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Methylation Reaction (methylation + reaction)
Selected AbstractsActivation barriers for DNA alkylation by carcinogenic methane diazonium ionsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 3 2006Kaushalya S. Ekanayake Abstract Methylation reactions of the DNA bases with the methane diazonium ion, which is the reactive intermediate formed from several carcinogenic methylating agents, were examined. The SN2 transition states of the methylation reactions at N7, N3, and O6 of guanine; N7, N3, and N1 of adenine; N3 and O2 of cytosine; and O2 and O4 of thymine were calculated using the B3LYP density functional method. Solvation effects were examined using the conductor-like polarizable continuum method and the combined discrete/SCRF method. The transition states for reactions at guanine N3, adenine N7, and adenine N1 are influenced by steric interactions between the methane diazonium ion and exocyclic amino groups. Both in the gas phase and in aqueous solution, the methylation reactions at N atoms have transition states that are looser, and generally occur earlier along the reaction pathways than reactions at O atoms. The forming bonds in the transition states in water are 0.03 to 0.13 Å shorter than those observed in the gas phase, and the activation energies are 13 to 35 kcal/mol higher. The combined discrete/SCRF solvation energy calculations using base-water complexes with three water molecules yield base solvation energies that are larger than those obtained from the CPCM continuum method, especially for cytosine. Reactivities calculated using barriers obtained with the discrete/SCRF method are consistent with the experimentally observed high reactivity at N7 of guanine. © 2005 Wiley Periodicals, Inc. J Comput Chem 27: 277,286, 2006 [source] The Effect of Confined Space on the Growth of Naphthalenic Species in a Chabazite-Type Catalyst: A Molecular Modeling StudyCHEMCATCHEM, Issue 3 2009Karen Hemelsoet Dr. Abstract Methylation reactions of naphthalenic species over the acidic microporous zeolite with chabazite topology have been investigated by means of two-layered ab,initio computations. Large cluster results combined with van,der Waals contributions provide thermodynamic and kinetic results of successive methylation steps. The growth of fused bicyclic species is important as these can act as hydrocarbon pool species within the methanol-to-olefin (MTO) process, but ultimately leads to the deactivation of the catalyst. The influence of the confined space of the zeolite pore on the resulting transition state or product shape selectivity is investigated in detail. [source] Facile Cleavage of Si,C Bonds during the Sol-Gel Hydrolysis of Aminomethyltrialkoxysilanes , A New Method for the Methylation of Primary AminesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 12 2004Augustin Adima Abstract The reaction of chloromethyltriethoxysilane with (1R,2R)-bis(methylamino)cyclohexane (1) afforded the corresponding bis-silylated compound 2. The sol-gel hydrolysis of 2 did not give the expected bridged silsesquioxane owing to quantitative Si,C-bond cleavage. Instead, silica and (1R,2R)-bis(dimethylamino)cyclohexane (3) were obtained. This reaction was exploited to propose a new route for the methylation of amines. Such methylation reaction of amines could be extended to other amines and provides a new method for the selective monomethylation of primary amines. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Fully automated high yield synthesis of (R)- and (S)-[11C]verapamil for measuring P-glycoprotein function with positron emission tomographyJOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 14 2002Gert Luurtsema Abstract Racemic (±) verapamil is a well characterized substrate for P-glycoprotein (P-gp). However, the in vivo pharmacokinetics and pharmacodynamics of both enantiomers are reported to be different. In the preparation of evaluation studies of both enantiomers in animals and humans, the purpose of the present study was to optimize and automate the synthesis of (R)- and (S)-[11C]verapamil. (R)- and (S)-[11C]verapamil were prepared from (R)- and (S)-desmethyl-verapamil, respectively, by methylation with no-carrier added [11C]methyliodide or [11C]methyltriflate. Different conditions of the methylation reaction were studied: reaction time, temperature, base and solvent, and chemical form of the precursor using either the hydrochloric acid salt or the free base of the starting material. After optimization, the synthesis was fully automated using home-made modules and performed according to GMP guidelines. Optimal yields of 60,70% for the methylation reaction were obtained using 1.5 mg of the free base of (R)- or (S)-desmethyl-verapamil in 0.5 ml of acetonitrile at 50°C for 5 min with [11C]methyltriflate as methylating agent. Under the same reaction conditions, but with a reaction temperature of 100°C, the radiochemical yield starting with [11C]methyliodide as methylation reagent was 40%. The specific activity of (R)- and (S)-[11C]verapamil was >20 GBq/,mol and the radiochemical purity was >99% for both methods. The total synthesis time was 45 min. The automated high yield synthesis of (R)- and (S)-[11C]verapamil provides the means for evaluating both enantiomers as in vivo tracers of P-gp function. Copyright © 2002 John Wiley & Sons, Ltd. [source] Methylation of acidic moieties in poly(methyl methacrylate-co-methacrylic acid) copolymers for end-group characterization by tandem mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 14 2010Rémi Giordanengo The complete structural characterization of a copolymer composed of methacrylic acid (MAA) and methyl methacrylate (MMA) units was achieved using tandem mass spectrometry. In a first step, collision-induced dissociation (CID) of sodiated MAA-MMA co-oligomers allowed us to determine the co-monomeric composition, the random nature of the copolymer and the sum of the end-group masses. However, dissociation reactions of MAA-based molecules mainly involve the acidic pendant groups, precluding individual characterization of the end groups. Therefore, methylation of all the acrylic acid moieties was performed to transform the MAA-MMA copolymer into a PMMA homopolymer, for which CID mainly proceeds via backbone cleavages. Using trimethylsilyldiazomethane as a derivatization agent, this methylation reaction was shown to be complete without affecting the end groups. Using fragmentation rules established for PMMA polymers together with accurate mass measurements of the product ions and knowledge of reagents used for the studied copolymer synthesis, a structure could be proposed for both end groups and it was found to be consistent with signals obtained in nuclear magnetic resonance spectra. Copyright © 2010 John Wiley & Sons, Ltd. [source] In vacuo isotope coded alkylation technique (IVICAT); an N-terminal stable isotopic label for quantitative liquid chromatography/mass spectrometry proteomics,RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 16 2006Brigitte L. Simons We present a new isotopic labeling strategy to modify the N-terminal amino group of peptides in a quantifiable reaction without the use of expensive reagents or solvents. The In Vacuo Isotope Coded Alkylation Technique (IVICAT) is a methylation reaction, carried out at low pressure (<100,mTorr), that results in a stable quaternary trimethylammonium group, thus adding a permanent positive charge at the N-terminus of peptides without modifying the , -amino groups of lysine. The methylation reaction increases the signal intensity of modified peptides in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and liquid chromatography (LC)/MS and the isotopic peak pair differs by 9 mass units which can be easily resolved by either instrument. N-terminally trimethylated peptides exhibit collision-induced dissociation (CID) mass spectra that differ from their unmodified analogues by an enhanced b -ion series in MS2 spectra due to the fixed positive charge. Using LC/MS/MS with an LTQ mass analyzer for quantification, the experimentally determined ratios of H9 - to D9 -trimethyl-labeled peptides of , -casein provided accurate estimates of the actual ratios with low % error. IVICAT labeling also accurately quantified proteins in rat kidney inner medullary collecting duct cell types, as judged by comparison with relative quantification by subsequent immunoblotting experiments. IVICAT labeling, when used in conjunction with the new proteomics software QUIL, can accurately report relative protein abundances and increase the sequence coverage of proteins of tissue proteomes. Published in 2006 by John Wiley & Sons, Ltd. [source] Methylation of tin(II) by methyl iodide: influences of different environmental factors on the efficiency and reaction kineticsAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 3 2006Chen Baowei Abstract The methylation reaction of Sn(II) with methyl iodide (MeI) in water has been studied using sensitive GC-QSIL-FPD technology. The pH value, amount of MeI and salinity (S) are the three important factors that influence the methylation reaction in an aquatic environment. In all experiments, monomethyltin (MMT) is the only methylation product of the tin(II) reacting with MeI observed. At the 95% confidence level, the pH, MeI and S are significant for the MMT yield. The concentration of MMT in the reactor increases with increase in pH within the selected pH range of 4,9 because four different species of Sn(II),Sn2+, SnOH+, Sn(OH)20 and Sn(OH)3,,have different reaction activities with MeI. The methylation activity of Sn(II) was found to be highest at a salinity of 0.1 M at three different pH levels: 5, 7 and 9. Higher concentration of Cl, (as a relatively weak nucleophilic ion) will obstruct nucleophilic attack of Sn(II) on MeI. MMT production also increases with rising volume of MeI. Moreover, first-order reaction rates have been calculated at different pH, salinity and MeI, and found to be in the range 0.0018,0.0199 h,1. The reaction rate also varies largely under different reaction conditions. One probable mechanism for the methylation reaction of Sn(II) with MeI is a SN2 nucleophilic attack on the methyl group of MeI by Sn(II), via a process of oxidative methyl-transfer. Copyright © 2006 John Wiley & Sons, Ltd. [source] Heterologous expression of the biosynthetic gene clusters of coumermycin A1, clorobiocin and caprazamycins in genetically modified Streptomyces coelicolor strainsBIOPOLYMERS, Issue 9 2010Katrin Flinspach Abstract The biosynthetic gene clusters of the aminocoumarin antibiotics clorobiocin and coumermycin A1 and of the liponucleoside antibiotic caprazamycin were stably integrated into the genomes of different host strains derived from Streptomyces coelicolor A3(2). For the heterologous expression of clorobiocin derivatives in a chemically defined medium, inclusion of 0.6% of the siloxylated ethylene oxide/propylene oxide copolymer Q2-5247 into the growth medium proved to result in a 4.8-fold increase of productivity. Presumably, this copolymer acts as an oxygen carrier. The additional inclusion of cobalt chloride (0.2,2 mg l,1) dramatically increased the percentage of the desired compound clorobiocin within the total produced clorobiocin derivatives. This is very likely due to a stimulation of a cobalamin-dependent methylation reaction catalyzed by the enzyme CloN6 of clorobiocin biosynthesis. All three investigated host strains (S. coelicolor M512, M1146 and M1154) gave similar production rates of total clorobiocin derivatives (on average, 158 mg l,1 in the presence of 0.6% Q2-5247 and 0.2 mg l,1 CoCl2). In contrast, heterologous production of caprazamycin derivatives was optimal in strain M1154 (amounts of 152 mg l,1 on average). © 2010 Wiley Periodicals, Inc. Biopolymers 93: 823,832, 2010. [source] A-ring ortho -specific monohydroxylation of daidzein by cytochrome P450s of Nocardia farcinica IFM10152BIOTECHNOLOGY JOURNAL, Issue 11 2009Kwon-Young Choi Abstract The bioconversion of the isoflavonoid daidzein using whole cell Nocardia farcinica IFM10152 showed two kinds of major metabolic modifications, i.e. mono-hydroxylation and subsequent O -methylation. The major hydroxylated products of daidzein prior to the O -methylation reaction were 3',4',7-trihydroxyisoflavone (3'-ODI), 4',6,7-trihydroxyisoflavone (6-ODI) and 4',7,8-trihydroxyisoflavone (8-ODI), which are mono-hydroxylated at the ortho position of each hydroxyl group of daidzein. To identify monooxygenases playing a key role in the monohydroxylation of the A-ring of daidzein, all genes of 27 cytochrome P450s from N. farcinica IFM10152 were cloned and transformed into a E. coli BL21 (DE3) host system. By this enzymatic reaction using the mutants and the genome sequence analysis of N. farcinica IFM10152, it was revealed that nfa12130 and nfa33880 P450 genes clustered with their own ferredoxins and ferredoxin reductases (nfa12140+nfa12150 and nfa338870+nfa33860, respectively) are responsible for the hydroxylation of the A-ring of daidzein, and their major reaction products were 6-ODI and 8-ODI, respectively. [source] Protein methylation in full length Chlamydomonas flagellaCYTOSKELETON, Issue 8 2009Roger D. Sloboda Abstract Post-translational protein modification occurs extensively in eukaryotic flagella. Here we examine protein methylation, a protein modification that has only recently been reported to occur in flagella [Schneider MJ, Ulland M, Sloboda RD.2008. Mol Biol Cell 19(10):4319,4327.]. The cobalamin (vitamin B12) independent form of the enzyme methionine synthase (MetE), which catalyzes the final step in methionine production, is localized to flagella. Here we demonstrate, using immunogold scanning electron microscopy, that MetE is bound to the outer doublets of the flagellum. Methionine can be converted to S-adenosyl methionine, which then serves as the methyl donor for protein methylation reactions. Using antibodies that recognize symmetrically or asymmetrically methylated arginine residues, we identify three highly methylated proteins in intact flagella: two symmetrically methylated proteins of about 30 and 40 kDa, and one asymmetrically methylated protein of about 75 kDa. Several other relatively less methylated proteins could also be detected. Fractionation and immunoblot analysis shows that these proteins are components of the flagellar axoneme. Immunogold thin section electron microscopy indicates that the symmetrically methylated proteins are located in the central region of the axoneme, perhaps as components of the central pair complex and the radial spokes, while the asymmetrically methylated proteins are associated with the outer doublets. Cell Motil. Cytoskeleton 2009. © 2009 Wiley-Liss, Inc. [source] Ubiquinone biosynthesis in microorganismsFEMS MICROBIOLOGY LETTERS, Issue 2 2001R Meganathan Abstract The quinoid nucleus of the benzoquinone, ubiquinone (coenzyme Q; Q), is derived from the shikimate pathway in bacteria and eukaryotic microorganisms. Ubiquinone is not considered a vitamin since mammals synthesize it from the essential amino acid tyrosine. Escherichia coli and other Gram-negative bacteria derive the 4-hydroxybenzoate required for the biosynthesis of Q directly from chorismate. The yeast, Saccharomyces cerevisiae, can either form 4-hydroxybenzoate from chorismate or tyrosine. However, unlike mammals, S. cerevisiae synthesizes tyrosine in vivo by the shikimate pathway. While the reactions of the pathway leading from 4-hydroxybenzoate to Q are the same in both organisms the order in which they occur differs. The 4-hydroxybenzoate undergoes a prenylation, a decarboxylation and three hydroxylations alternating with three methylation reactions, resulting in the formation of Q. The methyl groups for the methylation reactions are derived from S -adenosylmethionine. While the prenyl side chain is formed by the 2- C -methyl- d -erythritol 4-phosphate (non-mevalonate) pathway in E. coli, it is formed by the mevalonate pathway in the yeast. [source] [1.1]Ferrocenophane-1,12-dione as a Precursor of 1,12-Di(cyclopenta-2,4-dienylidene)-[1.1]ferrocenophane, a Doubly Bridged DifulveneADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 7-8 2009José Ramon Garabatos-Perera Abstract An improved synthesis of [1.1]ferrocenophane-1,12-dione (2) by oxidation of [1.1]ferrocenophane with 2,3-dichloro-5,6-dicyano- p -benzoquinone (DDQ) is presented. The syn conformer of dione 2 is structurally characterized. The compound undergoes various addition reactions at the bridging carbonyl groups. Attempts to add 1,1,-dilithioferrocene result, however, in the diadduct 9, not in the symmetric trinuclear diol 8. Reaction of 2 with sodium cyclopentadienide in the presence of aluminium trichloride (AlCl3) gives the respective difulvene 11 in excellent yield. The dynamic behavior of 11 is investigated by variable temperature 1H,NMR measurements (VT-NMR). The cyclovoltammogram of 11 indicates two reversible oxidation steps. Reduction of difulvene 11 with lithium aluminium hydride (LiAlH4) results in the formation of [1.1]ferrocenophane 12 with cyclopentadienyl anion substituents at either one of the two bridges. While attempts to generate a third ferrocene moiety by reaction with iron(II) choride (FeCl2) have failed so far, the formation of 12 is established by protonolysis and methylation reactions. [source] Activation barriers for DNA alkylation by carcinogenic methane diazonium ionsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 3 2006Kaushalya S. Ekanayake Abstract Methylation reactions of the DNA bases with the methane diazonium ion, which is the reactive intermediate formed from several carcinogenic methylating agents, were examined. The SN2 transition states of the methylation reactions at N7, N3, and O6 of guanine; N7, N3, and N1 of adenine; N3 and O2 of cytosine; and O2 and O4 of thymine were calculated using the B3LYP density functional method. Solvation effects were examined using the conductor-like polarizable continuum method and the combined discrete/SCRF method. The transition states for reactions at guanine N3, adenine N7, and adenine N1 are influenced by steric interactions between the methane diazonium ion and exocyclic amino groups. Both in the gas phase and in aqueous solution, the methylation reactions at N atoms have transition states that are looser, and generally occur earlier along the reaction pathways than reactions at O atoms. The forming bonds in the transition states in water are 0.03 to 0.13 Å shorter than those observed in the gas phase, and the activation energies are 13 to 35 kcal/mol higher. The combined discrete/SCRF solvation energy calculations using base-water complexes with three water molecules yield base solvation energies that are larger than those obtained from the CPCM continuum method, especially for cytosine. Reactivities calculated using barriers obtained with the discrete/SCRF method are consistent with the experimentally observed high reactivity at N7 of guanine. © 2005 Wiley Periodicals, Inc. J Comput Chem 27: 277,286, 2006 [source] Multi-site genetic modulation of monolignol biosynthesis suggests new routes for formation of syringyl lignin and wall-bound ferulic acid in alfalfa (Medicago sativa L.)THE PLANT JOURNAL, Issue 1 2006Fang Chen Summary Genes encoding seven enzymes of the monolignol pathway were independently downregulated in alfalfa (Medicago sativa) using antisense and/or RNA interference. In each case, total flux into lignin was reduced, with the largest effects arising from the downregulation of earlier enzymes in the pathway. The downregulation of l -phenylalanine ammonia-lyase, 4-coumarate 3-hydroxylase, hydroxycinnamoyl CoA quinate/shikimate hydroxycinnamoyl transferase, ferulate 5-hydroxylase or caffeic acid 3- O -methyltransferase resulted in compositional changes in lignin and wall-bound hydroxycinnamic acids consistent with the current models of the monolignol pathway. However, downregulating caffeoyl CoA 3- O -methyltransferase neither reduced syringyl (S) lignin units nor wall-bound ferulate, inconsistent with a role for this enzyme in 3- O -methylation ofS monolignol precursors and hydroxycinnamic acids. Paradoxically, lignin composition differed in plants downregulated in either cinnamate 4-hydroxylase or phenylalanine ammonia-lyase. No changes in the levels of acylated flavonoids were observed in the various transgenic lines. The current model for monolignol and ferulate biosynthesis appears to be an over-simplification, at least in alfalfa, and additional enzymes may be needed for the 3- O -methylation reactions of S lignin and ferulate biosynthesis. [source] | |||||||||||||