoalkyl or 3-alkyl substituents linked to weakly basic soluble amines. The selection was further refined using pharmacokinetic/pharmacodynamic model predictions of the in vivo hypoxic potency (AUC req) and selectivity (HCD) with 12 TTO analogues predicted to be active in vivo, subject to the achievement of adequate plasma pharmacokinetics.

  18. Tricyclic [1,2,4]Triazine 1,4-Dioxides As Hypoxia Selective Cytotoxins

    PubMed Central

    Hay, Michael P.; Hicks, Kevin O.; Pchalek, Karin; Lee, Ho H.; Blaser, Adrian; Pruijn, Frederik B.; Anderson, Robert F.; Shinde, Sujata S.; Wilson, William R.; Denny, William A.

    2009-01-01

    A series of novel tricyclic triazine-di-N-oxides (TTOs) related to tirapazamine have been designed and prepared. A wide range of structural arrangements with cycloalkyl, oxygen- and nitrogen-containing saturated rings fused to the triazine core, coupled with various side chains linked to either hemisphere, resulted in TTO analogues that displayed hypoxia-selective cytotoxicity in vitro. Optimal rates of hypoxic metabolism and tissue diffusion coefficients were achieved with fused cycloalkyl rings in combination with both the 3-aminoalkyl or 3-alkyl substituents linked to weakly basic soluble amines. The selection was further refined using pharmacokinetic/pharmacodynamic model predictions of the in vivo hypoxic potency (AUCreq) and selectivity (HCD) with 12 TTO analogues predicted to be active in vivo, subject to the achievement of adequate plasma pharmacokinetics. PMID:18847185

  19. Substitution of the nitro group with Grignard reagents: facile arylation and alkenylation of pyridine N-oxides.

    PubMed

    Zhang, Fang; Zhang, Song; Duan, Xin-Fang

    2012-11-02

    The unprecedented substitution of a nitro group with aryl or alkenyl groups of Grignard reagents affords 2-aryl or alkenylpyridine N-oxides in modest to high yields with high chemoselectivity. This protocol allows a simple and clean synthesis of various 2-substituted pyridine N-oxides and the corresponding pyridine derivatives. Furthermore, straightforward one-pot iterative functionality of pyridine N-oxides could also be achieved simply by successive applications of two Grignard reagents.

  20. A broadly applicable NHC-Cu-catalyzed approach for efficient, site-, and enantioselective coupling of readily accessible (pinacolato)alkenylboron compounds to allylic phosphates and applications to natural product synthesis.

    PubMed

    Gao, Fang; Carr, James L; Hoveyda, Amir H

    2014-02-05

    A set of protocols for catalytic enantioselective allylic substitution (EAS) reactions that allow for additions of alkenyl units to readily accessible allylic electrophiles is disclosed. Transformations afford 1,4-dienes that contain a tertiary carbon stereogenic site and are promoted by 1.0-5.0 mol % of a copper complex of an N-heterocyclic carbene (NHC). Aryl- as well as alkyl-substituted electrophiles bearing a di- or trisubstituted alkene may be employed. Reactions can involve a variety of robust alkenyl-(pinacolatoboron) [alkenyl-B(pin)] compounds that can be either purchased or prepared by various efficient, site-, and/or stereoselective catalytic reactions, such as cross-metathesis or proto-boryl additions to terminal alkynes. Vinyl-, E-, or Z-disubstituted alkenyl-, 1,1-disubstituted alkenyl-, acyclic, or heterocyclic trisubstituted alkenyl groups may be added in up to >98% yield, >98:2 SN2':SN2, and 99:1 enantiomeric ratio (er). NHC-Cu-catalyzed EAS with alkenyl-B(pin) reagents containing a conjugated carboxylic ester or aldehyde group proceed to provide the desired 1,4-diene products in good yield and with high enantioselectivity despite the presence of a sensitive stereogenic tertiary carbon center that could be considered prone to epimerization. In most instances, the alternative approach of utilizing an alkenylmetal reagent (e.g., an Al-based species) represents an incompatible option. The utility of the approach is illustrated through applications to enantioselective synthesis of natural products such as santolina alcohol, semburin, nyasol, heliespirone A, and heliannuol E.

  1. Alkyl–Alkyl Suzuki Cross-Couplings of Unactivated Secondary Alkyl Chlorides**

    PubMed Central

    Lu, Zhe; Fu, Gregory C.

    2010-01-01

    The first method for achieving alkyl–alkyl Suzuki reactions of unactivated secondary alkyl chlorides has been developed. Carbon–carbon bond formation occurs under mild conditions (at room temperature) with the aid of commercially available catalyst components. This method has proved to be versatile: without modification, it can be applied to Suzuki reactions of secondary and primary alkyl bromides and iodides, as well as primary alkyl chlorides. Mechanistic investigations suggest that oxidative addition is not the turnover-limiting step of the catalytic cycle for unactivated secondary alkyl iodides and bromides, whereas it may be (partially) for chlorides. PMID:20715038

  2. Lanthanum Tricyanide-Catalyzed Acyl Silane-Ketone Benzoin Additions and Kinetic Resolution of Resultant α-Silyloxyketones

    PubMed Central

    Tarr, James C.

    2010-01-01

    We report the full account of our efforts on the lanthanum tricyanide-catalyzed acyl silane-ketone benzoin reaction. The reaction exhibits a wide scope in both acyl silane (aryl, alkyl) and ketone (aryl-alkyl, alkyl-alkyl, aryl-aryl, alkenyl-alkyl, alkynyl-alkyl) coupling partners. The diastereoselectivity of the reaction has been examined in both cyclic and acyclic systems. Cyclohexanones give products arising from equatorial attack by the acyl silane. The diastereoselectivity of acyl silane addition to acyclic α-hydroxy ketones can be controlled by varying the protecting group to obtain either Felkin-Ahn or chelation control. The resultant α-silyloxyketone products can be resolved with selectivity factors from 10 to 15 by subjecting racemic ketone benzoin products to CBS reduction. PMID:20392127

  3. Lanthanum tricyanide-catalyzed acyl silane-ketone benzoin additions and kinetic resolution of resultant alpha-silyloxyketones.

    PubMed

    Tarr, James C; Johnson, Jeffrey S

    2010-05-21

    We report the full account of our efforts on the lanthanum tricyanide-catalyzed acyl silane-ketone benzoin reaction. The reaction exhibits a wide scope in both acyl silane (aryl, alkyl) and ketone (aryl-alkyl, alkyl-alkyl, aryl-aryl, alkenyl-alkyl, alkynyl-alkyl) coupling partners. The diastereoselectivity of the reaction has been examined in both cyclic and acyclic systems. Cyclohexanones give products arising from equatorial attack by the acyl silane. The diastereoselectivity of acyl silane addition to acyclic alpha-hydroxy ketones can be controlled by varying the protecting group to obtain either Felkin-Ahn or chelation control. The resultant alpha-silyloxyketone products can be resolved with selectivity factors from 10 to 15 by subjecting racemic ketone benzoin products to CBS reduction.

  4. Stereoselective Vinylation of Aryl N-(2-Pyridylsulfonyl) Aldimines with 1-Alkenyl-1,1-Heterobimetallic Reagents

    PubMed Central

    Hussain, Nusrah; Hussain, Mahmud M.; Ziauddin, Muhammed; Triyawatanyu, Plengchat; Walsh, Patrick J.

    2011-01-01

    Vinylation of aryl N-(2-pyridylsulfonyl) aldimines with versatile 1-alkenyl-1,1-borozinc heterobimetallic reagents is disclosed. In situ hydroboration of air-stable B(pin)-alkynes followed by chemoselective transmetallation with dimethylzinc and addition to aldimines provides B(pin)-substituted allylic amines in 60–93% yield in a one-pot procedure. The addition step can be followed by either B–C bond oxidation to provide α-amino ketones (71–98% yield) or Suzuki cross-coupling to furnish trisubstituted 2-arylated (E)-allylic amines (51–73% yield). PMID:22085226

  5. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl sulfates...

  6. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl sulfates...

  7. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl sulfates...

  8. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl sulfates...

  9. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl sulfates...

  10. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to reporting...

  11. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to reporting...

  12. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to reporting...

  13. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to reporting...

  14. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to reporting...

  15. Pyrrolo isoquinolines

    DOEpatents

    Goodman, Mark M.; Shi, Bing Z.

    2000-01-01

    Compounds of the formula: ##STR1## wherein X, Y, and R, independently of one another, is each a H; halogen, wherein said halogen is selected from the group consisting of .sup.123 I, .sup.124 I, .sup.125 I, .sup.131 I, .sup.75 Br, .sup.76 Br, .sup.77 Br, .sup.82 Br, .sup.18 F, or .sup.210 At; small alkyl, small alkenyl, or small alkynyl, any of which contains from one to about six carbon atoms and optionally having a carbon atom replaced by an O or S; or halogen substituted-small alkyl, halogen substituted-small alkenyl, or halogen substituted-small alkynyl wherein said compound contains at least one radioacitve halogen. The compounds bind to the serotonin transporter. Depending upon the choice of halogen substituent, the compounds are useful for PET or SPECT imaging, diagnosis and treatment of psychiatric disorders such as depression, anxiety, obsessive-compulsive disorder, and other conditions associated with defects of serotonin transporter function.

  16. Derivatives of cardanol through the ene reaction with diethyl azodicarboxylate

    USDA-ARS?s Scientific Manuscript database

    Cardanol is an alkyl/alkenyl phenolic material obtained from cashew nut shell liquid (CNSL), which is a byproduct of cashew nut processing. In an effort to develop new uses, cardanol was derivatized for the first time with diethyl azodicarboxylate (DEAD) through the ene reaction. The reaction was fa...

  17. 21 CFR 178.3400 - Emulsifiers and/or surface-active agents.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... paperboard. α-[p-(1,1,3,3-Tetramethylbutyl)phenyl] omega-hydroxypoly(oxyethylene) produced by the... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Emulsifiers and/or surface-active agents. 178.3400... substances: List of substances Limitations α-Alkyl-, α-alkenyl-, and α-alkylaryl-omega-hydroxypoly...

  18. A Critical Evaluation of Studies Employing Alkenyl Halide ’Mechanistic Probe’ as Indicators of Single Electron Transfer Processes.

    DTIC Science & Technology

    1987-07-07

    College Station, TX 77843 Pittsburgh, PA 15260 Introduction: Chemical reactions come about through the reorganization of valence electrons. The notion...Contmnue on reverie of necessary and odentify 0)’ Wooc ,7umor r) Recently it has been suggested that many reaction traditionally classed in polar terms may...evaluates the utility of these alkenyl halide probes as mechanistic probes for SET. Reactions which interfere with the standard analysis ~ include the

  19. [Alkylating agents].

    PubMed

    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.

  20. Asymmetric synthesis of α-alkenyl homoallylic primary amines via 1,2-addition of Grignard reagent to α,β-unsaturated phosphonyl imines.

    PubMed

    Xiong, Yiwen; Mei, Haibo; Xie, Chen; Han, Jianlin; Li, Guigen; Pan, Yi

    2013-01-01

    A series of chiral N -phosphonyl protected α-alkenyl homoallylic primary amines were synthesized by asymmetric addition of allylmagnesium bromide Grignard reagent towards chiral α,β-unsaturated imines. Only 1,2-adduct was obtained for all the imines with good yields and excellent diastereoselectivities. The chiral auxiliary could be easily removed under simple conditions, giving free multiple functionalized primary amines.

  1. Imparting Catalyst-Control upon Classical Palladium-Catalyzed Alkenyl C–H Bond Functionalization Reactions

    PubMed Central

    Sigman, Matthew S.; Werner, Erik W.

    2011-01-01

    Conspectus The functional group transformations carried out by the palladium-catalyzed Wacker and Heck reactions are radically different, but they are both alkenyl C-H bond functionalization reactions that have found extensive use in organic synthesis. The synthetic community depends heavily on these important reactions, but selectivity issues arising from control by the substrate, rather than control by the catalyst, have prevented the realization of their full potential. Because of important similarities in the respective selectivity-determining nucleopalladation and β-hydride elimination steps of these processes, we posit that the mechanistic insight garnered through the development of one of these catalytic reactions may be applied to the other. In this Account, we detail our efforts to develop catalyst-controlled variants of both the Wacker oxidation and the Heck reaction to address synthetic limitations and provide mechanistic insight into the underlying organometallic processes of these reactions. In contrast to previous reports, we discovered that electrophilic palladium catalysts with non-coordinating counterions allowed for the use of a Lewis basic ligand to efficiently promote TBHP-mediated Wacker oxidation reactions of styrenes. This discovery led to the mechanistically guided development of a Wacker reaction catalyzed by a palladium complex with a bidentate ligand. This ligation may prohibit coordination of allylic heteroatoms, thereby allowing for the application of the Wacker oxidation to substrates that were poorly behaved under classical conditions. Likewise, we unexpectedly discovered that electrophilic Pd-σ-alkyl intermediates are capable of distinguishing between electronically inequivalent C–H bonds during β-hydride elimination. As a result, we have developed E-styrenyl selective oxidative Heck reactions of previously unsuccessful electronically non-biased alkene substrates using arylboronic acid derivatives. The mechanistic insight gained

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

    PubMed

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

    2017-03-09

    A wide range of hydroperoxides (C 1 -C 3 alkyl hydroperoxides, C 3 -C 7 alkenyl hydroperoxides, C 7 ketohydroperoxides, and hydrogen peroxide (H 2 O 2 )), 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 10 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.

  3. 21 CFR 176.300 - Slimicides.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... provided for under paragraph (d) of this section. (3) Slimicides are added to the process water used in the... substances Limitations Acrolein Alkenyl (C16-C18) dimethylethyl-ammonium bromide n-Alkyl (C12-C18) dimethyl benzyl ammonium chloride 1,2-Benzisothiazolin-3-one At a level of 0.06 pound per ton of dry weight fiber...

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

    PubMed Central

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

    2012-01-01

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

  5. Investigation of gamma-ray induced polymer formation of the carboranes. Annual progress report, November 1, 1972--September 30, 1973

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Klingen, T.J.

    1973-10-01

    Research is reported on the radiation chemistry of o-carborane STA 1, 2- dicarba-closo-dodecaborane (11)! and its l-alkyl and 1-alkenyl derivatives. The principal purpose of the research is to establish optirmum conditions for radiation-induced polymerization of such compounds. Properties and structures of polymeric products, identities and yields of minor products, and reaction mechanisms are being determined. (auth)

  6. Method of making alkyl esters

    DOEpatents

    Elliott, Brian

    2010-09-14

    Methods of making alkyl esters are described herein. The methods are capable of using raw, unprocessed, low-cost feedstocks and waste grease. Generally, the method involves converting a glyceride source to a fatty acid composition and esterifying the fatty acid composition to make alkyl esters. In an embodiment, a method of making alkyl esters comprises providing a glyceride source. The method further comprises converting the glyceride source to a fatty acid composition comprising free fatty acids and less than about 1% glyceride by mass. Moreover, the method comprises esterifying the fatty acid composition in the presence of a solid acid catalyst at a temperature ranging firm about 70.degree. C. to about 120.degree. C. to produce alkyl esters, such that at least 85% of the free fatty acids are converted to alkyl esters. The method also incorporates the use of packed bed reactors for glyceride conversion and/or fatty acid esterification to make alkyl esters.

  7. Stereoconvergent Amine-Directed Alkyl–Alkyl Suzuki Reactions of Unactivated Secondary Alkyl Chlorides

    PubMed Central

    Lu, Zhe; Wilsily, Ashraf; Fu, Gregory C.

    2011-01-01

    A new family of stereoconvergent cross-couplings of unactivated secondary alkyl electrophiles has been developed, specifically, arylamine-directed alkyl–alkyl Suzuki reactions. This represents the first such investigation to be focused on the use of alkyl chlorides as substrates. Structure-enantioselectivity studies are consistent with the nitrogen, not the aromatic ring, serving as the primary site of coordination of the arylamine to the catalyst. The rate law for this asymmetric cross-coupling is compatible with transmetalation being the turnover-limiting step of the catalytic cycle. PMID:21553917

  8. Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase.

    PubMed

    Kim, In-Hae; Park, Yong-Kyu; Nishiwaki, Hisashi; Hammock, Bruce D; Nishi, Kosuke

    2015-11-15

    Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase (sEH) were investigated. First, a series of alkyl or aryl groups were substituted on the carbon alpha to the phosphonate function in amide compounds to see whether substituted phosphonates can act as a secondary pharmacophore. A tert-butyl group (16) on the alpha carbon was found to yield most potent inhibition on the target enzyme. A 4-50-fold drop in inhibition was induced by other substituents such as aryls, substituted aryls, cycloalkyls, and alkyls. Then, the modification of the O-substituents on the phosphonate function revealed that diethyl groups (16 and 23) were preferable for inhibition to other longer alkyls or substituted alkyls. In amide compounds with the optimized diethylphosphonate moiety and an alkyl substitution such as adamantane (16), tetrahydronaphthalene (31), or adamantanemethane (36), highly potent inhibitions were gained. In addition, the resulting potent amide-phosphonate compounds had reasonable water solubility, suggesting that substituted phosphonates in amide inhibitors are effective for both inhibition potency on the human sEH and water solubility as a secondary pharmacophore. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Alkylation of enolates: An electrophilicity perspective

    NASA Astrophysics Data System (ADS)

    Elango, M.; Parthasarathi, R.; Subramanian, V.; Chattaraj, P. K.

    Enolates are ambient nucleophiles, and alkylation can occur either at a carbon or at an oxygen site. It is known that the ratio of C/O alkylation depends significantly on various factors, including the type of enolate, alkylating agent, site of alkylation, and solvent environment. Analysis of regioselectivity and solvent effects on alkylation of lithium enolates is investigated using various reactivity descriptors, including generalized philicity. These results point out the reliability of both global and local reactivity descriptors in providing significant information about site selectivity and chemical reactivity of lithium enolates.

  10. Process for conversion of lignin to reformulated, partially oxygenated gasoline

    DOEpatents

    Shabtai, Joseph S.; Zmierczak, Wlodzimierz W.; Chornet, Esteban

    2001-01-09

    A high-yield process for converting lignin into reformulated, partially oxygenated gasoline compositions of high quality is provided. The process is a two-stage catalytic reaction process that produces a reformulated, partially oxygenated gasoline product with a controlled amount of aromatics. In the first stage of the process, a lignin feed material is subjected to a base-catalyzed depolymerization reaction, followed by a selective hydrocracking reaction which utilizes a superacid catalyst to produce a high oxygen-content depolymerized lignin product mainly composed of alkylated phenols, alkylated alkoxyphenols, and alkylbenzenes. In the second stage of the process, the depolymerized lignin product is subjected to an exhaustive etherification reaction, optionally followed by a partial ring hydrogenation reaction, to produce a reformulated, partially oxygenated/etherified gasoline product, which includes a mixture of substituted phenyl/methyl ethers, cycloalkyl methyl ethers, C.sub.7 -C.sub.10 alkylbenzenes, C.sub.6 -C.sub.10 branched and multibranched paraffins, and alkylated and polyalkylated cycloalkanes.

  11. Thioimidazolium Ionic Liquids as Tunable Alkylating Agents.

    PubMed

    Guterman, Ryan; Miao, Han; Antonietti, Markus

    2018-01-19

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

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

    PubMed Central

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

    2009-01-01

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

  13. Transition-Metal-Catalyzed C-H Alkylation Using Alkenes.

    PubMed

    Dong, Zhe; Ren, Zhi; Thompson, Samuel J; Xu, Yan; Dong, Guangbin

    2017-07-12

    Alkylation reactions represent an important organic transformation to form C-C bonds. In addition to conventional approaches with alkyl halides or sulfonates as alkylating agents, the use of unactivated olefins for alkylations has become attractive from both cost and sustainability viewpoints. This Review summarizes transition-metal-catalyzed alkylations of various carbon-hydrogen bonds (addition of C-H bonds across olefins) using regular olefins or 1,3-dienes up to May 2016. According to the mode of activation, the Review is divided into two sections: alkylation via C-H activation and alkylation via olefin activation.

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

    PubMed

    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.

  15. Polyimides with pendant alkyl groups

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Young, P. R.

    1982-01-01

    The effect on selected polyimide properties when pendant alkyl groups were attached to the polymer backbone was investigated. A series of polymers were prepared using benzophenone tetracarboxylic acid dianhydride (BTDA) and seven different p-alkyl-m,p'-diaminobenzophenone monomers. The alkyl groups varied in length from C(1) (methyl) to C(9) (nonyl). The polyimide prepared from BTDA and m,p'-diaminobenzophenone was included as a control. All polymers were characterized by various chromatographic, spectroscopic, thermal, and mechanical techniques. Increasing the length of the pendant alkyl group resulted in a systematic decrease in glass transition temperature (Tg) for vacuum cured films. A 70 C decrease in Tg to 193 C was observed for the nonyl polymer compared to the Tg for the control. A corresponding systematic increase in Tg indicative of crosslinking, was observed for air cured films. Thermogravimetric analysis revealed a slight sacrifice in thermal stability with increasing alkyl length. No improvement in film toughness was observed.

  16. Molecular design of sequence specific DNA alkylating agents.

    PubMed

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

    2009-01-01

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

  17. Mass spectral analysis of long chain alkyl aromatic compounds synthesized from alpha-olefin alkylation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Cheng, M.T.; Hudson, J.D.

    1994-12-31

    Long chain alkyl aromatic compounds are important petrochemicals with many applications. They are generally synthesized by alkylating the corresponding aromatic nucleus. In this report, the authors will describe the mass spectral fragmentation of alkylphenols and alkylsalicylates.

  18. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  19. Stereocontrolled Alkylative Construction of Quaternary Carbon Centers

    PubMed Central

    Kummer, David A.; Chain, William J.; Morales, Marvin R.; Quiroga, Olga; Myers, Andrew G.

    2009-01-01

    Protocols for the stereodefined formation of α,α-disubstituted enolates of pseudoephedrine amides are presented followed by the implementation of these in diastereoselective alkylation reactions. Direct alkylation of α,α-disubstituted pseudoephedrine amide substrates is demonstrated to be both efficient and diastereoselective across a range of substrates, as exemplified by alkylation of the diastereomeric pseudoephedrine α-methylbutyramides, where both substrates are found to undergo stereospecific replacement of the α-C-H bond with α-C-alkyl, with retention of stereochemistry. This is shown to arise by sequential stereospecific enolization and alkylation reactions, with the alkyl halide attacking a common π-face of the E- and Z-enolates, proposed to be that opposite the pseudoephedrine alkoxide side-chain. Pseudoephedrine α-phenylbutyramides are found to undergo highly stereoselective but not stereospecific α-alkylation reactions, which evidence suggests is due to facile enolate isomerization. Also, we show that α, α-disubstituted pseudoephedrine amide enolates can be generated in a highly stereocontrolled fashion by conjugate addition of an alkyllithium reagent to the s-cis-conformer of an α-alkyl-α,β-unsaturated pseudoephedrine amide, providing α,α-disubstituted enolate substrates that undergo alkylation in the same sense as those formed by direct deprotonation. Methods are presented to transform the α-quaternary pseudoephedrine amide products into optically active carboxylic acids, ketones, primary alcohols, and aldehydes. PMID:18788739

  20. Sequential addition reactions of two molecules of Grignard reagents to thioformamides.

    PubMed

    Murai, Toshiaki; Ui, Kazuki; Narengerile

    2009-08-07

    Sequential addition reactions of two molecules of Grignard reagents to thioformamides were found to yield tertiary amines in an efficient manner. The addition of two different Grignard reagents can be accomplished by using one equivalent of arylmagnesium reagent in the first step. In the second step, a variety of reagents such as alkyl, alkenyl, aryl, and alkynyl reagents were used to afford the corresponding amines in good to high yields.

  1. Photoinduced, Copper-Catalyzed Carbon-Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature.

    PubMed

    Ratani, Tanvi S; Bachman, Shoshana; Fu, Gregory C; Peters, Jonas C

    2015-11-04

    We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C-N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C-C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2](-) may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride.

  2. Palladium-Catalyzed Borylation of Primary Alkyl Bromides

    PubMed Central

    Joshi-Pangu, Amruta; Ma, Xinghua; Diane, Mohamed; Iqbal, Sidra; Kribs, Robert J.; Huang, Richard; Wang, Chao-Yuan

    2012-01-01

    A mild Pd-catalyzed process for the borylation of alkyl bromides has been developed using bis(pinacolato)diboron as a boron source. This process accommodates the use of a wide range of functional groups on the alkyl bromide substrate. Primary bromides react with complete selectivity in the presence of a secondary bromide. The generality of this approach is demonstrated by its extension to the use of alkyl iodides and alkyl tosylates, as well as borylation reactions employing bis(neopentyl glycolato)diboron as the boron source. PMID:22774861

  3. In situ synthesis of alkenyl tetrazines for highly fluorogenic bioorthogonal live-cell imaging probes.

    PubMed

    Wu, Haoxing; Yang, Jun; Šečkutė, Jolita; Devaraj, Neal K

    2014-06-02

    In spite of the wide application potential of 1,2,4,5-tetrazines, particularly in live-cell and in vivo imaging, a major limitation has been the lack of practical synthetic methods. Here we report the in situ synthesis of (E)-3-substituted 6-alkenyl-1,2,4,5-tetrazine derivatives through an elimination-Heck cascade reaction. By using this strategy, we provide 24 examples of π-conjugated tetrazine derivatives that can be conveniently prepared from tetrazine building blocks and related halides. These include tetrazine analogs of biological small molecules, highly conjugated buta-1,3-diene-substituted tetrazines, and a diverse array of fluorescent probes suitable for live-cell imaging. These highly conjugated probes show very strong fluorescence turn-on (up to 400-fold) when reacted with dienophiles such as cyclopropenes and trans-cyclooctenes, and we demonstrate their application for live-cell imaging. This work provides an efficient and practical synthetic methodology for tetrazine derivatives and will facilitate the application of conjugated tetrazines, particularly as fluorogenic probes for live-cell imaging. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Aryl sulfonate based anticancer alkylating agents.

    PubMed

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

    2018-05-01

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

  5. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M [Idaho Falls, ID; Petkovic, Lucia [Idaho Falls, ID

    2009-09-22

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

  6. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

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

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

    PubMed

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

    2015-02-20

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

  8. Substrate-Directed Hydroacylation: Rh-Catalyzed Coupling of Vinyl Phenols and Non-Chelating Aldehydes

    PubMed Central

    Murphy, Stephen K.; Bruch, Achim

    2014-01-01

    We report a protocol for branched-selective hydroacylation of vinylphenols with aryl, alkenyl and alkyl aldehydes. This cross-coupling yields α-aryl ketones that can be cyclized to benzofurans, and it enables access to eupomatenoid natural products in four steps or less from eugenol. Excellent reactivity and high levels of branched regioselectivity are obtained. We propose that aldehyde decarbonylation is overcome by using an anionic directing group on the olefin and a small bite-angle diphosphine ligand. PMID:24478146

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

    PubMed

    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.

  10. A Broadly Applicable NHC–Cu-Catalyzed Approach for Efficient, Site-, and Enantioselective Coupling of Readily Accessible (Pinacolato)alkenylboron Compounds to Allylic Phosphates and Applications to Natural Product Synthesis

    PubMed Central

    2015-01-01

    A set of protocols for catalytic enantioselective allylic substitution (EAS) reactions that allow for additions of alkenyl units to readily accessible allylic electrophiles is disclosed. Transformations afford 1,4-dienes that contain a tertiary carbon stereogenic site and are promoted by 1.0–5.0 mol % of a copper complex of an N-heterocyclic carbene (NHC). Aryl- as well as alkyl-substituted electrophiles bearing a di- or trisubstituted alkene may be employed. Reactions can involve a variety of robust alkenyl–(pinacolatoboron) [alkenyl–B(pin)] compounds that can be either purchased or prepared by various efficient, site-, and/or stereoselective catalytic reactions, such as cross-metathesis or proto-boryl additions to terminal alkynes. Vinyl-, E-, or Z-disubstituted alkenyl-, 1,1-disubstituted alkenyl-, acyclic, or heterocyclic trisubstituted alkenyl groups may be added in up to >98% yield, >98:2 SN2′:SN2, and 99:1 enantiomeric ratio (er). NHC–Cu-catalyzed EAS with alkenyl–B(pin) reagents containing a conjugated carboxylic ester or aldehyde group proceed to provide the desired 1,4-diene products in good yield and with high enantioselectivity despite the presence of a sensitive stereogenic tertiary carbon center that could be considered prone to epimerization. In most instances, the alternative approach of utilizing an alkenylmetal reagent (e.g., an Al-based species) represents an incompatible option. The utility of the approach is illustrated through applications to enantioselective synthesis of natural products such as santolina alcohol, semburin, nyasol, heliespirone A, and heliannuol E. PMID:24467274

  11. The formation of quasi-alicyclic rings in alkyl-aromatic compounds

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  13. Reactions of Tributylstannyl Anioniods with Alkyl Bromides.

    DTIC Science & Technology

    1981-09-28

    g (12 mmol) of cesium tert-butoxide was added to the reaction vessel before the addition of n-butyllithium. Alkylation of Tributylstannyl Anionoids...Dry reaction vessels were purged with argon. The desired alkyl halide (1.0 mmol unless noted) and any desired additive were added to the reaction ...OFFICE OF NAVAL RESEARCH Contract N00014-79-C-0584 Task No. NR 053-714 TECHNICAL REPORT No. 2 Reactions of Tributylstannyl Anionoids with Alkyl

  14. Pestalols A-E, new alkenyl phenol and benzaldehyde derivatives from endophytic fungus Pestalotiopsis sp. AcBC2 isolated from the Chinese mangrove plant Aegiceras corniculatum.

    PubMed

    Sun, Jian-Fan; Lin, Xiuping; Zhou, Xue-Feng; Wan, Junting; Zhang, Tianyu; Yang, Bin; Yang, Xian-Wen; Tu, Zhengchao; Liu, Yonghong

    2014-06-01

    Five alkenyl phenol and benzaldehyde derivatives, pestalols A-E (1-5), as well as seven known compounds (6-12), were isolated from endophytic fungus Pestalotiopsis sp. AcBC2 derived from the Chinese mangrove plant Aegiceras corniculatum. Their structures were determined by spectroscopic analyses. Compounds 2 and 3 showed cytotoxicity against a panel of 10 tumor cell lines. Compounds 1-5, 8, 9, 11, and 12 showed inhibitory activities against Influenza A virus subtype (H3N2) and Swine Flu (H1N1) viruses. Compound 2 also showed inhibitory activity against tuberculosis.

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

    PubMed Central

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

    2014-01-01

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

  16. Alkylating agents for Waldenstrom's macroglobulinaemia.

    PubMed

    Yang, Kun; Tan, Jianlong; Wu, Taixiang

    2009-01-21

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

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

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

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

  18. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject to...

  19. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject to...

  20. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327) are...

  1. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327) are...

  2. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject to...

  3. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject to...

  4. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327) are...

  5. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327) are...

  6. Enantioselective construction of C-chiral allylic sulfilimines via the iridium-catalyzed allylic amination with S,S-diphenylsulfilimine: asymmetric synthesis of primary allylic amines† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc01317d Click here for additional data file.

    PubMed Central

    Grange, Rebecca L.; Clizbe, Elizabeth A.; Counsell, Emma J.

    2015-01-01

    We have devised a highly regio- and enantioselective iridium-catalyzed allylic amination reaction with the sulfur-stabilized aza-ylide, S,S-diphenylsulfilimine. This process provides a robust and scalable method for the construction of aryl-, alkyl- and alkenyl-substituted C-chiral allylic sulfilimines, which are important functional groups for organic synthesis. Additionally, the combination of the allylic amination with an in situ deprotection of the sulfilimine constitutes a convenient one-pot protocol for the construction of chiral nonracemic primary allylic amines. PMID:28936319

  7. Iron-catalyzed 1,2-addition of perfluoroalkyl iodides to alkynes and alkenes.

    PubMed

    Xu, Tao; Cheung, Chi Wai; Hu, Xile

    2014-05-05

    Iron catalysis has been developed for the intermolecular 1,2-addition of perfluoroalkyl iodides to alkynes and alkenes. The catalysis has a wide substrate scope and high functional-group tolerance. A variety of perfluoroalkyl iodides including CF3 I can be employed. The resulting perfluoroalkylated alkyl and alkenyl iodides can be further functionalized by cross-coupling reactions. This methodology provides a straightforward and streamlined access to perfluoroalkylated organic molecules. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Diastereoselective addition of Grignard reagents to α-epoxy N-sulfonyl hydrazones

    NASA Astrophysics Data System (ADS)

    Uteuliyev, Maulen M.; Nguyen, Thien T.; Coltart, Don M.

    2015-12-01

    The α-alkylation of ketones and their derivatives by the addition of their corresponding enolates to alkyl halides is a fundamental synthetic transformation, but its utility is limited because the key bond-forming step proceeds in a bimolecular nucleophilic substitution fashion. Here we describe how an umpolung strategy that involves the addition of Grignard reagents to α-epoxy N-sulfonyl hydrazones—directed by the alkoxide of the 1-azo-3-alkoxy propenes formed in situ via base-induced ring opening of the epoxide—leads to the syn-selective production of α-alkyl-β-hydroxy N-sulfonyl hydrazones with α-quaternary centres. This transformation is remarkable in its ability to incorporate an unprecedented range of carbon-based substituents, which include primary, secondary and tertiary alkyl, as well as alkenyl, aryl, allenyl and alkynyl groups. Subsequent hydrolysis of the β-hydroxy N-sulfonyl hydrazone products produces the corresponding β-hydroxy ketones. In addition to hydrolysis, the hydrazone products are poised to undergo numerous different known synthetic transformations via well-established chemistry, which would provide access to a wide array of useful structures.

  9. Polymerization of Conducting Polymers Confined to Free Surfaces: A comparison of the Langmuir-Blodgett Polymerization of 3-Alkyl Pyrroles and 2- Alkyl Anilines

    DTIC Science & Technology

    1992-05-19

    Confined to Free Surfaces: A Comparison of the Langmuir-Blodgett Polymerization of 3- Alkyl Pyrroles and 2- Alkyl Anilines Submitted for Publication in...Surfaces: A Comparison of the Langmuir Blodgett Polymerizations of 3- alkyl pyrroles and 2- alkyl anilines R. S. Duran and H.C. Zhou Dept. of Chemistry...polymerization reactions in more detail and compare them. To do this, the polymerization reactions were run under two conditions. In the first case

  10. 21 CFR 176.120 - Alkyl ketene dimers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... section. (a) The alkyl ketene dimers are manufactured by the dehydrohalogenation of the acyl halides derived from the fatty acids of animal or vegetable fats and oils. (b) The alkyl ketene dimers are used as...

  11. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Louda, J.W.; Baker, E.W.

    The premier molecular index for assessing the thermal maturity(history) of a bitumen is the DPEP-to-ETIO ratio. A restatement of that data set has appeared and is the %-DPEP. This is also preferred by the present authors. These indices (D/E, %D) chronicle the relative presence, absence, and changes in that relationship for porphyrins with ({open_quotes}DPEP{close_quotes}, {open_quotes}CAP{close_quotes}) or without ({open_quotes}ETIO{close_quotes}) exocyclic cycloalkyl ring moieties. An alternative index, the Alkylation Index (Al) has received scant attention since its inception nearly 2 decades ago. This index increasingly weights the higher (>C32), more alkylated, species and ratios those to the pigments at C32 and lower.more » The present report is an integration of several of our past and more recent studies on sediments, shales and petroleum crudes. The application of cross-plotting %-DPEP versus Alkylation Index (%D x Al), in order to {open_quote}fine-tune{close_quote} thermal maturity assessments, for source rocks and oils is covered. Potential problems due to (1) the {open_quote}contamination{close_quote} of mature bitumen with immature biomarkers or (2) biodegradation are also discussed.« less

  12. A Concentration-Dependent Insulin Immobilization Behavior of Alkyl-Modified Silica Vesicles: The Impact of Alkyl Chain Length.

    PubMed

    Zhang, Jun; Zhang, Long; Lei, Chang; Huang, Xiaodan; Yang, Yannan; Yu, Chengzhong

    2018-05-01

    The insulin immobilization behaviors of silica vesicles (SV) before and after modification with hydrophobic alkyl -C 8 and -C 18 groups have been studied and correlated to the grafted alkyl chain length. In order to minimize the influence from the other structural parameters, monolayered -C 8 or -C 18 groups are grafted onto SV with controlled density. The insulin immobilization capacity of SV is dependent on the initial insulin concentrations (IIC). At high IIC (2.6-3.0 mg/mL), the trend of insulin immobilization capacity of SV is SV-OH > SV-C 8 > SV-C 18 , which is determined mainly by the surface area of SV. At medium IIC (0.6-1.9 mg/mL), the trend changes to SV-C 8 ≥ SV-C 18 > SV-OH as both the surface area and alkyl chain length contribute to the insulin immobilization. At an extremely low IIC, the hydrophobic-hydrophobic interaction between the alkyl group and insulin molecules plays the most significant role. Consequently, SV-C 18 with longer alkyl groups and the highest hydrophobicity show the best insulin enrichment performance compared to SV-C 8 and SV-OH, as evidenced by an insulin detection limit of 0.001 ng/mL in phosphate buffered saline (PBS) and 0.05 ng/mL in artficial urine determined by mass spectrometry (MS).

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

    EPA Science Inventory

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

  14. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  15. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for the...

  16. Extended 3{beta}-alkyl steranes and 3-alkyl triaromatic steroids in crude oils and rock extracts

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dahl, J.; Moldowan, J.M.; Summons, R.E.

    1995-09-01

    In oils and Precambian- to Miocene-age source rocks from varying depositional environments, we have conclusively identified several novel 3-alkyl sterane and triaromatic steroid series, including (1) 3{beta}-n-pentyl steranes, (2) 3{beta}-isopentyl steranes, (3) 3{beta}-n-hexyl steranes, (4) 3{beta}-n-hepatyl steranes, (5) 3,4-dimethyl steranes, (6) 3{beta}-butyl,4-methyl steranes, (7) triaromatic 3-n-pentyl steroids, and (8) triaromatic 3-isopentyl steroids. We have also tentatively identified additional homologs with 3-alkyl substituents as large as C{sub 11}. The relative abundances of these compounds vary substantially between samples, as indicated by (1) the ratio of 3{beta}-n-pentyl steranes to 3{beta}-isopentyl steranes and (2) the ratio of 3-n-pentyl triaromatic steroids to 3-isopentyl triaromaticmore » steroids. These data suggest possible utility for these parameters as tools for oil-source rock correlations and reconstruction of depositional environments. Although no 3-alkyl steroid natural products are currently known, several lines of evidence suggest that 3{beta}-alkyl steroids result from bacterial side-chain additions to diagenetic {delta}{sup 2}-sterenes.« less

  17. Polyimide characterization studies - Effect of pendant alkyl groups

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Young, P. R.

    1984-01-01

    The effect on selected polyimide properties when pendant alkyl groups were attached to the polymer backbone was investigated. A series of polymers were prepared using benzophenone tetracarboxylic acid dianhydride (BTDA) and seven different p-alkyl-m,p'-diaminobenzophenone monomers. The alkyl groups varied in length from C(1) (methyl) to C(9) (nonyl). The polyimide prepared from BTDA and m,p'-diaminobenzophenone was included as a control. All polymers were characterized by various chromatographic, spectroscopic, thermal, and mechanical techniques. Increasing the length of the pendant alkyl group resulted in a systematic decrease in glass transition temperature (Tg) for vacuum cured films. A 70 C decrease in Tg to 193 C was observed for the nonyl polymer compared to the Tg for the control. A corresponding systematic increase in Tg indicative of crosslinking, was observed for air cured films. Thermogravimetric analysis revealed a slight sacrifice in thermal stability with increasing alkyl length. No improvement in film toughness was observed.

  18. Isomeric Detergent Comparison for Membrane Protein Stability: Importance of Inter-Alkyl-Chain Distance and Alkyl Chain Length

    PubMed Central

    Cho, Kyung Ho; Hariharan, Parameswaran; Mortensen, Jonas S.; Du, Yang; Nielsen, Anne K.; Byrne, Bernadette; Kobilka, Brian K.; Loland, Claus J.; Guan, Lan

    2017-01-01

    Membrane proteins encapsulated by detergent micelles are widely used for structural study. Because of their amphipathic property, detergents have the ability to maintain protein solubility and stability in an aqueous medium. However, conventional detergents have serious limitations in their scope and utility, particularly for eukaryotic membrane proteins and membrane protein complexes. Thus, a number of new agents have been devised; some have made significant contributions to membrane protein structural studies. However, few detergent design principles are available. In this study, we prepared meta and ortho isomers of the previously reported para-substituted xylene-linked maltoside amphiphiles (XMAs), along with alkyl chain-length variation. The isomeric XMAs were assessed with three membrane proteins, and the meta isomer with a C12 alkyl chain was most effective at maintaining solubility/stability of the membrane proteins. We propose that interplay between the hydrophile–lipophile balance (HLB) and alkyl chain length is of central importance for high detergent efficacy. In addition, differences in inter-alkyl-chain distance between the isomers influence the ability of the detergents to stabilise membrane proteins. PMID:27981750

  19. A Convenient Approach to Synthesizing Peptide C-Terminal N-Alkyl Amides

    PubMed Central

    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

  20. 40 CFR 721.10677 - Alkyl phosphonate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10677 Alkyl phosphonate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl phosphonate (PMN P-12-584...

  1. PREPARATION OF ALKYL PYROPHOSPHATE EXTRACTANTS

    DOEpatents

    Levine, C.A.; Skiens, W.E.; Moore, G.R.

    1960-08-01

    A process for providing superior solvent extractants for metal recovery processes is given wherein the extractant comprises an alkyl pyrophosphoric acid ester dissolved in an organic solvent diluent. Finely divided solid P/sub 2/O/ sub 5/ is slurried in an organic solvent-diluent selected from organic solvents such as kerosene, benzene, chlorobenzene, toluene, etc. An alcohol selected from the higher alcohols having 4 to 17 carbon atoms. e.g.. hexanol-1. heptanol-3, octanol-1. 2.6-dimethyl-heptanol-4, and decanol-1, is rapidly added to the P/sub 2/O/sub 5/ slurry in the amount of about 2 moles of alcohol to 1 mole of P/sub 2/ O/sub 5/. The temperature is maintained below about 110 deg C during the course of the P/sub 2/O/sub 5/-alcohol reaction. An alkyl pyrophosphate extractant compound is formed as a consequence of the reaction process. The alkyl pyrophosphate solvent-diluent extractant phase is useful in solvent extraction metal recovery processes.

  2. Antioxidant activity of alkyl gallates and glycosyl alkyl gallates in fish oil in water emulsions: relevance of their surface active properties and of the type of emulsifier.

    PubMed

    González, María J; Medina, Isabel; Maldonado, Olivia S; Lucas, Ricardo; Morales, Juan C

    2015-09-15

    The antioxidant activity of gallic acid and a series of alkyl gallates (C4-C18) and glycosylated alkyl gallates (C4-C18) on fish oil-in-water emulsions was studied. Three types of emulsifiers, lecithin, Tween-20 and sodium dodecyl sulphate (SDS) were tested. A nonlinear behavior of the antioxidant activity of alkyl gallates when increasing alkyl chain length was observed for emulsions prepared with lecithin. Medium-size alkyl gallates (C6-C12) were the best antioxidants. In contrast, for emulsions prepared with Tween-20, the antioxidants seem to follow the polar paradox. Glucosyl alkyl gallates were shown previously to be better surfactants than alkyl gallates. Nevertheless, they exhibited a worse antioxidant capacity than their corresponding alkyl gallates, in emulsions prepared with lecithin or Tween-20, indicating the greater relevance of having three OH groups at the polar head in comparison with having improved surfactant properties but just a di-ortho phenolic structure in the antioxidant. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Effect of the C-2 hydroxyl group on the mesomorphism of alkyl glycosides: synthesis and thermotropic behavior of alkyl 2-deoxy-D-arabino-hexopyranosides.

    PubMed

    Singh, Madan Kumar; Jayaraman, Narayanaswamy; Rao, D S Shankar; Prasad, S Krishna

    2008-10-01

    A homologous series of alkyl 2-deoxy-alpha-d-arabino-hexopyranosides and alkyl 2-deoxy-beta-d-arabino-hexopyranosides were synthesized, upon glycosylation of 1-alkanols (from C8 to C18 alkanols) with ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-d-arabino-hexopyranoside, followed by a deprotection. The thermotropic behavior of these new types of alkyl glycosides was investigated. It was observed that the beta-anomers of these alkyl glycosides, bearing nonyl to tetradecyl alkyl chain are mesomorphic, exhibiting monotropic smectic A phase. In contrast, the alpha-anomers are all non-mesomorphic. An effort to identify the liquid crystalline behavior of binary mixtures of the alpha- and beta-anomers was undertaken and it was found that mixtures containing equimolar amounts of the anomers exhibited mesomorphic behavior. A fine balance of the hydrophilic and hydrophobic components within the molecule is also found to be important for the alkyl 2-deoxy glycosides to form the mesophase.

  4. Direct N-alkylation of unprotected amino acids with alcohols

    PubMed Central

    Yan, Tao; Feringa, Ben L.; Barta, Katalin

    2017-01-01

    N-alkyl amino acids find widespread application as highly valuable, renewable building blocks. However, traditional synthesis methodologies to obtain these suffer from serious limitations, providing a major challenge to develop sustainable alternatives. We report the first powerful catalytic strategy for the direct N-alkylation of unprotected α-amino acids with alcohols. This method is highly selective, produces water as the only side product leading to a simple purification procedure, and a variety of α-amino acids are mono- or di-N-alkylated, in most cases with excellent retention of optical purity. The hydrophobicity of the products is tunable, and even simple peptides are selectively alkylated. An iron-catalyzed route to mono-N-alkyl amino acids using renewable fatty alcohols is also described that represents an ideal green transformation for obtaining fully bio-based surfactants. PMID:29226249

  5. Isomeric Detergent Comparison for Membrane Protein Stability: Importance of Inter-Alkyl-Chain Distance and Alkyl Chain Length.

    PubMed

    Cho, Kyung Ho; Hariharan, Parameswaran; Mortensen, Jonas S; Du, Yang; Nielsen, Anne K; Byrne, Bernadette; Kobilka, Brian K; Loland, Claus J; Guan, Lan; Chae, Pil Seok

    2016-12-14

    Membrane proteins encapsulated by detergent micelles are widely used for structural study. Because of their amphipathic property, detergents have the ability to maintain protein solubility and stability in an aqueous medium. However, conventional detergents have serious limitations in their scope and utility, particularly for eukaryotic membrane proteins and membrane protein complexes. Thus, a number of new agents have been devised; some have made significant contributions to membrane protein structural studies. However, few detergent design principles are available. In this study, we prepared meta and ortho isomers of the previously reported para-substituted xylene-linked maltoside amphiphiles (XMAs), along with alkyl chain-length variation. The isomeric XMAs were assessed with three membrane proteins, and the meta isomer with a C 12 alkyl chain was most effective at maintaining solubility/stability of the membrane proteins. We propose that interplay between the hydrophile-lipophile balance (HLB) and alkyl chain length is of central importance for high detergent efficacy. In addition, differences in inter-alkyl-chain distance between the isomers influence the ability of the detergents to stabilise membrane proteins. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Salvage of failed protein targets by reductive alkylation.

    PubMed

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

    2014-01-01

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

  7. Salvage of Failed Protein Targets by Reductive Alkylation

    PubMed Central

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

    2014-01-01

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

  8. Balancing repair and tolerance of DNA damage caused by alkylating agents.

    PubMed

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

    2012-01-12

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

  9. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations.

    PubMed

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A

    2013-10-01

    Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

  10. Identification of alkyl carbazoles and alkyl benzocarbazoles in Brazilian petroleum derivatives.

    PubMed

    Oliveira, Eniz Conceição; Vaz de Campos, Maria Cecília; Rodrigues, Maria Regina Alves; Pérez, Valéria Flores; Melecchi, Maria Inês Soares; Vale, Maria Goreti Rodrigues; Zini, Cláudia Alcaraz; Caramão, Elina Bastos

    2006-02-10

    Carbozoles are important compounds in crude oils, as they may be used as geochemical tracers, being the major type of nitrogen compounds in petroleum. At the same time, they are regarded as undesirable due to the problems they may cause in the refining process, such as catalyst poisoning, corrosion, gum or color formation in final products. As separation and identification of carbazoles are challenging goals, this work presents a chromatographic method, made of a pre-fractionation on neutral alumina followed by the separation and identification of two classes of carbazoles using FeCl(3)/Chromossorb W and gas chromatograph with mass spectrometer (GC/MS) (SIM-single ion monitoring mode) analysis. For the first time, a series of alkyl carbazoles and alkyl benzocarbazoles were identified in heavy gas oil (HGO) and atmospheric residue of distillation (ARD) obtained from Brazilian petroleum.

  11. Room temperature rechargeable magnesium batteries with sulfur-containing composite cathodes prepared from elemental sulfur and bis(alkenyl) compound having a cyclic or linear ether unit

    NASA Astrophysics Data System (ADS)

    Itaoka, Kanae; Kim, In-Tae; Yamabuki, Kazuhiro; Yoshimoto, Nobuko; Tsutsumi, Hiromori

    2015-11-01

    Room temperature rechargeable magnesium (Mg) batteries are constructed from Mg as a negative material, sulfur (S)-containing composite prepared from elemental sulfur and the bis(alkenyl) compound having a crown ether unit (BUMB18C6) or linear ether unit (UOEE) as a positive material and the simple electrolyte (0.7 mol dm-3 Mg[N(SO2CF3)2]2-triglyme (G3) solution). The reaction between molten S and the bis(alkenyl) compound (BUMB18C6 or UOEE) provides the sulfur-containing composite, S-BUMB18C6 or S-UOEE. Both of the sulfur-containing composites are electrochemically active in the Mg salt-based electrolyte, acetonitrile- or G3- Mg[N(SO2CF3)2]2 electrolyte. The first discharge capacity of the test cells with the sulfur-containing composite is 460 Ah kg-1 (per the weight of sulfur in the composite) with the S-BUMB18C6 electrode and 495 Ah kg-1 with the S-UOEE electrode. According to the continuous charge-discharge cycle tests (at 10th cycle), the discharge capacity of the test cell with the S-BUMB18C6 electrode (68.1 Ah kg-1) is higher than that with the S-UOEE electrode (0.18 Ah kg-1). The crown ether units in the S-BUMB18C6 composite may create ion-conducting paths in the cathode, prevent rise in the internal resistance of the cathode, and provide better cycle performance of the test cells with the S-BUMB18C6 composite electrode than that with the S-UOEE electrode.

  12. 40 CFR 721.10548 - Mixed alkyl phosphate esters alkoxylated (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed alkyl phosphate esters... Specific Chemical Substances § 721.10548 Mixed alkyl phosphate esters alkoxylated (generic). (a) Chemical... as mixed alkyl phosphate esters alkoxylated (PMN P-04-624) is subject to reporting under this section...

  13. 40 CFR 721.10548 - Mixed alkyl phosphate esters alkoxylated (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed alkyl phosphate esters... Specific Chemical Substances § 721.10548 Mixed alkyl phosphate esters alkoxylated (generic). (a) Chemical... as mixed alkyl phosphate esters alkoxylated (PMN P-04-624) is subject to reporting under this section...

  14. 40 CFR 721.5380 - Mixed alkyl phenolic novolak resin (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed alkyl phenolic novolak resin... Specific Chemical Substances § 721.5380 Mixed alkyl phenolic novolak resin (generic). (a) Chemical... as mixed alkyl phenolic novolak resin (PMN P-98-718) is subject to reporting under this section for...

  15. 40 CFR 721.5380 - Mixed alkyl phenolic novolak resin (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixed alkyl phenolic novolak resin... Specific Chemical Substances § 721.5380 Mixed alkyl phenolic novolak resin (generic). (a) Chemical... as mixed alkyl phenolic novolak resin (PMN P-98-718) is subject to reporting under this section for...

  16. 40 CFR 721.5380 - Mixed alkyl phenolic novolak resin (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixed alkyl phenolic novolak resin... Specific Chemical Substances § 721.5380 Mixed alkyl phenolic novolak resin (generic). (a) Chemical... as mixed alkyl phenolic novolak resin (PMN P-98-718) is subject to reporting under this section for...

  17. 40 CFR 721.5380 - Mixed alkyl phenolic novolak resin (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixed alkyl phenolic novolak resin... Specific Chemical Substances § 721.5380 Mixed alkyl phenolic novolak resin (generic). (a) Chemical... as mixed alkyl phenolic novolak resin (PMN P-98-718) is subject to reporting under this section for...

  18. 40 CFR 721.5380 - Mixed alkyl phenolic novolak resin (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed alkyl phenolic novolak resin... Specific Chemical Substances § 721.5380 Mixed alkyl phenolic novolak resin (generic). (a) Chemical... as mixed alkyl phenolic novolak resin (PMN P-98-718) is subject to reporting under this section for...

  19. 40 CFR 721.10493 - Tris-alkyl-alkoxy melamine polymer (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Tris-alkyl-alkoxy melamine polymer... Specific Chemical Substances § 721.10493 Tris-alkyl-alkoxy melamine polymer (generic). (a) Chemical... as tris-alkyl-alkoxy melamine polymer (PMN P-05-417) is subject to reporting under this section for...

  20. 40 CFR 721.10493 - Tris-alkyl-alkoxy melamine polymer (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Tris-alkyl-alkoxy melamine polymer... Specific Chemical Substances § 721.10493 Tris-alkyl-alkoxy melamine polymer (generic). (a) Chemical... as tris-alkyl-alkoxy melamine polymer (PMN P-05-417) is subject to reporting under this section for...

  1. Selective alkylation of T–T mismatched DNA using vinyldiaminotriazine–acridine conjugate

    PubMed Central

    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

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

    PubMed

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

    2017-11-01

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

  3. 40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated sulfonated diphenyl oxide... New Uses for Specific Chemical Substances § 721.2565 Alkylated sulfonated diphenyl oxide, alkali and... substances identified as alkylated sulfonated diphenyl oxide, alkali salt (PMN P-93-352) and alkylated...

  4. 40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkylated sulfonated diphenyl oxide... New Uses for Specific Chemical Substances § 721.2565 Alkylated sulfonated diphenyl oxide, alkali and... substances identified as alkylated sulfonated diphenyl oxide, alkali salt (PMN P-93-352) and alkylated...

  5. Detection and identification of alkylating agents by using a bioinspired "chemical nose".

    PubMed

    Hertzog-Ronen, Carmit; Borzin, Elena; Gerchikov, Yulia; Tessler, Nir; Eichen, Yoav

    2009-10-12

    Alkylating agents are simple and reactive molecules that are commonly used in many and diverse fields such as organic synthesis, medicine, and agriculture. Some highly reactive alkylating species are also being used as blister chemical-warfare agents. The detection and identification of alkylating agents is not a trivial issue because of their high reactivity and simple structure. Herein, we report on a new multispot luminescence-based approach to the detection and identification of alkylating agents. In order to demonstrate the potential of the approach, seven pi-conjugated oligomers and polymers bearing nucleophilic pyridine groups, 1-7, were adsorbed onto a solid support and exposed to vapors of alkylators 8-15. The alkylation-induced color-shift patterns of the seven-spot array allow clear discrimination of the different alkylators. The spots are sensitive to minute concentrations of alkylators and, because the detection is based on the formation of new covalent bonds, these spots saturate at about 50 ppb.

  6. A heterobimetallic Ga/Yb-Schiff base complex for catalytic asymmetric alpha-addition of isocyanides to aldehydes.

    PubMed

    Mihara, Hisashi; Xu, Yingjie; Shepherd, Nicholas E; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2009-06-24

    Development of a new heterobimetallic Ga(O-iPr)(3)/Yb(OTf)(3)/Schiff base 2d complex for catalytic asymmetric alpha-additions of isocyanides to aldehydes is described. Schiff base 2d derived from o-vanillin was suitable to utilize cationic rare earth metal triflates with good Lewis acidity in bimetallic Schiff base catalysis. The Ga(O-iPr)(3)/Yb(OTf)(3)/Schiff base 2d complex promoted asymmetric alpha-additions of alpha-isocyanoacetamides to aryl, heteroaryl, alkenyl, and alkyl aldehydes in good to excellent enantioselectivity (88-98% ee).

  7. Structure-biocompatibility and transfection activity relationships of cationic polyaspartamides with (dialkylamino)alkyl and alkyl or hydroxyalkyl side groups.

    PubMed

    Salakhieva, Diana; Shevchenko, Vesta; Németh, Csaba; Gyarmati, Benjámin; Szilágyi, András; Abdullin, Timur

    2017-01-30

    A series of 14 cationic derivatives of poly(aspartic acid) i.e. cationic polyaspartamides with different (dialkylamino)alkyl and alkyl or hydroxyalkyl side groups was synthesized by nucleophilic addition on polysuccinimide. The resulting polyaspartamides have moderate amphiphilic properties. Relationships between the structure and ratio of side groups and in vitro properties of polyaspartamides, including their cytotoxic and membrane-damaging activity towards human cell lines, primary skin fibroblasts and erythrocytes, were established and discussed. Cationic polyaspartamides vary in their DNA-binding, condensing and nuclease-protecting characteristics depending on the concentration ratio of (dialkylamino)alkyl and alkyl or hydroxyalkyl side groups. Effective cell transfection was achieved upon polyaspartamide-mediated plasmid DNA delivery in serum-free medium in the presence of chloroquine. Effect of serum proteins adsorption onto polyaspartamide based polyplexes, and the role of concentration of polyplexes in culture medium in their colloidal stability and transfection process were demonstrated. Synthesized polyaspartamides are biocompatible and long-acting gene carriers, which are applied to cells after dilution and without washing, thus providing transfection level comparable to that of commercial transfection reagent. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    PubMed

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

    2008-05-15

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

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

    NASA Astrophysics Data System (ADS)

    Jin, Jian; MacMillan, David W. C.

    2015-09-01

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

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

    PubMed

    Jin, Jian; MacMillan, David W C

    2015-09-03

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

  11. 40 CFR 721.10711 - Alkyl substituted catechol (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10711 Alkyl substituted catechol (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  12. 40 CFR 721.840 - Alkyl substituted diaromatic hydrocarbons.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... hydrocarbons. 721.840 Section 721.840 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.840 Alkyl substituted diaromatic hydrocarbons. (a) Chemical substance... alkyl substituted di-aro-matic hydrocarbons (PMN P-91-710) is subject to reporting under this section...

  13. 40 CFR 721.840 - Alkyl substituted diaromatic hydrocarbons.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... hydrocarbons. 721.840 Section 721.840 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.840 Alkyl substituted diaromatic hydrocarbons. (a) Chemical substance... alkyl substituted di-aro-matic hydrocarbons (PMN P-91-710) is subject to reporting under this section...

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

    PubMed

    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.

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

    PubMed

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

    2015-01-01

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

  16. Lithium perchlorate-nitromethane-promoted alkylation of anilines with arylmethanols.

    PubMed

    Zhou, Jun; Mao, Hai-Feng; Wang, Lu; Zou, Jian-Ping; Zhang, Wei

    2011-11-01

    A new application of lithium perchlorate-nitromethane (LPNM) for the formation of aromatic C-N and C-C bonds is introduced. LPNM-promoted reactions of anilines with diarylmethanols selectively generate N-alkylated anilines or mono and double Friedel-Crafts alkylation products under different conditions by changing the reaction time, reaction temperature, and the ratio of the reactants. This method does not require the use of transition metal catalysts to prepare alkylated aniline derivatives.

  17. Chiral Brønsted Base-Promoted Nitroalkane Alkylation: Enantioselective Synthesis of sec-Alkyl-3-Substituted Indoles

    PubMed Central

    Dobish, Mark C.; Johnston, Jeffrey N.

    2010-01-01

    A Brønsted base-catalyzed reaction of nitroalkanes with alkyl electrophiles provides indole heterocycles substituted at C3 bearing a sec-alkyl group with good enantioselectivity (up to 90% ee). Denitration by hydrogenolysis provides a product with equally high ee. An indolenine intermediate is implicated in the addition step, and surprisingly, water cosolvent was found to have a beneficial effect in this step, leading to a one-pot protocol for elimination/enantioselective addition using PBAM, a bis(amidine) chiral nonracemic base. PMID:21090654

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

    PubMed

    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.

  19. Synthesis and characterization of chitosan alkyl urea.

    PubMed

    Wang, Jing; Jiang, Ji-Zhou; Chen, Wei; Bai, Zheng-Wu

    2016-07-10

    Chitosan is a versatile material employed for various purposes in many fields including the development of chiral stationary phases for enantioseparation. Chitosan alkyl urea is a kind of intermediate used to prepare enantioseparation materials. In order to synthesize the intermediates, in the present work, a new way to prepare chitosan alkyl urea has been established: chitosan was first reacted with methyl chloroformate yielding N-methoxyformylated chitosan, which was then converted to chitosan alkyl urea through amine-ester exchange reaction. With a large excess of methyl chloroformate and primary amine of low stereohindrance, the amino group in chitosan could be almost completely converted to ureido group. The as-prepared chitosan alkyl urea derivatives were characterized by IR, (1)H NMR, (13)C NMR,(1)H-(1)H COSY and (1)H-(13)C HSQC NMR spectra. The chemical shifts of hydrogen and carbon atoms of glucose unit were assigned. It was found that the degree of substitution was obviously lower if cyclopropyl amine, aniline, tert-butyl amine and diethyl amine were used as reactants for the amine-ester exchange reaction. The reason was explained with the aid of theoretical calculations. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    PubMed Central

    Jin, Jian; MacMillan, David W. C.

    2015-01-01

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

  1. Detection of Alkylating Agents using Electrical and Mechanical Means

    NASA Astrophysics Data System (ADS)

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

    2011-08-01

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

  2. Direct catalytic cross-coupling of organolithium compounds

    NASA Astrophysics Data System (ADS)

    Giannerini, Massimo; Fañanás-Mastral, Martín; Feringa, Ben L.

    2013-08-01

    Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.

  3. Safety Assessment of Alkyl PEG/PPG Ethers as Used in Cosmetics.

    PubMed

    Fiume, Monice M; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2016-07-01

    The Cosmetic Ingredient Review (CIR) Expert Panel assessed the safety of 131 alkyl polyethylene glycol (PEG)/polypropylene glycol ethers as used in cosmetics, concluding that these ingredients are safe in the present practices of use and concentration described in this safety assessment when formulated to be nonirritating. Most of the alkyl PEG/PPG ethers included in this review are reported to function in cosmetics as surfactants, skin-conditioning agents, and/or emulsifying agents. The alkyl PEG/PPG ethers share very similar physiochemical properties as the alkyl PEG ethers, which were reviewed previously by the CIR Expert Panel and found safe when formulated to be nonirritating. The alkyl PEG ethers differ by the inclusion of PPG repeat units, which are used to fine-tune the surfactant properties of this group. The Panel relied heavily on data on analogous ingredients, extracted from the alkyl PEG ethers and PPG reports, when making its determination of safety. © The Author(s) 2016.

  4. Alkylation of 6-mercaptopurine (6-MP) with N-alkyl-N-alkoxycarbonylaminomethyl chlorides: S6-(N-alkyl-N-alkoxycarbonyl)aminomethyl-6-MP prodrug structure effect on the dermal delivery of 6-MP.

    PubMed

    Siver, K G; Sloan, K B

    1990-01-01

    The S6-(N-alkyl-N-alkoxycarbonyl)aminomethyl-6-MP (6-CARB-6-MP) prodrugs 5-20 were synthesized from the reaction of 6-MP with N-alkyl-N-alkyoxycarbonylaminomethyl chlorides (4) in dimethyl sulfoxide in overall yields of 5-62%, depending on the N-alkyl and the alkoxy groups involved. The derivatives were fully characterized by spectral and microanalyses. The assignment of the substitution pattern as S6-alkyl was based on comparisons of the UV, 1H NMR and 13C NMR spectra with model compounds. A S6, 9-bis-alkyl derivative was obtained from the reaction of 2 equivalents of 4 with 6-MP but the product was unstable and decomposed on standing to a 9-alkyl derivative. The 6-CARB-6-MP prodrugs reverted to 6-MP in water by an SN1-type mechanism involving unimolecular charge separation in the transition state of the rate determining step. There was no effect of dermal enzymes on the rate of hydrolysis. The solubilities in isopropyl myristate (IPM) for all of the 6-CARB-6-MP prodrugs were significantly greater than the solubility of 6-MP in IPM but only one prodrug (5) was apparently even as soluble as 6-MP in water. Selected 6-CARB-6-MP prodrugs were examined in diffusion cell experiments. Only the N-methyl-N-methoxycarbonyl derivative 5 gave a steady-state rate of delivery of 6-MP from IPM that was significantly greater than the steady-state rate of delivery of 6-MP from 6-MP in IPM. All the other derivatives gave steady-state rates of delivery of 6-MP from IPM that were either not significantly different, or were significantly lower than the rate obtained from 6-MP in IPM. In all cases, the effect of the 6-CARB-6-MP:IPM suspensions on the permeability of the skin, as determined by the second application flux of theophylline:propylene glycol, was of the same magnitude as the effect of IPM alone.

  5. Ultrasound promoted N-alkylation of pyrrole using potassium superoxide as base in crown ether.

    PubMed

    Yim, E S; Park, M K; Han, B H

    1997-04-01

    Ultrasound accelerates the N-alkylation of pyrrole by alkylating reagents using potassium superoxide as base in the presence of 18-crown-6. A much lower yield of N-alkylated pyrrole was realized in the absence of ultrasound. N-alkylating reagents employed for pyrrole are methyl iodide, ethyl bromide, benzyl bromide, as well as acrylonitrile allyl cyanide and methyl acrylate. In an extension of this work, we have found that ultrasound was not necessary for the N-alkylation of indole and alkyl amine, such as diphenyl amine and piperidine with alkyl halides using our reagents. In all cases we observed that the 18-crown-6 catalyzed N-alkylation reaction gives higher yields of N-alkylated products than that without crown ether, when potassium superoxide was used as base. These observations are probably due to the potassium-crown complex which can be released when the reaction goes to completion.

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

    PubMed

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

    2017-05-22

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

  7. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  8. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under this...

  9. 40 CFR 721.2094 - N,N′-di(alkyl heteromonocycle)amino chlorotriazine.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false N,Nâ²-di(alkyl heteromonocycle)amino... Specific Chemical Substances § 721.2094 N,N′-di(alkyl heteromonocycle)amino chlorotriazine. (a) Chemical... as N,N′-di(alkyl heteromonocycle)amino chlorotriazine (PMN P-93-1369) is subject to reporting under...

  10. 40 CFR 721.2094 - N,N′-di(alkyl heteromonocycle)amino chlorotriazine.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false N,Nâ²-di(alkyl heteromonocycle)amino... Specific Chemical Substances § 721.2094 N,N′-di(alkyl heteromonocycle)amino chlorotriazine. (a) Chemical... as N,N′-di(alkyl heteromonocycle)amino chlorotriazine (PMN P-93-1369) is subject to reporting under...

  11. 40 CFR 721.520 - Alanine, N-(2-carboxyethyl)-N-alkyl-, salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 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...

  12. 40 CFR 721.520 - Alanine, N-(2-carboxyethyl)-N-alkyl-, salt.

    Code of Federal Regulations, 2010 CFR

    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...

  13. 40 CFR 721.644 - Amines, C12-14-tert-alkyl, sulfonates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Amines, C12-14-tert-alkyl, sulfonates... Substances § 721.644 Amines, C12-14-tert-alkyl, sulfonates. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amines, C12-14-tert-alkyl, sulfonates (PMN...

  14. 40 CFR 721.644 - Amines, C12-14-tert-alkyl, sulfonates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amines, C12-14-tert-alkyl, sulfonates... Substances § 721.644 Amines, C12-14-tert-alkyl, sulfonates. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as amines, C12-14-tert-alkyl, sulfonates (PMN...

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed Central

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

    2016-01-01

    Alkylation chemotherapy is one of the most widely used systemic therapies for cancer. While somewhat effective, clinical responses and toxicities of these agents are highly variable. A major contributing factor for this variability is the numerous distinct lesions that are created upon alkylation damage. These adducts activate multiple repair pathways. There is mounting evidence that the individual pathways function cooperatively, suggesting that coordinated regulation of alkylation repair is critical to prevent toxicity. Furthermore, some alkylating agents produce adducts that overlap with newly discovered methylation marks, making it difficult to distinguish between bona fide damaged bases and so called ‘epigenetic’ adducts. We discuss new efforts aimed at deciphering the mechanisms that regulate these repair pathways, emphasizing their implications for cancer chemotherapy. PMID:27816326

  17. Palladium-catalyzed Heck-type cross-couplings of unactivated alkyl iodides.

    PubMed

    McMahon, Caitlin M; Alexanian, Erik J

    2014-06-02

    A palladium-catalyzed, intermolecular Heck-type coupling of alkyl iodides and alkenes is described. This process is successful with a variety of primary and secondary unactivated alkyl iodides as reaction partners, including those with hydrogen atoms in the β position. The mild catalytic conditions enable intermolecular C-C bond formations with a diverse set of alkyl iodides and alkenes, including substrates containing base- or nucleophile-sensitive functionality. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Chiral Alkyl Halides: Underexplored Motifs in Medicine

    PubMed Central

    Gál, Bálint; Bucher, Cyril; Burns, Noah Z.

    2016-01-01

    While alkyl halides are valuable intermediates in synthetic organic chemistry, their use as bioactive motifs in drug discovery and medicinal chemistry is rare in comparison. This is likely attributable to the common misconception that these compounds are merely non-specific alkylators in biological systems. A number of chlorinated compounds in the pharmaceutical and food industries, as well as a growing number of halogenated marine natural products showing unique bioactivity, illustrate the role that chiral alkyl halides can play in drug discovery. Through a series of case studies, we demonstrate in this review that these motifs can indeed be stable under physiological conditions, and that halogenation can enhance bioactivity through both steric and electronic effects. Our hope is that, by placing such compounds in the minds of the chemical community, they may gain more traction in drug discovery and inspire more synthetic chemists to develop methods for selective halogenation. PMID:27827902

  19. Selective sp3 C-H alkylation via polarity-match-based cross-coupling.

    PubMed

    Le, Chip; Liang, Yufan; Evans, Ryan W; Li, Ximing; MacMillan, David W C

    2017-07-06

    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp 3 )-C(sp 2 ) coupling, there is a growing demand for C-H alkylation reactions, wherein sp 3 C-H bonds are replaced with sp 3 C-alkyl groups. Here we describe a polarity-match-based selective sp 3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp 3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  20. mTOR target NDRG1 confers MGMT-dependent resistance to alkylating chemotherapy.

    PubMed

    Weiler, Markus; Blaes, Jonas; Pusch, Stefan; Sahm, Felix; Czabanka, Marcus; Luger, Sebastian; Bunse, Lukas; Solecki, Gergely; Eichwald, Viktoria; Jugold, Manfred; Hodecker, Sibylle; Osswald, Matthias; Meisner, Christoph; Hielscher, Thomas; Rübmann, Petra; Pfenning, Philipp-Niklas; Ronellenfitsch, Michael; Kempf, Tore; Schnölzer, Martina; Abdollahi, Amir; Lang, Florian; Bendszus, Martin; von Deimling, Andreas; Winkler, Frank; Weller, Michael; Vajkoczy, Peter; Platten, Michael; Wick, Wolfgang

    2014-01-07

    A hypoxic microenvironment induces resistance to alkylating agents by activating targets in the mammalian target of rapamycin (mTOR) pathway. The molecular mechanisms involved in this mTOR-mediated hypoxia-induced chemoresistance, however, are unclear. Here we identify the mTOR target N-myc downstream regulated gene 1 (NDRG1) as a key determinant of resistance toward alkylating chemotherapy, driven by hypoxia but also by therapeutic measures such as irradiation, corticosteroids, and chronic exposure to alkylating agents via distinct molecular routes involving hypoxia-inducible factor (HIF)-1alpha, p53, and the mTOR complex 2 (mTORC2)/serum glucocorticoid-induced protein kinase 1 (SGK1) pathway. Resistance toward alkylating chemotherapy but not radiotherapy was dependent on NDRG1 expression and activity. In posttreatment tumor tissue of patients with malignant gliomas, NDRG1 was induced and predictive of poor response to alkylating chemotherapy. On a molecular level, NDRG1 bound and stabilized methyltransferases, chiefly O(6)-methylguanine-DNA methyltransferase (MGMT), a key enzyme for resistance to alkylating agents in glioblastoma patients. In patients with glioblastoma, MGMT promoter methylation in tumor tissue was not more predictive for response to alkylating chemotherapy in patients who received concomitant corticosteroids.

  1. Aag DNA Glycosylase Promotes Alkylation-Induced Tissue Damage Mediated by Parp1

    PubMed Central

    Calvo, Jennifer A.; Moroski-Erkul, Catherine A.; Lake, Annabelle; Eichinger, Lindsey W.; Shah, Dharini; Jhun, Iny; Limsirichai, Prajit; Bronson, Roderick T.; Christiani, David C.; Meira, Lisiane B.; Samson, Leona D.

    2013-01-01

    Alkylating agents comprise a major class of front-line cancer chemotherapeutic compounds, and while these agents effectively kill tumor cells, they also damage healthy tissues. Although base excision repair (BER) is essential in repairing DNA alkylation damage, under certain conditions, initiation of BER can be detrimental. Here we illustrate that the alkyladenine DNA glycosylase (AAG) mediates alkylation-induced tissue damage and whole-animal lethality following exposure to alkylating agents. Aag-dependent tissue damage, as observed in cerebellar granule cells, splenocytes, thymocytes, bone marrow cells, pancreatic β-cells, and retinal photoreceptor cells, was detected in wild-type mice, exacerbated in Aag transgenic mice, and completely suppressed in Aag −/− mice. Additional genetic experiments dissected the effects of modulating both BER and Parp1 on alkylation sensitivity in mice and determined that Aag acts upstream of Parp1 in alkylation-induced tissue damage; in fact, cytotoxicity in WT and Aag transgenic mice was abrogated in the absence of Parp1. These results provide in vivo evidence that Aag-initiated BER may play a critical role in determining the side-effects of alkylating agent chemotherapies and that Parp1 plays a crucial role in Aag-mediated tissue damage. PMID:23593019

  2. mTOR target NDRG1 confers MGMT-dependent resistance to alkylating chemotherapy

    PubMed Central

    Weiler, Markus; Blaes, Jonas; Pusch, Stefan; Sahm, Felix; Czabanka, Marcus; Luger, Sebastian; Bunse, Lukas; Solecki, Gergely; Eichwald, Viktoria; Jugold, Manfred; Hodecker, Sibylle; Osswald, Matthias; Meisner, Christoph; Hielscher, Thomas; Rübmann, Petra; Pfenning, Philipp-Niklas; Ronellenfitsch, Michael; Kempf, Tore; Schnölzer, Martina; Abdollahi, Amir; Lang, Florian; Bendszus, Martin; von Deimling, Andreas; Winkler, Frank; Weller, Michael; Vajkoczy, Peter; Platten, Michael; Wick, Wolfgang

    2014-01-01

    A hypoxic microenvironment induces resistance to alkylating agents by activating targets in the mammalian target of rapamycin (mTOR) pathway. The molecular mechanisms involved in this mTOR-mediated hypoxia-induced chemoresistance, however, are unclear. Here we identify the mTOR target N-myc downstream regulated gene 1 (NDRG1) as a key determinant of resistance toward alkylating chemotherapy, driven by hypoxia but also by therapeutic measures such as irradiation, corticosteroids, and chronic exposure to alkylating agents via distinct molecular routes involving hypoxia-inducible factor (HIF)-1alpha, p53, and the mTOR complex 2 (mTORC2)/serum glucocorticoid-induced protein kinase 1 (SGK1) pathway. Resistance toward alkylating chemotherapy but not radiotherapy was dependent on NDRG1 expression and activity. In posttreatment tumor tissue of patients with malignant gliomas, NDRG1 was induced and predictive of poor response to alkylating chemotherapy. On a molecular level, NDRG1 bound and stabilized methyltransferases, chiefly O6-methylguanine-DNA methyltransferase (MGMT), a key enzyme for resistance to alkylating agents in glioblastoma patients. In patients with glioblastoma, MGMT promoter methylation in tumor tissue was not more predictive for response to alkylating chemotherapy in patients who received concomitant corticosteroids. PMID:24367102

  3. Selective sp3 C-H alkylation via polarity-match-based cross-coupling

    NASA Astrophysics Data System (ADS)

    Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

    2017-07-01

    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp3)-C(sp2) coupling, there is a growing demand for C-H alkylation reactions, wherein sp3 C-H bonds are replaced with sp3 C-alkyl groups. Here we describe a polarity-match-based selective sp3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  4. 40 CFR 721.9530 - Bis(2,2,6,6-tetra-methyl-piper-idinyl) ester of cycloalkyl spir-o-ke-tal.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...-clo-alkyl spir-o-ke-tal (PMN P-88-0083) is subject to reporting under this section for the significant... may cause: systemic effects, eye irritation. (iii) Industrial, commercial, and consumer activities....125 (a), (b), (c), (d), (f), (g), (h), (i), and (k). (2) Limitations or revocation of certain...

  5. 40 CFR 721.9530 - Bis(2,2,6,6-tetra-methyl-piper-idinyl) ester of cycloalkyl spir-o-ke-tal.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-clo-alkyl spir-o-ke-tal (PMN P-88-0083) is subject to reporting under this section for the significant... may cause: systemic effects, eye irritation. (iii) Industrial, commercial, and consumer activities....125 (a), (b), (c), (d), (f), (g), (h), (i), and (k). (2) Limitations or revocation of certain...

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

    PubMed

    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.

  7. Alkyl gallates, intensifiers of beta-lactam susceptibility in methicillin-resistant Staphylococcus aureus.

    PubMed

    Shibata, Hirofumi; Kondo, Kyoko; Katsuyama, Ryo; Kawazoe, Kazuyoshi; Sato, Yoichi; Murakami, Kotaro; Takaishi, Yoshihisa; Arakaki, Naokatu; Higuti, Tomihiko

    2005-02-01

    We found that ethyl gallate purified from a dried pod of tara (Caesalpinia spinosa) intensified beta-lactam susceptibility in methicillin-resistant and methicillin-sensitive strains of Staphylococcus aureus (MRSA and MSSA strains, respectively). This compound and several known alkyl gallates were tested with MRSA and MSSA strains to gain new insights into their structural functions in relation to antimicrobial and beta-lactam susceptibility-intensifying activities. The maximum activity of alkyl gallates against MRSA and MSSA strains occurred at 1-nonyl and 1-decyl gallate, with an MIC at which 90% of the isolates tested were inhibited of 15.6 microg/ml. At concentrations lower than the MIC, alkyl gallates synergistically elevated the susceptibility of MRSA and MSSA strains to beta-lactam antibiotics. Such a synergistic activity of the alkyl gallates appears to be specific for beta-lactam antibiotics, because no significant changes were observed in the MICs of other classes of antibiotics examined in this study. The length of the alkyl chain was also associated with the modifying activity of the alkyl gallates, and the optimum length was C5 to C6. The present work clearly demonstrates that the length of the alkyl chain has a key role in the elevation of susceptibility to beta-lactam antibiotics.

  8. 40 CFR 721.10517 - Alkyl methacrylates, polymer with substituted carbomonocycle, hydroxymethyl acrylamide and...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl methacrylates, polymer with... Substances § 721.10517 Alkyl methacrylates, polymer with substituted carbomonocycle, hydroxymethyl acrylamide... reporting. (1) The chemical substance identified generically as alkyl methacrylates, polymer with...

  9. Ultrasonic Relaxation Study of 1-Alkyl-3-methylimidazolium-Based Room-Temperature Ionic Liquids: Probing the Role of Alkyl Chain Length in the Cation.

    PubMed

    Zorębski, Michał; Zorębski, Edward; Dzida, Marzena; Skowronek, Justyna; Jężak, Sylwia; Goodrich, Peter; Jacquemin, Johan

    2016-04-14

    Ultrasound absorption spectra of four 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides were determined as a function of the alkyl chain length on the cation from 1-propyl to 1-hexyl from 293.15 to 323.15 K at ambient pressure. Herein, the ultrasound absorption measurements were carried out using a standard pulse technique within a frequency range from 10 to 300 MHz. Additionally, the speed of sound, density, and viscosity have been measured. The presence of strong dissipative processes during the ultrasound wave propagation was found experimentally, i.e., relaxation processes in the megahertz range were observed for all compounds over the whole temperature range. The relaxation spectra (both relaxation amplitude and relaxation frequency) were shown to be dependent on the alkyl side chain length of the 1-alkyl-3-methylimidazolium ring. In most cases, a single-Debye model described the absorption spectra very well. However, a comparison of the determined spectra with the spectra of a few other imidazolium-based ionic liquids reported in the literature (in part recalculated in this work) shows that the complexity of the spectra increases rapidly with the elongation of the alkyl chain length on the cation. This complexity indicates that both the volume viscosity and the shear viscosity are involved in relaxation processes even in relatively low frequency ranges. As a consequence, the sound velocity dispersion is present at relatively low megahertz frequencies.

  10. 40 CFR 721.3900 - Alkyl polyethylene glycol phosphate, potassium salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., potassium salt. 721.3900 Section 721.3900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3900 Alkyl polyethylene glycol phosphate, potassium salt. (a) Chemical... as alkyl polyethylene glycol phosphate, potassium salt (P-90-481), is subject to reporting under this...

  11. 40 CFR 721.3900 - Alkyl polyethylene glycol phosphate, potassium salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., potassium salt. 721.3900 Section 721.3900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3900 Alkyl polyethylene glycol phosphate, potassium salt. (a) Chemical... as alkyl polyethylene glycol phosphate, potassium salt (P-90-481), is subject to reporting under this...

  12. 40 CFR 721.3900 - Alkyl polyethylene glycol phosphate, potassium salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., potassium salt. 721.3900 Section 721.3900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3900 Alkyl polyethylene glycol phosphate, potassium salt. (a) Chemical... as alkyl polyethylene glycol phosphate, potassium salt (P-90-481), is subject to reporting under this...

  13. 40 CFR 721.3900 - Alkyl polyethylene glycol phosphate, potassium salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., potassium salt. 721.3900 Section 721.3900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3900 Alkyl polyethylene glycol phosphate, potassium salt. (a) Chemical... as alkyl polyethylene glycol phosphate, potassium salt (P-90-481), is subject to reporting under this...

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

    PubMed Central

    Penketh, P. G.; Shyam, K.; Baumann, R. P; Zhu, Rui; Ishiguro, K.; Sartorelli, A. C.; Ratner, E. S.

    2016-01-01

    Alkylating agents are a significant class of environmental carcinogens as well as commonly used anticancer therapeutics. Traditional alkylating activity assays have utilized the colorimetric reagent 4-(4-nitrobenzyl)pyridine (4NBP). However, 4NBP based assays have a relatively low sensitivity towards harder, more oxophilic alkylating species and are not well suited for the identification of the trapped alkyl moiety due to adduct instability. Herein we describe a method using water as the trapping agent which permits the trapping of simple alkylating electrophiles with a comparatively wide range of softness/hardness and permits the identification of donated simple alkyl moieties. PMID:27188264

  15. Quantum chemical characterization of zwitterionic structures: Supramolecular complexes for modifying the wettability of oil-water-limestone system.

    PubMed

    Lopez-Chavez, Ernesto; Garcia-Quiroz, Alberto; Gonzalez-Garcia, Gerardo; Orozco-Duran, Gabriela E; Zamudio-Rivera, Luis S; Martinez-Magadan, José M; Buenrostro-Gonzalez, Eduardo; Hernandez-Altamirano, Raul

    2014-06-01

    In this work, we present a quantum chemical study pertaining to some supramolecular complexes acting as wettability modifiers of oil-water-limestone system. The complexes studied are derived from zwitterionic liquids of the types N'-alkyl-bis, N-alquenil, N-cycloalkyl, N-amyl-bis-beta amino acid or salts acting as sparkling agents. We studied two molecules of zwitterionic liquids (ZL10 and ZL13), HOMO and LUMO levels, and the energy gap between them, were calculated, as well as the electron affinity (EA) and ionization potential (IP), chemical potential, chemical hardness, chemical electrophilicity index and selectivity descriptors such Fukui indices. In this work, electrochemical comparison was realized with cocamidopropyl betaine (CPB), which is a structure zwitterionic liquid type, nowadays widely applied in enhanced recovery processes. Copyright © 2014 Elsevier Inc. All rights reserved.

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

    PubMed

    Chamberlain, Marc C; Raizer, Jeffrey

    2009-06-01

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

  17. Alkyl Glucosides in Contact Dermatitis.

    PubMed

    Loranger, Camille; Alfalah, Maisa; Ferrier Le Bouedec, Marie-Christine; Sasseville, Denis

    Ecologically sound because they are synthesized from natural and renewable sources, the mild surfactants alkyl glucosides are being rediscovered by the cosmetic industry. They are currently found in rinse-off products such as shampoos, liquid cleansers, and shower gels, but also in leave-on products that include moisturizers, deodorants, and sunscreens. During the past 15 years, numerous cases of allergic contact dermatitis have been published, mostly to lauryl and decyl glucosides, and these compounds are considered emergent allergens. Interestingly, the sunscreen Tinosorb M contains decyl glucoside as a hidden allergen, and most cases of allergic contact dermatitis reported to this sunscreen ingredient are probably due to sensitization to decyl glucoside. This article will review the chemistry of alkyl glucosides, their sources of exposure, as well as their cutaneous adverse effects reported in the literature and encountered in various patch testing centers.

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

    PubMed

    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.

  19. Selective sp3 C–H alkylation via polarity-match-based cross-coupling

    PubMed Central

    Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

    2017-01-01

    The functionalization of carbon–hydrogen (C–H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence1. Although many C–H functionalization reactions involve C(sp3)–C(sp2) coupling, there is a growing demand for C–H alkylation reactions, wherein sp3 C–H bonds are replaced with sp3 C–alkyl groups. Here we describe a polarity-match-based selective sp3 C–H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C–H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl–alkyl fragment coupling. The sp3 C–H alkylation is highly selective for the α-C–H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry. PMID:28636596

  20. Discovery and identification of a series of alkyl decalin isomers in petroleum geological samples.

    PubMed

    Wang, Huitong; Zhang, Shuichang; Weng, Na; Zhang, Bin; Zhu, Guangyou; Liu, Lingyan

    2015-07-07

    The comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) has been used to characterize a crude oil and a source rock extract sample. During the process, a series of pairwise components between monocyclic alkanes and mono-aromatics have been discovered. After tentative assignments of decahydronaphthalene isomers, a series of alkyl decalin isomers have been synthesized and used for identification and validation of these petroleum compounds. From both the MS and chromatography information, these pairwise compounds were identified as 2-alkyl-decahydronaphthalenes and 1-alkyl-decahydronaphthalenes. The polarity of 1-alkyl-decahydronaphthalenes was stronger. Their long chain alkyl substituent groups may be due to bacterial transformation or different oil cracking events. This systematic profiling of alkyl-decahydronaphthalene isomers provides further understanding and recognition of these potential petroleum biomarkers.

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

    PubMed

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

    2016-09-01

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

  2. Nickel-Catalyzed Reductive Allylation of Tertiary Alkyl Halides with Allylic Carbonates.

    PubMed

    Chen, Haifeng; Jia, Xiao; Yu, Yingying; Qian, Qun; Gong, Hegui

    2017-10-09

    The construction of all C(sp 3 ) quaternary centers has been successfully achieved under Ni-catalyzed cross-electrophile coupling of allylic carbonates with unactivated tertiary alkyl halides. For allylic carbonates bearing C1 or C3 substituents, the reaction affords excellent regioselectivity through the addition of alkyl groups to the unsubstituted allylic carbon terminus. The allylic alkylation method also exhibits excellent functional-group compatibility, and delivers the products with high E selectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Hybrid ligand-alkylating agents targeting telomeric G-quadruplex structures.

    PubMed

    Doria, Filippo; Nadai, Matteo; Folini, Marco; Di Antonio, Marco; Germani, Luca; Percivalle, Claudia; Sissi, Claudia; Zaffaroni, Nadia; Alcaro, Stefano; Artese, Anna; Richter, Sara N; Freccero, Mauro

    2012-04-14

    The synthesis, physico-chemical properties and biological effects of a new class of naphthalene diimides (NDIs) capable of reversibly binding telomeric DNA and alkylate it through an electrophilic quinone methide moiety (QM), are reported. FRET and circular dichroism assays showed a marked stabilization and selectivity towards telomeric G4 DNA folded in a hybrid topology. NDI-QMs' alkylating properties revealed a good reactivity on single nucleosides and selectivity towards telomeric G4. A selected NDI was able to significantly impair the growth of melanoma cells by causing telomere dysfunction and down-regulation of telomerase expression. These findings points to our hybrid ligand-alkylating NDIs as possible tools for the development of novel targeted anticancer therapies. This journal is © The Royal Society of Chemistry 2012

  4. Alkyl Azides, Diazides, Haloazides and Bridged Polycyclic Diazides

    DTIC Science & Technology

    1991-05-16

    temperature. Most of the methyl ether was removed during this process. The ehtyl ether was distilled from the reaction mixture using a water aspirator into a...Street PROGRAM IPROJECT ITASK IWORK li1111? ArliiqIoh, VA 22217-5000 EILIMENT NO I NO. I oACCESSION P10) Alkyl Azides, Dlazides, laloazides and...REPRODUCE LEGIBLY. ALKYL AZIDES, DIAZIDES, HALOAZIDES AND BRIDGED POLYCYCLIC DIAZIDES Final REPORTe July 1, 1989-November 14, 1990 A6jd.%4gi0 F’or

  5. Enantiomerically Pure Acetals in Organic Synthesis: Resolutions and Diastereoselective Alkylations of Alpha-Hydroxy Esters

    DTIC Science & Technology

    1990-01-01

    sensitivity of the alkylating agent to the reaction conditions. In either case , a decision was made to use 5-iodo-2- methyl -l-pentene as the alkylating ...agent, and the reaction conditions. In most cases the diastereomeric products of the alkylation were also separated by column chromatography. This...equatorially substituted product. Oxidation of the alcohol to the ketone followed by treatment with an alkyl Grignard reagent gave only the product which

  6. Novel fluconazole derivatives with promising antifungal activity.

    PubMed

    Thamban Chandrika, Nishad; Shrestha, Sanjib K; Ngo, Huy X; Howard, Kaitlind C; Garneau-Tsodikova, Sylvie

    2018-02-01

    The fungistatic nature and toxicity concern associated with the azole drugs currently on the market have resulted in an increased demand for new azole antifungal agents for which these problematic characteristics do not exist. The extensive use of azoles has resulted in fungal strains capable of resisting the action of these drugs. Herein, we report the synthesis and antifungal activity of novel fluconazole (FLC) analogues with alkyl-, aryl-, cycloalkyl-, and dialkyl-amino substituents. We evaluated their antifungal activity by MIC determination and time-kill assay as well as their safety profile by hemolytic activity against murine erythrocytes as well as cytotoxicity against mammalian cells. The best compounds from our study exhibited broad-spectrum activity against most of the fungal strains tested, with excellent MIC values against a number of clinical isolates. The most promising compounds were found to be less hemolytic than the least hemolytic FDA-approved azole antifungal agent voriconazole (VOR). Finally, we demonstrated that the synthetic alkyl-amino FLC analogues displayed chain-dependent fungal membrane disruption as well as inhibition of ergosterol biosynthesis as possible mechanisms of action. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Synthesis and antimalarial activity study of some new Mannich bases of 7-chloro-4-aminoquinoline.

    PubMed

    Roy, Susanta; Chetia, Dipak; Rudrapal, Mithun; Prakash, Anil

    2013-05-01

    New derivatives of 7-chloro-4-aminoquinoline Mannich base were prepared by selectively modifying the aliphatic diethyl amino function of isoquine with different aliphatic/aromatic heterocyclic primary amino moieties at Mannich side chain. The synthesized compounds were characterized by their analytical and spectral data, and screened for in-vitro antimalarial activity against a chloroquine-sensitive 3D7 strain of Plasmodium falciparum. All the compounds showed in-vitro antimalarial activity at the tested dose; which, however, was considerably less than that of the standard reference drug, chloroquine. Among synthesized compounds, compounds with cyclohexyl (2f), methyl (2c) substitutions showed better activity than compounds substituted with n-octyl (2a), propyl (2b), 3-aminopropyl (2d) and furan-2- ylmethyl (2e) moieties at aminomethyl side chain. The results clearly demonstrate that the compound substituted with saturated cycloalkyl moiety (cyclohexyl) exhibited to some extent increased activity as compared to the compound containing heterocyclic moiety (furan-2-ylmethyl), and compounds with short chain alkyl substitutions (methyl, propyl) were found to be more active than that of compounds with long chain alkyl substitution (n-octyl).

  8. 40 CFR 721.5860 - Methylphenol, bis(sub-sti-tuted)alkyl.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.5860 Methylphenol, bis(sub-sti-tuted)alkyl. (a) Chemical substance and significant new uses...-ed)alkyl (P-84-417) is subject to reporting under this section for the significant new uses described...

  9. Direct β-Alkylation of Aldehydes via Photoredox Organocatalysis

    PubMed Central

    2015-01-01

    Direct β-alkylation of saturated aldehydes has been accomplished by synergistically combining photoredox catalysis and organocatalysis. Photon-induced enamine oxidation provides an activated β-enaminyl radical intermediate, which readily combines with a wide range of Michael acceptors to produce β-alkyl aldehydes in a highly efficient manner. Furthermore, this redox-neutral, atom-economical C–H functionalization protocol can be achieved both inter- and intramolecularly. Mechanistic studies by various spectroscopic methods suggest that a reductive quenching pathway is operable. PMID:24754456

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

    PubMed

    Puyo, Stéphane; Montaudon, Danièle; Pourquier, Philippe

    2014-01-01

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

  11. Methods of producing alkylated hydrocarbons from an in situ heat treatment process liquid

    DOEpatents

    Roes, Augustinus Wilhelmus Maria [Houston, TX; Mo, Weijian [Sugar Land, TX; Muylle, Michel Serge Marie [Houston, TX; Mandema, Remco Hugo [Houston, TX; Nair, Vijay [Katy, TX

    2009-09-01

    A method for producing alkylated hydrocarbons is disclosed. Formation fluid is produced from a subsurface in situ heat treatment process. The formation fluid is separated to produce a liquid stream and a first gas stream. The first gas stream includes olefins. The liquid stream is fractionated to produce at least a second gas stream including hydrocarbons having a carbon number of at least 3. The first gas stream and the second gas stream are introduced into an alkylation unit to produce alkylated hydrocarbons. At least a portion of the olefins in the first gas stream enhance alkylation.

  12. 40 CFR 721.3812 - Substituted phenols and formaldehyde polymer, alkylated (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... polymer, alkylated (generic). 721.3812 Section 721.3812 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3812 Substituted phenols and formaldehyde polymer... substance identified generically as substituted phenols and formaldehyde polymer, alkylated (PMN P-00-0542...

  13. 40 CFR 721.3812 - Substituted phenols and formaldehyde polymer, alkylated (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... polymer, alkylated (generic). 721.3812 Section 721.3812 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3812 Substituted phenols and formaldehyde polymer... substance identified generically as substituted phenols and formaldehyde polymer, alkylated (PMN P-00-0542...

  14. 40 CFR 721.3812 - Substituted phenols and formaldehyde polymer, alkylated (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... polymer, alkylated (generic). 721.3812 Section 721.3812 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3812 Substituted phenols and formaldehyde polymer... substance identified generically as substituted phenols and formaldehyde polymer, alkylated (PMN P-00-0542...

  15. 40 CFR 721.3812 - Substituted phenols and formaldehyde polymer, alkylated (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... polymer, alkylated (generic). 721.3812 Section 721.3812 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3812 Substituted phenols and formaldehyde polymer... substance identified generically as substituted phenols and formaldehyde polymer, alkylated (PMN P-00-0542...

  16. 40 CFR 721.3812 - Substituted phenols and formaldehyde polymer, alkylated (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... polymer, alkylated (generic). 721.3812 Section 721.3812 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3812 Substituted phenols and formaldehyde polymer... substance identified generically as substituted phenols and formaldehyde polymer, alkylated (PMN P-00-0542...

  17. Alkylation Induced DNA Repair and Mutagenesis in Escherichia coli.

    DTIC Science & Technology

    1987-11-23

    III (Gates and inn, 1977), Micrococcus luteus UV endo- nuclease (Grossman et al, 1978) and bacteriophage T UV endonuclease (Warner et al, 1980) have DNA...34, Garland Publishing, Inc. New York & London USA. Ather, A., Z. Ahmed and S. Riazxxddin, 1984. Adaptive response of Micrococcus luteus to alkylating...Laval, J., 3. Pierre and F. Laval. 1981. Release of 7-nmthylguanine residues frain alkylated ENA by extracts of Micrococcus luteus and Escherichia

  18. 40 CFR 721.10621 - Distillation bottoms, alkylated benzene by-product (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... benzene by-product (generic). 721.10621 Section 721.10621 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.10621 Distillation bottoms, alkylated benzene by... substance identified generically as distillation bottoms, alkylated benzene by-product (PMN P-12-196) is...

  19. 40 CFR 721.10621 - Distillation bottoms, alkylated benzene by-product (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... benzene by-product (generic). 721.10621 Section 721.10621 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.10621 Distillation bottoms, alkylated benzene by... substance identified generically as distillation bottoms, alkylated benzene by-product (PMN P-12-196) is...

  20. 40 CFR 721.10702 - Polyfluorinated alkyl thio polyacrylic acid-acrylamide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... acid-acrylamide (generic). 721.10702 Section 721.10702 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.10702 Polyfluorinated alkyl thio polyacrylic acid... substance identified generically as polyfluorinated alkyl thio polyacrylic acid-acrylamide (PMN P-11-534) is...

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

    PubMed

    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

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

    PubMed Central

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

    2013-01-01

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

  3. Poly(ethyleneoxide) functionalization through alkylation

    DOEpatents

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

    2015-04-21

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

  4. Versatile assembly of p-carboxylatocalix[4]arene-O-alkyl ethers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kennedy, Stuart; Teat, Simon J.; Dalgarno, Scott J.

    Crystallisation of lower-rim tetra-O-alkylated p-carboxylatocalix[4]arenes from pyridine results in the formation of both bi-layer and pillar type supramolecular motifs. Full alkylation at the calixarene lower rim has significant influence over the supramolecular self-assembly motif, including preclusion of pyridine guest molecules from the calixarene cavity in the solid state.

  5. 40 CFR 721.10044 - Metal oxide, modified with alkyl and vinyl terminated polysiloxanes (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Metal oxide, modified with alkyl and... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10044 Metal oxide, modified with alkyl... to reporting. (1) The chemical substance identified generically as metal oxide, modified with alkyl...

  6. Oxidative 1,2-carboamination of alkenes with alkyl nitriles and amines toward γ-amino alkyl nitriles

    NASA Astrophysics Data System (ADS)

    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.

  7. Safety Assessment of Alkyl Ethylhexanoates as Used in Cosmetics.

    PubMed

    Fiume, Monice; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2015-01-01

    The Cosmetic Ingredient Review (CIR) Expert Panel (Panel) assessed the safety of 16 alkyl ethylhexanoates for use in cosmetics, concluding that these ingredients are safe in cosmetic formulations in the present practices of use and concentrations when formulated to be nonirritating. The alkyl ethylhexanoates primarily function as skin-conditioning agents in cosmetics. The highest concentration of use reported for any of the alkyl ethylhexanoates is 77.3% cetyl ethylhexanoate in rinse-off formulations used near the eye, and the highest leave-on use reported is 52% cetyl ethylhexanoate in lipstick formulations. The Panel reviewed available animal and clinical data related to these ingredients, and the similarities in structure, properties, functions, and uses of ingredients from previous CIR assessments on constituent alcohols that allowed for extrapolation of the available toxicological data to assess the safety of the entire group. © The Author(s) 2015.

  8. Experimental and QSAR study on the surface activities of alkyl imidazoline surfactants

    NASA Astrophysics Data System (ADS)

    Kong, Xiangjun; Qian, Chengduo; Fan, Weiyu; Liang, Zupei

    2018-03-01

    15 alkyl imidazoline surfactants with different structures were synthesized and their critical micelle concentration (CMC) and surface tension under the CMC (σcmc) in aqueous solution were measured at 298 K. 54 kinds of molecular structure descriptors were selected as independent variables and the quantitative structure-activity relationship (QSAR) between surface activities of alkyl imidazoline and molecular structure were built through the genetic function approximation (GFA) method. Experimental results showed that the maximum surface excess of alkyl imidazoline molecules at the gas-liquid interface increased and the area occupied by each surfactant molecule and the free energies of micellization ΔGm decreased with increasing carbon number (NC) of the hydrophobic chain or decreasing hydrophilicity of counterions, which resulted in a CMC and σcmc decrease, while the log CMC and NC had a linear relationship and a negative correlation. The GFA-QSAR model, which was generated by a training set composed of 13 kinds of alkyl imidazoline though GFA method regression analysis, was highly correlated with predicted values and experimental values of the CMC. The correlation coefficient R was 0.9991, which means high prediction accuracy. The prediction error of 2 kinds of alkyl imidazoline CMCs in the Validation Set that quantitatively analyzed the influence of the alkyl imidazoline molecular structure on the CMC was less than 4%.

  9. Extensive reprogramming of the genetic code for genetically encoded synthesis of highly N-alkylated polycyclic peptidomimetics.

    PubMed

    Kawakami, Takashi; Ishizawa, Takahiro; Murakami, Hiroshi

    2013-08-21

    Cyclic structures can increase the proteolytic stability and conformational rigidity of peptides, and N-alkylation of the peptide backbone can make peptides more cell-permeable and resistant to proteolysis. Therefore, cyclic N-alkyl amino acids are expected to be useful building blocks to increase simultaneously these pharmacological properties of peptides. In this study, we screened various cyclic N-alkyl amino acids for their ribosomal incorporation into peptides and identified cyclic N-alkyl amino acids that can be efficiently and successively incorporated. We also demonstrated genetic code reprogramming for reassigning 16 NNU codons to 16 different cyclic N-alkyl amino acids with high fidelity to synthesize highly N-alkylated polycyclic peptidomimetics and an mRNA-displayed library of completely N-alkylated polycyclic peptidomimetics by using our recently developed TRAP (transcription/translation coupled with association of puromycin linker) display. In vitro selection from a highly diverse library of such completely N-alkylated polycyclic peptidomimetics could become a powerful means to discover small-molecule ligands such as drug candidates that can be targeted to biomolecules inside living cells.

  10. Stochastic resonance algorithm applied to quantitative analysis for weak chromatographic signals of alkyl halides and alkyl benzenes in water samples.

    PubMed

    Xiang, Suyun; Wang, Wei; Xia, Jia; Xiang, Bingren; Ouyang, Pingkai

    2009-09-01

    The stochastic resonance algorithm is applied to the trace analysis of alkyl halides and alkyl benzenes in water samples. Compared to encountering a single signal when applying the algorithm, the optimization of system parameters for a multicomponent is more complex. In this article, the resolution of adjacent chromatographic peaks is first involved in the optimization of parameters. With the optimized parameters, the algorithm gave an ideal output with good resolution as well as enhanced signal-to-noise ratio. Applying the enhanced signals, the method extended the limit of detection and exhibited good linearity, which ensures accurate determination of the multicomponent.

  11. Persistence of DNA adducts, hypermutation and acquisition of cellular resistance to alkylating agents in glioblastoma.

    PubMed

    Head, R J; Fay, M F; Cosgrove, L; Y C Fung, K; Rundle-Thiele, D; Martin, J H

    2017-12-02

    Glioblastoma is a lethal form of brain tumour usually treated by surgical resection followed by radiotherapy and an alkylating chemotherapeutic agent. Key to the success of this multimodal approach is maintaining apoptotic sensitivity of tumour cells to the alkylating agent. This initial treatment likely establishes conditions contributing to development of drug resistance as alkylating agents form the O 6 -methylguanine adduct. This activates the mismatch repair (MMR) process inducing apoptosis and mutagenesis. This review describes key juxtaposed drivers in the balance between alkylation induced mutagenesis and apoptosis. Mutations in MMR genes are the probable drivers for alkylation based drug resistance. Critical to this interaction are the dose-response and temporal interactions between adduct formation and MMR mutations. The precision in dose interval, dose-responses and temporal relationships dictate a role for alkylating agents in either promoting experimental tumour formation or inducing tumour cell death with chemotherapy. Importantly, this resultant loss of chemotherapeutic selective pressure provides opportunity to explore novel therapeutics and appropriate combinations to minimise alkylation based drug resistance and tumour relapse.

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

    NASA Astrophysics Data System (ADS)

    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.

  13. Safety Assessment of Alkyl PEG Sulfosuccinates as Used in Cosmetics.

    PubMed

    Johnson, Wilbur; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2015-09-01

    The Cosmetic Ingredient Review (CIR) Expert Panel (Panel) reviewed the safety of alkyl polyethylene glycol (PEG) sulfosuccinates, which function in cosmetics mostly as surfactants/cleansing agents. Although these ingredients may cause ocular and skin irritation, dermal penetration is unlikely because of the substantial polarity and molecular size of these ingredients. The Panel considered the negative oral carcinogenicity and reproductive and developmental toxicity data on chemically related laureths (PEG lauryl ethers) and negative repeated dose toxicity and skin sensitization data on disodium laureth sulfosuccinate supported the safety of these alkyl PEG sulfosuccinates in cosmetic products, but. The CIR Expert Panel concluded that the alkyl PEG sulfosuccinates are safe in the present practices of use and concentration when formulated to be nonirritating. © The Author(s) 2015.

  14. ATM regulates 3-Methylpurine-DNA glycosylase and promotes therapeutic resistance to alkylating agents

    PubMed Central

    Agnihotri, Sameer; Burrell, Kelly; Buczkowicz, Pawel; Remke, Marc; Golbourn, Brian; Chornenkyy, Yevgen; Gajadhar, Aaron; Fernandez, Nestor A.; Clarke, Ian D.; Barszczyk, Mark S.; Pajovic, Sanja; Ternamian, Christian; Head, Renee; Sabha, Nesrin; Sobol, Robert W.; Taylor, Michael D; Rutka, James T.; Jones, Chris; Dirks, Peter B.; Zadeh, Gelareh; Hawkins, Cynthia

    2014-01-01

    Alkylating agents are a frontline therapy for the treatment of several aggressive cancers including pediatric glioblastoma, a lethal tumor in children. Unfortunately, many tumors are resistant to this therapy. We sought to identify ways of sensitizing tumor cells to alkylating agents while leaving normal cells unharmed; increasing therapeutic response while minimizing toxicity. Using a siRNA screen targeting over 240 DNA damage response genes, we identified novel sensitizers to alkylating agents. In particular the base excision repair (BER) pathway, including 3-methylpurine-DNA glycosylase (MPG), as well as ataxia telangiectasia mutated (ATM) were identified in our screen. Interestingly, we identified MPG as a direct novel substrate of ATM. ATM-mediated phosphorylation of MPG was required for enhanced MPG function. Importantly, combined inhibition or loss of MPG and ATM resulted in increased alkylating agent-induced cytotoxicity in vitro and prolonged survival in vivo. The discovery of the ATM-MPG axis will lead to improved treatment of alkylating agent-resistant tumors. PMID:25100205

  15. Optoelectronic functional materials based on alkylated-π molecules: self-assembled architectures and nonassembled liquids.

    PubMed

    Li, Hongguang; Choi, Jiyoung; Nakanishi, Takashi

    2013-05-07

    The engineering of single molecules into higher-order hierarchical assemblies is a current research focus in molecular materials chemistry. Molecules containing π-conjugated units are an important class of building blocks because their self-assembly is not only of fundamental interest, but also the key to fabricating functional systems for organic electronic and photovoltaic applications. Functionalizing the π-cores with "alkyl chains" is a common strategy in the molecular design that can give the system desirable properties, such as good solubility in organic solvents for solution processing. Moreover, the alkylated-π system can regulate the self-assembly behavior by fine-tuning the intermolecular forces. The optimally assembled structures can then exhibit advanced functions. However, while some general rules have been revealed, a comprehensive understanding of the function played by the attached alkyl chains is still lacking, and current methodology is system-specific in many cases. Better clarification of this issue requires contributions from carefully designed libraries of alkylated-π molecular systems in both self-assembly and nonassembly materialization strategies. Here, based on recent efforts toward this goal, we show the power of the alkyl chains in controlling the self-assembly of soft molecular materials and their resulting optoelectronic properties. The design of alkylated-C60 is selected from our recent research achievements, as the most attractive example of such alkylated-π systems. Some other closely related systems composed of alkyl chains and π-units are also reviewed to indicate the universality of the methodology. Finally, as a contrast to the self-assembled molecular materials, nonassembled, solvent-free, novel functional liquid materials are discussed. In doing so, a new journey toward the ultimate organic "soft" materials is introduced, based on alkylated-π molecular design.

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

    PubMed

    Provencher, Philip A; Love, Jennifer A

    2015-10-02

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

  17. ATM regulates 3-methylpurine-DNA glycosylase and promotes therapeutic resistance to alkylating agents.

    PubMed

    Agnihotri, Sameer; Burrell, Kelly; Buczkowicz, Pawel; Remke, Marc; Golbourn, Brian; Chornenkyy, Yevgen; Gajadhar, Aaron; Fernandez, Nestor A; Clarke, Ian D; Barszczyk, Mark S; Pajovic, Sanja; Ternamian, Christian; Head, Renee; Sabha, Nesrin; Sobol, Robert W; Taylor, Michael D; Rutka, James T; Jones, Chris; Dirks, Peter B; Zadeh, Gelareh; Hawkins, Cynthia

    2014-10-01

    Alkylating agents are a first-line therapy for the treatment of several aggressive cancers, including pediatric glioblastoma, a lethal tumor in children. Unfortunately, many tumors are resistant to this therapy. We sought to identify ways of sensitizing tumor cells to alkylating agents while leaving normal cells unharmed, increasing therapeutic response while minimizing toxicity. Using an siRNA screen targeting over 240 DNA damage response genes, we identified novel sensitizers to alkylating agents. In particular, the base excision repair (BER) pathway, including 3-methylpurine-DNA glycosylase (MPG), as well as ataxia telangiectasia mutated (ATM), were identified in our screen. Interestingly, we identified MPG as a direct novel substrate of ATM. ATM-mediated phosphorylation of MPG was required for enhanced MPG function. Importantly, combined inhibition or loss of MPG and ATM resulted in increased alkylating agent-induced cytotoxicity in vitro and prolonged survival in vivo. The discovery of the ATM-MPG axis will lead to improved treatment of alkylating agent-resistant tumors. Inhibition of ATM and MPG-mediated BER cooperate to sensitize tumor cells to alkylating agents, impairing tumor growth in vitro and in vivo with no toxicity to normal cells, providing an ideal therapeutic window. ©2014 American Association for Cancer Research.

  18. Near Infrared Spectroscopic Identification of Alkyl Aromatic Esters and Phenyl Ketones

    NASA Astrophysics Data System (ADS)

    Nelyubov, D. V.; Vazhenin, D. A.; Kudriavtsev, A. A.; Buzolina, A. Yu.

    2018-03-01

    Bands characterizing the content of carbon atoms in alkyl (7177-7205 cm-1) and phenyl structural fragments (9175-9192 cm-1) in organic molecules were revealed by studying the near infrared spectra of such compounds. The optical density at the maxima of these absorption bands was shown to depend strongly on the fraction of carbon atoms in the corresponding fragments. The developed models proved to be adequate for determining the fraction of carbon atoms in alkyl aromatic esters and phenyl ketones. The feasibility of modeling the molecular structure of alkyl aromatic esters using regression models was demonstrated for the product of the condensation of oleic acid and benzyl alcohol.

  19. Electrochemical and thermal grafting of alkyl grignard reagents onto (100) silicon surfaces.

    PubMed

    Vegunta, Sri Sai S; Ngunjiri, Johnpeter N; Flake, John C

    2009-11-03

    Passivation of (100) silicon surfaces using alkyl Grignard reagents is explored via electrochemical and thermal grafting methods. The electrochemical behavior of silicon in methyl or ethyl Grignard reagents in tetrahydrofuran is investigated using cyclic voltammetry. Surface morphology and chemistry are investigated using atomic force microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results show that electrochemical pathways provide an efficient and more uniform passivation method relative to thermal methods, and XPS results demonstrate that electrografted terminations are effective at limiting native oxide formation for more than 55 days in ambient conditions. A two-electron per silicon mechanism is proposed for electrografting a single (1:1) alkyl group per (100) silicon atom. The mechanism includes oxidation of two Grignard species and subsequent hydrogen abstraction and alkylation reaction resulting in a covalent attachment of alkyl groups with silicon.

  20. Deciphering the genomic targets of alkylating polyamide conjugates using high-throughput sequencing

    PubMed Central

    Chandran, Anandhakumar; Syed, Junetha; Taylor, Rhys D.; Kashiwazaki, Gengo; Sato, Shinsuke; Hashiya, Kaori; Bando, Toshikazu; Sugiyama, Hiroshi

    2016-01-01

    Chemically engineered small molecules targeting specific genomic sequences play an important role in drug development research. Pyrrole-imidazole polyamides (PIPs) are a group of molecules that can bind to the DNA minor-groove and can be engineered to target specific sequences. Their biological effects rely primarily on their selective DNA binding. However, the binding mechanism of PIPs at the chromatinized genome level is poorly understood. Herein, we report a method using high-throughput sequencing to identify the DNA-alkylating sites of PIP-indole-seco-CBI conjugates. High-throughput sequencing analysis of conjugate 2 showed highly similar DNA-alkylating sites on synthetic oligos (histone-free DNA) and on human genomes (chromatinized DNA context). To our knowledge, this is the first report identifying alkylation sites across genomic DNA by alkylating PIP conjugates using high-throughput sequencing. PMID:27098039

  1. Synthesis and evaluation of novel caged DNA alkylating agents bearing 3,4-epoxypiperidine structure.

    PubMed

    Kawada, Yuji; Kodama, Tetsuya; Miyashita, Kazuyuki; Imanishi, Takeshi; Obika, Satoshi

    2012-07-14

    Previously, we reported that the 3,4-epoxypiperidine structure, whose design was based on the active site of DNA alkylating antitumor antibiotics, azinomycins A and B, possesses prominent DNA cleavage activity. In this report, novel caged DNA alkylating agents, which were designed to be activated by UV irradiation, were synthesized by the introduction of four photo-labile protecting groups to a 3,4-epoxypiperidine derivative. The DNA cleavage activity and cytotoxicity of the caged DNA alkylating agents were examined under UV irradiation. Four caged DNA alkylating agents showed various degrees of bioactivity depending on the photosensitivity of the protecting groups.

  2. Profound impairment of adaptive immune responses by alkylating chemotherapy

    PubMed Central

    Litterman, Adam J.; Zellmer, David M.; Grinnen, Karen L.; Hunt, Matthew A.; Dudek, Arkadiusz Z.; Salazar, Andres M.; Ohlfest, John R.

    2013-01-01

    Cancer vaccines have overall had a record of failure as an adjuvant therapy for malignancies that are treated with alkylating chemotherapy, and the contribution of standard treatment to that failure remains unclear. Vaccines aim to harness the proliferative potential of the immune system by expanding a small number of tumor-specific lymphocytes into a large number of anti-tumor effectors. Clinical trials are often conducted after treatment with alkylating chemotherapy, given either as standard therapy or for immunomodulatory effect. There is mounting evidence for synergy between chemotherapy and adoptive immunotherapy or vaccination against self-antigens; however, the impact of chemotherapy on lymphocytes primed against tumor neo-antigens remains poorly defined. We report here that clinically relevant dosages of standard alkylating chemotherapies such as temozolomide and cyclophosphamide significantly inhibit the proliferative abilities of lymphocytes in mice. This proliferative impairment was long lasting and led to quantitative and qualitative defects in B and T cell responses to neo-antigen vaccines. High affinity responder lymphocytes receiving the strongest proliferative signals from vaccines experienced the greatest DNA damage responses, skewing the response toward lower affinity responders with inferior functional characteristics. Together these defects lead to inferior efficacy and overall survival in murine tumor models treated by neo-antigen vaccines. These results suggest that clinical protocols for cancer vaccines should be designed to avoid exposing responder lymphocytes to alkylating chemotherapy. PMID:23686484

  3. Persubstituted p-benzoquinone monoxime alkyl ethers and their molecular structure

    NASA Astrophysics Data System (ADS)

    Slaschinin, D. G.; Alemasov, Y. A.; Ilushkin, D. I.; Sokolenko, W. A.; Tovbis, M. S.; Kirik, S. D.

    2012-05-01

    Theoretical and experimental approaches were applied for the investigation of the reactivity of persubstituted 4-nitrosophenols in the reaction with alkyl iodides, in particular the potassium salt of 2,6-di(alkoxycarbonyl)-3,5-dimethyl-4-nitrosophenol. Hartre-Fock calculations showed that the anion negative charge was located mostly on the oxygen of hydroxyl group, while estimation of the total energy of the alkylated products pointed out the benefit of alkylation on the oxygen atom of the nitroso group yielding p-benzoquinone monoxime alkyl ethers. Methylation and ethylation of persubstituted nitrosophenols were carried out. The products obtained were investigated using X-ray diffraction, 1Н NMR spectroscopy and mass spectrometry. The crystal structure of the methyl ether of 2,6-di(alkoxycarbonyl)-3,5-dimethyl-1,4-benzoquinone-1-oxime (С15H19NO6) (I) was determined by the X-ray powder diffraction technique. The unit cell parameters were: a = 7.3322(6) Å, b = 10.5039(12) Å, c = 21.1520(20) Å, β = 93.742(6)°, V = 1625.58(2) Å3Z = 4, Sp.Gr. P21/c. The structure modeling was made in direct space by the Monte-Carlo approach using rigid and soft restrictions. The structure refinement was completed by the Rietveld method. It was established that the alkylation occurred on the oxygen atom of the nitroso group. The molecules (I) in the crystal structure were packed in columns along the axis a with pairwise convergence in a column up to the distance of 3.63 Å due to a 180° turn of every second molecule around the column axis. In the molecular structure the methyloxime group was oriented in the benzene plane and had π-conjugation with the ring. The ethoxycarbonyl groups were turned nearly perpendicular to the ring. Other compounds obtained had the structure of the alkyl ethers of 1.4-benzoquinone-1-oxime, which was proved by 1Н NMR spectroscopy and mass-spectrometry.

  4. One-step formation of bifunctionnal aryl/alkyl grafted films on conducting surfaces by the reduction of diazonium salts in the presence of alkyl iodides.

    PubMed

    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.

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

    PubMed Central

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

    2009-01-01

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

  6. Design and synthesis of 2-nitroimidazoles with variable alkylating and acylating functionality.

    PubMed

    Winters, Thomas; Sercel, Anthony; Suto, Carla; Elliott, William; Leopold, Wilbur; Leopold, Judith; Showalter, Hollis

    2014-01-01

    The synthesis of a small series of 2-nitroimidazoles in which the β-amino alcohol side chain was amidated with a range of alkylating/acylating functionality is described. Synthetic methodologies were developed that generally provided for selective N-acyl versus N,O-bisacyl products. In vitro, target analogs showed minimal radiosensitization activity, with only a few exhibiting a sensitizer enhancement ratio (SER) >2.0 and C(1.6) values comparable to reference agents RB-6145 and RSU-1069. In an assay to determine potential to alkylate biomolecules, representative analogs showed <1% of the alkylating activity of RSU-1069. In vivo, one analog showed an enhancement ratio of 1.6 relative to vehicle control when tested in B6C3F1 mice with an implanted KHT sarcoma. The data reinforce prior findings that there is a correlation between alkylation potential and in vivo activity.

  7. The clinical pharmacology of alkylating agents in high-dose chemotherapy.

    PubMed

    Huitema, A D; Smits, K D; Mathôt, R A; Schellens, J H; Rodenhuis, S; Beijnen, J H

    2000-08-01

    Alkylating agents are widely used in high-dose chemotherapy regimens in combination with hematological support. Knowledge about the pharmacokinetics and pharmacodynamics of these agents administered in high doses is critical for the safe and efficient use of these regimens. The aim of this review is to summarize the clinical pharmacology of the alkylating agents (including the platinum compounds) in high-dose chemotherapy. Differences between conventional and high doses will be discussed.

  8. Kinetic study of the anaerobic biodegradation of alkyl polyglucosides and the influence of their structural parameters.

    PubMed

    Ríos, Francisco; Fernández-Arteaga, Alejandro; Lechuga, Manuela; Jurado, Encarnación; Fernández-Serrano, Mercedes

    2016-05-01

    This paper reports a study of the anaerobic biodegradation of non-ionic surfactants alkyl polyglucosides applying the method by measurement of the biogas production in digested sludge. Three alkyl polyglucosides with different length alkyl chain and degree of polymerization of the glucose units were tested. The influence of their structural parameters was evaluated, and the characteristics parameters of the anaerobic biodegradation were determined. Results show that alkyl polyglucosides, at the standard initial concentration of 100 mgC L(-1), are not completely biodegradable in anaerobic conditions because they inhibit the biogas production. The alkyl polyglucoside having the shortest alkyl chain showed the fastest biodegradability and reached the higher percentage of final mineralization. The anaerobic process was well adjusted to a pseudo first-order equation using the carbon produced as gas during the test; also, kinetics parameters and a global rate constant for all the involved metabolic process were determined. This modeling is helpful to evaluate the biodegradation or the persistence of alkyl polyglucosides under anaerobic conditions in the environment and in the wastewater treatment.

  9. N-Alkyl-PEI Functional Iron Oxide Nanocluster for Efficient siRNA Delivery**

    PubMed Central

    Liu, Gang; Xie, Jin; Zhang, Fan; Wang, Zhi-Yong; Luo, Kui; Zhu, Lei; Quan, Qi-Meng; Niu, Gang; Lee, Seulki

    2013-01-01

    Small interfering RNA (siRNA) is an emerging class of therapeutics, working by regulating the expression of a specific gene involved in disease progression. Despite the promises, effective transport of siRNA with minimal side effects remains a challenge. In this study, a non-viral nanoparticle gene carrier has been developed and its efficiency for siRNA delivery and transfection has been validated at both in vitro and in vivo levels. Such a nanocarrier, abbreviated as Alkyl-PEI2k-IO, was constructed with a core of iron oxide (IO) and a shell of alkylated PEI2000 (Alkyl-PEI2k). It was found to be able to bind with siRNA, resulting in well-dispersed nanoparticles with a controlled clustering structure and narrow size distribution. Electrophoresis studies showed that the Alkyl-PEI2k-IOs could retard siRNA completely at N/P ratios above 10, protect siRNA from enzymatic degradation in serum and release complexed siRNA efficiently in the presence of polyanionic heparin. The knockdown efficiency of the siRNA loaded nanocarriers was assessed with 4T1 cells stably expressing luciferase (fluc-4T1) and further, with a fluc-4T1 xenograft model. Significant downregulation of luciferase was observed, and unlike the high molecular weight analogs, the Alkyl-PEI2k coated IOs showed a good biocompatibility. In conclusion, Alkyl-PEI2k-IOs demonstrate highly efficient delivery of siRNA and an innocuous toxic profile, making it a potential carrier for gene therapy. PMID:21861295

  10. Formation of furan fatty alkyl esters from their bis-epoxide fatty esters

    USDA-ARS?s Scientific Manuscript database

    Reactions of epoxidized alkyl soyate with four different alcohols: ethanol, isopropyl alcohol, 2-ethylhexanol, and benzyl alcohol were investigated in the presence of Bronsted acid catalyst. Products not reported in prior studies of similar reactions were found. These were furan fatty acid alkyl est...

  11. In vitro induction of micronuclei by monofunctional methanesulphonic acid esters: possible role of alkylation mechanisms.

    PubMed

    Eder, Erwin; Kütt, Wolfgang; Deininger, Christoph

    2006-12-01

    Six monofunctional alkylating methanesulphonates of widely varying structures were investigated in the in vitro micronucleus assay with Syrian hamster embryo fibroblast cells. The results were compared with the alkylating activities measured in the 4-(nitrobenzyl)pyridine test (NBP-test) and the N-methyl mercaptoimidazole (MMI-test) as measures for S(N)2 reactivity as well as in the triflouoroacetic acid (TFA) solvolysis and the hydrolysis reaction as measures for S(N)1 reactivity in order to provide insights into the role of alkylation mechanisms on induction of micronuclei. Moreover we compared the results of micronucleus assay with those of the Ames tests in strain TA 100 and TA1535 and with those of the SOS chromotest with the strains PQ37, PQ243, PM21 and GC 4798. The potency of methanesulphonates to induce micronuclei depended only to a certain degree, on the total alkylating activity (S(N)1 and S(N)2 reactivity). An inverse, significant correlation between the Ames test and the micronucleus assay was observed and an inverse correlation between the micronucleus assay and the SOS chromotest with the different strains. The results indicate that the primary mechanism leading to induction of micronuclei is not O-alkylation in DNA as it is the case in the Ames test with the hisG46 strains TA1535 and TA100 and not N-alkylation as with the SOS chromotest. There is evidence that protein alkylation, e.g. in the spindle apparatus in mitosis is decisive for induction of micronuclei by alkylating compounds. The structurally voluminous methanesulphonates 2-phenyl ethyl methanesulphonate and 1-phenyl-2-propyl methanesulphonate show a clear higher micronuclei inducing potency than the other tested though the bulky methanesulphonates possess a lower total alkylating activity than the others. This effect can be explained by a higher disturbance during mitosis after alkylation of the spindle apparatus with the structurally more bulky methanesulphonates.

  12. Chemotherapy-induced pulmonary hypertension: role of alkylating agents.

    PubMed

    Ranchoux, Benoît; Günther, Sven; Quarck, Rozenn; Chaumais, Marie-Camille; Dorfmüller, Peter; Antigny, Fabrice; Dumas, Sébastien J; Raymond, Nicolas; Lau, Edmund; Savale, Laurent; Jaïs, Xavier; Sitbon, Olivier; Simonneau, Gérald; Stenmark, Kurt; Cohen-Kaminsky, Sylvia; Humbert, Marc; Montani, David; Perros, Frédéric

    2015-02-01

    Pulmonary veno-occlusive disease (PVOD) is an uncommon form of pulmonary hypertension (PH) characterized by progressive obstruction of small pulmonary veins and a dismal prognosis. Limited case series have reported a possible association between different chemotherapeutic agents and PVOD. We evaluated the relationship between chemotherapeutic agents and PVOD. Cases of chemotherapy-induced PVOD from the French PH network and literature were reviewed. Consequences of chemotherapy exposure on the pulmonary vasculature and hemodynamics were investigated in three different animal models (mouse, rat, and rabbit). Thirty-seven cases of chemotherapy-associated PVOD were identified in the French PH network and systematic literature analysis. Exposure to alkylating agents was observed in 83.8% of cases, mostly represented by cyclophosphamide (43.2%). In three different animal models, cyclophosphamide was able to induce PH on the basis of hemodynamic, morphological, and biological parameters. In these models, histopathological assessment confirmed significant pulmonary venous involvement highly suggestive of PVOD. Together, clinical data and animal models demonstrated a plausible cause-effect relationship between alkylating agents and PVOD. Clinicians should be aware of this uncommon, but severe, pulmonary vascular complication of alkylating agents. Copyright © 2015 American Society for Investigative Pathology. Published by Elsevier Inc. All rights reserved.

  13. 40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Modified reaction products of alkyl... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... identified generically as modified reaction products of alkyl alcohol, halogenated alkane, substituted...

  14. 40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified reaction products of alkyl... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... identified generically as modified reaction products of alkyl alcohol, halogenated alkane, substituted...

  15. Theoretical studies of alkyl radicals in the NaY and HY zeolites.

    PubMed

    Ghandi, Khashayar; Zahariev, Federico E; Wang, Yan Alexander

    2005-08-18

    Interplay of quantum mechanical calculations and experimental data on hyperfine coupling constants of ethyl radical in zeolites at several temperatures was engaged to study the geometries and binding energies and to predict the temperature dependence of hyperfine splitting of a series of alkyl radicals in zeolites for the first time. The main focus is on the hyperfine interaction of alkyl radicals in the NaY and HY zeolites. The hyperfine splitting for neutral free radicals and free radical cations is predicted for different zeolite environments. This information can be used to establish the nature of the muoniated alkyl radicals in the NaY and HY zeolites via muSR experiments. The muon hyperfine coupling constants of the ethane radical cation in these zeolites are very large with relatively little dependence on temperature. It was found that the intramolecular dynamics of alkyl free radicals are only weakly affected by their strong binding to zeolites. In contrast, the substrate binding has a significant effect on their intermolecular dynamics.

  16. Catalytic enantioselective synthesis of atropisomeric biaryls by a cation-directed O-alkylation

    NASA Astrophysics Data System (ADS)

    Jolliffe, John D.; Armstrong, Roly J.; Smith, Martin D.

    2017-06-01

    Axially chiral biaryls, as exemplified by 1,1‧-bi-2-naphthol (BINOL), are key components of catalysts, natural products and medicines. These materials are synthesized conventionally in enantioenriched form through metal-mediated cross coupling, de novo construction of an aromatic ring, point-to-axial chirality transfer or an atropselective transformation of an existing biaryl. Here, we report a highly enantioselective organocatalytic method for the synthesis of atropisomeric biaryls by a cation-directed O-alkylation. Treatment of racemic 1-aryl-2-tetralones with a chiral quinidine-derived ammonium salt under basic conditions in the presence of an alkylating agent leads to atropselective O-alkylation with e.r. up to 98:2. Oxidation with DDQ gives access to C2-symmetric and non-symmetric BINOL derivatives without compromising e.r. We propose that the chiral ammonium counterion differentiates between rapidly equilibrating atropisomeric enolates, leading to highly atropselective O-alkylation. This dynamic kinetic resolution process offers a general approach to the synthesis of enantioenriched atropisomeric materials.

  17. Effect of the alkyl chain length on the rotational dynamics of nonpolar and dipolar solutes in a series of N-alkyl-N-methylmorpholinium ionic liquids.

    PubMed

    Khara, Dinesh Chandra; Kumar, Jaini Praveen; Mondal, Navendu; Samanta, Anunay

    2013-05-02

    Rotational dynamics of two dipolar solutes, 4-aminophthalimide (AP) and 6-propionyl-2-dimethylaminonaphthalene (PRODAN), and a nonpolar solute, anthracene, have been studied in N-alkyl-N-methylmorpholinium (alkyl = ethyl, butyl, hexyl, and octyl) bis(trifluoromethansulfonyl)imide (Tf2N) ionic liquids as a function of temperature and excitation wavelength to probe the microheterogeneous nature of these ionic liquids, which are recently reported to be more structured than the imidazolium ionic liquids (Khara and Samanta, J. Phys. Chem. B2012, 116, 13430-13438). Analysis of the measured rotational time constants of the solutes in terms of the Stokes-Einstein-Debye (SED) hydrodynamic theory reveals that with increase in the alkyl chain length attached to the cationic component of the ionic liquids, AP shows stick to superstick behavior, PRODAN rotation lies between stick and slip boundary conditions, whereas anthracene exhibits slip to sub slip behavior. The contrasting rotational dynamics of these probe molecules is a reflection of their location in distinct environments of the ionic liquids thus demonstrating the heterogeneity of these ionic liquids. The microheterogeneity of these media, in particular, those with the long alkyl chain, is further evidence from the excitation wavelength dependence study of the rotational diffusion of the dipolar probe molecules.

  18. 21 CFR 176.120 - Alkyl ketene dimers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

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

  19. Enantioconvergent Cross-Couplings of Racemic Alkylmetal Reagents with Unactivated Secondary Alkyl Electrophiles: Catalytic Asymmetric Negishi α-Alkylations of N-Boc-pyrrolidine

    PubMed Central

    Cordier, Christopher J.; Lundgren, Rylan J.; Fu, Gregory C.

    2013-01-01

    Although enantioconvergent alkyl-alkyl couplings of racemic electrophiles have been developed, there have been no reports of the corresponding reactions of racemic nucleophiles. Herein, we describe Negishi cross-couplings of racemic α-zincated N-Boc-pyrrolidine with unactivated secondary halides, thus providing a one-pot, catalytic asymmetric method for the synthesis of a range of 2-alkylpyrrolidines (an important family of target molecules) from N-Boc-pyrrolidine, a commercially available precursor. Preliminary mechanistic studies indicate that two of the most straightforward mechanisms for enantioconvergence (a dynamic kinetic resolution of the organometallic coupling partner and a simple β-hydride elimination/β-migratory insertion pathway) are unlikely to be operative. PMID:23869442

  20. 46 CFR 151.50-86 - Alkyl (C7-C9) nitrates.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Alkyl (C7-C9) nitrates. 151.50-86 Section 151.50-86... CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-86 Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to...

  1. 46 CFR 151.50-86 - Alkyl (C7-C9) nitrates.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Alkyl (C7-C9) nitrates. 151.50-86 Section 151.50-86... CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-86 Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to...

  2. 46 CFR 151.50-86 - Alkyl (C7-C9) nitrates.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Alkyl (C7-C9) nitrates. 151.50-86 Section 151.50-86... CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-86 Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to...

  3. 46 CFR 151.50-86 - Alkyl (C7-C9) nitrates.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Alkyl (C7-C9) nitrates. 151.50-86 Section 151.50-86... CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-86 Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to...

  4. 46 CFR 151.50-86 - Alkyl (C7-C9) nitrates.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Alkyl (C7-C9) nitrates. 151.50-86 Section 151.50-86... CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-86 Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to...

  5. 40 CFR 721.10417 - Biphenyl alkyl morpholino ketone (generic) (P-11-338).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... (generic) (P-11-338). 721.10417 Section 721.10417 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10417 Biphenyl alkyl morpholino ketone (generic) (P-11-338). (a... generically as biphenyl alkyl morpholino ketone (PMN P-11-338) is subject to reporting under this section for...

  6. 40 CFR 721.10417 - Biphenyl alkyl morpholino ketone (generic) (P-11-338).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... (generic) (P-11-338). 721.10417 Section 721.10417 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10417 Biphenyl alkyl morpholino ketone (generic) (P-11-338). (a... generically as biphenyl alkyl morpholino ketone (PMN P-11-338) is subject to reporting under this section for...

  7. 40 CFR 721.10417 - Biphenyl alkyl morpholino ketone (generic) (P-11-338).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... (generic) (P-11-338). 721.10417 Section 721.10417 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10417 Biphenyl alkyl morpholino ketone (generic) (P-11-338). (a... generically as biphenyl alkyl morpholino ketone (PMN P-11-338) is subject to reporting under this section for...

  8. Spatially-dependent alkyl quinolone signaling responses to antibiotics in Pseudomonas aeruginosa swarms.

    PubMed

    Morales-Soto, Nydia; Dunham, Sage J B; Baig, Nameera F; Ellis, Joseph F; Madukoma, Chinedu S; Bohn, Paul W; Sweedler, Jonathan V; Shrout, Joshua D

    2018-03-27

    There is a general lack of understanding about how communities of bacteria respond to exogenous toxins such as antibiotics. Most of our understanding of community-level stress responses comes from the study of stationary biofilm communities. Although several community behaviors and production of specific biomolecules affecting biofilm development and associated behavior have been described for Pseudomonas aeruginosa and other bacteria, we have little appreciation for the production and dispersal of secreted metabolites within the 2D and 3D spaces they occupy as they colonize, spread, and grow on surfaces. Here we specifically studied the phenotypic responses and spatial variability of alkyl quinolones, including the Pseudomonas quinolone signal (PQS) and members of the alkyl hydroxyquinoline (AQNO) subclass, in P. aeruginosa plate-assay swarming communities. We found that PQS production was not a universal signaling response to antibiotics as tobramycin elicited an alkyl quinolone response while carbenicillin did not. We also found that PQS and AQNO profiles in response to tobramycin were markedly distinct and influenced these swarms on different spatial scales. The distribution of alkyl quinolones varied by several orders of magnitude within the same swarm. At some tobramycin exposures, P. aeruginosa swarms produced alkyl quinolones in the range of 150 µM PQS and 400 µM AQNO that accumulated as aggregates. Our collective findings show that the distribution of alkyl quinolones can vary by several orders of magnitude within the same swarming community.  More notably, our results suggest that multiple intercellular signals acting on different spatial scales can be triggered by one common cue. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

  9. Fabrication of carbon nanotube films from alkyne-transition metal complexes

    DOEpatents

    Iyer, Vivekanantan S [Delft, NL; Vollhardt, K Peter C. [Oakland, CA

    2007-08-28

    A simple method for the production or synthesis of carbon nanotubes as free-standing films or nanotube mats by the thermal decomposition of transition metal complexed alkynes with aryl, alkyl, alkenyl, or alkynyl substituents. In particular, transition metal (e.g. Co, Ni, Fe, Mo) complexes of diarylacetylenes, e.g. diphenylacetylene, and solid mixtures of these complexes with suitable, additional carbon sources are heated in a vessel. More specifically, the heating of the transition metal complex is completed at a temperature between 400-800.degree. C. and more particularly 550-700.degree. C. for between 0.1 to 24 hours and more particularly 0.5-3 hours in a sealed vessel under a partial pressure of argon or helium.

  10. Diorganosilacetylene-alt-diorganosilvinylene polymers and a process densifying porous silicon-carbide bodies

    DOEpatents

    Barton, Thomas J.; Ijadi-Maghsoodi, Sina; Pang, Yi

    1994-05-17

    The present invention provides linear organosilicon polymers including acetylene and vinylene moieties, and a process for their preparation. These diorganosilacetylene-alt-diorganosilvinylene linear polymers can be represented by the formula: --[--(R.sup.1)(R.sup.2)Si--C.tbd.C--(R.sup.3)(R.sup.4)Si--CH=CH--].sub.n-- , wherein n.gtoreq.2; and each R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, aryl, and aralkyl radicals. The polymers are soluble in organic solvents, air stable, and can be pulled into fibers or cast into films. They can be thermally converted into silicon carbide ceramic materials.

  11. Diorganosilacetylene-alt-diorganosilvinylene polymers and a process of preparation

    DOEpatents

    Barton, Thomas J.; Ijadi-Maghsoodi, Sina; Pang, Yi

    1993-08-31

    The present invention provides linear organosilicon polymers including acetylene and vinylene moieties, and a process for their preparation. These diorganosilacetylenealt-diorganosilvinylene linear polymers can be represented by the formula: --[--(R.sup.1)(R.sup.2)Si--C.ident.C--(R.sup.3)(R.sup.4)Si--CH=CH--].sub.n --, wherein n.gtoreq.2; each R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, aryl, and aralkyl radicals. The polymers are soluble in organic solvents, air stable, and can be pulled into fibers or cast into films. They can be thermally converted into silicon carbide ceramic materials.

  12. Diorganosilacetylene-alt-diorganosilvinylene polymers and a process of preparation

    DOEpatents

    Barton, Thomas J.; Ijadi-Maghsoodi, Sina; Pang, Yi

    1995-10-10

    The present invention provides linear organosilicon polymers including acetylene and vinylene moieties, and a process for their preparation. These diorganosilacetylene-alt-diorganosilvinylene linear polymers can be represented by the formula: --[--(R.sup.1)(R.sup.2)Si--C.tbd.C--(R.sup.3)(R.sup.4)Si--CH.dbd.CH--].sub .n --, wherein n.gtoreq.2; and each R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, aryl, and aralkyl radicals. The polymers are soluble in organic solvents, air stable, and can be pulled into fibers or cast into films. They can be thermally converted into silicon carbide ceramic materials.

  13. Diorganosilacetylene-alt-diorganosilvinylene polymers and a process of preparation

    DOEpatents

    Barton, T.J.; Ijadi-Maghsoodi, S.; Yi Pang.

    1993-08-31

    The present invention provides linear organosilicon polymers including acetylene and vinylene moieties, and a process for their preparation. These diorganosilacetylene-alt-diorganosilvinylene linear polymers can be represented by the formula: -[-(R[sup 1])(R[sup 2])Si-C[triple bond]C-(R[sup 3])(R[sup 4])Si-CH[double bond]CH-][sub n]-, wherein n[>=]2; each R[sup 1], R[sup 2], R[sup 3], and R[sup 4] is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, aryl, and aralkyl radicals. The polymers are soluble in organic solvents, air stable, and can be pulled into fibers or cast into films. They can be thermally converted into silicon carbide ceramic materials.

  14. Non-aqueous electrolytes for electrochemical cells

    DOEpatents

    Dong, Jian; Zhang, Zhengcheng; Amine, Khalil

    2016-07-12

    A electrolyte for a lithium battery includes a silane/siloxane compound represented by SiR.sub.4-x-yR'.sub.xR''.sub.y, by Formula II, or Formula III: ##STR00001## where each R is individually an alkenyl, alkynyl, alk(poly)enyl, alk(poly)ynyl, aryl; each R' is represented by; ##STR00002## each R'' is represented by Formula I-B; ##STR00003## R.sup.1 is an organic spacer; R.sup.2 is a bond or an organic spacer; R.sup.3 is alkyl or aryl; k is 1-15; m is 1-15; n is 1 or 2; p is 1-3; x' is 1-2; and y' is 0-2.

  15. Diorganosilacetylene-alt-diorganosilvinylene polymers and a process densifying porous silicon-carbide bodies

    DOEpatents

    Barton, T.J.; Ijadi-Maghsoodi, S.; Pang, Y.

    1994-05-17

    The present invention provides linear organosilicon polymers including acetylene and vinylene moieties, and a process for their preparation. These diorganosilacetylene-alt-diorganosilvinylene linear polymers can be represented by the formula: --[--(R[sup 1])(R[sup 2])Si--C[triple bond]C-(R[sup 3])(R[sup 4])Si--CH[double bond]CH--][sub n]--, wherein n[>=]2; and each R[sup 1], R[sup 2], R[sup 3], and R[sup 4] is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, aryl, and aralkyl radicals. The polymers are soluble in organic solvents, air stable, and can be pulled into fibers or cast into films. They can be thermally converted into silicon carbide ceramic materials.

  16. Diorganosilacetylene-alt-diorganosilvinylene polymers and a process of preparation

    DOEpatents

    Barton, T.J.; Ijadi-Maghsoodi, S.; Pang, Y.

    1995-10-10

    The present invention provides linear organosilicon polymers including acetylene and vinylene moieties, and a process for their preparation. These diorganosilacetylene-alt-diorganosilvinylene linear polymers can be represented by the formula: --[--(R{sup 1})(R{sup 2})Si--C{triple_bond}C--(R{sup 3})(R{sup 4})Si--CH{double_bond}CH--]{sub n}--, wherein n{>=}2; and each R{sup 1}, R{sup 2}, R{sup 3}, and R{sup 4} is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, aryl, and aralkyl radicals. The polymers are soluble in organic solvents, air stable, and can be pulled into fibers or cast into films. They can be thermally converted into silicon carbide ceramic materials.

  17. The photochemical alkylation and reduction of heteroarenes.

    PubMed

    McCallum, T; Pitre, S P; Morin, M; Scaiano, J C; Barriault, L

    2017-11-01

    The functionalization of heteroarenes has been integral to the structural diversification of medicinally active molecules such as quinolines, pyridines, and phenanthridines. Electron-deficient heteroarenes are electronically compatible to react with relatively nucleophilic free radicals such as hydroxyalkyl. However, the radical functionalization of such heteroarenes has been marked by the use of transition-metal catalyzed processes that require initiators and stoichiometric oxidants. Herein, we describe the photochemical alkylation of quinolines, pyridines and phenanthridines, where through direct excitation of the protonated heterocycle, alcohols and ethers, such as methanol and THF, can serve as alkylating agents. We also report the discovery of a photochemical reduction of these heteroarenes using only iPrOH and HCl. Mechanistic studies to elucidate the underlying mechanism of these transformations, and preliminary results on catalytic methylations are also reported.

  18. Endocrine disrupting potential of PAHs and their alkylated analogues associated with oil spills.

    PubMed

    Lee, Sangwoo; Hong, Seongjin; Liu, Xiaoshan; Kim, Cheolmin; Jung, Dawoon; Yim, Un Hyuk; Shim, Won Joon; Khim, Jong Seong; Giesy, John P; Choi, Kyungho

    2017-09-20

    Polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs are known to be major toxic contaminants in spills of petroleum hydrocarbons (oil). Spilled oil undergoes weathering and over time, PAHs go through a series of compositional changes. PAHs can disrupt endocrine functions, and the type of functions affected and associated potencies vary with the type and alkylation status of PAH. In this study, the potential of five major PAHs of crude oil, i.e., naphthalene, fluorene, dibenzothiophene, phenanthrene, and chrysene, and their alkylated analogues (n = 25), to disrupt endocrine functions was evaluated by use of MVLN-luc and H295R cell lines. In the MVLN-luc bioassay, seven estrogen receptor (ER) agonists were detected among 30 tested PAHs. The greatest ER-mediated potency was observed for 1-methylchrysene (101.4%), followed by phenanthrene and its alkylated analogues (range of %-E2max from 1.6% to 47.3%). In the H295R bioassay, significantly greater syntheses of steroid hormones were observed for 20 PAHs. For major PAHs and their alkylated analogues, disruption of steroidogenesis appeared to be more significant than ER-mediated effects. The number and locations of alkyl-moieties alone could not explain differences in the types or the potencies of toxicities. This observation shows that disruption of endocrine functions by some constituents of oil spills could be underestimated if only parent compounds are considered in assessments of hazard and risk.

  19. 'Petite' mutagenesis and mitotic crossing-over in yeast by DNA-targeted alkylating agents.

    PubMed

    Ferguson, L R; Turner, P M; Gourdie, T A; Valu, K K; Denny, W A

    1989-12-01

    Although the biological properties (cytotoxicity, mutagenicity and carcinogenicity) of alkylating agents result from their bonding interactions with DNA, such compounds generally do not show any special binding affinity for DNA. A series of acridine-linked aniline mustards of widely-varying alkylator reactivity have been designed as DNA-directed alkylating agents. We have considered whether such DNA targeting has an effect on mutagenic properties by evaluating this series of drugs in comparison with their untargeted counterparts for toxic, recombinogenic and mutagenic properties in Saccharomyces cerevisiae strain D5. The simple untargeted aniline mustards are effective inducers of mitotic crossing-over in this strain, but resemble other reported alkylators in being rather inefficient inducers of the "petite" or mitochondrial mutation in yeast. However, the majority of the DNA-targeted mustards were very efficient petite mutagens, while showing little evidence of mitotic crossing-over or other nuclear events. The 100% conversion of cells into petites and the lack of a differential between growing and non-growing cells are similar to the effects of the well characterised mitochondrial mutagen ethidium bromide. These data suggest very different modes of action between the DNA-targeted alkylators and their non-targeted counterparts.

  20. Practical Alkoxythiocarbonyl Auxiliaries for Iridium(I)-Catalyzed C-H Alkylation of Azacycles.

    PubMed

    Tran, Anh T; Yu, Jin-Quan

    2017-08-21

    The development of new and practical 3-pentoxythiocarbonyl auxiliaries for Ir I -catalyzed C-H alkylation of azacycles is described. This method allows for the α-C-H alkylation of a variety of substituted pyrrolidines, piperidines, and tetrahydroisoquinolines through alkylation with alkenes. While the practicality of these simple carbamate-type auxiliaries is underscored by the ease of installation and removal, the method's utility is demonstrated in its ability to functionalize biologically relevant l-proline and l-trans-hydroxyproline, delivering unique 2,5-dialkylated amino acid analogues that are not accessible by other C-H functionalization methods. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Alkylation effects on the energy transfer of highly vibrationally excited naphthalene.

    PubMed

    Hsu, Hsu Chen; Tsai, Ming-Tsang; Dyakov, Yuri A; Ni, Chi-Kung

    2011-11-04

    The energy transfer of highly vibrationally excited isomers of dimethylnaphthalene and 2-ethylnaphthalene in collisions with krypton were investigated using crossed molecular beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques at a collision energy of approximately 300 cm(-1). Angular-resolved energy-transfer distribution functions were obtained directly from the images of inelastic scattering. The results show that alkyl-substituted naphthalenes transfer more vibrational energy to translational energy than unsubstituted naphthalene. Alkylation enhances the V→T energy transfer in the range -ΔE(d)=-100~-1500 cm(-1) by approximately a factor of 2. However, the maximum values of V→T energy transfer for alkyl-substituted naphthalenes are about 1500~2000 cm(-1), which is similar to that of naphthalene. The lack of rotation-like wide-angle motion of the aromatic ring and no enhancement in very large V→T energy transfer, like supercollisions, indicates that very large V→T energy transfer requires special vibrational motions. This transfer cannot be achieved by the low-frequency vibrational motions of alkyl groups. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. DNA Damage Induced by Alkylating Agents and Repair Pathways

    PubMed Central

    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

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

    PubMed

    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.

  4. REVISITING CLASSICAL NUCLEOPHILIC SUBSTITUTIONS IN AQUEOUS MEDIUM: MICROWAVE-ASSISTED SYNTHESIS OF ALKYL AZIDES

    EPA Science Inventory

    An efficient and clean synthesis of alkyl azides using microwave (MW) radiation is described in aqueous medium by reacting alkyl halides or tosylates with alkali azides. This general and expeditious MW-enhanced approach to nucleophilic substitution reactions is applicable to the ...

  5. A novel type of highly effective nonionic gemini alkyl O-glucoside surfactants: a versatile strategy of design.

    PubMed

    Liu, Songbai; Sang, Ruocheng; Hong, Shan; Cai, Yujing; Wang, Hua

    2013-07-09

    A novel type of highly effective gemini alkyl glucosides has been rationally designed and synthesized. The gemini surfactants have been readily prepared by glycosylation of the gemini alkyl chains that are synthesized with regioselective ring-opening of ethylene glycol epoxides by the alkyl alcohols. The new gemini alkyl glucosides exhibit significantly better surface activity than the known results. Then rheological, DLS, and TEM studies have revealed the intriguing self-assembly behavior of the novel gemini surfactants. This study has proved the effectiveness of the design of gemini alkyl glucosides which is modular, extendable, and synthetically simple. The new gemini surfactants have great potential as nano carriers in drug and gene delivery.

  6. Lithiated imines: solvent-dependent aggregate structures and mechanisms of alkylation.

    PubMed

    Zuend, Stephan J; Ramirez, Antonio; Lobkovsky, Emil; Collum, David B

    2006-05-03

    We describe efforts to understand the structure and reactivity of lithiated cyclohexanone N-cyclohexylimine. The lithioimine affords complex solvent-dependent distributions of monomers, dimers, and trimers in a number of ethereal solvents. Careful selection of solvent provides exclusively monosolvated dimers. Rate studies on the C-alkylations reveal chronic mixtures of monomer- and dimer-based pathways. We explore the factors influencing reactants and alkylation transition structures and the marked differences between lithioimines and isostructural lithium dialkylamides with the aid of density functional theory calculations.

  7. Discovery of 4-(5-(Cyclopropylcarbamoyl)-2-methylphenylamino)-5-methyl-N-propylpyrrolo[1,2-f][1,2,4]triazine-6-carboxamide (BMS-582949), a Clinical p38[alpha] MAP Kinase Inhibitor for the Treatment of Inflammatory Diseases

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, Chunjian; Lin, James; Wrobleski, Stephen T.

    The discovery and characterization of 7k (BMS-582949), a highly selective p38{alpha} MAP kinase inhibitor that is currently in phase II clinical trials for the treatment of rheumatoid arthritis, is described. A key to the discovery was the rational substitution of N-cyclopropyl for N-methoxy in 1a, a previously reported clinical candidate p38{alpha} inhibitor. Unlike alkyl and other cycloalkyls, the sp{sup 2} character of the cyclopropyl group can confer improved H-bonding characteristics to the directly substituted amide NH. Inhibitor 7k is slightly less active than 1a in the p38{alpha} enzymatic assay but displays a superior pharmacokinetic profile and, as such, was moremore » effective in both the acute murine model of inflammation and pseudoestablished rat AA model. The binding mode of 7k with p38{alpha} was confirmed by X-ray crystallographic analysis.« less

  8. 40 CFR 721.950 - Sodium salt of an alkylated, sulfonated aromatic (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., sulfonated aromatic (generic name). 721.950 Section 721.950 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.950 Sodium salt of an alkylated, sulfonated... chemical substance identified generically as a sodium salt of an alkylated, sulfonated aromatic (PMN P-84...

  9. 40 CFR 721.950 - Sodium salt of an alkylated, sulfonated aromatic (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., sulfonated aromatic (generic name). 721.950 Section 721.950 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.950 Sodium salt of an alkylated, sulfonated... chemical substance identified generically as a sodium salt of an alkylated, sulfonated aromatic (PMN P-84...

  10. Comparison of the reactivity of alkyl and alkyl amine precursors with native oxide GaAs(100) and InAs(100) surfaces

    NASA Astrophysics Data System (ADS)

    Henegar, A. J., , Dr.; Gougousi, T., , Prof.

    2016-12-01

    In this manuscript we compare the interaction of alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition with III-V native oxides. For that purpose we deposit Al2O3 and TiO2, using H2O as the oxidizer, on GaAs(100) and InAs(100) native oxide surfaces. We find that there are distinct differences in the behavior of the two films. For the Al2O3 ALD very little native oxide removal happens after the first few ALD cycles while the interaction of the alkyl amine precursor for TiO2 and the native oxides continues well after the surface has been covered with 2 nm of TiO2. This difference is traced to the superior properties of Al2O3 as a diffusion barrier. Differences are also found in the behavior of the arsenic oxides of the InAs and GaAs substrates. The arsenic oxides from the InAs surface are found to mix more efficiently in the growing dielectric film than those from the GaAs surface. This difference is attributed to lower native oxide stability as well as an initial diffusion path formation by the indium oxides.

  11. Lanthanide alkyl and silyl compounds: Synthesis, reactivity and catalysts for green

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pindwal, Aradhana

    2016-01-01

    The last few decades have witnessed enormous research in the field of organometallic lanthanide chemistry. Our research group has developed a few rare earth alkyl compounds containing tris(dimethylsilyl)methyl ligand and explored their reactivity. This thesis focusses on extending the study of lanthanide alkyl and silyl compounds to develop strategies for their synthesis and explore their reactivity and role as catalysts in processes such as hydrosilylation and cross-dehydrocoupling.

  12. Binding of alkylphenols and alkylated non-phenolics to rainbow trout (Oncorhynchus mykiss) hepatic estrogen receptors.

    PubMed

    Tollefsen, Knut-Erik; Julie Nilsen, Anja

    2008-02-01

    Alkylphenols are well-known endocrine disrupters, mediating effects through the estrogen receptor (ER). In the present work, the interaction of alkylphenols and alkylated non-phenolics with hepatic rainbow trout (Oncorhynchus mykiss) estrogen receptors (rtERs) was determined. The role of alkyl chain length and branching, substituent position, number of alkylated groups, and the requirement of a phenolic ring structure was assessed. The results showed that the rtERs bound most alkylphenols, although with 20,000 to 2 million times lower affinity than the endogenous estrogen 17beta-estradiol. Mono-substituted alkylphenols with moderate (C4-C6) and long (C8 and C12) alkyl chain length in the para position exhibited the highest affinity for the rtERs. Substitution with multiple alkyl groups, presence of substituents in the ortho- and meta-position, and lack of a hydroxyl group on the benzene ring reduced the binding affinity. The rtERs resembled the reported binding specificity of the human ER for alkylphenols, although some exceptions were identified.

  13. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction products of secondary alkyl... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... substances identified generically as reaction products of secondary alkyl amines with a substituted...

  14. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction products of secondary alkyl... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... substances identified generically as reaction products of secondary alkyl amines with a substituted...

  15. Enhanced Synthesis of Alkyl Amino Acids in Miller's 1958 H2S Experiment

    NASA Technical Reports Server (NTRS)

    Parker, Eric T.; Cleaves, H. James; Callahan, Michael P.; Dworkin, James P.; Glavin, Daniel P.; Lazcano, Antonio; Bada, Jeffrey L.

    2011-01-01

    Stanley Miller's 1958 H2S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH4), ammonia (NH3), carbon dioxide (CO2), and hydrogen sulfide (H2S) produced several alkyl amino acids, including the alpha-, beta-, and gamma-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H2S, aspariic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H2S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H2S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.

  16. Influence of N-alkylation on organ distribution of radioiodinated amphetamines

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Machulla, H.J.; Schmidt, U.; Mehdorn, H.M.

    1985-05-01

    In spite of numerous animal data and the widespread clinical application of p-(I-123)-N-isopropyl-amphetamine, questions remain open about the role of N-alkylation. Therefore, amphetamine (AP), N-methyl- (MeAP), and N-isopropyl-amphetamine (IsAP) were radioiodinated in the para position and the organ distribution was determined in male mice (Freiburg tribe) 10 weeks of age. In the lungs, all derivatives showed principally the same kinetics. In brain, the maximum uptake was reached after 30 min with 12%/g for AP and MeAP, and 10.5%/g for IsAP. In liver, the radioactivity similarly increased during the first 15 min to approx. 12%/g; afterwards, AP clearly decreased but MeAPmore » remained almost constant up to 120 min and, even more, IsAP increased to a maximum of 18%/g at 30 min. The same brain uptake kinetics for all 3 substances exclude the importance of lipophilicity increased by the N-alkylation. Furthermore, the differences in the liver kinetics of AP and both MeAP and IsAP indicate the importance of liver metabolism on the alkylated amphetamines. The results support the hypothesis that the first important metabolite of the N-alkylated derivatives is the amphetamine which accumulates in the brain as do MeAP and IsAP. On the basis of these findings, AP was applied clinically showing the same efficient brain uptake and distribution in SPECT as IsAP.« less

  17. 40 CFR 721.2520 - Alkylated diphenyls.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... reporting. (1) The chemical substances identified generically as alkylated diphenyls (PMN Nos. P-90-237, P-90-248, and P-90-249) are subject to reporting under this section for the significant new uses.... Requirements as specified in § 721.90 (a)(4), (b)(4), and (c)(4) (where N = 1 ppb). (ii) [Reserved] (b...

  18. Mechanism of Phenol Alkylation in Zeolite H-BEA Using In Situ Solid-State NMR Spectroscopy

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhao, Zhenchao; Shi, Hui; Wan, Chuan

    Alkylation of phenolic compounds in the liquid phase is of fundamental and practical importance to the conversion of biomass-derived feedstocks into fuels and chemicals. In this work, the reaction mechanism for phenol alkylation with cyclohexanol and cyclohexene has been investigated on a commercial HBEA zeolite by in situ 13C MAS NMR, using decalin as the solvent. From the variable temperature 13C MAS NMR measurements of phenol and cyclohexanol adsorption on HBEA from decalin solutions, it is shown that the two molecules have similar adsorption strength in the HBEA pore. Phenol alkylation with cyclohexanol, however, becomes significantly measurable only after cyclohexanolmore » is largely converted to cyclohexene via dehydration. This is in contrast to the initially rapid alkylation of phenol when using cyclohexene as the co-reactant. 13C isotope scrambling results demonstrate that the electrophile, presumably cyclohexyl carbenium ion, is directly formed in a protonation step when cyclohexene is the co-reactant, but requires re-adsorption of the alcohol dehydration product, cyclohexene, when cyclohexanol dimer is the dominant surface species (e.g., at 0.5 M cyclohexanol concentration) that is unable to generate carbenium ion. At the initial reaction stage of phenol-cyclohexanol alkylation on HBEA, the presence of the cyclohexanol dimer species hinders the adsorption of cyclohexene at the Brønsted acid site and the subsequent activation of the more potent electrophile (carbenium ion). Isotope scrambling data also show that intramolecular rearrangement of cyclohexyl phenyl ether, the O-alkylation product, does not significantly contribute to the formation of C-alkylation products.« less

  19. Melamine-bridged alkyl resorcinol modified urea - formaldehyde resin for bonding hardwood plywood

    Treesearch

    Chung-Yun Hse; Mitsuo Higuchi

    2010-01-01

    A powdery product was obtained by the reaction of methylolated melamine with alkyl resorcinols to form melamine-bridged alkyl resorcinols (MARs). The effects of the addition of this powder on the bonding strength and formaldehyde emission of urea–formaldehyde (UF) resins were investigated. Three types of UF resins with a formaldehyde/urea molar ratio of 1.3 synthesized...

  20. Glutamine deficiency induces DNA alkylation damage and sensitizes cancer cells to alkylating agents through inhibition of ALKBH enzymes.

    PubMed

    Tran, Thai Q; Ishak Gabra, Mari B; Lowman, Xazmin H; Yang, Ying; Reid, Michael A; Pan, Min; O'Connor, Timothy R; Kong, Mei

    2017-11-01

    Driven by oncogenic signaling, glutamine addiction exhibited by cancer cells often leads to severe glutamine depletion in solid tumors. Despite this nutritional environment that tumor cells often experience, the effect of glutamine deficiency on cellular responses to DNA damage and chemotherapeutic treatment remains unclear. Here, we show that glutamine deficiency, through the reduction of alpha-ketoglutarate, inhibits the AlkB homolog (ALKBH) enzymes activity and induces DNA alkylation damage. As a result, glutamine deprivation or glutaminase inhibitor treatment triggers DNA damage accumulation independent of cell death. In addition, low glutamine-induced DNA damage is abolished in ALKBH deficient cells. Importantly, we show that glutaminase inhibitors, 6-Diazo-5-oxo-L-norleucine (DON) or CB-839, hypersensitize cancer cells to alkylating agents both in vitro and in vivo. Together, the crosstalk between glutamine metabolism and the DNA repair pathway identified in this study highlights a potential role of metabolic stress in genomic instability and therapeutic response in cancer.

  1. Glutamine deficiency induces DNA alkylation damage and sensitizes cancer cells to alkylating agents through inhibition of ALKBH enzymes

    PubMed Central

    Tran, Thai Q.; Ishak Gabra, Mari B.; Lowman, Xazmin H.; Yang, Ying; Reid, Michael A.; Pan, Min; O’Connor, Timothy R.

    2017-01-01

    Driven by oncogenic signaling, glutamine addiction exhibited by cancer cells often leads to severe glutamine depletion in solid tumors. Despite this nutritional environment that tumor cells often experience, the effect of glutamine deficiency on cellular responses to DNA damage and chemotherapeutic treatment remains unclear. Here, we show that glutamine deficiency, through the reduction of alpha-ketoglutarate, inhibits the AlkB homolog (ALKBH) enzymes activity and induces DNA alkylation damage. As a result, glutamine deprivation or glutaminase inhibitor treatment triggers DNA damage accumulation independent of cell death. In addition, low glutamine-induced DNA damage is abolished in ALKBH deficient cells. Importantly, we show that glutaminase inhibitors, 6-Diazo-5-oxo-L-norleucine (DON) or CB-839, hypersensitize cancer cells to alkylating agents both in vitro and in vivo. Together, the crosstalk between glutamine metabolism and the DNA repair pathway identified in this study highlights a potential role of metabolic stress in genomic instability and therapeutic response in cancer. PMID:29107960

  2. Ionic liquids as refolding additives: N′-alkyl and N′-(ω-hydroxyalkyl) N-methylimidazolium chlorides

    PubMed Central

    Lange, Christian; Patil, Ganesh; Rudolph, Rainer

    2005-01-01

    The purpose of this work was to investigate the influence of a series of N′-alkyl and N′-(ω-hydroxy-alkyl)-N-methylimidazolium chlorides on the renaturation of two model proteins, namely hen egg white lysozyme and the single-chain antibody fragment ScFvOx. All tested ionic liquids acted as refolding enhancers, with varying efficacies and efficiencies. The results of the refolding screening could be interpreted by taking into account the effect of the studied ionic liquids on protein aggregation, together with the systematic variations of their influence on the stability of native proteins in solution. More hydrophobic imidazolium cations carrying longer alkyl chains were increasingly destabilizing, while terminal hydroxylation of the alkyl chain made the salts more compatible with protein stability. The studied ionic liquids can be classified as preferentially bound, slightly to moderately chaotropic cosolvents for proteins. PMID:16195554

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

    PubMed

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

    2014-01-01

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

  4. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkylphenol... Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and formaldehyde... identified generically as reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene...

  5. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkylphenyl... Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl dibenzene... identified generically as reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl...

  6. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkylphenyl... Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl dibenzene... identified generically as reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl...

  7. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkylphenol... Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and formaldehyde... identified generically as reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene...

  8. ALKBH7 drives a tissue and sex-specific necrotic cell death response following alkylation-induced damage

    PubMed Central

    Jordan, Jennifer J; Chhim, Sophea; Margulies, Carrie M; Allocca, Mariacarmela; Bronson, Roderick T; Klungland, Arne; Samson, Leona D; Fu, Dragony

    2017-01-01

    Regulated necrosis has emerged as a major cell death mechanism in response to different forms of physiological and pharmacological stress. The AlkB homolog 7 (ALKBH7) protein is required for regulated cellular necrosis in response to chemotherapeutic alkylating agents but its role within a whole organism is unknown. Here, we show that ALKBH7 modulates alkylation-induced cellular death through a tissue and sex-specific mechanism. At the whole-animal level, we find that ALKBH7 deficiency confers increased resistance to MMS-induced toxicity in male but not female mice. Moreover, ALKBH7-deficient mice exhibit protection against alkylation-mediated cytotoxicity in retinal photoreceptor and cerebellar granule cells, two cell types that undergo necrotic death through the initiation of the base excision repair pathway and hyperactivation of the PARP1/ARTD1 enzyme. Notably, the protection against alkylation-induced cerebellar degeneration is specific to ALKBH7-deficient male but not female mice. Our results uncover an in vivo role for ALKBH7 in mediating a sexually dimorphic tissue response to alkylation damage that could influence individual responses to chemotherapies based upon alkylating agents. PMID:28726787

  9. Alkyl ether lipids, ion channels and lipid raft reorganization in cancer therapy.

    PubMed

    Jaffrès, Paul-Alain; Gajate, Consuelo; Bouchet, Ana Maria; Couthon-Gourvès, Hélène; Chantôme, Aurélie; Potier-Cartereau, Marie; Besson, Pierre; Bougnoux, Philippe; Mollinedo, Faustino; Vandier, Christophe

    2016-09-01

    Synthetic alkyl lipids, such as the ether lipids edelfosine (1-O-octadecyl-2-O-methyl-rac-glycero-3-phosphocholine) and ohmline (1-O-hexadecyl-2-O-methyl-rac-glycero-3-β-lactose), are forming a class of antitumor agents that target cell membranes to induce apoptosis and to decrease cell migration/invasion, leading to the inhibition of tumor and metastasis development. In this review, we present the structure-activity relationship of edelfosine and ohmline, and we point out differences and similarities between these two amphiphilic compounds. We also discuss the mechanisms of action of these synthetic alkyl ether lipids (involving, among other structures and molecules, membrane domains, Fas/CD95 death receptor signaling, and ion channels), and highlight a key role for lipid rafts in the underlying process. The reorganization of lipid raft membrane domains induced by these alkyl lipids affects the function of death receptors and ion channels, thus leading to apoptosis and/or inhibition of cancer cell migration. The possible therapeutic use of these alkyl lipids and the clinical perspectives for these lipids in prevention or/and treatment of tumor development and metastasis are also discussed. Copyright © 2016 Elsevier Inc. All rights reserved.

  10. Alkylation of phenol by alcohols in the presence of aluminum phenolate

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Koshchii, V.A.; Kozlikovskii, Ya.B.; Matyusha, A.A.

    1988-12-20

    The reaction of phenol with alcohols in the presence of aluminum phenolate leads to a mixture of 2- and 4-alkylphenols, of which the former predominate in the case of benzyl, tert-butyl, and cyclohexyl alcohols, and the latter in the case of dimethylphenyl- and diphenylmethylcarbinols. Only triphenyl(4-hydroxyphenyl)-methane is formed during the alkylation of phenol by triphenylcarbinol. In individual experiments the formation of small amounts of alkyl phenyl ethers and 2,6-dialkylphenols was observed.

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

    PubMed

    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.

  12. Thermally Reduced Graphene Oxide Electrochemically Activated by Bis-Spiro Quaternary Alkyl Ammonium for Capacitors.

    PubMed

    He, Tieshi; Meng, Xiangling; Nie, Junping; Tong, Yujin; Cai, Kedi

    2016-06-08

    Thermally reduced graphene oxide (RGO) electrochemically activated by a quaternary alkyl ammonium-based organic electrolytes/activated carbon (AC) electrode asymmetric capacitor is proposed. The electrochemical activation process includes adsorption of anions into the pores of AC in the positive electrode and the interlayer intercalation of cations into RGO in the negative electrode under high potential (4.0 V). The EA process of RGO by quaternary alkyl ammonium was investigated by X-ray diffraction and electrochemical measurements, and the effects of cation size and structure were extensively evaluated. Intercalation by quaternary alkyl ammonium demonstrates a small degree of expansion of the whole crystal lattice (d002) and a large degree of expansion of the partial crystal lattice (d002) of RGO. RGO electrochemically activated by bis-spiro quaternary alkyl ammonium in propylene carbonate/AC asymmetric capacitor exhibits good activated efficiency, high specific capacity, and stable cyclability.

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

    PubMed

    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. Enzymic aromatization of 6-alkyl-substituted androgens, potent competitive and mechanism-based inhibitors of aromatase.

    PubMed Central

    Numazawa, M; Yoshimura, A; Oshibe, M

    1998-01-01

    To gain insight into the relationships between the aromatase inhibitory activity of 6-alkyl-substituted androgens, potent competitive inhibitors, and their ability to serve as a substrate of aromatase, we studied the aromatization of a series of 6alpha- and 6beta-alkyl (methyl, ethyl, n-propyl, n-pentyl and n-heptyl)-substituted androst-4-ene-3,17-diones (ADs) and their androsta-1,4-diene-3,17-dione (ADD) derivatives with human placental aromatase, by gas chromatography-mass spectrometry. Among the inhibitors examined, ADD and its 6alpha-alkyl derivatives with alkyl functions less than three carbons long, together with 6beta-methyl ADD, are suicide substrates of aromatase. All of the steroids, except for 6beta-n-pentyl ADD and its n-heptyl analogue as well as 6beta-n-heptyl AD, were found to be converted into the corresponding 6-alkyl oestrogens. The 6-methyl steroids were aromatized most efficiently in each series, and the aromatization rate essentially decreased in proportion to the length of the 6-alkyl chains in each series, where the 6alpha-alkyl androgens were more efficient substrates than the corresponding 6beta isomers. The Vmax of 6alpha-methyl ADD was approx. 2.5-fold that of the natural substrate AD and approx. 3-fold that of the parent ADD. On the basis of this, along with the facts that the rates of a mechanism-based inactivation of aromatase by ADD and its 6alpha-methyl derivative are similar, it is implied that alignment of 6alpha-methyl ADD in the active site could favour the pathway leading to oestrogen over the inactivation pathway, compared with that of ADD. The relative apparent Km values for the androgens obtained in this study are different from the relative Ki values obtained previously, indicating that there is a difference between the ability to serve as an inhibitor and the ability to serve as a substrate in the 6-alkyl androgen series. PMID:9405288

  15. Synthesis and in vitro evaluation of thiododecaborated α, α- cycloalkylamino acids for the treatment of malignant brain tumors by boron neutron capture therapy.

    PubMed

    Hattori, Yoshihide; Kusaka, Shintaro; Mukumoto, Mari; Ishimura, Miki; Ohta, Yoichiro; Takenaka, Hiroshi; Uehara, Kouki; Asano, Tomoyuki; Suzuki, Minoru; Masunaga, Shin-Ichiro; Ono, Koji; Tanimori, Shinji; Kirihata, Mitsunori

    2014-12-01

    Boron-neutron capture therapy (BNCT) is an attractive technique for cancer treatment. As such, α, α-cycloalkyl amino acids containing thiododecaborate ([B12H11](2-)-S-) units were designed and synthesized as novel boron delivery agents for BNCT. In the present study, new thiododecaborate α, α-cycloalkyl amino acids were synthesized, and biological evaluation of the boron compounds as boron carrier for BNCT was carried out.

  16. PROCESS FOR PRODUCING ALKYL ORTHOPHOSPHORIC ACID EXTRACTANTS

    DOEpatents

    Grinstead, R.R.

    1962-01-23

    A process is given for producing superior alkyl orthophosphoric acid extractants for use in solvent extraction methods to recover and purify various metals such as uranium and vanadium. The process comprises slurrying P/sub 2/O/ sub 5/ in a solvent diluent such as kerosene, benzene, isopropyl ether, and the like. An alipbatic alcohol having from nine to seventeen carbon atoms, and w- hcrein ihc OH group is situated inward of the terminal carbon atoms, is added to the slurry while the reaction temperature is mainiained below 60 deg C. The alcohol is added in the mole ratio of about 2 to l, alcohol to P/sub 2/O/sub 5/. A pyrophosphate reaotion product is formed in the slurry-alcohol mixture. Subsequently, the pyrophosphate reaction product is hydrolyzed with dilute mineral acid to produce the desired alkyl orthophosphoric aeid extractant. The extraetant may then be separated and utilized in metal-recovery, solvent- extraction processes. (AEC)

  17. Merging Photoredox with 1,2-Metallate Rearrangements: The Photochemical Alkylation of Vinyl Boronate Complexes.

    PubMed

    Silvi, Mattia; Sandford, Christopher; Aggarwal, Varinder K

    2017-04-26

    Vinyl boronates react with electron-deficient alkyl iodides in the presence of visible light to give boronic esters in which two new C-C bonds have been created. The reaction occurs by radical addition of an electron-deficient alkyl radical to the vinyl boronate followed by electron transfer with another molecule of alkyl iodide, continuing the chain, and triggering a 1,2-metalate rearrangement. In a number of cases, the use of a photoredox catalyst enhances yields significantly. The scope of the radical precursor includes α-iodo ketones, esters, nitriles, primary amides, α-fluorinated halo-acetates and perfluoroalkyl iodides.

  18. Chemical vapor deposition of group IIIB metals

    DOEpatents

    Erbil, Ahmet

    1989-01-01

    Coatings of Group IIIB metals and compounds thereof are formed by chemical vapor deposition, in which a heat decomposable organometallic compound of the formula (I) ##STR1## where M is a Group IIIB metal, such as lanthanum or yttrium and R is a lower alkyl or alkenyl radical containing from 2 to about 6 carbon atoms, with a heated substrate which is above the decomposition temperature of the organometallic compound. The pure metal is obtained when the compound of the formula I is the sole heat decomposable compound present and deposition is carried out under nonoxidizing conditions. Intermetallic compounds such as lanthanum telluride can be deposited from a lanthanum compound of formula I and a heat decomposable tellurium compound under nonoxidizing conditions.

  19. Chemical vapor deposition of group IIIB metals

    DOEpatents

    Erbil, A.

    1989-11-21

    Coatings of Group IIIB metals and compounds thereof are formed by chemical vapor deposition, in which a heat decomposable organometallic compound of the formula given in the patent where M is a Group IIIB metal, such as lanthanum or yttrium and R is a lower alkyl or alkenyl radical containing from 2 to about 6 carbon atoms, with a heated substrate which is above the decomposition temperature of the organometallic compound. The pure metal is obtained when the compound of the formula 1 is the sole heat decomposable compound present and deposition is carried out under nonoxidizing conditions. Intermetallic compounds such as lanthanum telluride can be deposited from a lanthanum compound of formula 1 and a heat decomposable tellurium compound under nonoxidizing conditions.

  20. Synthesis and Reactivity of Alkyl-1,1,1-trisphosphonate Esters

    PubMed Central

    Smits, Jacqueline P.; Wiemer, David F.

    2011-01-01

    The α–trisphosphonic acid esters provide a unique spatial arrangement of three phosphonate groups, and may represent an attractive motif for inhibitors of enzymes that utilize di- or triphosphate substrates. To advance studies of this unique functionality, a general route to alkyl derivatives of the parent system (R = H) has been developed. A set of new α-alkyl-1,1,1-trisphosphonate esters has been prepared through phosphinylation and subsequent oxidation of tetraethyl alkylbisphosphonates, and the reactivity of these new compounds has been studied in representative reactions that afford additional examples of this functionality. PMID:21916407

  1. Alkyl phospholipid antihypertensive agents in method of lowering blood pressure

    DOEpatents

    Snyder, Fred L.; Blank, Merle L.; Muirhead, Ernest E.; Leach, deceased, Byron E.; Byers, Lawrence W.

    1988-01-01

    The composition of this invention is 1-O-alkyl-2-acetoyl-sn-glycero-3-phosphocholine, having the ionic structural formula; ##STR1## wherein R is saturated alkyl having 9-21 carbon atoms, or salts or hydrates of the composition. Preferably R has 13-19 carbon atoms and most preferably R has 15 carbon atoms. The composition of this invention is useful for reducing hypertension in warm-blooded animals, including humans, when administered either orally or by injection or innoculation, e.g., intravenous injection. The composition can be prepared from naturally occurring lipids or synthetically from commercially available material.

  2. 40 CFR 721.8700 - Halogenated alkyl pyridine.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8700 Halogenated alkyl pyridine. (a) Chemical substances and significant new uses subject to... subject to reporting under this section for the significant new uses described in paragraph (a)(1)(i) of...

  3. 40 CFR 721.8700 - Halogenated alkyl pyridine.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8700 Halogenated alkyl pyridine. (a) Chemical substances and significant new uses subject to... subject to reporting under this section for the significant new uses described in paragraph (a)(1)(i) of...

  4. Methods of making alkyl esters

    DOEpatents

    Elliott, Brian

    2010-08-03

    A method comprising contacting an alcohol, a feed comprising one or more glycerides and equal to or greater than 2 wt % of one or more free fatty acids, and a solid acid catalyst, a nanostructured polymer catalyst, or a sulfated zirconia catalyst in one or more reactors, and recovering from the one or more reactors an effluent comprising equal to or greater than about 75 wt % alkyl ester and equal to or less than about 5 wt % glyceride.

  5. Mild and Low-Pressure fac-Ir(ppy)3 -Mediated Radical Aminocarbonylation of Unactivated Alkyl Iodides through Visible-Light Photoredox Catalysis.

    PubMed

    Chow, Shiao Y; Stevens, Marc Y; Åkerbladh, Linda; Bergman, Sara; Odell, Luke R

    2016-06-27

    A novel, mild and facile preparation of alkyl amides from unactivated alkyl iodides employing a fac-Ir(ppy)3 -catalyzed radical aminocarbonylation protocol has been developed. Using a two-chambered system, alkyl iodides, fac-Ir(ppy)3 , amines, reductants, and CO gas (released ex situ from Mo(CO)6 ), were combined and subjected to an initial radical reductive dehalogenation generating alkyl radicals, and a subsequent aminocarbonylation with amines affording a wide range of alkyl amides in moderate to excellent yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    PubMed Central

    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

  7. Rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides: is solute rotation always influenced by the length of the alkyl chain on the imidazolium cation?

    PubMed

    Gangamallaiah, V; Dutt, G B

    2012-10-25

    In an attempt to find out whether the length of the alkyl chain on the imidazolium cation has a bearing on solute rotation, temperature-dependent fluorescence anisotropies of three structurally similar solutes have been measured in a series of 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides. Solute-solvent coupling constants obtained from the experimentally measured reorientation times with the aid of Stokes-Einstein-Debye hydrodynamic theory indicate that there is no influence of the length of the alkyl chain on the rotation of nonpolar, anionic, and cationic solutes 9-phenylanthracene (9-PA), fluorescein (FL), and rhodamine 110 (R110), respectively. It has also been noticed that the rotational diffusion of 9-PA is closer to the predictions of slip hydrodynamics, whereas the rotation of negatively charged FL and positively charged R110 is almost identical and follows stick hydrodynamics in these ionic liquids. Despite having similar shape and size, ionic solutes rotate slower by a factor of 3-4 compared to the nonpolar solute. Interplay of specific and electrostatic interactions between FL and the imidazolium cation of the ionic liquids, and between R110 and the bis(trifluoromethylsulfonyl)imide anion, appear to be responsible for the observed behavior. These results are an indication that the length of the alkyl chain on the imidazolium cation does not alter their physical properties in a manner that has an effect on solute rotation.

  8. The photodissociation dynamics of alkyl radicals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Giegerich, Jens; Fischer, Ingo, E-mail: ingo.fischer@uni-wuerzburg.de

    2015-01-28

    The photodisscociation dynamics of the alkyl radicals i-propyl (CH(CH{sub 3}){sub 2}) and t-butyl (C(CH{sub 3}){sub 3}) are investigated by H-atom photofragment imaging. While i-propyl is excited at 250 nm, the photodynamics of t-butyl are explored over a large energy range using excitation wavelengths between 347 nm and 233 nm. The results are compared to those obtained previously for ethyl, CH{sub 3}CH{sub 2}, and to those reported for t-butyl using 248 nm excitation. The translational energy (E{sub T}) distribution of the H-atom photofragments is bimodal and appears rather similar for all three radicals. The low E{sub T} part of the distributionmore » shows an isotropic photofragment angular distribution, while the high E{sub T} part is associated with a considerable anisotropy. Thus, for t-butyl, two H-atom loss channels of roughly equal importance have been identified in addition to the CH{sub 3}-loss channel reported previously. A mechanism for the photodissociation of alkyl radicals is suggested that is based on interactions between Rydberg- and valence states.« less

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

    PubMed

    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.

  10. Alkylating agent (MNU)-induced mutation in space environment

    NASA Astrophysics Data System (ADS)

    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.

  11. 46 CFR 153.560 - Special requirements for Alkyl (C7-C9) nitrates.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Special requirements for Alkyl (C7-C9) nitrates. 153.560... Equipment Special Requirements § 153.560 Special requirements for Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to prevent the occurrence of a...

  12. 46 CFR 153.560 - Special requirements for Alkyl (C7-C9) nitrates.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Special requirements for Alkyl (C7-C9) nitrates. 153.560... Equipment Special Requirements § 153.560 Special requirements for Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to prevent the occurrence of a...

  13. 46 CFR 153.560 - Special requirements for Alkyl (C7-C9) nitrates.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Special requirements for Alkyl (C7-C9) nitrates. 153.560... Equipment Special Requirements § 153.560 Special requirements for Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to prevent the occurrence of a...

  14. 46 CFR 153.560 - Special requirements for Alkyl (C7-C9) nitrates.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Special requirements for Alkyl (C7-C9) nitrates. 153.560... Equipment Special Requirements § 153.560 Special requirements for Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to prevent the occurrence of a...

  15. 46 CFR 153.560 - Special requirements for Alkyl (C7-C9) nitrates.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Special requirements for Alkyl (C7-C9) nitrates. 153.560... Equipment Special Requirements § 153.560 Special requirements for Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to prevent the occurrence of a...

  16. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols and...

  17. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols and...

  18. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols and...

  19. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols and...

  20. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols and...

  1. Inert Reassessment Document for Alkyl (C8-C24)

    EPA Pesticide Factsheets

    Inert Ingredient Tolerance Reassessments: Two Exemptions from theRequirement of a Tolerance for Alkyl (C8-C24) Benzenesulfonic Acid and its Ammonium, Calcium, Magnesium, Potassium, Sodium, and Zinc Salts

  2. Safety Assessment of Alkyl Esters as Used in Cosmetics.

    PubMed

    Fiume, Monice M; Heldreth, Bart A; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2015-09-01

    The Cosmetic Ingredient Review Expert Panel (Panel) assessed the safety of 237 alkyl esters for use in cosmetics. The alkyl esters included in this assessment have a variety of reported functions in cosmetics, with skin-conditioning agent being the most common function. The Panel reviewed available animal and clinical data in making its determination of safety on these ingredients, and where there were data gaps, similarity in structure, properties, functions, and uses of these ingredients allowed for extrapolation of the available toxicological data to assess the safety of the entire group. The Panel concluded that these ingredients are safe in cosmetic formulations in the present practices of use and concentration when formulated to be nonirritating. © The Author(s) 2015.

  3. Synthesis of Alkyl-Glycerolipids Standards for Gas Chromatography Analysis: Application for Chimera and Shark Liver Oils

    PubMed Central

    Pinault, Michelle; Guimaraes, Cyrille; Couthon, Hélène; Thibonnet, Jérôme; Fontaine, Delphine; Chantôme, Aurélie; Chevalier, Stephan; Jaffrès, Paul-Alain; Vandier, Christophe

    2018-01-01

    Natural O-alkyl-glycerolipids, also known as alkyl-ether-lipids (AEL), feature a long fatty alkyl chain linked to the glycerol unit by an ether bond. AEL are ubiquitously found in different tissues but, are abundant in shark liver oil, breast milk, red blood cells, blood plasma, and bone marrow. Only a few AEL are commercially available, while many others with saturated or mono-unsaturated alkyl chains of variable length are not available. These compounds are, however, necessary as standards for analytical methods. Here, we investigated different reported procedures and we adapted some of them to prepare a series of 1-O-alkyl-glycerols featuring mainly saturated alkyl chains of various lengths (14:0, 16:0, 17:0, 19:0, 20:0, 22:0) and two monounsaturated chains (16:1, 18:1). All of these standards were fully characterized by NMR and GC-MS. Finally, we used these standards to identify the AEL subtypes in shark and chimera liver oils. The distribution of the identified AEL were: 14:0 (20–24%), 16:0 (42–54%) and 18:1 (6–16%) and, to a lesser extent, (0.2–2%) for each of the following: 16:1, 17:0, 18:0, and 20:0. These standards open the possibilities to identify AEL subtypes in tumours and compare their composition to those of non-tumour tissues. PMID:29570630

  4. Alkyl nitrate (C1-C3) depth profiles in the tropical Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Dahl, E. E.; Yvon-Lewis, S. A.; Saltzman, E. S.

    2007-01-01

    This paper reports the first depth profile measurements of methyl, ethyl, isopropyl and n-propyl nitrates in the tropical Pacific Ocean. Depth profile measurements were made at 22 stations during the Project Halocarbon Air Sea Exchange cruise, in warm pool, equatorial, subequatorial, and gyre waters. The highest concentrations, up to several hundred pM of methyl nitrate, were observed in the central Pacific within 8 degrees of the equator. In general, alkyl nitrate levels were highest in the surface mixed layer, and decreased with depth below the mixed layer. The spatial distribution of the alkyl nitrates suggests that there is a strong source associated with biologically productive ocean regions, that is characterized by high ratios of methyl:ethyl nitrate. However, the data do not allow discrimination between direct biological emissions and photochemistry as production mechanisms. Alkyl nitrates were consistently detectable at several hundred meters depth. On the basis of the estimated chemical loss rate of these compounds, we conclude that deep water alkyl nitrates must be produced in situ. Possible sources include free radical processes initiated by radioactive decay or cosmic rays, enzymatically mediated reactions involving bacteria, or unidentified chemical mechanisms involving dissolved organic matter.

  5. BIODEGRADABILITY OF ALKYLATES AS A SOLE CARBON SOURCE IN THE PRESENCE OF ETHANOL OR BTEX

    EPA Science Inventory

    The biodegradability of alkylate compounds in serum bottles was investigated in the presence and absence of ethanol or benzene, toluene, ethylbenzene, and p-xylene (BTEX). The biomass was acclimated to three different alkylates, 2,3-dimethylpentane, 2,4-dimethylpentane, an...

  6. Fluorinated Alkyl Ether Epoxy Resin Compositions and Applications Thereof

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Wohl, Christopher J. (Inventor); Siochi, Emilie J. (Inventor); Gardner, John M. (Inventor); Smith, Joseph G. (Inventor); Palmieri, Frank M. (Inventor)

    2017-01-01

    Epoxy resin compositions prepared using amino terminated fluoro alkyl ethers. The epoxy resin compositions exhibit low surface adhesion properties making them useful as coatings, paints, moldings, adhesives, and fiber reinforced composites.

  7. The Discovery of Citral-Like Thiophenes in Fried Chicken.

    PubMed

    Cannon, Robert J; Curto, Nicole L; Esposito, Cynthia M; Payne, Richard K; Janczuk, Adam J; Agyemang, David O; Cai, Tingwei; Tang, Xiao-Qing; Chen, Michael Z

    2017-07-19

    The isomers of 3,7-dimethyl-2,6-octadienal, more commonly known together as citral, are two of the most notable natural compounds in the flavor and fragrance industry. However, both isomers are inherently unstable, limiting their potential use in various applications. To identify molecules in nature that can impart the fresh lemon character of citral while demonstrating stability under acidic and thermal conditions has been a major challenge and goal for the flavor and fragrance industry. In the study of fried chicken, several alkyl thiophenecarbaldehydes were identified by gas chromatography-mass spectrometry and gas chromatography-olfactometry that provided a similar citral-like aroma. The potential mechanism of formation in fried chicken is discussed. Furthermore, in order to explore the organoleptic properties of this structural backbone, a total of 35 thiophenecarbaldehyde derivatives were synthesized or purchased for evaluation by odor and taste. Certain organoleptic trends were observed as the length of the alkyl or alkenyl chain increased or when the chain was moved to different positions on the thiophene backbone. The 3-substituted alkyl thiophenecarbaldehydes, specifically 3-butyl-2-thiophenecarbaldehyde and 3-(3-methylbut-2-en-1-yl)-2-thiophenecarbaldehyde, exhibited strong citrus and citral-like notes. Several alkyl thiophenecarbaldehydes were tested in high acid stability trials (4 °C vs 38 °C) and outperformed citral both in terms of maintaining freshness over time and minimizing off-notes. Additional measurements were completed to calculate the odor thresholds for a select group of thiophenecarbaldehydes, which were found to be between 4.7-215.0 ng/L in air.

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

    PubMed

    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

  9. 40 CFR 721.647 - Alkoxylated alkyl amine (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ....647 Section 721.647 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.647 Alkoxylated alkyl amine (generic). (a) Chemical substance and significant new uses...

  10. 40 CFR 721.2155 - Alkoxyamino-alkyl-coumarin (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...). 721.2155 Section 721.2155 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.2155 Alkoxyamino-alkyl-coumarin (generic). (a) Chemical substance and significant new uses...

  11. Inducible repair of alkylated DNA in microorganisms.

    PubMed

    Mielecki, Damian; Wrzesiński, Michał; Grzesiuk, Elżbieta

    2015-01-01

    Alkylating agents, which are widespread in the environment, also occur endogenously as primary and secondary metabolites. Such compounds have intrinsically extremely cytotoxic and frequently mutagenic effects, to which organisms have developed resistance by evolving multiple repair mechanisms to protect cellular DNA. One such defense against alkylation lesions is an inducible Adaptive (Ada) response. In Escherichia coli, the Ada response enhances cell resistance by the biosynthesis of four proteins: Ada, AlkA, AlkB, and AidB. The glycosidic bonds of the most cytotoxic lesion, N3-methyladenine (3meA), together with N3-methylguanine (3meG), O(2)-methylthymine (O(2)-meT), and O(2)-methylcytosine (O(2)-meC), are cleaved by AlkA DNA glycosylase. Lesions such as N1-methyladenine (1meA) and N3-methylcytosine (3meC) are removed from DNA and RNA by AlkB dioxygenase. Cytotoxic and mutagenic O(6)-methylguanine (O(6)meG) is repaired by Ada DNA methyltransferase, which transfers the methyl group onto its own cysteine residue from the methylated oxygen. We review (i) the individual Ada proteins Ada, AlkA, AlkB, AidB, and COG3826, with emphasis on the ubiquitous and versatile AlkB and its prokaryotic and eukaryotic homologs; (ii) the organization of the Ada regulon in several bacterial species; (iii) the mechanisms underlying activation of Ada transcription. In vivo and in silico analysis of various microorganisms shows the widespread existence and versatile organization of Ada regulon genes, including not only ada, alkA, alkB, and aidB but also COG3826, alkD, and other genes whose roles in repair of alkylated DNA remain to be elucidated. This review explores the comparative organization of Ada response and protein functions among bacterial species beyond the classical E. coli model. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Synthesis and Antioxidant Activity of Hydroxytyrosol Alkyl-Carbonate Derivatives.

    PubMed

    Fernandez-Pastor, Ignacio; Fernandez-Hernandez, Antonia; Rivas, Francisco; Martinez, Antonio; Garcia-Granados, Andres; Parra, Andres

    2016-07-22

    Three procedures have been investigated for the isolation of tyrosol (1) and hydroxytyrosol (2) from a phenolic extract obtained from the solid residue of olive milling. These three methods, which facilitated the recovery of these phenols, were chemical or enzymatic acetylation, benzylation, and carbomethoxylation, and subsequent carbonylation or acetonation reactions. Several new lipophilic alkyl-carbonate derivatives of hydroxytyrosol have been synthesized, coupling the primary hydroxy group of this phenol, through a carbonate linker, using alcohols with different chain lengths. The antioxidant properties of these lipophilic derivatives have been evaluated by different methods and compared with free hydroxytyrosol (2) and also with the well-known antioxidants BHT and α-tocopherol. Three methods were used for the determination of this antioxidant activity: FRAP and ABTS assays, to test the antioxidant power in hydrophilic media, and the Rancimat test, to evaluate the antioxidant capacity in a lipophilic matrix. These new alkyl-carbonate derivatives of hydroxytyrosol enhanced the antioxidant activity of this natural phenol, with their antioxidant properties also being higher than those of the commercial antioxidants BHT and α-tocopherol. There was no clear influence of the side-chain length on the antioxidant properties of the alkyl-carbonate derivatives of 2, although the best results were achieved mainly by the compounds with a longer chain on the primary hydroxy group of this natural phenolic substance.

  13. Cu/Mn bimetallic catalysis enables carbonylative Suzuki-Miyaura coupling with unactivated alkyl electrophiles.

    PubMed

    Pye, Dominic R; Cheng, Li-Jie; Mankad, Neal P

    2017-07-01

    A bimetallic system consisting of Cu-carbene and Mn-carbonyl co-catalysts was employed for carbonylative C-C coupling of arylboronic esters with alkyl halides, allowing for the convergent synthesis of ketones. The system operates under mild conditions and exhibits complementary reactivity to Pd catalysis. The method is compatible with a wide range of arylboronic ester nucleophiles and proceeds smoothly for both primary and secondary alkyl iodide electrophiles. Preliminary mechanistic experiments corroborate a hypothetical catalytic mechanism consisting of co-dependent cycles wherein the Cu-carbene co-catalyst engages in transmetallation to generate an organocopper nucleophile, while the Mn-carbonyl co-catalyst activates the alkyl halide electrophile by single-electron transfer and then undergoes reversible carbonylation to generate an acylmanganese electrophile. The two cycles then intersect with a heterobimetallic, product-releasing C-C coupling step.

  14. Theoretical DFT, vibrational and NMR studies of benzimidazole and alkyl derivatives

    NASA Astrophysics Data System (ADS)

    Infante-Castillo, Ricardo; Rivera-Montalvo, Luis A.; Hernández-Rivera, Samuel P.

    2008-04-01

    Benzimidazoles are heterocyclic compounds that have awaked great interest during the last few years because of their proven biological activity as antiviral, antimicrobial, and antitumoral agents. For this reason, the development of a systematic FT-IR, FT-Raman and NMR study of 1-substituted compounds in 2-methylbenzimidazole constitutes a significant tool in understanding the molecular dynamics and the structural parameters that govern their behavior. Two new 1-alkyl-2-methylbenzimidazoles compounds were synthesized from reaction of 2-methylbenzimidazole with primary and secondary alkyl halides using a strong base as a catalyst. These compounds were purified and characterized by elemental analysis and different spectroscopic methods. The comparative analysis of vibrational modes of benzimidazole and its alkyl derivatives show that regions of absorption are very similar in all of them. However, changes are produced at low frequencies specifically in the C-H out of plane deformations, ring breathing and ring skeletal vibrations. The ring out-of plane bending modes shift by 10-15 cm -1 in some cases as results of alkyl substitution. The theoretical calculated spectra, using Density Functional Theory (DFT) approximation, and experimental results were consistent with each other. The GIAO method was used to calculate absolute shieldings, which agree consistently with those measured by 1H and 13C NMR. The consistency and efficiency of the GIAO 13C and 1H NMR calculations were thoroughly checked by the analysis of statistical parameters concerning computed and experimental 13C and 1H NMR chemical shift values of the studied compounds.

  15. Alkyl Caffeates Improve the Antioxidant Activity, Antitumor Property and Oxidation Stability of Edible Oil

    PubMed Central

    Wang, Jun; Gu, Shuang-Shuang; Pang, Na; Wang, Fang-Qin; Pang, Fei; Cui, Hong-Sheng; Wu, Xiang-Yang; Wu, Fu-An

    2014-01-01

    Caffeic acid (CA) is distributed widely in nature and possesses strong antioxidant activity. However, CA has lower solubility in non-polar media, which limits its application in fat-soluble food. To increase the lipophilicity of natural antioxidant CA, a series of alkyl caffeates were synthesized and their antioxidant and antitumor activities were investigated. The antioxidant parameters, including the induction period, acid value and unsaturated fatty acid content, of the alkyl caffeates in edible oil were firstly investigated. The results indicated that alkyl caffeates had a lower DPPH IC50 (14–23 µM) compared to CA, dibutyl hydroxy toluene (BHT) and Vitamin C (24–51 µM), and significantly inhibited four human cancer cells (SW620, SW480, SGC7901 and HepG2) with inhibition ratio of 71.4–78.0% by a MTT assay. With regard to the induction period and acid value assays, methyl and butyl caffeates had higher abilities than BHT to restrain the oxidation process and improve the stability of edible oil. The addition of ethyl caffeate to oil allowed maintenance of a higher unsaturated fatty acid methyl ester content (68.53%) at high temperatures. Overall, the alkyl caffeats with short chain length (n<5) assessed better oxidative stability than those with long chain length. To date, this is the first report to the correlations among the antioxidant activity, anticancer activity and oxidative stability of alkyl caffeates. PMID:24760050

  16. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction...

  17. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction...

  18. Safety Assessment of Amino Acid Alkyl Amides as Used in Cosmetics.

    PubMed

    Burnett, Christina L; Heldreth, Bart; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    The Cosmetic Ingredient Review Expert Panel (Panel) reviewed the product use, formulation, and safety data of 115 amino acid alkyl amides, which function as skin and hair conditioning agents and as surfactants-cleansing agents in personal care products. Safety test data on dermal irritation and sensitization for the ingredients with the highest use concentrations, lauroyl lysine and sodium lauroyl glutamate, were reviewed and determined to adequately support the safe use of the ingredients in this report. The Panel concluded that amino acid alkyl amides are safe in the present practices of use and concentration in cosmetics, when formulated to be nonirritating.

  19. Effect of alkyl glycerophosphate on the activation of peroxisome proliferator-activated receptor gamma and glucose uptake in C2C12 cells

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tsukahara, Tamotsu, E-mail: ttamotsu@shinshu-u.ac.jp; Haniu, Hisao; Matsuda, Yoshikazu

    Highlights: •Alkyl-LPA specifically interacts with PPARγ. •Alkyl-LPA treatments induces lipid accumulation in C2C12 cells. •Alkyl-LPA enhanced glucose uptake in C2C12 cells. •Alkyl-LPA-treated C2C12 cells express increased amounts of GLUT4 mRNA. •Alkyl-LPA is a novel therapeutic agent that can be used for the treatment of obesity and diabetes. -- Abstract: Studies on the effects of lipids on skeletal muscle cells rarely examine the effects of lysophospholipids. Through our recent studies, we identified select forms of phospholipids, such as alkyl-LPA, as ligands for the intracellular receptor peroxisome proliferator-activated receptor gamma (PPARγ). PPARγ is a nuclear hormone receptor implicated in many human diseases,more » including diabetes and obesity. We previously showed that alkyl-LPA is a specific agonist of PPARγ. However, the mechanism by which the alkyl-LPA–PPARγ axis affects skeletal muscle cells is poorly defined. Our objective in the present study was to determine whether alkyl-LPA and PPARγ activation promotes glucose uptake in skeletal muscle cells. Our findings indicate that PPARγ1 mRNA is more abundant than PPARγ2 mRNA in C2C12 cells. We showed that alkyl-LPA (3 μM) significantly activated PPARγ and increased intracellular glucose levels in skeletal muscle cells. We also showed that incubation of C2C12 cells with alkyl-LPA led to lipid accumulation in the cells. These findings suggest that alkyl-LPA activates PPARγ and stimulates glucose uptake in the absence of insulin in C2C12 cells. This may contribute to the plasma glucose-lowering effect in the treatment of insulin resistance.« less

  20. Occurrence and Biosynthesis of Alkyl Hydroxycinnamates in Plant Lipid Barriers

    PubMed Central

    Domergue, Frédéric; Kosma, Dylan K.

    2017-01-01

    The plant lipid barriers cuticle and suberin represent one of the largest biological interfaces on the planet. They are comprised of an insoluble polymeric domain with associated organic solvent-soluble waxes. Suberin-associated and plant cuticular waxes contain mixtures of aliphatic components that may include alkyl hydroxycinnamates (AHCs). The canonical alkyl hydroxycinnamates are comprised of phenylpropanoids, typically coumaric, ferulic, or caffeic acids, esterified with long chain to very long chain fatty alcohols. However, many related structures are also present in the plant kingdom. Although their functions remain elusive, much progress has been made on understanding the distribution, biosynthesis, and deposition of AHCs. Herein a summary of the current state of knowledge on plant AHCs is provided. PMID:28665304

  1. Identification of isopropylbiphenyl, alkyl diphenylmethanes, diisopropylnaphthalene, linear alkyl benzenes and other polychlorinated biphenyl replacement compounds in effluents, sediments and fish in the Fox River System, Wisconsin

    USGS Publications Warehouse

    Peterman, Paul H.; Delfino, Joseph J.

    1990-01-01

    Five polychlorinated biphenyl replacement dye solvents and a diluent present in carbonless copy paper were identified by gas chromatography/mass spectrometry in the following matrices: effluents from a de-inking–recycling paper mill and a municipal wastewater treatment plant receiving wastewaters from a carbonless copy paper manufacturing plant; sediments; and fish collected near both discharges in the Fox River System, Wisconsin. An isopropylbiphenyl dye solvent mixture included mono-, di- and triisopropylbiphenyls. Also identified were two dye solvent mixtures marketed under the trade name Santosol. Santosol 100 comprised ethyl-diphenylmethanes (DPMs), benzyl-ethyl-DPMs, and dibenzyl-ethyl-DPMs. Similarly, Santosol 150 comprised dimethyl-DPMs, benzyl-dimethyl-DPMs, and dibenzyl-dimethyl-DPMs. Diisopropylnaphthalenes, widely used as a dye solvent in Japan, were identified for the first time in the US environment. sec-Butylbiphenyls and di-sec-butylbiphenyls, likely constituents of a sec-butylbiphenyl dye solvent mixture, were tentatively identified. Linear alkyl benzenes (C10 to C13-LABs) constituted the Alkylate 215 diluent mixture. Although known to occur as minor constituents in linear alkyl sulfonate detergents, LAB residues have not been previously attributed to commercial use of LABs.

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

    PubMed

    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.

  3. Binding of alkylphenols and alkylated non-phenolics to the rainbow trout (Oncorhynchus mykiss) plasma sex steroid-binding protein.

    PubMed

    Tollefsen, K-E

    2007-09-01

    Alkylphenols are well-known endocrine disrupters, mediating effects through the estrogen receptor (ER). Although the estrogenic properties of the alkylphenols are well documented, alternative mechanisms of action are poorly described. In the present work, the interaction of a range of alkyl-substituted phenols and alkyl-substituted non-phenolics with the rainbow trout (Oncorhynchus mykiss) sex steroid-binding protein (rtSBP) were determined by competitive ligand-binding studies. The role of alkyl chain length and branching, substituent position, number of alkylated groups, and the requirement of a phenolic ring structure were assessed. The results showed that the rtSBP binds to most chemical structures tested, although the highest affinity was obtained for mono-substituted alkylphenols with a chain length of four to eight methyl groups. Interestingly, rtSBP binding was also observed for non-phenolic compounds such as 4-t-butylcyclohexanol and 4-t-butylnitrobenzene suggesting that the rtSBP has a broad binding specificity for alkylphenols and alkylated non-phenolics.

  4. Understanding the effect of alkyl chains of gemini cations on the physicochemical and cellular properties of polyurethane micelles.

    PubMed

    Pan, Zhicheng; Fang, Danxuan; Song, Yuanqing; Song, Nijia; Ding, Mingming; Li, Jiehua; Luo, Feng; Li, Jianshu; Tan, Hong; Fu, Qiang

    2018-06-06

    Cationic gemini quaternary ammonium (GQA) has been used as a cell internalization promoter to improve the permeability of the cell membrane and enhance the cellular uptake. However, the effect of the alkyl chain length on the cellular properties of nanocarriers has not been elucidated yet. In this study, we developed a series of polyurethane micelles containing GQAs with various alkyl chain lengths. The alteration of the gemini alkyl chain length was found to change the distribution of GQA surfactants in the micellar structure and affect the surface charge exposure, stability, and the protein absorption properties of nanocarriers. Moreover, we also clarified the role of the alkyl chain length in tumor cell internalization and macrophage uptake of polyurethane micelles. This work provides a new understanding on the effect of the GQA alkyl chain length on the physicochemical and biological properties of nanomedicines, and offers guidance on the rational design of effective drug delivery systems where the issue of functional group exposure at the micellar surface should be considered.

  5. Mechanism of the Reaction between Alkyl- and Aryl Grignard Reagents and Hexachlorocyclotriphosphazene: An Explanation of Bi(Cyclophosphazene Formation).

    DTIC Science & Technology

    1982-06-24

    ADAI& "I PENNSYLVANIA STATE UNIV UNIVERSITY PARK DEPT OF CHEMISTRY F/S 7/3 ADA MECHANISM OF THE REACTION BETWEEN ALKYL - AND ARYL GRIGNARD REMG-ETC (U...TITLE (and Subliflo) S. TYPE OF REPORT A PERIOD COVERED MECHANISM OF THE REACTION BETWEEN ALKYL - AND ARYL GRIGNARD REAGENTS AND HEXACHLOROCYCLOTRIPHOS...Report No. 27 MECHANISM OF THE REACTION BETWEEN ALKYL - AND ARYL GRIGNARD REAGENTS AND HEXACHLOROCYCLOTRIPHOSPHAZENE: AN EXPLANATION OF BI(CYCLOPHOSPHAZENE

  6. 40 CFR 721.6183 - Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow alkyl amines...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... - maleic anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine... Substances § 721.6183 Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow... anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine (PMN P-00...

  7. 40 CFR 721.6183 - Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow alkyl amines...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... - maleic anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine... Substances § 721.6183 Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow... anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine (PMN P-00...

  8. 40 CFR 721.10625 - Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... benzene by-product, brominated and bromo diphenyl alkane (generic). 721.10625 Section 721.10625 Protection... Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic). (a... generically as distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (PMNs...

  9. 40 CFR 721.10625 - Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... benzene by-product, brominated and bromo diphenyl alkane (generic). 721.10625 Section 721.10625 Protection... Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic). (a... generically as distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (PMNs...

  10. Relationship between Antimalarial Activity and Heme Alkylation for Spiro- and Dispiro-1,2,4-Trioxolane Antimalarials▿

    PubMed Central

    Creek, Darren J.; Charman, William N.; Chiu, Francis C. K.; Prankerd, Richard J.; Dong, Yuxiang; Vennerstrom, Jonathan L.; Charman, Susan A.

    2008-01-01

    The reaction of spiro- and dispiro-1,2,4-trioxolane antimalarials with heme has been investigated to provide further insight into the mechanism of action for this important class of antimalarials. A series of trioxolanes with various antimalarial potencies was found to be unreactive in the presence of Fe(III) hemin, but all were rapidly degraded by reduced Fe(II) heme. The major reaction product from the heme-mediated degradation of biologically active trioxolanes was an alkylated heme adduct resulting from addition of a radical intermediate. Under standardized reaction conditions, a correlation (R2 = 0.88) was found between the extent of heme alkylation and in vitro antimalarial activity, suggesting that heme alkylation may be related to the mechanism of action for these trioxolanes. Significantly less heme alkylation was observed for the clinically utilized artemisinin derivatives compared to the equipotent trioxolanes included in this study. PMID:18268087

  11. 40 CFR 721.555 - Alkyl amino nitriles (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (c). A full face shield is required if splashing or spraying occurs. (ii) Hazard communication... to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96-1674 and P-96-1675) are subject to reporting under this section for the significant new uses described...

  12. Stereospecific Cross-Coupling of Secondary Alkyl β-Trifluoroboratoamides

    PubMed Central

    Sandrock, Deidre L.; Jean-Gérard, Ludivine; Chen, Cheng-yi; Dreher, Spencer D.; Molander, Gary A.

    2010-01-01

    The stereospecific cross-coupling of enantioenriched non-benzylic secondary alkyl boron compounds has been achieved. The high selectivity toward product formation over an undesired β-H elimination pathway is achieved via an intramolecular coordination of an ancillary carbonyl to the metal center in the diorganopalladium intermediate. PMID:21077687

  13. Regioselective N1-alkylation of 3,4-dihydropyrimidine-2(1H)-ones: screening of their biological activities against Ca(2+)-ATPase.

    PubMed

    Putatunda, Salil; Chakraborty, Srabasti; Ghosh, Swatilekha; Nandi, Pinki; Chakraborty, Supriya; Sen, Parimal C; Chakraborty, Arijit

    2012-08-01

    A regioselective N1-alkylation of 3,4-dihydropyrimidin-2(1H)-ones using a very efficient mild base Cs(2)CO(3) and alkyl halides at room temperature has been reported. The selectivity of this methodology is excellent and the yields of the alkylated products are very good. Furthermore inhibitory action of both the 3,4-dihydropyrimidin-2(1H)-ones and the N1-alkylated derivatives were tested on Ca(2+)-ATPase, which revealed that the parent compounds can act as Ca(2+)-ATPase inhibitors whereas the N1-alkylated derivatives are inefficient for this purpose. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  14. HeI photoelectron spectroscopic studies on the electronic structure of alkyl nitrosamines

    NASA Astrophysics Data System (ADS)

    Jiang, Peng; Qian, Ximei; Li, Chunhui; Qiao, Chunhua; Wang, Dianxun

    1997-10-01

    HeI photoelectron spectroscopic (PES) studies on the electronic structure of alkyl nitrosamines R 2N 2O (R = CH 3-, CH 3CH 2-, and CH 3CH 2CH 2-) are reported. The assignment of the PES bands for this series of compounds has been made with the aid of the band shapes, the band intensity and ab initio SCF MO calculations based on the 631 ∗ G basis sets. Both PES experiment and the ab initio SCF MO calculations show that the detoxification ability of nitrosamine with longer alkyl chain is stronger.

  15. DNA injection and genetic recombination of alkylated bacteriophage T7 in the presence of nalidixic acid.

    PubMed Central

    Karska-Wysocki, B; Mamet-Bratley, M D; Przewlocki, G

    1977-01-01

    Marker rescue experiments with alkylated T7 bacteriophage carried out in the presence and in the absence of nalidixic acid suggest that the gradient in rescue is due to two alkylation-induced causes: a DNA injection defect and an interference with DNA synthesis. PMID:916036

  16. Alkylating chemotherapy may exert a uniquely deleterious effect upon neo-antigen-targeting anticancer vaccination

    PubMed Central

    Litterman, Adam J; Dudek, Arkadiusz Z; Largaespada, David A

    2013-01-01

    Alkylating chemotherapy exerts both antineoplastic and immunostimulatory effects. However, in addition to depleting regulatory T cells (Treg), alkylating agents also mediate a long lasting antiproliferative effect on responder lymphocytes. Our recent findings indicate that this antiproliferative effect profoundly impairs vaccination-induced immune responses, especially in the case of vaccines that target specific tumor-associated neo-antigens that do not require Treg depletion. PMID:24251080

  17. 40 CFR 721.10200 - Benzenacetonitrile, cyclohexylidene-alkyl substituted (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Benzenacetonitrile, cyclohexylidene-alkyl substituted (generic). 721.10200 Section 721.10200 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES...

  18. Estrogenicity of alkylphenols and alkylated non-phenolics in a rainbow trout (Oncorhynchus mykiss) primary hepatocyte culture.

    PubMed

    Tollefsen, K-E; Eikvar, Sissel; Finne, Eivind Farmen; Fogelberg, Oscar; Gregersen, Inger Katharina

    2008-10-01

    Alkylphenols act as estrogen mimics by binding to and transactivating estrogen receptors (ERs) in fish. In the present study, activation of ER-mediated production of the estrogenic biomarker vitellogenin (vtg) in a primary culture of rainbow trout (Oncorhynchus mykiss) hepatocytes was used to construct a structure-activity relationship for this ubiquitous group of aquatic pollutants. The role of alkyl chain length and branching, substituent position, number of alkylated groups, and the requirement of a phenolic ring structure was assessed. The results showed that most alkylphenols were estrogenic, although with 3-300 thousand times lower affinity than the endogenous estrogen 17beta-estradiol. Mono-substituted tertiary alkylphenols with moderate (C4-C5) and long alkyl chain length (C8-C9) in the para position exhibited the highest estrogenic potency. Substitution with multiple alkyl groups, presence of substituents in the ortho- and meta-position and lack of a hydroxyl group on the benzene ring reduced the estrogenic activity, although several estrogenic alkylated non-phenolics were identified. Co-exposures with the natural estrogen 17beta-estradiol led to identification of additional estrogenic compounds as well as some anti-estrogens. A combination of low affinity for the ER and cytotoxicity was identified as factors rendering some of the alkylphenols non-estrogenic in the bioassay when tested alone.

  19. Reductive alkylation of ribosomes as a probe to the topography of ribosomal proteins*

    PubMed Central

    Moore, Graham; Crichton, Robert R.

    1974-01-01

    Escherichia coli ribosomes were treated with a number of different aldehydes of various sizes in the presence of NaBH4. After incorporation of either 3H or 14C, the ribosomal proteins were separated by two-dimensional polyacrylamide-gel electrophoresis and the extent of alkylation of the lysine residues in each protein was measured. The same pattern of alkylation was observed with the four reagents used, namely formaldehyde, acetone, benzaldehyde and 3,4,5-trimethoxybenzaldehyde. Every protein in 30S and 50S subunits was modified, although there was considerable variation in the degree of alkylation of individual proteins. A topographical classification of ribosomal proteins is presented, based on the degree of exposure of lysine residues. The data indicate that every protein of the ribosome has at least one lysine residue exposed at or near the surface of the ribonucleo-protein complex. PMID:4462744

  20. On the Boiling Points of the Alkyl Halides.

    ERIC Educational Resources Information Center

    Correia, John

    1988-01-01

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

  1. Synthesis of 4-alkyl and 4-(beta-alkylvinyl) derivatives of primaquine as potential antimalarials.

    PubMed

    Carroll, F I; Berrang, B D; Linn, C P

    1979-11-01

    4(beta-Alkylvinyl)-6-methoxy-8-nitroquinolines (6) were prepared from 6-methoxy-8-nitroquinoline-4-carboxaldehyde (5) via a Wittig reaction. Stannous chloride reduction of 6 gave 4-(beta-alkylvinyl)-8-amino-6-methoxyquinolines (8), whereas catalytic reduction of 6 using Raney nickel catalyst gave 4-alkyl-8-amino-6-methoxyquinolines (7). Alkylation of 7 and 8 with 4-iodo-1-phthalimidopentane, followed by removal of the phthaloyl-protecting group with hydrazine, gave 4-alkyl and 4-(beta-alkylvinyl) derivatives of primiquine, respectively. These compounds were evaluated for antimalarial activity against P. berghei and P. berghei yoelii in mice and against P. cynomolgi in rhesus monkeys. Several of the compounds were active in the P. bergheii yoelii screen. None of the compounds showed significant activity in the other two screens.

  2. Multidimensional Self-Assembled Structures of Alkylated Cellulose Oligomers Synthesized via in Vitro Enzymatic Reactions.

    PubMed

    Yataka, Yusuke; Sawada, Toshiki; Serizawa, Takeshi

    2016-10-04

    The self-assembly of biomolecules into highly ordered nano-to-macroscale structures is essential in the construction of biological tissues and organs. A variety of biomolecular assemblies composed of nucleic acids, peptides, and lipids have been used as molecular building units for self-assembled materials. However, crystalline polysaccharides have rarely been utilized in self-assembled materials. In this study, we describe multidimensional self-assembled structures of alkylated cellulose oligomers synthesized via in vitro enzymatic reactions. We found that the alkyl chain length drastically affected the assembled morphologies and allomorphs of cellulose moieties. The modulation of the intermolecular interactions of cellulose oligomers by alkyl substituents was highly effective at controlling their assembly into multidimensional structures. This study proposes a new potential of crystalline oligosaccharides for structural components of molecular assemblies with controlled morphologies and crystal structures.

  3. Oxidation of Alkyl-substituted Cyclic Hydrocarbons by a Nocardia during Growth on n-Alkanes

    PubMed Central

    Davis, J. B.; Raymond, R. L.

    1961-01-01

    Nocardia 107-332, a soil isolate, oxidizes short-chain alkyl-substituted cyclic hydrocarbons to cyclic acids while growing on n-alkanes. Cyclic acids are produced also from relatively long-chain alkyl-substituted cyclics such as n-nonylbenzene or n-dodecylbenzene which alone support growth in a mineral-salts medium. ω-Oxidation of the alkyl substituents is followed by β-oxidation. It is of particular interest that cyclic acids such as cyclohexaneacetic and phenylacetic with C2 residual carboxylic acid substituents are resistant to further oxidation by the nocardia but cyclic acids with C1 or C3 substituents are readily oxidized and utilized for growth. The specificity of microbial oxidations is demonstrated by the conversion of p-isopropyltoluene (p-cymene) to p-isopropylbenzoic acid in n-alkane, growth-supported nocardia cultures. PMID:13720182

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

    DOEpatents

    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.

  5. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substances identified...

  6. 40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically...

  7. Characterization of alkyl carbon in forest soils by CPMAS 13C NMR spectroscopy and dipolar dephasing

    USGS Publications Warehouse

    Kogel-Knabner, I.; Hatcher, P.G.

    1989-01-01

    Samples obtained from forest soils at different stages of decomposition were treated sequentially with chloroform/methanol (extraction of lipids), sulfuric acid (hydrolysis), and sodium chlorite (delignification) to enrich them in refractory alkyl carbon. As revealed by NMR spectroscopy, this treatment yielded residues with high contents of alkyl carbon. In the NMR spectra of residues obtained from litter samples, resonances for carbohydrates are also present, indicating that these carbohydrates are tightly bound to the alkyl carbon structures. During decomposition in the soils this resistant carbohydrate fraction is lost almost completely. In the litter samples the alkyl carbon shows a dipolar dephasing behavior indicative of two structural components, a rigid and a more mobile component. As depth and decomposition increase, only the rigid component is observed. This fact could be due to selective degradation of the mobile component or to changes in molecular mobility during decomposition, e.g., because of an increase in cross linking or contact with the mineral matter of the soil.

  8. A new procedure for N1-alkylation of imidazolidin-4-ones and its NMR characterization

    NASA Astrophysics Data System (ADS)

    Vale, Nuno; Figueiredo, Patrícia

    2016-12-01

    N1-unsubstituted imidazolidin-4-ones of primaquine (PQ) can be stabilized by N1-alkylation under basic conditions. Here we report the development, with our conditions, of peptidomimetic derivatives of PQ with L-amino acid and alkyl derivatives. The new derivatives represent potential new therapeutics for use against protozoan parasites, through enzymatic protection of aminopeptidases.

  9. Synthesis and antifungal activity of natural product-based 6-alkyl-2 3 4 5-tetrahydropyridines

    USDA-ARS?s Scientific Manuscript database

    Seven 6-alkyl-2,3,4,5-tetrahydropyridines (5a–5g) that mimic the natural products piperideines that were recently identified in the fire ant venom have been synthesized. Compounds 5c–5g with the C-6 alkyl chain lengths from C14 to C18 showed varying degrees of antifungal activities, with 5e (6-hexa...

  10. Vapor pressures of 1,3-dialkylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids with long alkyl chains

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Rocha, Marisa A. A., E-mail: lbsantos@fc.up.pt, E-mail: marisa.alexandra.rocha@gmail.com; Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Den Dolech 2, 5612 AZ Eindhoven; Coutinho, João A. P.

    2014-10-07

    This work presents the vapor pressure at several temperatures for the 1,3-dialkylimidazolium bis(trifluoromethylsulfonyl)imide series, [C{sub N/2}C{sub N/2}im][NTf{sub 2}] (N = 14, 16, 18, and 20), measured by a Knudsen effusion method combined with a quartz crystal microbalance. The thermodynamic properties of vaporization of the ionic liquids under study are analysed together with the results obtained previously for the shorter alkyl chain length [C{sub N/2}C{sub N/2}im][NTf{sub 2}] (N = 2, 4, 6, 8, 10, and 12), in order to evaluate the effect of the alkyl side chains of the cation and to get additional insights concerning the nanostructuration of ionic liquids.more » The symmetry effect is explored, based on the comparison with the asymmetric imidazolium based ionic liquids, [C{sub N-1}C{sub 1}im][NTf{sub 2}]. A trend shift on the thermodynamic properties of vaporization along the alkyl side chains of the extended symmetric ionic liquids, around [C{sub 6}C{sub 6}im][NTf{sub 2}], was detected. An intensification of the odd-even effect was observed starting from [C{sub 6}C{sub 6}im][NTf{sub 2}], with higher enthalpies and entropies of vaporization for the odd numbered ionic liquids, [C{sub 7}C{sub 7}im][NTf{sub 2}] and [C{sub 9}C{sub 9}im][NTf{sub 2}]. Similar, but less pronounced, odd-even effect was found for the symmetric ionic liquids with lower alkyl side chains length, [C{sub N/2}C{sub N/2}im][NTf{sub 2}] (with N = 4, 6, 8, 10, and 12). This effect is related with the predominant orientation of the terminal methyl group of the alkyl chain to the imidazolium ring and their influence in the cation-anion interaction. The same Critical Alkyl length at the hexyl, (C{sub 6}C{sub 1}and C{sub 6}C{sub 6}) was found for both asymmetric and symmetric series indicating that the nanostructuration of the ionic liquids is related with alkyl chain length.« less

  11. Influence of some DNA-alkylating drugs on thermal stability, acid and osmotic resistance of the membrane of whole human erythrocytes and their ghosts.

    PubMed

    Ivanov, I T; Gadjeva, V

    2000-09-01

    Human erythrocytes and their resealed ghosts were alkylated under identical conditions using three groups of alkylating antitumor agents: mustards, triazenes and chloroethyl nitrosoureas. Osmotic fragility, acid resistance and thermal stability of membranes were changed only in alkylated ghosts in proportion to the concentration of the alkylating agent. All the alkylating agents decreased acid resistance in ghosts. The clinically used drugs sarcolysine, dacarbazine and lomustine all decreased osmotic fragility and thermal stability of ghost membranes depending on their lipophilicity. DM-COOH did not decrease osmotic fragility and thermal stability of ghost membranes, while NEM increased thermal stability of membranes. The preliminary but not subsequent treatment of ghosts with DM-COOH fully abolished the alkylation-induced thermal labilization of ghost membrane proteins while NEM had a partial effect only. The present study gives direct evidence that alkylating agents, having a high therapeutic activity against malignant growth, bind covalently to proteins of cellular membranes.

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

    PubMed

    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

  13. Solubilization of cyclohexane in aqueous solutions of sodium. cap alpha. -alkyl alkanoates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sagitani, H.; Suzuki, T.; Nagai, M.

    1982-01-01

    The effect of branched alkyl chain length and the position of the COONa group on the solubilizing power of n-alkane sodium carboxylates was studied. The lipophilic property and the amount of solubilized cyclohexane increased with the branched chain length of branched soaps, and with the change of the position of the -COONa group from 3 to 7 in the alkyl chain of pentadecane -3, -5, and -7 sodium carboxylates. Alpha-branched soaps having proper branched alkyl chains were better solubilizers for cyclohexane than straight chain compounds. The amount of cyclohexane solublized by C/sub 10/ H/sub 21/ CH(C/sub 6/H/sub 13/) COONa wasmore » about three times greater than the amount solubilized by C/sub 17/ H/sub 35/ COONa. There was a marked increase in the solubilization of cyclohexane replacing ..cap alpha..-branched fatty acid soaps with optimum amount of cosurfactants such as C/sub 8/H/sub 17/ (OCH/sub 2/CH/sub 2/)/sub 2/OH. Namely, solubilization increased markedly at the optimum hydrophile-lipophile balance of mixed surfactant. 21 references.« less

  14. Synthesis and DNA cleavage activity of Bis-3-chloropiperidines as alkylating agents.

    PubMed

    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. 40 CFR 721.648 - Alkyl dialkylamino phenylsulfonyl alkenoate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.648 Alkyl dialkylamino phenylsulfonyl alkenoate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically...

  16. Atorvastatin Downregulates In Vitro Methyl Methanesulfonate and Cyclophosphamide Alkylation-Mediated Cellular and DNA Injuries

    PubMed Central

    Christoni, Larissa S. A.; Justo, Graça; Soeiro, Maria N. C.

    2018-01-01

    Statins are 3-hydroxy-3-methylglutaryl-coenzyme A (HMG-CoA) reductase inhibitors, and this class of drugs has been studied as protective agents against DNA damages. Alkylating agents (AAs) are able to induce alkylation in macromolecules, causing DNA damage, as DNA methylation. Our objective was to evaluate atorvastatin (AVA) antimutagenic, cytoprotective, and antigenotoxic potentials against DNA lesions caused by AA. AVA chemopreventive ability was evaluated using antimutagenicity assays (Salmonella/microsome assay), cytotoxicity, cell cycle, and genotoxicity assays in HepG2 cells. The cells were cotreated with AVA and the AA methyl methanesulfonate (MMS) or cyclophosphamide (CPA). Our datum showed that AVA reduces the alkylation-mediated DNA damage in different in vitro experimental models. Cytoprotection of AVA at low doses (0.1–1.0 μM) was observed after 24 h of cotreatment with MMS or CPA at their LC50, causing an increase in HepG2 survival rates. After all, AVA at 10 μM and 25 μM had decreased effect in micronucleus formation in HepG2 cells and restored cell cycle alterations induced by MMS and CPA. This study supports the hypothesis that statins can be chemopreventive agents, acting as antimutagenic, antigenotoxic, and cytoprotective components, specifically against alkylating agents of DNA. PMID:29849914

  17. Biological alkylation and colloid formation of selenium in methanogenic UASB reactors.

    PubMed

    Lenz, Markus; Smit, Martijn; Binder, Patrick; van Aelst, Adriaan C; Lens, Piet N L

    2008-01-01

    Bioalkylation and colloid formation of selenium during selenate removal in upflow anaerobic sludge bed (UASB) bioreactors was investigated. The mesophilic (30 degrees C) UASB reactor (pH = 7.0) was operated for 175 d with lactate as electron donor at an organic loading rate of 2 g COD L(-1) d(-1) and a selenium loading rate of 3.16 mg Se L(-1) d(-1). Combining sequential filtration with ion chromatographic analysis for selenium oxyanions and solid phase micro extraction gas chromatography mass spectrometry (SPME-GC-MS) for alkylated selenium compounds allowed to entirely close the selenium mass balance in the liquid phase for most of the UASB operational runtime. Although selenate was removed to more than 98.6% from the liquid phase, a less efficient removal of dissolved selenium was observed due to the presence of dissolved alkylated selenium species (dimethylselenide and dimethyldiselenide) and colloidal selenium particles in the effluent. The alkylated and the colloidal fractions contributed up to 15 and 31%, respectively, to the dissolved selenium concentration. The size fractions of the colloidal dispersion were: 4 to 0.45 mum: up to 21%, 0.45 to 0.2 mum: up to 11%, and particles smaller than 0.2 mum: up to 8%. Particles of 4 to 0.45 mum were formed in the external settler, but did not settle. SEM-EDX analysis showed that microorganisms form these selenium containing colloidal particles extracellularly on their surface. Lowering the temperature by 10 degrees C for 6 h resulted in drastically reduced selenate removal efficiencies (after a delay of 1.5 d), accompanied by the temporary formation of an unknown, soluble, organic selenium species. This study shows that a careful process control is a prerequisite for selenium treatment in UASB bioreactors, as disturbances in the operational conditions induce elevated selenium effluent concentrations by alkylation and colloid formation.

  18. Catalyst-free dehydrative α-alkylation of ketones with alcohols: green and selective autocatalyzed synthesis of alcohols and ketones.

    PubMed

    Xu, Qing; Chen, Jianhui; Tian, Haiwen; Yuan, Xueqin; Li, Shuangyan; Zhou, Chongkuan; Liu, Jianping

    2014-01-03

    Direct dehydrative α-alkylation reactions of ketones with alcohols are now realized under simple, practical, and green conditions without using external catalysts. These catalyst-free autocatalyzed alkylation methods can efficiently afford useful alkylated ketone or alcohol products in a one-pot manner and on a large scale by CC bond formation of the in situ generated intermediates with subsequent controllable and selective Meerwein-Pondorf-Verley-Oppenauer-type redox processes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Surface Structures Formed by a Copper(II) Complex of Alkyl-Derivatized Indigo

    PubMed Central

    Honda, Akinori; Noda, Keisuke; Tamaki, Yoshinori; Miyamura, Kazuo

    2016-01-01

    Assembled structures of dyes have great influence on their coloring function. For example, metal ions added in the dyeing process are known to prevent fading of color. Thus, we have investigated the influence of an addition of copper(II) ion on the surface structure of alkyl-derivatized indigo. Scanning tunneling microscope (STM) analysis revealed that the copper(II) complexes of indigo formed orderly lamellar structures on a HOPG substrate. These lamellar structures of the complexes are found to be more stable than those of alkyl-derivatized indigos alone. Furthermore, 2D chirality was observed. PMID:28773957

  20. Involvement of Escherichia coli DNA Polymerase IV in Tolerance of Cytotoxic Alkylating DNA Lesions in Vivo

    PubMed Central

    Bjedov, Ivana; Dasgupta, Chitralekha Nag; Slade, Dea; Le Blastier, Sophie; Selva, Marjorie; Matic, Ivan

    2007-01-01

    Escherichia coli PolIV, a DNA polymerase capable of catalyzing synthesis past replication-blocking DNA lesions, belongs to the most ubiquitous branch of Y-family DNA polymerases. The goal of this study is to identify spontaneous DNA damage that is bypassed specifically and accurately by PolIV in vivo. We increased the amount of spontaneous DNA lesions using mutants deficient for different DNA repair pathways and measured mutation frequency in PolIV-proficient and -deficient backgrounds. We found that PolIV performs an error-free bypass of DNA damage that accumulates in the alkA tag genetic background. This result indicates that PolIV is involved in the error-free bypass of cytotoxic alkylating DNA lesions. When the amount of cytotoxic alkylating DNA lesions is increased by the treatment with chemical alkylating agents, PolIV is required for survival in an alkA tag-proficient genetic background as well. Our study, together with the reported involvement of the mammalian PolIV homolog, Polκ, in similar activity, indicates that Y-family DNA polymerases from the DinB branch can be added to the list of evolutionarily conserved molecular mechanisms that counteract cytotoxic effects of DNA alkylation. This activity is of major biological relevance because alkylating agents are continuously produced endogenously in all living cells and are also present in the environment. PMID:17483416

  1. The chemical structure of Gloeocapsomorpha prisca microfossils: implications for their origin

    NASA Astrophysics Data System (ADS)

    Blokker, Peter; van Bergen, Pim; Pancost, Rich; Collinson, Margaret E.; de Leeuw, Jan W.; Sinninghe Damste, Jaap S.

    2001-03-01

    Two Estonian Kukersites (Ordovician) and two samples from the Guttenberg Member (Ordovician) of the Decorah formation (North America) containing botryoidal aggregates of Gloeocapsomorpha prisca were investigated by RuO 4 chemical degradation, FTIR, and flash pyrolysis-GC/MS to obtain information about the polymeric structure of these microfossils. The products formed upon oxidation by RuO 4 were analysed by GC/MS and revealed the presence of a wide range of carboxyl and/or carbonyl moiety containing compounds with carbon skeletons ranging from C 5 to C 20. The Estonian Kukersites reveal the presence of a characteristic set of mono-, di-, and tricarboxylic acids. These compounds suggest that the Estonian Kukersites are composed of a polymer consisting of mainly C 21 and C 23n-alkenyl resorcinol building blocks. Similarly, although the tricarboxylic acids are not present, the RuO 4 degradation product mixtures of the Guttenberg Member samples, suggest a poly( n-alkyl resorcinol) structure. The higher thermal maturity is most likely responsible for the different chemistry and morphology of the G. prisca microfossils in these samples. Because compounds like n-alkenyl resorcinols are known to polymerise under oxygenated conditions even in an aqueous environment, it is not per se necessary that these microfossils are composed of a selectively preserved biopolymeric cell wall. It is also possible that G. prisca microfossils are composed of a cell wall or sheath component that polymerised during senescence or diagenesis of the organism.

  2. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Qian, Wen-Jian; Park, Jung-Eun; Grant, Robert

    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.

  4. Mechanism for stabilization of the molten globule state of papain by sodium n-alkyl sulfates: spectroscopic and calorimetric approaches.

    PubMed

    Chamani, J; Heshmati, M

    2008-06-01

    Papain exists in a molten globule (MG) state at pH 2 and in this state protein tends to aggregate in the presence of lower concentrations of guanidine hydrochloride (GuHCl). Such aggregation is prevented if low concentrations of sodium n-alkyl sulfates are also present in the buffer; in addition, stabilization of the protein is also induced. The guanidine hydrochloride and temperature-induced unfolding of papain, in the presence of n-alkyl sulfates, indicate stabilization of the protein as seen from the higher transition midpoints when monitored by fluorescence, circular dichroism, and differential scanning calorimetry. However, a similar phenomenon is not seen under neutral conditions in the presence of n-alkyl sulfate concentrations. The effect of n-alkyl sulfates on the structure of the MG state of papain was utilized to investigate the contribution of hydrophobic interaction to the stability of the MG state. The Td values of the MG states of papain in the presence of n-alkyl sulfates at different concentrations showed substantial variation. The enhancement of Td values at the stability criterion of MG states corresponded with increasing chain length of the cited n-alkyl sulfates. The present results suggest that the hydrophobic interactions play important roles in stabilizing and preventing the aggregation of the MG state of papain.

  5. Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

    PubMed Central

    Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Novák, Zoltán; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.

    2012-01-01

    α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursors: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. PMID:22083969

  6. ALKYL PYROPHOSPHATE METAL SOLVENT EXTRACTANTS AND PROCESS

    DOEpatents

    Long, R.L.

    1958-09-30

    A process is presented for the recovery of uranium from aqueous mineral acidic solutions by solvent extraction. The extractant is a synmmetrical dialkyl pyrophosphate in which the alkyl substituents have a chain length of from 4 to 17 carbon atoms. Mentioned as a preferred extractant is dioctyl pyrophosphate. The uranium is precipitated irom the organic extractant phase with an agent such as HF, fluoride salts. alcohol, or ammonia.

  7. Alkyl amine and vegetable oil mixture-a viable candidate for CO2 capture and utilization.

    PubMed

    Uma Maheswari, A; Palanivelu, K

    2017-02-01

    In this present work, the absorption of CO 2 in alkyl amines and vegetable oil mixture has been evaluated. The results showed that the absorption is higher in alkyl amines and vegetable oil mixture compared with the aqueous alkyl amines. In addition to that, by employing the greener and non-toxic vegetable oil media, the CO 2 gas has been captured as well as converted into value-added products, such as carbamates of ethylenediamine, diethylenetriamine, and triethylenetetramine. The carbamates have been isolated and characterized by Fourier transform infrared and 1 H and 13 C nuclear magnetic resonance spectroscopic techniques. The formation of these products in precipitate form has not been observed in the case of aqueous medium. Among the various alkyl amine and vegetable oil combinations, triethylenetetramine in coconut oil medium showed the maximum CO 2 capture capacity of 72%. The coconut oil used for the process has been recovered, recycled, and reused for 3 cycles. Thus, this novel scheme seems to be a better alternative to conquer the drawback of aqueous amine-based CO 2 capture as well as for the capture and utilization of the CO 2 gas to gain the value-added products.

  8. Long alkyl-chain imidazolium ionic liquids: Antibiofilm activity against phototrophic biofilms.

    PubMed

    Reddy, G Kiran Kumar; Nancharaiah, Y V; Venugopalan, V P

    2017-07-01

    Biofilm formation is problematic and hence undesirable in medical and industrial settings. In addition to bacteria, phototrophic organisms are an integral component of biofilms that develop on surfaces immersed in natural waters. 1-Alkyl-3-methyl imidazolium ionic liquids (IL) with varying alkyl chain length were evaluated for their influence on the formation of monospecies (Navicula sp.) and multispecies biofilms under phototrophic conditions. An IL with a long alkyl side chain, 1-hexadecyl-3-methylimidaazolium chloride ([C 16 (MIM)][Cl]) retarded growth, adhesion and biofilm formation of Navicula sp. at concentrations as low as 5μM. Interestingly, [C 16 (MIM)][Cl] was very effective in preventing multispecies phototrophic biofilms on fibre reinforced plastic surfaces immersed in natural waters (fresh and seawater). SYTOX ® Green staining and chlorophyll leakage assay confirmed that the biocidal activity of the IL was exerted through cell membrane disruption. The data show that [C 16 (MIM)][Cl] is a potent inhibitor of phototrophic biofilms at micromolar concentrations and a promising agent for biofilm control in re-circulating cooling water systems. This is the first report that ionic liquids inhibit biofilm formation by phototrophic organisms which are important members of biofilms in streams and cooling towers. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Quantitative Determination of Fluorinated Alkyl Substances by Large-Volume-Injection LC/MS/MS—Characterization of Municipal Wastewaters

    PubMed Central

    Schultz, Melissa M.; Barofsky, Douglas F.; Field, Jennifer A.

    2008-01-01

    A quantitative method was developed for the determination of fluorinated alkyl substances in municipal wastewater influents and effluents. The method consisted of centrifugation followed by large-volume injection (500 μL) of the supernatant onto a liquid chromatograph with a reverse-phase column and detection by electrospray ionization, and tandem mass spectrometry (LC/MS/MS). The fluorinated analytes studied include perfluoroalkyl sulfonates, fluorotelomer sulfonates, perfluorocarboxylates, and select fluorinated alkyl sulfonamides. Recoveries of the fluorinated analytes from wastewater treatment plant (WWTP) raw influents and final effluent ranged from 77% – 96% and 80% – 99%, respectively. The lower limit of quantitation ranged from 0.5 to 3.0 ng/L depending on the analyte. The method was applied to flow-proportional composites of raw influent and final effluent collected over a 24 hr period from ten WWTPs nationwide. Fluorinated alkyl substances were observed in wastewater at all treatment plants and each plant exhibited unique distributions of fluorinated alkyl substances despite similarities in treatment processes. In nine out of the ten plants sampled, at least one class of fluorinated alkyl substances exhibited increased concentrations in the effluent as compared to the influent concentrations. In some instances, decreases in certain fluorinated analyte concentrations were observed and attributed to sorption to sludge. PMID:16433363

  10. PAH phototoxicity: Identification of sensitive marine infaunal crustaceans and the effects of alkylation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Boese, B.; Swartz, R.; Lamberson, J.

    1995-12-31

    The toxicity of some polycyclic aromatic hydrocarbons (PAHs) has been shown to be greatly enhanced in the presence of UV light. The objectives of the research were to: (1) test for PAH phototoxicity using seven marine infaunal crustacean species, (2) determine if the sensitivity to PAH phototoxicity was related to their potential exposure to sunlight in nature, and (3) determine if alkylation alters PAH phototoxicity. The first objective was accomplished by exposing test species to fluoranthene in 4-day, water-only bioassays. Survivors of the tests were then exposed to UV light in an exposure chamber for one hour. The differences betweenmore » EC50s (the ability to bury in sediment) before and after UV exposure were used to access phototoxicity. The results indicated that species having the greatest potential for natural exposure to sunlight were the least sensitive UV-enhanced fluoranthene toxicity. The amphipod, Rhepoxynius abronius, which in nature has the least potential for exposure to sunlight among the organisms tested, was the most sensitive. Rhepoxynius abronius was subsequently used in a series of tests to determine if alkylation of PAHs alters phototoxicity. This was done by conducting standard 10-day sediment bioassay using alkylated and unalkylated PAHs. As in the water-only tests, EC{sub 50}s were determined before and after UV light exposures. The results indicated that alkylation of PAHs, in general, did not alter phototoxicity.« less

  11. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances §...

  12. Isolation of the antibiotic pseudopyronine B and SAR evaluation of C3/C6 alkyl analogs.

    PubMed

    Bouthillette, Leah M; Darcey, Catherine A; Handy, Tess E; Seaton, Sarah C; Wolfe, Amanda L

    2017-06-15

    Natural products are an abundant source of structurally diverse compounds with antibacterial activity that can be used to develop new and potent antibiotics. One such class of natural products is the pseudopyronines. Here we present the isolation of pseudopyronine B (2) from a Pseudomonas species found in garden soil in Western North Carolina, and SAR evaluation of C3 and C6 alkyl analogs of the natural product for antibacterial activity against Gram-positive and Gram-negative bacteria. We found a direct relationship between antibacterial activity and C3/C6 alkyl chain length. For inhibition of Gram-positive bacteria, alkyl chain lengths between 6 and 7 carbons were found to be the most active (IC 50 =0.04-3.8µg/mL) whereas short alkyl chain analogs showed modest activity against Gram-negative bacteria (IC 50 =223-304µg/mL). This demonstrates the potential for this class of natural products to be optimized for selective activity against either Gram-positive or Gram-negative bacteria. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Reevaluation of the effect of ellagic acid on N-methyl-N-nitrosourea DNA alkylation and mutagenicity

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lord, H.L.; Josephy, P.D.; Snieckus, V.A.

    N-Methyl-N-nitrosourea (MNU) is a reactive, mutagenic methylating agent. MNU methylates DNA at various sites, including guanine N{sup 7}, guanine O{sup 6}, and adenine N{sup 3}. Dixit and Gold ((1986) Proc. Natl, Acad. Sci. U.S.A. 83, 8039-8043) reported that ellagic acid, a phenolic natural product, inhibited the mutagenicity of MNU in Salmonella typhimurium strain TA 100, inhibited salmon sperm DNA alkylation by ({sup 3}H)MNU, and also greatly reduced the ratio of guanine O{sup 6} to guanine N{sup 7} alkylation. We have examined the MNU-induced alkylation of calf thymus DNA and evaluated the effect of ellagic acid on this binding. Ellagic acidmore » had only a slight effect on total alkylation and did not alter the ratio of methylation at guanine-O{sup 6} and -N{sup 7} positions. In further experiments, ellagic acid did not significantly inhibit MNU mutagenicity. These findings do not support the potential use of ellagic acid as an inhibitor of biological damage induced by nitrosoureas.« less

  14. Synthesis and evaluation of thermo-rheological behaviour and ionotropic crosslinking of new gellan gum-alkyl derivatives.

    PubMed

    Agnello, Stefano; Palumbo, Fabio Salvatore; Pitarresi, Giovanna; Fiorica, Calogero; Giammona, Gaetano

    2018-04-01

    This paper reports the synthesis and the physicochemical characterization of two series of gellan gum (GG) derivatives functionalized with alkyl chains with different number of carbon, from 8 to 18. In particular, low molecular weight gellan gum samples with 52.6 or 96.7 kDa, respectively, were functionalized with octylamine (C 8 ), dodecylamine (C 12 ) and octadecylamine (C 18 ) by using bis(4-nitrophenyl) carbonate (4-NPBC) as a coupling agent. Thermo-rheological and ionotropic crosslinking properties of these gellan gum-alkyl derivatives were evaluated and related to the degree of derivatization in alkyl chains. Results suggested as length and degree of derivatization differently influenced coil-to-helix gelation mechanism of GG derivatives, ionotropic crosslinking, and strength of crosslinked hydrogels obtained in CaCl 2 0.102 M and NaCl 0.15 M. Statement of hypothesis: The insertion of alkyl chains on the gellan gum backbone interferes with coil-to-helix transition mechanism and allows the production of hydrophobically assembled hydrogels. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Direct, enantioselective α-alkylation of aldehydes using simple olefins.

    PubMed

    Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

    2017-11-01

    Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

  16. Method for reactivating solid catalysts used in alkylation reactions

    DOEpatents

    Ginosar, Daniel M.; Thompson, David N.; Coates, Kyle; Zalewski, David J.; Fox, Robert V.

    2003-06-17

    A method for reactivating a solid alkylation catalyst is provided which can be performed within a reactor that contains the alkylation catalyst or outside the reactor. Effective catalyst reactivation is achieved whether the catalyst is completely deactivated or partially deactivated. A fluid reactivating agent is employed to dissolve catalyst fouling agents and also to react with such agents and carry away the reaction products. The deactivated catalyst is contacted with the fluid reactivating agent under pressure and temperature conditions such that the fluid reactivating agent is dense enough to effectively dissolve the fouling agents and any reaction products of the fouling agents and the reactivating agent. Useful pressures and temperatures for reactivation include near-critical, critical, and supercritical pressures and temperatures for the reactivating agent. The fluid reactivating agent can include, for example, a branched paraffin containing at least one tertiary carbon atom, or a compound that can be isomerized to a molecule containing at least one tertiary carbon atom.

  17. Direct, enantioselective α-alkylation of aldehydes using simple olefins

    NASA Astrophysics Data System (ADS)

    Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

    2017-11-01

    Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

  18. Sources and proxy potential of long chain alkyl diols in lacustrine environments

    NASA Astrophysics Data System (ADS)

    Rampen, Sebastiaan W.; Datema, Mariska; Rodrigo-Gámiz, Marta; Schouten, Stefan; Reichart, Gert-Jan; Sinninghe Damsté, Jaap S.

    2014-11-01

    Long chain 1,13- and 1,15-alkyl diols form the base of a number of recently proposed proxies used for climate reconstruction. However, the sources of these lipids and environmental controls on their distribution are still poorly constrained. We have analyzed the long chain alkyl diol (LCD) composition of cultures of ten eustigmatophyte species, with three species from different families grown at various temperatures, to identify the effect of species composition and growth temperature on the LCD distribution. The results were compared with the LCD distribution of sixty-two lake surface sediments, and with previously reported LCD distributions from marine environments. The different families within the Eustigmatophyceae show distinct LCD patterns, with the freshwater family Eustigmataceae most closely resembling LCD distributions in both marine and lake environments. Unlike the other two eustigmatophyte families analyzed (Monodopsidaceae and Goniochloridaceae), C28 and C30 1,13-alkyl diols and C30 and C32 1,15-alkyl diols are all relatively abundant in the family Eustigmataceae, while the mono-unsaturated C32 1,15-alkyl diol was below detection limit. In contrast to the marine environment, LCD distributions in lakes did not show a clear relationship with temperature. The Long chain Diol Index (LDI), a proxy previously proposed for sea surface temperature reconstruction, showed a relatively weak correlation (R2 = 0.33) with mean annual air temperature used as an approximation for annual mean surface temperature of the lakes. A much-improved correlation (R2 = 0.74, p-value <0.001) was observed applying a multiple linear regression analysis between LCD distributions and lake temperatures reconstructed using branched tetraether lipid distributions. The obtained regression model provides good estimates of temperatures for cultures of the family Eustigmataceae, suggesting that algae belonging to this family have an important role as a source for LCDs in lacustrine

  19. Inducible Alkylation of DNA by a Quinone Methide-Peptide Nucleic Acid Conjugate†

    PubMed Central

    Liu, Yang; Rokita, Steven E.

    2012-01-01

    The reversibility of alkylation by a quinone methide intermediate (QM) avoids the irreversible consumption that plagues most reagents based on covalent chemistry and allows for site specific reaction that is controlled by the thermodynamics rather than kinetics of target association. This characteristic was originally examined with an oligonucleotide QM conjugate but broad application depends on alternative derivatives that are compatible with a cellular environment. Now, a peptide nucleic acid (PNA) derivative has been constructed and shown to exhibit an equivalent ability to delivery the reactive QM in a controlled manner. This new conjugate demonstrates high selectivity for a complementary sequence of DNA even when challenged with an alternative sequence containing a single T/T mismatch. Alkylation of non-complementary sequences is only possible when a template strand is present to co-localize the conjugate and its target. For efficient alkylation in this example, a single-stranded region of the target is required adjacent to the QM conjugate. Most importantly, the intrastrand self adducts formed between the PNA and its attached QM remained active and reversible over more than eight days in aqueous solution prior to reaction with a chosen target added subsequently. PMID:22243337

  20. Environmental Impact of Alkyl Lead(IV) Derivatives: Perspective after Their Phase-out.

    PubMed

    Filella, Montserrat; Bonet, Josep

    2017-04-10

    The use of alkyl lead derivatives as antiknock agents in gasoline can be considered as one of the main pollution disasters of the 20th century because of both the global character of the pollution emitted and the seriousness of the impact on human health. Alkyl lead derivatives in themselves cannot be considered to be persistent pollutants because they readily degrade either before being released from the tailpipes or soon afterwards in the atmosphere. However, the inorganic lead they produced has been deposited in soils all over the planet, largely, but not exclusively in urban areas and along motorways, since the direct emission of lead into the atmosphere favored its dispersal over great distances: The signal of the massive use of alkyl lead derivatives has been found all over the world, including in remote sites such as polar areas. The short residence time of lead in the atmosphere implies that this compartment is highly responsive to changes in emissions. This was demonstrated when leaded gasoline was phased-out and is in striking contrast to the very long permanence of inorganic lead in soils, where resuspension is a permanent source of toxic lead.

  1. Simultaneous determination of the potential carcinogen 1,4-dioxane and malodorous alkyl-1,3-dioxanes and alkyl-1,3-dioxolanes in environmental waters by solid-phase extraction and gas chromatography tandem mass spectrometry.

    PubMed

    Carrera, Guillem; Vegué, Lídia; Boleda, Mª Rosa; Ventura, Francesc

    2017-03-03

    1,4-dioxane is a synthetic industrial solvent used in various industrial processes, and it is a probable human carcinogen whose presence in the aquatic environment is frequently reported. Alkyl-1,3-dioxanes and alkyl-1,3-dioxolanes are compounds that have been identified as causing several odor episodes in waters over the last years, with the result of downtime of drinking water treatment plants. According to published studies, some of these episodes may be caused either by resins synthesis processes, or by industrial residues added to dehydrated sludge in wastewater treatment plants (WWTPs) in order to increase biogas production efficiency. Analytical methods based on closed loop stripping analysis (CLSA) are routinely used when taste and odor events appear, but this technique has demonstrated to be unsuitable to determine 1,4-dioxane at trace levels. In this context, drinking water companies tend to focus on determining odorous compounds, but not on those compounds that are potentially harmful. The suitability of a SPE method and further analysis by GC/MS-MS to simultaneously determine 1,4-dioxane and alkyl-1,3-dioxanes and dioxolanes has been demonstrated. Recoveries in surface waters spiked at 25ng/L ranged from 76% to 105%, whereas method quantification limits (MQLs) varied from 0.7 to 26ng/L for dioxanes, and dioxolanes and 50ng/L for 1,4-dioxane. Uncertainties were evaluated at two different concentrations, 0.02μg/L and 0.4μg/L, with values of 25% for 1,4-dioxane, and of 16-28% for alkyl-1,3-dioxanes and alkyl-1,3-dioxolanes for the later. The methodology has been successfully applied to samples from the aquifer of the Llobregat River (NE. Spain). Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Catalytic Gas-Phase Production of Lactide from Renewable Alkyl Lactates.

    PubMed

    De Clercq, Rik; Dusselier, Michiel; Makshina, Ekaterina; Sels, Bert F

    2018-03-12

    A new route to lactide, which is a key building block of the bioplastic polylactic acid, is proposed involving a continuous catalytic gas-phase transesterification of renewable alkyl lactates in a scalable fixed-bed setup. Supported TiO 2 /SiO 2 catalysts are highly selective to lactide, with only minimal lactide racemization. The solvent-free process allows for easy product separation and recycling of unconverted alkyl lactates and recyclable lactyl intermediates. The catalytic activity of TiO 2 /SiO 2 catalysts was strongly correlated to their optical properties by DR UV/Vis spectroscopy. Catalysts with high band-gap energy of the supported TiO 2 phase, indicative of a high surface spreading of isolated Ti centers, show the highest turnover frequency per Ti site. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

    DOEpatents

    Ginosar, Daniel M.; Fox, Robert V.; Kong, Peter C.

    2000-01-01

    This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

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

    DTIC Science & Technology

    1992-01-01

    Later, Loveless isolated an 0 6 - methylated product from treatment with MNU and was the first to suggest a relevance of O6 alkylation 11 to the...replication. The ultimate metabolite involved in the alkylation reaction has generally been thought to be an alkyldiazonium ion or, its decomposition... Methylation of Formamide by the Methyldiazonium Ion .................... 60 Table 3.10: Intrinsic Barriers for Degenerate SN 2 Reactions .......... 66 Table

  5. A New Family of Ionic Liquids 1-amino-3-alkyl-1,2,3-Triazolium Nitrates

    NASA Technical Reports Server (NTRS)

    Drake, Greg; Kaplan, Greg; Hall, Leslie; Hawkins, Tommy; Larue, Joann

    2004-01-01

    A new class of ionic liquids based upon 1-amino-3-alkyl-1,2,3-triazolium nitrates (alkyl = methyl, ethyl, n-propyl, 2-propeny1, and n-butyl) have been synthesized and characterized by vibrational spectra, multinuclear NMR, elemental analysis, and DSC studies. A single crystal x-ray study was carried out for 1-amino-3-methyl-1,2,3-triazolium nitrate and the details will be presented.

  6. Perfluorinated Alkyl Compounds: Challenges To Develop Robust And Reliable Methods

    EPA Science Inventory

    An increasing number of studies have been conducted to investigate the environmental distribution of perfluorinated alkyl compounds (PFCs), some of which are known to be toxic in laboratory studies. Despite growing public concerns, environmental monitoring data are still limited...

  7. Alkyl Aryl Ether Bond Formation with PhenoFluor**

    PubMed Central

    Shen, Xiao; Neumann, Constanze N.; Kleinlein, Claudia; Claudia, Nathaniel W.; Ritter, Tobias

    2015-01-01

    An alkyl aryl ether bond formation reaction between phenols and primary and secondary alcohols with PhenoFluor has been developed. The reaction features a broad substrate scope and tolerates many functional groups, and substrates that are challenging for more conventional ether bond forming processes may be coupled. A preliminary mechanistic study indicates reactivity distinct from conventional ether bond formation. PMID:25800679

  8. Parallel and automated library synthesis of 2-long alkyl chain benzoazoles and azole[4,5-b]pyridines under microwave irradiation.

    PubMed

    Martínez-Palou, Rafael; Zepeda, L Gerardo; Höpfl, Herbert; Montoya, Ascensión; Guzmán-Lucero, Diego J; Guzmán, Javier

    2005-01-01

    A versatile route to 40-membered library of 2-long alkyl chain substituted benzoazoles (1 and 2) and azole[4,5-b]pyridines (3 and 4) via microwave-assisted combinatorial synthesis was developed. The reactions were carried out in both monomode and multimode microwave oven. With the latter, all reactions were performed in high-throughput experimental settings consisting of an 8 x 5 combinatorial library designed to synthesize 40 compounds. Each step, from the addition of reagents to the recovery of final products, was automated. The microwave-assisted N-long chain alkylation reactions of 2-alkyl-1H-benzimidazole (1) and 2-alkyl-1H-benzimidazole[4,5-b] pyridines (3) were also studied.

  9. Activated-Sludge Nitrification in the Presence of Linear and Branched-Chain Alkyl Benzene Sulfonates

    PubMed Central

    Baillod, Charles R.; Boyle, W. C.

    1968-01-01

    The effects of biodegradable linear alkyl benzene sulfonate and branched-chain alkyl benzene sulfonate detergents on activated-sludge nitrification were investigated by administering a synthetic waste containing up to 23 mg of each detergent per liter to eight bench-scale, batch, activated-sludge units. It was found that both detergents tended to promote complete oxidation of ammonia to nitrate, whereas control units produced approximately equal amounts of nitrite and nitrate. Various hypotheses are offered to explain the phenomenon. PMID:5636474

  10. Poly(alkyl methacrylate) Brush-Grafted Silica Nanoparticles as Oil Lubricant Additives: Effects of Alkyl Pendant Groups on Oil Dispersibility, Stability, and Lubrication Property

    DOE PAGES

    Seymour, Bryan T.; Wright, Roger A. E.; Parrott, Alexander C.; ...

    2017-07-03

    This paper reports on the synthesis of a series of poly(alkyl methacrylate) brush-grafted, 23 nm silica nanoparticles (hairy NPs) and the study of the effect of alkyl pendant length on their use as oil lubricant additives for friction and wear reduction. The hairy NPs were prepared by surface-initiated reversible addition–fragmentation chain transfer polymerization from trithiocarbonate chain transfer agent (CTA)-functionalized silica NPs in the presence of a free CTA. We found that hairy NPs with sufficiently long alkyl pendant groups (containing >8 carbon atoms, such as 12, 13, 16, and 18 in this study) could be readily dispersed in poly(alphaolefin) (PAO),more » forming clear, homogeneous dispersions, and exhibited excellent stability at low and high temperatures as revealed by visual inspection and dynamic light scattering studies. Whereas poly(n-hexyl methacrylate) hairy NPs cannot be dispersed in PAO under ambient conditions or at 80 °C, interestingly, poly(2-ethylhexyl methacrylate) hairy NPs can be dispersed in PAO at 80 °C but not at room temperature, with a reversible clear-to-cloudy transition observed upon cooling. High-contact-stress ball-on-flat reciprocating sliding tribological tests at 100 °C showed significant reductions in both the coefficient of friction (up to 38%) and wear volume (up to 90% for iron flat) for transparent, homogeneous dispersions of hairy NPs in PAO at a concentration of 1.0 wt % compared with neat PAO. Finally, the formation of a load-bearing tribofilm at the rubbing interface was confirmed using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy.« less

  11. Poly(alkyl methacrylate) Brush-Grafted Silica Nanoparticles as Oil Lubricant Additives: Effects of Alkyl Pendant Groups on Oil Dispersibility, Stability, and Lubrication Property

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Seymour, Bryan T.; Wright, Roger A. E.; Parrott, Alexander C.

    This paper reports on the synthesis of a series of poly(alkyl methacrylate) brush-grafted, 23 nm silica nanoparticles (hairy NPs) and the study of the effect of alkyl pendant length on their use as oil lubricant additives for friction and wear reduction. The hairy NPs were prepared by surface-initiated reversible addition–fragmentation chain transfer polymerization from trithiocarbonate chain transfer agent (CTA)-functionalized silica NPs in the presence of a free CTA. We found that hairy NPs with sufficiently long alkyl pendant groups (containing >8 carbon atoms, such as 12, 13, 16, and 18 in this study) could be readily dispersed in poly(alphaolefin) (PAO),more » forming clear, homogeneous dispersions, and exhibited excellent stability at low and high temperatures as revealed by visual inspection and dynamic light scattering studies. Whereas poly(n-hexyl methacrylate) hairy NPs cannot be dispersed in PAO under ambient conditions or at 80 °C, interestingly, poly(2-ethylhexyl methacrylate) hairy NPs can be dispersed in PAO at 80 °C but not at room temperature, with a reversible clear-to-cloudy transition observed upon cooling. High-contact-stress ball-on-flat reciprocating sliding tribological tests at 100 °C showed significant reductions in both the coefficient of friction (up to 38%) and wear volume (up to 90% for iron flat) for transparent, homogeneous dispersions of hairy NPs in PAO at a concentration of 1.0 wt % compared with neat PAO. Finally, the formation of a load-bearing tribofilm at the rubbing interface was confirmed using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy.« less

  12. A Green Alternative to Aluminum Chloride Alkylation of Xylene

    ERIC Educational Resources Information Center

    Sereda, Grigoriy A.; Rajpara, Vikul B.

    2007-01-01

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

  13. Pharmacology of dimethanesulfonate alkylating agents: busulfan and treosulfan.

    PubMed

    Galaup, Ariane; Paci, Angelo

    2013-03-01

    Among the dimethanesulfonates, busulfan, in combination with other alkylating agents or nucleoside analogues, is the cornerstone of high-dose chemotherapy. It is used, and followed hematopoietic stem cell transplantation, for the treatment of various hematologic malignancies and immunodeficiencies. Treosulfan, which is a hydrophilic analogue of busulfan, was the first dimethanesufonate registered for the treatment of ovarian cancer. Recently, treosulfan has been investigated for the treatment of hematologic malignancies in combination with the same second agents before hematopoietic stem cell transplantation. This work reviews the pharmacological data of these two dimethanesulfonates alkylating agents. Specifically, the article looks at their chemistry, metabolism, anticancer activity, and their pharmacokinetics and pharmacodynamics. Busulfan has been investigated widely for more than three decades leading to a large and precise handling of this agent with numerous studies on activity and pharmacokinetics and pharmacodynamics. In contrast, the behavior of treosulfan is still under investigation and not fully described. The complexity of treosulfan's metabolism and mechanism of action gives rise to the need of a deeper understanding of its pharmacological activity in a context of high-dose chemotherapy. Specifically, there is a great need to better understand its pharmacokinetics/pharmacodynamics relationship.

  14. Quantitative chemoproteomics for site-specific analysis of protein alkylation by 4-hydroxy-2-nonenal in cells.

    PubMed

    Yang, Jing; Tallman, Keri A; Porter, Ned A; Liebler, Daniel C

    2015-03-03

    Protein alkylation by 4-hydroxy-2-nonenal (HNE), an endogenous lipid derived electrophile, contributes to stress signaling and cellular toxicity. Although previous work has identified protein targets for HNE alkylation, the sequence specificity of alkylation and dynamics in a cellular context remain largely unexplored. We developed a new quantitative chemoproteomic platform, which uses isotopically tagged, photocleavable azido-biotin reagents to selectively capture and quantify the cellular targets labeled by the alkynyl analogue of HNE (aHNE). Our analyses site-specifically identified and quantified 398 aHNE protein alkylation events (386 cysteine sites and 12 histidine sites) in intact cells. This data set expands by at least an order of magnitude the number of such modification sites previously reported. Although adducts formed by Michael addition are thought to be largely irreversible, we found that most aHNE modifications are lost rapidly in situ. Moreover, aHNE adduct turnover occurs only in intact cells and loss rates are site-selective. This quantitative chemoproteomics platform provides a versatile general approach to map bioorthogonal-chemically engineered post-translational modifications and their cellular dynamics in a site-specific and unbiased manner.

  15. 40 CFR 721.625 - Alkylated diarylamine, sul-furized (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.625 Alkylated diarylamine, sul-furized (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically...

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

    PubMed

    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 < 0.001). No toxicity-related death was reported. The use of anti-cancer systemic therapy is safe and efficient in gastric MALT lymphoma. In this retrospective study, the combination of rituximab plus chlorambucil seems more efficient than rituximab or alkylating agents alone. Rituximab has a better safety profile than regimens containing alkylating agents. © 2014 John Wiley & Sons Ltd.

  17. Oncometabolite D-2-Hydroxyglutarate Inhibits ALKBH DNA Repair Enzymes and Sensitizes IDH Mutant Cells to Alkylating Agents.

    PubMed

    Wang, Pu; Wu, Jing; Ma, Shenghong; Zhang, Lei; Yao, Jun; Hoadley, Katherine A; Wilkerson, Matthew D; Perou, Charles M; Guan, Kun-Liang; Ye, Dan; Xiong, Yue

    2015-12-22

    Chemotherapy of a combination of DNA alkylating agents, procarbazine and lomustine (CCNU), and a microtubule poison, vincristine, offers a significant benefit to a subset of glioma patients. The benefit of this regimen, known as PCV, was recently linked to IDH mutation that occurs frequently in glioma and produces D-2-hydroxyglutarate (D-2-HG), a competitive inhibitor of α-ketoglutarate (α-KG). We report here that D-2-HG inhibits the α-KG-dependent alkB homolog (ALKBH) DNA repair enzymes. Cells expressing mutant IDH display reduced repair kinetics, accumulate more DNA damages, and are sensitized to alkylating agents. The observed sensitization to alkylating agents requires the catalytic activity of mutant IDH to produce D-2-HG and can be reversed by the deletion of mutant IDH allele or overexpression of ALKBH2 or AKLBH3. Our results suggest that impairment of DNA repair may contribute to tumorigenesis driven by IDH mutations and that alkylating agents may merit exploration for treating IDH-mutated cancer patients. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  18. Effect of alkyl glycerophosphate on the activation of peroxisome proliferator-activated receptor gamma and glucose uptake in C2C12 cells.

    PubMed

    Tsukahara, Tamotsu; Haniu, Hisao; Matsuda, Yoshikazu

    2013-04-12

    Studies on the effects of lipids on skeletal muscle cells rarely examine the effects of lysophospholipids. Through our recent studies, we identified select forms of phospholipids, such as alkyl-LPA, as ligands for the intracellular receptor peroxisome proliferator-activated receptor gamma (PPARγ). PPARγ is a nuclear hormone receptor implicated in many human diseases, including diabetes and obesity. We previously showed that alkyl-LPA is a specific agonist of PPARγ. However, the mechanism by which the alkyl-LPA-PPARγ axis affects skeletal muscle cells is poorly defined. Our objective in the present study was to determine whether alkyl-LPA and PPARγ activation promotes glucose uptake in skeletal muscle cells. Our findings indicate that PPARγ1 mRNA is more abundant than PPARγ2 mRNA in C2C12 cells. We showed that alkyl-LPA (3 μM) significantly activated PPARγ and increased intracellular glucose levels in skeletal muscle cells. We also showed that incubation of C2C12 cells with alkyl-LPA led to lipid accumulation in the cells. These findings suggest that alkyl-LPA activates PPARγ and stimulates glucose uptake in the absence of insulin in C2C12 cells. This may contribute to the plasma glucose-lowering effect in the treatment of insulin resistance. Copyright © 2013 Elsevier Inc. All rights reserved.

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

    PubMed

    Schärer, Orlando D

    2012-07-13

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

  20. Anti-biofilm action of nitric oxide-releasing alkyl-modified poly(amidoamine) dendrimers against Streptococcus mutans.

    PubMed

    Backlund, Christopher J; Worley, Brittany V; Schoenfisch, Mark H

    2016-01-01

    The effect of nitric oxide (NO)-releasing dendrimer hydrophobicity on Streptococcus mutans killing and biofilm disruption was examined at pH 7.4 and 6.4, the latter relevant to dental caries. Generation 1 (G1) poly(amidoamine) (PAMAM) dendrimers were modified with alkyl epoxides to generate propyl-, butyl-, hexyl-, octyl-, and dodecyl-functionalized dendrimers. The resulting secondary amines were reacted with NO to form N-diazeniumdiolate NO donor-modified dendrimer scaffolds (total NO ∼1μmol/mg). The bactericidal action of the NO-releasing dendrimers against both planktonic and biofilm-based S. mutans proved greatest with increasing alkyl chain length and at lower pH. Improved bactericidal efficacy at pH 6.4 was attributed to increased scaffold surface charge that enhanced dendrimer-bacteria association and ensuing membrane damage. For shorter alkyl chain (i.e., propyl and butyl) dendrimer modifications, increased antibacterial action at pH 6.4 was due to faster NO-release kinetics from proton-labile N-diazeniumdiolate NO donors. Octyl- and dodecyl-modified PAMAM dendrimers proved most effective for eradicating S. mutans biofilms with NO release mitigating dendrimer scaffold cytotoxicity. We report the antibacterial and anti-biofilm efficacy of dual-action nitric oxide (NO)-releasing dendrimers against S. mutans, an etiological agent in dental caries. This work was undertaken to enhance the anti-biofilm action of these scaffolds by employing various alkyl chain modifications. Furthermore, we evaluated the ability of NO to eradicate cariogenic biofilms. We found that at the lower pH associated with dental caries (pH ∼6.4), NO has a more pronounced antibacterial effect for alkyl modifications less capable of biofilm penetration and membrane disruption. Of greatest significance, we introduce dendrimers as a new macromolecular antibacterial agent against the cariogenic bacteria S. mutans. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All

  1. The effect of the cation alkyl chain branching on mutual solubilities with water and toxicities.

    PubMed

    Kurnia, Kiki A; Sintra, Tânia E; Neves, Catarina M S S; Shimizu, Karina; Canongia Lopes, José N; Gonçalves, Fernando; Ventura, Sónia P M; Freire, Mara G; Santos, Luís M N B F; Coutinho, João A P

    2014-10-07

    The design of ionic liquids has been focused on the cation-anion combinations but other more subtle approaches can be used. In this work the effect of the branching of the cation alkyl chain on the design of ionic liquids (ILs) is evaluated. The mutual solubilities with water and toxicities of a series of bis(trifluoromethylsulfonyl)-based ILs, combined with imidazolium, pyridinium, pyrrolidinium, and piperidinium cations with linear or branched alkyl chains, are reported. The mutual solubility measurements were carried out in the temperature range from (288.15 to 323.15) K. From the obtained experimental data, the thermodynamic properties of the solution (in the water-rich phase) were determined and discussed. The COnductor like Screening MOdel for Real Solvents (COSMO-RS) was used to predict the liquid-liquid equilibrium. Furthermore, molecular dynamic simulations were also carried out aiming to get a deeper understanding of these fluids at the molecular level. The results show that the increase in the number of atoms at the cation ring (from five to six) leads to a decrease in the mutual solubilities with water while increasing their toxicity, and as expected from the well-established relationship between toxicities and hydrophobicities of ILs. The branching of the alkyl chain was observed to decrease the water solubility in ILs, while increasing the ILs solubility in water. The inability of COSMO-RS to correctly predict the effect of branching alkyl chains toward water solubility on them was confirmed using molecular dynamic simulations to be due to the formation of nano-segregated structures of the ILs that are not taken into account by the COSMO-RS model. In addition, the impact of branched alkyl chains on the toxicity is shown to be not trivial and to depend on the aromatic nature of the ILs.

  2. Direct, enantioselective α-alkylation of aldehydes using simple olefins

    PubMed Central

    Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

    2017-01-01

    Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons. PMID:29064486

  3. Cyclic 3-alkyl pyridinium alkaloid monomers from a New Zealand Haliclona sp. marine sponge.

    PubMed

    Damodaran, Vidhiya; Ryan, Jason L; Keyzers, Robert A

    2013-10-25

    Bioassay and NMR approaches have been used to guide the isolation of one known and two new cyclic 3-alkyl pyridinium alkaloid (3-APA) monomers from the New Zealand marine sponge Haliclona sp. The new compounds, dehydrohaliclocyclins C (3) and F (4), are the first reported examples of cyclic 3-APA monomers with unsaturation in the alkyl chain. The known compound haliclocyclin C (2) was also isolated from a mixture with 4. The structures of compounds 2-4 were elucidated using NMR spectroscopy, mass spectrometry, and chemical degradation.

  4. The Scope of Direct Alkylation of Gold Surface with Solutions of C1-C4 n-Alkylstannanes.

    PubMed

    Kaletová, Eva; Kohutová, Anna; Hajduch, Jan; Kaleta, Jiří; Bastl, Zdeněk; Pospíšil, Lubomír; Stibor, Ivan; Magnera, Thomas F; Michl, Josef

    2015-09-23

    Treatment of cleaned gold surfaces with dilute tetrahydrofuran or chloroform solutions of tetraalkylstannanes (alkyl = methyl, ethyl, n-propyl, n-butyl) or di-n-butylmethylstannyl tosylate under ambient conditions causes a self-limited growth of disordered monolayers consisting of alkyls and tin oxide. Extensive use of deuterium labeling showed that the alkyls originate from the stannane and not from ambient impurities, and that trialkylstannyl groups are absent in the monolayers, contrary to previous proposals. Methyl groups attached to the Sn atom are not transferred to the surface. Ethyl groups are transferred slowly, and propyl and butyl rapidly. In all cases, tin oxide is codeposited in submonolayer amounts. The monolayers were characterized by ellipsometry, contact angle goniometry, polarization modulated IR reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy with ferrocyanide/ferricyanide, which revealed a very low charge-transfer resistance. The thermal stability of the monolayers and their resistance to solvents are comparable with those of an n-octadecanethiol monolayer. A preliminary examination of the kinetics of monolayer deposition from a THF solution of tetra-n-butylstannane revealed an approximately half-order dependence on the bulk solution concentration of the stannane, hinting that more than one alkyl can be transferred from a single stannane molecule. A detailed structure of the attachment of the alkyl groups is not known, and it is proposed that it involves direct single or multiple bonding of one or more C atoms to one or more Au atoms.

  5. Synthesis of prostaglandins by conjugate addition and alkylation of a directed enolate ion. 4,5-allenyl prostaglandins

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Patterson, J.W.

    1990-09-28

    Over the previous two decades many elegant syntheses of prostaglandins, which in more sophisticated forms, allow the stereospecific introduction of the various asymmetric carbons have been accomplished. However, among these approaches the cuprate addition/enolate alkylation of suitable cyclopentenone {sup 2} stands out because of brevity and convergence. The recent reports by Noyori{sup 3} and Corey{sup 4} and their colleagues have reduced to practice the conversion of 4-alkoxycyclopentenones to prostaglandin E{sub 2} (PGE{sub 2}) by conjugate addition of an organocopper derivative of the lower side chain followed by alkylation of the resulting carbanion with methyl 7-halohept-2-enoate. The subject of this papermore » is application of the Tardella tin enolate alkylation developed by Noyori to the synthesis of 4, 5-allenic prostaglandins, a pharmacologically important class of compounds. The authors results demonstrate that the tandem alkylation of an enone precursor with a cuprate reagent followed by alkylation of the corresponding tin enolate with bromide reagent is a viable synthetic method for 4,5-didehydro-PGE{sub 2}. Because the optically active forms of 1 and the vinyl iodide precursor of the PGE{sub 2} lower side chain have been employed to produce a single enantiomer of PGE{sub 2}, the extension of the methodology described here to the synthesis of single enantiomers of 4a awaits only the preparation of the separate enantiomers of allene 14.« less

  6. Cooperative alpha-helix formation of beta-lactoglobulin induced by sodium n-alkyl sulfates.

    PubMed

    Chamani, J; Moosavi-Movahedi, A A; Rajabi, O; Gharanfoli, M; Momen-Heravi, M; Hakimelahi, G H; Neamati-Baghsiah, A; Varasteh, A R

    2006-01-01

    It is generally assumed that folding intermediates contain partially formed native-like secondary structures. However, if we consider the fact that the conformational stability of the intermediate state is simpler than that of the native state, it would be expected that the secondary structures in a folding intermediate would not necessarily be similar to those of the native state. beta-Lactoglobulin is a predominantly beta-sheet protein, although it has a markedly high intrinsic preference for alpha-helical structure. The formation of non-native alpha-helical intermediate of beta-lactoglobulin was induced by n-alkyl sulfates including sodium octyl sulfate, SOS; sodium decyl sulfate, SDeS; sodium dodecyl sulfate, SDS; and sodium tetradecyl sulfate, STS at special condition. The effect of n-alkyl sulfates on the structure of native beta-lactoglobulin at pH 2 was utilized to investigate the contribution of hydrophobic interactions to the stability of non-native alpha-helical intermediate. The addition of various concentrations of n-alkyl sulfates to the native state of beta-lactoglobulin (pH 2) appears to support the stabilized form of non-native alpha-helical intermediate at pH 2. The m values of the intermediate state of beta-lactoglobulin by SOS, SDeS, SDS and STS showed substantial variation. The enhancement of m values as the stability criterion of non-native alpha-helical intermediate state corresponded with increasing chain length of the cited n-alkyl sulfates. The present results suggest that the folding reaction of beta-lactoglobulin follows a non-hierarchical mechanism and hydrophobic interactions play important roles in stabilizing the non-native alpha-helical intermediate state.

  7. 1,6-Conjugate addition of zinc alkyls to para-quinone methides in a continuous-flow microreactor.

    PubMed

    Jadhav, Abhijeet S; Anand, Ramasamy Vijaya

    2016-12-20

    An efficient method for the synthesis of alkyl diarylmethanes through the 1,6-conjugate addition of dialkylzinc reagents to para-quinone methides (p-QMs) has been developed under continuous flow conditions using a microreactor. This protocol allows to access unsymmetrical alkyl diarylmethanes in moderate to excellent yields using a wide range of p-QMs and dialkylzinc reagents. Interestingly, this transformation worked well without the requirement of a catalyst.

  8. Aerobic and anaerobic degradation of a range of alkyl sulfides by a denitrifying marine bacterium

    USGS Publications Warehouse

    Visscher, P.T.; Taylor, B.F.

    1993-01-01

    A pure culture of a bacterium was obtained from a marine microbial mat by using an anoxic medium containing dimethyl sulfide (DMS) and nitrate. The isolate grew aerobically or anaerobically as a denitrifier on alkyl sulfides, including DMS, dimethyl disulfide, diethyl sulfide (DES), ethyl methyl sulfide, dipropyl sulfide, dibutyl sulfide, and dibutyl disulfide. Cells grown on an alkyl sulfide or disulfide also oxidized the corresponding thiols, namely, methanethiol, ethanethiol, propanethiol, or butanethiol. Alkyl sulfides were metabolized by induced or derepressed cells with oxygen, nitrate, or nitrite as electron acceptor. Cells grown on DMS immediately metabolized DMS, but there was a lag before DES was consumed; with DES-grown cells, DES was immediately used but DMS was used only after a lag. Chloramphenicol prevented the eventual use of DES by DMS-grown cells and DMS use by DES-grown cells, respectively, indicating separate enzymes for the metabolism of methyl and ethyl groups. Growth was rapid on formate, acetate, propionate, and butyrate but slow on methanol. The organism also grew chemolithotrophically on thiosulfate with a decrease in pH; growth required carbonate in the medium. Growth on sulfide was also carbonate dependent but slow. The isolate was identified as a Thiobacillus sp. and designated strain ASN-1. It may have utility for removing alkyl sulfides, and also nitrate, nitrite, and sulfide, from wastewaters.

  9. Cobalt-catalyzed cross-coupling reactions of alkyl halides with allylic and benzylic Grignard reagents and their application to tandem radical cyclization/cross-coupling reactions.

    PubMed

    Ohmiya, Hirohisa; Tsuji, Takashi; Yorimitsu, Hideki; Oshima, Koichiro

    2004-11-05

    Details of cobalt-catalyzed cross-coupling reactions of alkyl halides with allylic Grignard reagents are disclosed. A combination of cobalt(II) chloride and 1,2-bis(diphenylphosphino)ethane (DPPE) or 1,3-bis(diphenylphosphino)propane (DPPP) is suitable as a precatalyst and allows secondary and tertiary alkyl halides--as well as primary ones--to be employed as coupling partners for allyl Grignard reagents. The reaction offers a facile synthesis of quaternary carbon centers, which has practically never been possible with palladium, nickel, and copper catalysts. Benzyl, methallyl, and crotyl Grignard reagents can all couple with alkyl halides. The benzylation definitely requires DPPE or DPPP as a ligand. The reaction mechanism should include the generation of an alkyl radical from the parent alkyl halide. The mechanism can be interpreted in terms of a tandem radical cyclization/cross-coupling reaction. In addition, serendipitous tandem radical cyclization/cyclopropanation/carbonyl allylation of 5-alkoxy-6-halo-4-oxa-1-hexene derivatives is also described. The intermediacy of a carbon-centered radical results in the loss of the original stereochemistry of the parent alkyl halides, creating the potential for asymmetric cross-coupling of racemic alkyl halides.

  10. Tris(thioimidazolyl)borate-zinc-thiolate complexes for the modeling of biological thiolate alkylations.

    PubMed

    Ibrahim, Mohamed M; Seebacher, Jan; Steinfeld, Gunther; Vahrenkamp, Heinrich

    2005-11-14

    The S3Zn-SR coordination of thiolate-alkylating enzymes such as the Ada DNA repair protein was reproduced in tris(thioimidazolyl)borate-zinc-thiolate complexes Tti(R)Zn-SR'. Four different Tti(R) ligands and nine different thiolates were employed, yielding a total of 12 new complexes. In addition, one Tti(R)Zn-SH complex and two thiolate-bridged [Tti(R)-SEt-Tti(R)]+ complexes were obtained. A selection of six thiolate complexes was converted with methyl iodide to the corresponding methyl thioethers and Tti(R)Zn-I. According to a kinetic analysis these reactions are second-order processes, which implies that the alkylations are likely to occur at the zinc-bound thiolates. They are much faster than the alkylations of zinc thiolates with N3 or N2S tripod ligands. The most reactive thiolate, Tti(Xyl)Zn-SEt, reacts slowly with trimethyl phosphate in a nonpolar medium at room temperature, yielding methyl-ethyl-thioether and Tti(Xyl)Zn-OPO(OMe)2 which can be converted back to the thiolate complex with NaSEt. This is the closest reproduction of the Ada repair process so far.

  11. MULTISPECTRAL IDENTIFICATION OF ALKYL AND CHLOROALKYL PHOSPHATES FROM AN INDUSTRIAL EFFLUENT

    EPA Science Inventory

    Multispectral techniques (gas chromatography combined with low and high resolution electron-impact mass spectrometry, low and high resolution chemical ionization mass spectrometry, and Fourier transform infrared mass spectroscopy) were used to identify 13 alkyl and chloralkyl pho...

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

    ERIC Educational Resources Information Center

    Cruz-Ramirez de Arellano, Daniel

    2013-01-01

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

  13. Interfacial assignment of branched-alkyl benzene sulfonates: A molecular simulation

    NASA Astrophysics Data System (ADS)

    Liu, Zi-Yu; Wei, Ning; Wang, Ce; Zhou, He; Zhang, Lei; Liao, Qi; Zhang, Lu

    2015-11-01

    A molecular dynamics simulation was conducted to analyze orientations of sodium branched-alkyl benzene sulfonates molecules at nonane/water interface, which is helpful to design optimal surfactant structures to achieve ultralow interfacial tension (IFT). Through the two dimensional density profiles, monolayer collapses are found when surfactant concentration continues to increase. Thus the precise scope of monolayer is certain and orientation can be analyzed. Based on the simulated results, we verdict the interfacial assignment of branched-alkyl benzene sulfonates at the oil-water interface, and discuss the effect of hydrophobic tail structure on surfactant assignment. Bigger hydrophobic size can slow the change rate of surfactant occupied area as steric hindrance, and surfactant meta hydrophobic tails have a stronger tendency to stretch to the oil phase below the collapsed concentration. Furthermore, an interfacial model with reference to collapse, increasing steric hindrance and charge repulsive force between interfacial surfactant molecules, responsible for effecting of surfactant concentration and structure has been supposed.

  14. Asymmetric Benzylic Allylic Alkylation Reaction of 3-Furfural Derivatives by Dearomatizative Dienamine Activation.

    PubMed

    He, Xiao-Long; Zhao, Hui-Ru; Duan, Chuan-Qi; Han, Xu; Du, Wei; Chen, Ying-Chun

    2018-04-20

    The dearomatizative dienamine-type ortho-quinodimethane species are smoothly generated between 2-alkyl-3-furfurals and chiral secondary amine catalysts, which undergo asymmetric benzylic allylic alkylation reactions with 2-nitroallylic acetates efficiently. A spectrum of densely functionalized 3-furfural derivatives are delivered in moderate to high yields with good to excellent diastereo- and enantioselectivity (up to 98 % yield, >19:1 d.r., >99 % ee). The latent transformations allow the facile production of some enantioenriched architectures, such as 1,1,2,2-tetraarylethanes and triarylmethanes, which are not easily available from other protocols. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Simple introduction of carboxyl head group with alkyl spacer onto multiwalled carbon nanotubes by solution plasma process

    NASA Astrophysics Data System (ADS)

    Nemoto, Shimpei; Ueno, Tomonaga; Watthanaphanit, Anyarat; Hieda, Junko; Bratescu, Maria Antoaneta; Saito, Nagahiro

    2017-09-01

    A simple method of fabricating carboxyl-terminated multiwalled carbon nanotubes (MWCNTs) with alkyl spacers was developed to improve the dispersion quality of MWCNTs in aqueous solutions using solution plasma (SP) in a 6-aminocaproic acid solution. The formation of SP in the solution led to better dispersion of MWCNTs in aqueous solutions. Fourier transform infrared spectroscopy (FT-IR) results indicate that a carboxyl group with an alkyl spacer can be introduced by SP treatment in the 6-aminocaproic acid solution. Sedimentation tests show that the SP-treated MWCNTs in the 6-aminocaproic acid solution retained their good dispersion quality in aqueous solutions of pHs 5, 6, and 9. The alkyl spacer plays an important role in the preservation of dispersion states particularly at pH 6.

  16. Profiling the nucleobase and structure selectivity of anticancer drugs and other DNA alkylating agents by RNA sequencing.

    PubMed

    Gillingham, Dennis; Sauter, Basilius

    2018-05-06

    Drugs that covalently modify DNA are components of most chemotherapy regimens, often serving as first-line treatments. Classically the chemical reactivity of DNA alkylators has been determined in vitro with short oligonucleotides. Here we use next generation RNA sequencing to report on the chemoselectivity of alkylating agents. We develop the method with the well-known clinically used DNA modifiying drugs streptozotocin and temozolomide, and then apply the technique to profile RNA modification with uncharacterized alkylation reactions such as with powerful electrophiles like trimethylsilyldiazomethane. The multiplexed and massively parallel format of NGS offers analyses of chemical reactivity in nucleic acids to be accomplished in less time with greater statistical power. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. A mild hand cleanser, alkyl ether sulphate supplemented with alkyl ether carboxylic acid and alkyl glucoside, improves eczema on the hand and prevents the growth of Staphylococcus aureus on the skin surface.

    PubMed

    Fukui, S; Morikawa, T; Hirahara, M; Terada, Y; Shimizu, M; Takeuchi, K; Takagi, Y

    2016-12-01

    Washing the hands using cleansers with antiseptic materials is the most popular method for hand hygiene and helps maintain health by preventing food poisoning and bacterial infections. However, repeated hand washing tends to induce eczema of the hand, such as dryness, cracking and erythema. Moreover, eczema on the hand leads to increased levels in Staphylococcus aureus (S. aureus) on the skin surface in contrast to expectations. Thus, mild hand cleansers which induce less eczema even with repeated washings are desired. Here, we evaluated the efficacy of a hand cleanser formulated with alkyl ether sulphate (AES), alkyl ether carboxylic acid (AEC) and alkyl glucoside (AG) that contains isopropyl methylphenol (IPMP) on skin symptoms and S. aureus levels. Eczema of the hand and the presence of S. aureus on the skin surface were analysed prior to and following 4 weeks of usage of the hand cleanser. A soap-based hand cleanser with IPMP was used as a reference cleanser. Eczema and cutaneous conditions were evaluated by visual grading, transepidermal water loss (TEWL), stratum corneum moisture-retention ability (MRA) and skin surface pH. The repeated use of the soap-based hand cleanser significantly worsened the hand dryness, scaling and cracks on the tips of the fingers and significantly increased the TEWL and decreased the MRA. In contrast, usage of the test cleanser only induced a significant increase in skin dryness but did not induce skin scaling or cracking and did not increase TEWL or decrease the MRA. Corresponding to these changes in skin symptoms, the presence of S. aureus increased the following use of the reference cleanser but not the test cleanser. There was no significant difference in skin surface pH between the two cleansers. Moreover, the increase in S. aureus was significantly correlated to the worsening of skin dryness and scaling. These results suggest that not only antimicrobial activity but also the mildness, which minimizes cutaneous effects

  18. Rapid screening of fatty acid alkyl esters in olive oils by time domain reflectometry.

    PubMed

    Berardinelli, Annachiara; Ragni, Luigi; Bendini, Alessandra; Valli, Enrico; Conte, Lanfranco; Guarnieri, Adriano; Toschi, Tullia Gallina

    2013-11-20

    The main aim of the present research is to assess the possibility of quickly screening fatty acid alkyl esters (FAAE) in olive oils using time domain reflectometry (TDR) and partial least-squares (PLS) multivariate statistical analysis. Eighteen virgin olive oil samples with fatty acid alkyl ester contents and fatty acid ethyl ester/methyl ester ratios (FAEE/FAME) ranging from 3 to 100 mg kg(-1) and from 0.3 to 2.6, respectively, were submitted to tests with time domain resolution of 1 ps. The results obtained in test set validation demonstrated that this new and fast analytical approach is able to predict FAME, FAEE, and FAME + FAEE contents with R(2) values of 0.905, 0.923, and 0.927, respectively. Further measurements on mixtures between olive oil and FAAE standards confirmed that the prediction is based on a direct influence of fatty acid alkyl esters on the TDR signal. The suggested technique appeared potentially suitable for monitoring one of the most important quality attribute of the olive oil in the extraction process.

  19. 40 CFR 721.10556 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. 721.10556 Section 721.10556 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. (a) Chemical substance...

  20. 40 CFR 721.10556 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. 721.10556 Section 721.10556 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. (a) Chemical substance...

  1. 40 CFR 721.10558 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. 721.10558 Section 721.10558 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. (a) Chemical substance...

  2. 40 CFR 721.10557 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. 721.10557 Section 721.10557 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. (a) Chemical substance...

  3. 40 CFR 721.10558 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. 721.10558 Section 721.10558 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. (a) Chemical substance...

  4. 40 CFR 721.10557 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. 721.10557 Section 721.10557 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. (a) Chemical substance...

  5. Protic ammonium carboxylate ionic liquids: insight into structure, dynamics and thermophysical properties by alkyl group functionalization.

    PubMed

    Reddy, Th Dhileep N; Mallik, Bhabani S

    2017-04-19

    This study is aimed at characterising the structure, dynamics and thermophysical properties of five alkylammonium carboxylate ionic liquids (ILs) from classical molecular dynamics simulations. The structural features of these ILs were characterised by calculating the site-site radial distribution functions, g(r), spatial distribution functions and structure factors. The structural properties demonstrate that ILs show greater interaction between cations and anions when alkyl chain length increases on the cation or anion. In all ILs, spatial distribution functions show that the anion is close to the acidic hydrogen atoms of the ammonium cation. We determined the role of alkyl group functionalization of the charged entities, cations and anions, in the dynamical behavior and the transport coefficients of this family of ionic liquids. The dynamics of ILs are described by studying the mean square displacement (MSD) of the centres of mass of the ions, diffusion coefficients, ionic conductivities and hydrogen bonds as well as residence dynamics. The diffusion coefficients and ionic conductivity decrease with an increase in the size of the cation or anion. The effect of alkyl chain length on ionic conductivity calculated in this article is consistent with the findings of other experimental studies. Hydrogen bond lifetimes and residence times along with structure factors were also calculated, and are related to alkyl chain length.

  6. Influence of alkyl chain length compatibility on microemulsion structure and solubilization

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bansal, V.K.; O'Connell, J.P.; Shah, D.O.

    1980-06-01

    The water solubilization capacity of water/oil microemulsions is studied as a function of alkyl chain length of oil (C/sub 8/ to C/sub 16/), surfactant (C/sub 14/ and C/sub 18/ fatty acid soaps), and alcohol (C/sub 4/ to C/sub 7/). Sodium stearate and sodium myristate were used as surfactants. For n-butanol microemulsions the maximum amount of water solubilized in the microemulsion decreased continuously with increasing oil chain length; for n-heptanol it increased continuously. For n-pentanol and n-hexanol systems, water solubilization reached a maximum when the oil chain length plus alcohol chain length was equal to that of the surfactant. The electricmore » resistance and dielectric constant of the microemulsions also are measured as a function of alkyl chain length of the oil. 48 references.« less

  7. Formation of 2-alkyl-(2H)-thiapyrans and 2-alkylthiophenes in cooked beef and lamb.

    PubMed

    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.

  8. Reduction and alkylation of peanut allergen isoforms Ara h 2 and Ara h 6; characterization of intermediate- and end products.

    PubMed

    Apostolovic, Danijela; Luykx, Dion; Warmenhoven, Hans; Verbart, Dennis; Stanic-Vucinic, Dragana; de Jong, Govardus A H; Velickovic, Tanja Cirkovic; Koppelman, Stef J

    2013-12-01

    Conglutins, the major peanut allergens, Ara h 2 and Ara h 6, are highly structured proteins stabilized by multiple disulfide bridges and are stable towards heat-denaturation and digestion. We sought a way to reduce their potent allergenicity in view of the development of immunotherapy for peanut allergy. Isoforms of conglutin were purified, reduced with dithiothreitol and subsequently alkylated with iodoacetamide. The effect of this modification was assessed on protein folding and IgE-binding. We found that all disulfide bridges were reduced and alkylated. As a result, the secondary structure lost α-helix and gained some β-structure content, and the tertiary structure stability was reduced. On a functional level, the modification led to a strongly decreased IgE-binding. Using conditions for limited reduction and alkylation, partially reduced and alkylated proteins were found with rearranged disulfide bridges and, in some cases, intermolecular cross-links were found. Peptide mass finger printing was applied to control progress of the modification reaction and to map novel disulfide bonds. There was no preference for the order in which disulfides were reduced, and disulfide rearrangement occurred in a non-specific way. Only minor differences in kinetics of reduction and alkylation were found between the different conglutin isoforms. We conclude that the peanut conglutins Ara h 2 and Ara h 6 can be chemically modified by reduction and alkylation, such that they substantially unfold and that their allergenic potency decreases. © 2013.

  9. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.

    1989-07-18

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

  10. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1994-01-01

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

  11. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.

    1989-01-01

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

  12. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1994-06-14

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

  13. Microbial biodegradation of aromatic alkanoic naphthenic acids is affected by the degree of alkyl side chain branching

    PubMed Central

    Johnson, Richard J; Smith, Ben E; Sutton, Paul A; McGenity, Terry J; Rowland, Steven J; Whitby, Corinne

    2011-01-01

    Naphthenic acids (NAs) occur naturally in oil sands and enter the environment through natural and anthropogenic processes. NAs comprise toxic carboxylic acids that are difficult to degrade. Information on NA biodegradation mechanisms is limited, and there are no studies on alkyl branched aromatic alkanoic acid biodegradation, despite their contribution to NA toxicity and recalcitrance. Increased alkyl side chain branching has been proposed to explain NA recalcitrance. Using soil enrichments, we examined the biodegradation of four aromatic alkanoic acid isomers that differed in alkyl side chain branching: (4′-n-butylphenyl)-4-butanoic acid (n-BPBA, least branched); (4′-iso-butylphenyl)-4-butanoic acid (iso-BPBA); (4′-sec-butylphenyl)-4-butanoic acid (sec-BPBA) and (4′-tert-butylphenyl)-4-butanoic acid (tert-BPBA, most branched). n-BPBA was completely metabolized within 49 days. Mass spectral analysis confirmed that the more branched isomers iso-, sec- and tert-BPBA were transformed to their butylphenylethanoic acid (BPEA) counterparts at 14 days. The BPEA metabolites were generally less toxic than BPBAs as determined by Microtox assay. n-BPEA was further transformed to a diacid, showing that carboxylation of the alkyl side chain occurred. In each case, biodegradation of the carboxyl side chain proceeded through beta-oxidation, which depended on the degree of alkyl side chain branching, and a BPBA degradation pathway is proposed. Comparison of 16S rRNA gene sequences at days 0 and 49 showed an increase and high abundance at day 49 of Pseudomonas (sec-BPBA), Burkholderia (n-, iso-, tert-BPBA) and Sphingomonas (n-, sec-BPBA). PMID:20962873

  14. AN INTERLABORATORY STUDY OF PERFLUORINATED ALKYL COMPOUND LEVELS IN HUMAN PLASMA

    EPA Science Inventory

    The present study was designed to investigate intra- and interlaboratory variability in results from six laboratories experienced in the analysis of perfluorinated alkyl compounds in blood matrices and that use stringent procedures to control and assure accuracy and precision. Ea...

  15. Versatile Alkylation of (Hetero)Aryl Iodides with Ketones via β-C(sp3)-H Activation.

    PubMed

    Zhu, Ru-Yi; Liu, Luo-Yan; Park, Han Seul; Hong, Kai; Wu, Yongwei; Senanayake, Chris H; Yu, Jin-Quan

    2017-11-15

    We report Pd(II)-catalyzed β-C(sp 3 )-H (hetero)arylation of a variety of ketones using a commercially available 2,2-dimethyl aminooxyacetic acid auxiliary. Facile installation and removal of the auxiliary as well as its superior scope for both ketones and (hetero)aryl iodides overcome the significant limitations of the previously reported β-C(sp 3 )-H arylation of ketones. The ready availability of ketones renders this reaction a broadly useful method for alkyl-(hetero)aryl coupling involving both primary and secondary alkyls.

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

    PubMed

    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.

  17. A detachable ester bond enables perfect Z-alkylations of olefins for the synthesis of tri- and tetrasubstituted alkenes.

    PubMed

    Nishikata, Takashi; Nakamura, Kimiaki; Inoue, Yuki; Ishikawa, Shingo

    2015-06-25

    2-Vinyl-substituted phenol and an alpha-bromoester undergo a tandem esterification-alkylation reaction in the presence of a Cu-amine catalyst system to produce benzene-fused lactone. Z-Alkylated styrene is obtained after hydrolysis of the lactone with perfect selectivity. The simple protocol developed in this work opens a new avenue in the multi-substitution chemistry of alkenes.

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

    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

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

    PubMed

    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

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

    PubMed

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

    2014-12-19

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