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Methyl Groups (methyl + groups)
Selected AbstractsInnentitelbild: Stereospecific Isotopic Labeling of Methyl Groups for NMR Spectroscopic Studies of High-Molecular-Weight Proteins (Angew. Chem.ANGEWANDTE CHEMIE, Issue 11 201011/2010) NMR-Spektroskopie großer Proteinsysteme gelingt nur nach gezielter Protonierung ausgewählter Positionen vor einem perdeuterierten Hintergrund. In der Zuschrift auf S.,2002,ff. von J. Boisbouvier et,al. wird eine Acetolactatvorstufe vorgestellt, um biosynthetisch 13C1H3 -Gruppen spezifisch in die pro- S -Methyl-Positionen von Leucin und Valin einzuführen. Dieses Markierungsverfahren verbessert die Spektrenqualität erheblich und schafft eine einfache und effiziente Grundlage für die Anwendung von Lösungs-NMR-Techniken auf komplexe Biomoleküle. [source] Stereospecific Isotopic Labeling of Methyl Groups for NMR Spectroscopic Studies of High-Molecular-Weight Proteins,ANGEWANDTE CHEMIE, Issue 11 2010Pierre Gans Dr. Manchmal ist weniger mehr: 13C1H3 -Methylisotopomere können biosynthetisch mithilfe einer Acetolactatvorstufe spezifisch als pro- S -Methylgruppen von Leucin- und Valinresten in ansonsten perdeuterierte Proteine eingefügt werden. Durch diese Markierungsstrategie wird die Qualität der NMR-Spektren großer Proteinassoziationen deutlich verbessert. [source] Innentitelbild: Stereocontrolled Synthesis of Carbon Chains Bearing Contiguous Methyl Groups by Iterative Boronic Ester Homologations: Application to the Total Synthesis of (+)-Faranal (Angew. Chem.ANGEWANDTE CHEMIE, Issue 34 200934/2009) In einem neuen Syntheseansatz werden Gruppen sukzessive an einen Boronsäureester addiert , ein Verfahren, das an ein molekulares Fließband erinnert. V.,K. Aggarwal et,al. demonstrieren dieses Homologisierungskonzept in ihrer Zuschrift auf S.,6435,ff. anhand der stereoselektiven Synthese von (+)-Faranal. [source] Stereocontrolled Synthesis of Carbon Chains Bearing Contiguous Methyl Groups by Iterative Boronic Ester Homologations: Application to the Total Synthesis of (+)-Faranal,ANGEWANDTE CHEMIE, Issue 34 2009Guillaume Dutheuil Dr. ,Ketten"-Reaktionen: Durch vierfache Homologisierung eines Boronsäureesters lässt sich ein einfaches Vinyliodid mit hoher Diastereo- und Enantioselektivität in eine komplexe Faranalvorstufe umwandeln. Auf diesem Weg kann (+)-Faranal in nur sechs Stufen und mit einer Gesamtausbeute von 18,% aus Propin hergestellt werden. [source] A New Non-Azole Inhibitor of ABA 8,-Hydroxylase: Effect of the Hydroxyl Group Substituted for Geminal Methyl Groups in the Six-Membered Ring.CHEMINFORM, Issue 38 2006Yoshiharu Araki Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Pd-Catalyzed Stereoselective Oxidation of Methyl Groups by Inexpensive Oxidants under Mild Conditions: A Dual Role for Carboxylic Anhydrides in Catalytic C,H Bond Oxidation.CHEMINFORM, Issue 12 2006Ramesh Giri Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Methyl TROSY: explanation and experimental verificationMAGNETIC RESONANCE IN CHEMISTRY, Issue 10 2003Jason E. Ollerenshaw Abstract In TROSY experiments, relaxation interference effects are exploited to produce spectra with improved resolution and signal-to-noise. Such experiments cannot be explained using the standard product operator formalism, but must instead be analyzed at the level of individual density matrix elements. Herein we illustrate this point using an example from our recent work on a TROSY 1H,13C correlation experiment for methyl groups in large proteins. Methyl groups are useful spectroscopic probes of protein structure and dynamics because they are found throughout the critical core region of a folded protein and their resonances are intense and well dispersed. Additionally, it is relatively easy to produce highly deuterated protein samples that are 1H,13C labeled at selected methyl positions, facilitating studies of high molecular weight systems. Methyl groups are relaxed by a network of 1H,1H and 1H,13C dipolar interactions, and in the macromolecular limit the destructive interference of these interactions leads to unusually slow relaxation for certain density matrix elements. It is this slow relaxation that forms the basis for TROSY experiments. We present a detailed analysis of evolution and relaxation during HSQC and HMQC pulse schemes for the case of a 13C1H3 spin system attached to a macromolecule. We show that the HMQC sequence is already optimal with respect to the TROSY effect, offering a significant sensitivity enhancement over HSQC at any spectrometer field strength. The gain in sensitivity is established experimentally using samples of two large proteins, malate synthase G (81.4 kDa) and ClpP protease (305 kDa), both highly deuterated and selectively 1H,13C-labeled at isoleucine , methyl positions. Copyright © 2003 John Wiley & Sons, Ltd. [source] NMR T1 -Relaxation Measurements on Paramagnetic Organolanthanides:An Alternative Tool for Structure Determination in SolutionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2005Laurent Brachais Abstract 1H NMR investigations were conducted on four paramagnetic organolanthanides, all bearing the tetraisopropylcyclopentadienyl ligand Cp4i (HC5iPr4) in order to verify whether or not interactions observed in the solid state are maintained in solution. In some cases variable-temperature experiments were necessary to enhance the resolution and determine the best conditions for the study. The 1D NMR spectrum could be interpreted in every case. Complementary 2D COSY experiments allowed the full attribution of the signals. T1 (1H) relaxation values were determined for all the paramagnetic complexes at the most suitable temperature, and compared with those of the diamagnetic KCp4i. The same tendency was observed, with particular features concerning the isopropyl groups. Among the four methyl groups, one exhibits a much higher T1 value and one a much lower value; the two others are intermediate. This was interpreted as the result of a privileged conformation of the Cp4i ligand: the two ,-isopropyl groups take up a spatial orientation with one methyl group in the exo position, opposite to the metal atom, whereas the methyl groups of the two ,-isopropyl groups are equidistant from the metal atom. Whatever the nature of the metal (Nd, Sm), the oxidation state (SmII, SmIII) or the temperature (298, 363 K), this conformation is retained. The structure in solution seems to be different from that previously determined in the solid state. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Reactions of the Aluminum(I) Monomer LAl [L = HC{(CMe)(NAr)}2; Ar = 2,6- iPr2C6H3] with Imidazol-2-ylidene and Diphenyldiazomethane.EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2004A Hydrogen Transfer from the L Ligand to the Central Aluminum Atom, Formation of the Diiminylaluminum Compound LAl(N=CPh2) Abstract The solid-state reaction of LAl and imidazol-2-ylidene at elevated temperature (120 °C) yielded the aluminum monohydride N -heterocyclic carbene adduct [{HC[C(CH2)NAr] (CMeNAr)}AlH-{CN(R)C2Me2N(R)}] [R = iPr (1), Me (2)]. Compounds 1 and 2 have been characterized by spectroscopic (IR, and 1H and 13C NMR), mass spectrometric, and elemental analyses, and 1 was further characterized by X-ray structural analysis. These experimental data indicate that the Al,H bond is formed by hydrogen migration from one of the methyl groups of the ,-diketiminato ligand backbone. The reaction of LAl with two equivalents of diphenyldiazomethane afforded the diiminylaluminum compound LAl(N=CPh2)2 (3), while an excess of diphenyldiazomethane resulted in the formation of Ph2C=N,N=CPh2. This suggests that Ph2C=N,N=CPh2 is initially generated and then reacts further by oxidative addition to yield 3. The X-ray structural analysis reveals that compound 3 contains the shortest Al,Niminyl bond among those with a four-coordinate aluminum center. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Synthesis and Dynamic Features of (Chloro)zirconocene Cations Stabilised by Pendant (Diarylphosphanyl)alkyl and (Dimethylamino)alkyl Substituents at Their Cyclopentadienyl Ring SystemsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2003Steve Döring Abstract Treatment of the substituted (diarylphosphanyl)methyl group-4 metallocene complexes [(C5H4,CR1R2,PAr2)2ZrCl2] (2: R1/R2 = CH3/CH3, H/CH3, H/aryl) with Li[B(C6F5)4] in dichloromethane solution results in chloride ligand abstraction (with LiCl precipitation) to yield the complexes [(C5H4,CR1R2,PAr2)2Zr,Cl+] (5), with both phosphanyl groups internally coordinated to the metal centre. Three possible diastereoisomers are observed in the case of 5c (R1 = H; R2 = CH3), while bulkier R2 substituents give higher selectivities. The thermally induced (reversible) cleavage of the Zr,phosphane linkage results in dynamic NMR behaviour. Gibbs activation energies of ,G,(298 K) = 14.8 ± 0.5 and 14.5 ± 0.5 kcal/mol were obtained for these intramolecular equilibration processes in the complexes trans - 5d (R1 = H; R2 = Ph) and trans - 5e (R1 = H; R2 = ferrocenyl), respectively. Treatment of the substituted (dimethylamino)methyl metallocene complexes [(C5H4,CR1R2,NMe2)2ZrCl2] (6a, 6b) with Li[B(C6F5)4] proceeds analogously to yield the cation systems [{C5H4,C(CH3)2,NMe2}2ZrCl+] (12a) and [{C5H4,CH(CH3),NMe2}2ZrCl+] (12b, three possible diastereoisomers). Both complexes have their pairs of amino groups coordinated to the metal centre. The complexes exhibit dynamic NMR spectra. Selective equilibration of the diastereotopic N(CH3)A(CH3)B resonances of complex 12a is observed [,G,(233 K) = 11.5 ± 0.2 kcal/mol], whereas the adjacent C(CH3)A(CH3)B methyl groups remain diastereotopic. The dynamic equilibration of the latter was observed at a markedly higher temperature [,G,(333 K) = 17.3 ± 0.2 kcal/mol]. Treatment of [{C5H4,C(CH3)2,NMe2}CpZrCl2] (10) with Li[B(C6F5)4] resulted in the formation of complex [{C5H4,C(CH3)2,NMe2}CpZr,Cl+] (11), which shows the internal ,N(CH3)A(CH)B equilibration proceeding with a markedly higher activation barrier [,G,(333 K) = 17.6 ± 0.2 kcal/mol] than in 12a, and a stereochemical memory effect indicative of solvent coordination to the metal centre of the resulting highly electrophilic chlorozirconocene cation intermediate. Complex 11 was characterised by an X-ray crystal structure analysis, which shows the internal Zr,amine coordination. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Chondrochloren A and B, New ,-Amino Styrenes from Chondromyces crocatus (Myxobacteria)EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 14 2003Rolf Jansen Abstract In a screening for biologically active metabolites of the genus Chondromyces, two novel metabolites, chondrochloren A (1) and B (2), were isolated from several strains of C. crocatus. Compounds 1 and 2 are unique chloro-hydroxy-styryl amides of a highly modified C14 carboxylic acid, which comprises an unsaturated ketone, two hydroxy, two methoxy and three methyl groups. After assignment of the absolute configuration of both carbinol stereocenters by Mosher's method, NMR spectroscopic data combined with MM2 calculations allowed the prediction of the preferred conformation in solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Exploring the primary electron acceptor (QA)-site of the bacterial reaction center from Rhodobacter sphaeroidesFEBS JOURNAL, Issue 4 2002Binding mode of vitamin K derivatives The functional replacement of the primary ubiquinone (QA) in the photosynthetic reaction center (RC) from Rhodobacter sphaeroides with synthetic vitamin K derivatives has provided a powerful tool to investigate the electron transfer mechanism. To investigate the binding mode of these quinones to the QA binding site we have determined the binding free energy and charge recombination rate from QA, to D+ (kAD) of 29 different 1,4-naphthoquinone derivatives with systematically altered structures. The most striking result was that none of the eight tested compounds carrying methyl groups in both positions 5 and 8 of the aromatic ring exhibited functional binding. To understand the binding properties of these quinones on a molecular level, the structures of the reaction center-naphthoquinone complexes were predicted with ligand docking calculations. All protein,ligand structures show hydrogen bonds between the carbonyl oxygens of the quinone and AlaM260 and HisM219 as found for the native ubiquinone-10 in the X-ray structure. The center-to-center distance between the naphthoquinones at QA and the native ubiquinone-10 at QB (the secondary electron acceptor) is essentially the same, compared to the native structure. A detailed analysis of the docking calculations reveals that 5,8-disubstitution prohibits binding due to steric clashes of the 5-methyl group with the backbone atoms of AlaM260 and AlaM249. The experimentally determined binding free energies were reproduced with an rmsd of ,,4 kJ·mol,1 in most cases providing a valuable tool for the design of new artificial electron acceptors and inhibitors. [source] Quenching of Singlet Oxygen by Tertiary Aliphatic Amines.HELVETICA CHIMICA ACTA, Issue 10 2006Products, Structural Effects on Rates Abstract A kinetic and product study of the reaction of a series of , -methyl-substituted N -methylpiperidines with thermally generated 1O2 in MeCN was carried out. It was found that as the number of , -methyl groups (Me in , -position relative to the N-atom) increases, the rate of 1O2 quenching (physical plus chemical) slightly decreases. This finding shows that, with respect to the reaction rate, steric effects are much more important than electronic effects as the latter should have produced the opposite result. The opposite outcome was instead found for the chemical quenching that leads to the N -demethylation products and N -formyl derivatives. The same trend was observed for the ratio between N -demethylation and formation of the N -formyl derivatives (NH/NCHO ratio). All these results are consistent with the mechanism reported in Scheme,1 where an exciplex is first formed that by a H-atom transfer process produces an , -amino-substituted C-radical. The latter forms the product of N -demethylation by one electron oxidation, or affords the N -formyl derivative by radical coupling (Scheme,1). Similar results were obtained with N,N -dimethylcyclohexanamine. However, this ,acyclic' amine exhibited behaviors quite distinct from those of the N -methylpiperidines series, with respect to reaction rate, extent of chemical quenching, and NH/NCHO ratio. [source] Solvent-free alkali and alkaline earth metal complexes of di-imine ligands,HETEROATOM CHEMISTRY, Issue 6 2006Igor L. Fedushkin Compound [(dph-BIAN)Mg(THF)]2(2) was prepared by reacting magnesium metal with 1,2- bis[(2-biphenyl)imino]acenaphthene (dph-BIAN) in THF, followed by crystallization from toluene. Reac- tion of CaI2 with (dpp-BIAN)Li2 in toluene afforded [(dpp-BIAN)Li]2Ca (3) (dpp-BIAN = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene). Both complexes 2 and 3 were characterized by single crystal X-ray diffraction. The 1H NMR spectroscopic data obtained for complex 3 in toluene solution indicated an agostic interaction between the methyl groups of the ligand and lithium atoms. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:663,670, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20277 [source] Methylenetetrahydrofolate reductase 677C/T gene polymorphism, gastric cancer susceptibility and genomic DNA hypomethylation in an at-risk Italian populationINTERNATIONAL JOURNAL OF CANCER, Issue 3 2006Francesco Graziano Abstract We performed a case-control study to examine the relationship between MTHFR C677T gene polymorphism (MTHFR677C/T) and gastric cancer susceptibility in at-risk populations in central Italy. To explore genomic DNA hypomethylation as a potential etiologic mechanism, this phenomenon was evaluated in carriers of the MTHFR677T/T genotype and carriers of the wild-type MTHFR677C/C genotype. Lymphocyte genomic DNA from 162 gastric cancer patients and 164 controls was used for MTHFR677C/T genotyping. Unconditional regression analysis with ORs and 95% CIs was used to investigate the association of the polymorphism with disease. Genomic DNA methylation status by an established enzymatic assay that measures the DNA accepting capacity of methyl groups (inversely related to endogenous methylation) was assessed in a random sample of 40 carriers of the wild-type MTHFR677C/C genotype and 40 carriers of the MTHFR677T/T genotype. The global allelic distribution was in Hardy-Weinberg equilibrium. The MTHFR677T allele was significantly associated with gastric cancer risk with an OR of 2.49 (95% CI 1.48,4.20) in heterozygous MTHFR677C/T carriers and an OR of 2.85 (95% CI 1.52,5.35) in homozygous MTHFR677T/T carriers. This risk association was retained in subgroup analyses by tumor histotype and location. Genomic DNA hypomethylation status in MTHFR677T/T carriers was significantly higher than in subjects with wild-type MTHF677C/C genotype (p = 0.012). In the studied population, MTHFR677T played the role of a moderate-penetrance gastric cancer susceptibility allele. Possession of the MTHFR677T/T genotype was significantly associated with genomic DNA hypomethylation. These findings deserve further investigation in the context of novel strategies for gastric cancer prevention. © 2005 Wiley-Liss, Inc. [source] Detecting methylation patterns of p16, MGMT, DAPK and E-cadherin genes in multiple myeloma patientsINTERNATIONAL JOURNAL OF LABORATORY HEMATOLOGY, Issue 2 2010O. OZALP YUREGIR Summary Multiple myeloma (MM) is a B-cell neoplasia characterized by the clonal proliferation of plasma cells. Besides known genetic abnormalities, epigenetic changes are also known to effect MM pathogenesis. DNA methylation is an epigenetic mechanism that silences genes by adding methyl groups to cytosine-guanine dinucleotides at the promoter regions. In this study, the methylation status of four genes; p16, O6-methyl guanine DNA methyl transferase (MGMT), death-associated protein kinase (DAPK) and E-cadherin (ECAD); at the time of diagnosis was investigated using methylation-specific polymerase chain reaction (MS-PCR). In the 20 cases studied; methylation of the promoter regions of p16, MGMT, DAPK and ECAD genes was detected in 10%, 40%, 10% and 45% of the cases, respectively. In 65% (13/20) of cases, at least one of the genes studied had promoter methylation; while 35% of cases (7/20) had methylated promoters of more than one gene. There was a significant correlation between promoter hypermethylation of MGMT and the presence of extramedullary involvement; but for the other genes no correlation was found regarding disease properties like age, disease stage, clinical course and the presence of lytic bone lesions. Determining the methylation profiles of genes in MM, could lead to a new understanding of the disease pathogenesis and guide the assessment of treatment options. [source] Iron-Catalyzed Oxidative Mono- and Bis-Phosphonation of N,N -DialkylanilinesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2010Wei Han Abstract The dehydrogenative ,-phosphonation of substituted N,N -dialkylanilines by dialkyl H -phosphonates was achieved under mild conditions by using environmentally benign iron(II) chloride as catalyst and tert -butyl hydroperoxide as oxidant. The reaction proceeded in the presence of electron-donating (methoxy, methyl, benzyl) and electron-withdrawing ring-substitutents (bromo, carbonyl, carboxyl, m -nitro) in moderate to good yields. The X-ray crystal structure of N -(5,5-dimethyl-2-oxo-2,5 -[1,3,2]dioxaphosphinan-2-yl-methyl)- N -methyl- p -toluidine was determined. Bis-(4-(dimethylamino)phenyl)methane and bis-4,4,-(dimethylamino)benzophenone underwent bisphosphonation selectively by respective monophosphonation at the remote dimethylamino groups. Furthermore, the use of excess dialkyl H -phosphonate and oxidant allowed us to functionalize both methyl groups of N(CH3)2 in N,N -dimethyl- p -toluidine and N,N -dimethylaminomesidine, respectively, to obtain ,,,,-bisphosphonatoamines in high yield. [source] Dependence of the wittig reaction mechanism on the environment and on the substituents at the aldehyde group and at the phosphonium ylideINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2010Giuliano Alagona Abstract The B3P86/6-31G* mechanistic results for the Wittig reaction of acetaldehyde, CH3CHO, in vacuo and in tetrahydrofuran (THF) solution in the IEF-PCM framework, with an unsubstituted trimethylphosphonium or triphenylphosphonium ylide, that is Me3PCH2 or Ph3PCH2, have been compared to those recently obtained at the same levels for the reaction of Ph3PCH2 with a bulky chiral aldehyde, (2S,3R)-2,4-dimethyl-3-pyrrol-1-yl-pentanal [TCA (DOI: 10.1007/s00214-009-0521-4)], here named sys for short. The two model systems show distinct, but similar, behaviors that however differ from the large system one. In particular, betaine-type intermediates are not located in vacuo when Me3PCH2 is used, while only a gauche betaine is obtained using Ph3PCH2; the relevant barriers are anyway smaller than those found for sys. Conversely, in THF, the concerted and stepwise mechanisms are both represented and show TS1/TSb barriers, which are negligibly small for sys. Thus, in contrast to assessed literature, models with methyl groups in place of phenyl rings and branched aldehyde chains show a different behavior from realistic systems and prevent inferring general rules from their use, suggesting to resort to Ph3PCH2 whose results in vacuo and in THF are closer to sys. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Comparative study on the nonadditivity of methyl group in lithium bonding and hydrogen bondingINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2009Qingzhong Li Abstract Quantum chemical calculations at the second-order Moeller,Plesset (MP2) level with 6-311++G(d,p) basis set have been performed on the lithium-bonded and hydrogen-bonded systems. The interaction energy, binding distance, bond length, and stretch frequency in these systems have been analyzed to study the nonadditivity of methyl group in the lithium bonding and hydrogen bonding. In the complexes involving with NH3, the introduction of one methyl group into NH3 molecule results in an increase of the strength of lithium bonding and hydrogen bonding. The insertion of two methyl groups into NH3 molecule also leads to an increase of the hydrogen bonding strength but a decrease of the lithium bonding strength relative to that of the first methyl group. The addition of three methyl groups into NH3 molecule causes the strongest hydrogen bonding and the weakest lithium bonding. Although the presence of methyl group has a different influence on the lithium bonding and hydrogen bonding, a negative nonadditivity of methyl group is found in both interactions. The effect of methyl group on the lithium bonding and hydrogen bonding has also been investigated with the natural bond orbital and atoms in molecule analyses. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Interaction of FeO+ cation with benzene, aniline, and 3-methylaniline: DFT study of oxygen insertion mechanismINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 11 2008Karolina Kwapien Abstract The reaction pathways and energetics for oxygen insertion into CH bond in benzene, aniline, and 3-methylaniline by FeO+ in the gas phase were investigated by means of the DFT methodology with the B3LYP exchange-correlation functional and 6-311G** basis set. The main aim of this work was to elucidate the influence of substituents in phenyl ring on stationary points along the energy profile on sextet and quartet surfaces for the reaction of FeO+ with substituted benzenes. The studies show that the amino and methyl groups change the energetics of oxygen insertion by lowering the energy profile along the reaction pathway. The substituents studied in this work facilitate the insertion of oxygen into the aromatic CH bond by stabilizing the intermediate sigma complex (,-complex), the amino group being by far more effective. On the other hand, both functional groups increase the activation energy of the rate-determining step in the gas phase, so that they have unfavorable influence on the kinetics. The comparison of the energy diagrams for the sextet and quartet spin states indicates the dominance of the low-spin reactivity in oxygen insertion into aromatic CH bond. Aniline and 3-methylaniline oxidation occurs via electrophilic addition while the conversion of benzene to phenol by FeO+ is mediated by a ,-complex with mixed radical and cationic character. Present results are also discussed in the context of oxyferryl group reactivity. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Effects of Methyl Substituents on the Activity and Enantioselectivity of Homobenzotetramisole-Based Catalysts in the Kinetic Resolution of AlcoholsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 14-15 2009Yuhua Zhang Abstract Substitution of the tetrahydropyrimidine ring in the enantioselective acyl transfer catalyst homobenzotetramisole (HBTM) 6 with methyl groups exerts a dramatic influence on its performance in the kinetic resolution of secondary alcohols. The syn- 3-methyl analogue of HBTM (9a) has proved to be superior to the parent compound in terms of catalytic activity, enantioselectivity, and synthetic accessibility. [source] Biocatalytic Asymmetric Dihydroxylation of Conjugated Mono- and Poly-alkenes to Yield Enantiopure Cyclic cis -DiolsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 7-8 2005Derek Abstract Dioxygenase-catalysed asymmetric dihydroxylation, of a series of conjugated monoalkenes and polyenes, was found to yield the corresponding monols and 1,2-dihydrodiols. The diol metabolites were obtained from monosubstituted, gem -disubstituted, cis -disubstituted, and trisubstituted alkene substrates, using whole cells of Pseudomonas putida strains containing toluene and naphthalene dioxygenases. Dioxygenase selection and alkene type were established as important factors, in the preference for dioxygenase-catalysed 1,2-dihydroxylation of conjugated alkene or arene groups, and monohydroxylation at benzylic or allylic centres. Competition from allylic hydroxylation of methyl groups was observed only when naphthalene dioxygenase was used as biocatalyst. The structures, enantiomeric excess values and absolute configurations of the bioproducts, were determined by a combination of stereochemical correlation, spectroscopy (NMR and CD) and X-ray diffraction methods. cis -1,2-Diol metabolites from arenes, cyclic alkenes and dienes were generally observed to be enantiopure (>98% ee), while 1,2-diols from acyclic alkenes had lower enantiomeric excess values (<88% ee). The enantiopure cis -diol metabolite of a gem -disubstituted fulvene was used as precursor in a new chemoenzymatic route to a novel C2 -symmetrical ketone. [source] Synthesis and properties of novel organosoluble aromatic poly(ether ketone)s containing pendant methyl groups and sulfone linkagesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2008Shou-Ri Sheng Abstract Several novel aromatic poly(ether ketone)s containing pendant methyl groups and sulfone linkages with inherent viscosities of 0.62,0.65 dL/g were prepared from 2-methyldiphenylether and 3-methyldiphenylether with 4,4,-bis(4-chloroformylphenoxy)diphenylsulfone and 4,4,-bis (3-chloroformylphenoxy)diphenylsulfone by electrophilic Friedel,Crafts acylation in the presence of N,N -dimethylformamide with anhydrous AlCl3 as a catalyst in 1,2-dichloroethane. These polymers, having weight-average molecular weights in the range of 57,000,71,000, were all amorphous and showed high glass-transition temperatures ranging from 160.5 to 167°C, excellent thermal stability at temperatures over 450°C in air or nitrogen, high char yields of 52,57% in nitrogen, and good solubility in CHCl3 and polar solvents such as N,N -dimethylformamide, dimethyl sulfoxide, and N -methyl-2-pyrrolidone at room temperature. All the polymers formed transparent, strong, and flexible films, with tensile strengths of 84.6,90.4 MPa, Young's moduli of 2.33,2.71 GPa, and elongations at break of 26.1,27.4%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Modification of carbon black through grafting multihydroxyl hyperbranched polyether onto its surfaceJOURNAL OF APPLIED POLYMER SCIENCE, Issue 4 2007Qiang Yang Abstract The hydroxy methyl groups were introduced onto the pristine carbon black surface through the reaction between unsaturated hydrogen atoms of the polycondensed aromatic rings of carbon black and formaldehyde in alkali condition. Using the resultant hydroxy methyl groups on the carbon black surface as the growth point, multihydroxyl hyperbranched polyether was grafted onto the carbon black surface by cationic ring-opening polymerization of 3-ethyl-3-(hydroxymethyl)-oxetane in the presence of BF3·OEt2 to improve its dispersion ability in solvents. It was found that the modified carbon black could be dispersed in polar solvents, such as ethanol, chloroform, and DMF. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2086,2092, 2007 [source] Synthesis of models of metabolites: Oxidation of variously substituted chromenes including acronycine, by a porphyrin catalytic systemJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 7 2005Bernardin Akagah The influence of chemical neighbouring on oxidation of substituted 2,2-dimethylchromenes derivatives 5-8 by a biomimetic catalytic system was first studied. It was then applied to acronycine an anti-cancer drug in order to obtain in one single step oxidized products resulting from the reactivity of the 1,2-double bond in the pyranic D-ring. These 2,2-dimethylchromenes constitute the structural moiety responsible for the activity of acronycine. This oxidation showed the sensitivity of the ethylenic bond, leading to the formation of the corresponding epoxides, diols and/or ketoalcohol. In the case of 5-dimethylamino-2,2-dimethylchromene 8, the double bond was not sensitive to oxidation, but the N -methyl groups reacted to lead to the formamide derivative 16 and an imino-alcohol 17. This methodology applied to acronycine molecule 1, allowed to obtain in one step, two oxidized compounds, a trans -diol 3 and a ketoalcohol 4 under preparative conditions. [source] Mass spectrometric analysis of 7-sulfoxymethyl-12-methylbenz[a]anthracene and related electrophilic polycyclic aromatic hydrocarbon metabolitesJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 11 2004Andreas F. Lehner Abstract The Meso-region theory of polycyclic aromatic hydrocarbon (PAH) carcinogenesis predicts that the development of pronounced carcinogenicity depends on the introduction of a good leaving group on alkyl side-chains attached to the exceptionally reactive meso-anthracenic or L-region positions of PAHs. Thus, the first step in carcinogenesis by methylated PAHs such as 7,12-dimethylbenz[a]anthracene (DMBA) would be the hydroxylation of the L-region methyl groups, particularly the 7-methyl group. The second would be the formation of a metabolite, e.g. a sulfate ester, which is expected to be a good leaving group capable of generating a highly reactive benzylic carbocation. 7-Hydroxymethyl-12-methylbenz[a]anthracene (7-HMBA) is a metabolite of DMBA, and sulfation of 7-HMBA to a 7-sulfoxymethyl metabolite (7-SMBA) is a known Phase II metabolic process designed to facilitate excretion, but actually enabling more destructive side-reactions. These side-reactions occur with generation of an electrophilic 7-methylene carbonium ion, and/or by in vivo halide exchange to provide neutral side-products more capable of entering cells, especially those of DMBA target tissues. Electrospray ionization mass spectrometry (MS) enabled us to visualize 7-SMBA as an intact m/z 351 conjugate anion by negative mode, and as a released m/z 255 carbonium ion by positive mode. Upon prolonged refrigeration, 7-SMBA accumulated an m/z 383 photooxide, which appeared capable of re-evolving the starting material as visualized by tandem quadrupole MS, or MS/MS. The 7-SMBA carbonium ion provided interpretable fragments when studied by fragment ion MS/MS, including those representing the loss of up to several protons. Subtle differences in this property were encountered upon perturbing 7-SMBA, either by warming it at 37 °C for 2 h or by substituting the initial sulfoxy group with an iodo group. Side-reactions accounting for such proton losses are proposed, and are of interest whether they occur in the mass spectrometer, in solution or both; these proposals include acidity at the 12-methyl position and cyclization between the 12-methyl group and the adjacent C-1 position. It is also suggested that such side-reactions may comprise one route to relieving steric strain arising between the 12-methyl group and the angular benzo ring of 7-SMBA. Copyright © 2004 John Wiley & Sons, Ltd. [source] HIGH-RESOLUTION MAGIC ANGLE SPINNING NMR ANALYSIS OF WHOLE CELLS OF CHAETOCEROS MUELLERI (BACILLARIOPHYCEAE) AND COMPARISON WITH 13C-NMR AND DISTORTIONLESS ENHANCEMENT BY POLARIZATION TRANSFER 13C-NMR ANALYSIS OF LIPOPHILIC EXTRACTS,JOURNAL OF PHYCOLOGY, Issue 3 2004Matilde S. Chauton Lipid composition in extracted samples of Chaetoceros muelleri Lemmermann was studied with 13C-NMR and distortionless enhancement by polarization transfer (DEPT) 13C-NMR, resulting in well-resolved 13C-NMR spectra with characteristic resonance signals from carboxylic, olefinic, glyceryl, methylene, and methyl groups. The application of a DEPT pulse sequence aided in the assignment of methylene and methine groups. Resonance signals were compared with literature references, and signal assignment included important unsaturated fatty acids such as eicosapentaenoic and docosahexaenoic and also phospholipids and glycerols. Results from the extracted samples were used to assign resonance signals in a high-resolution magic angle spinning (HR MAS) DEPT 13C spectrum from whole cells of C. muelleri. The NMR analysis on whole cells yielded equally good information on fatty acids and also revealed signals from carbohydrates and amino acids. Broad resonance signals and peak overlapping can be a problem in whole cell analysis, but we found that application of HR MAS gave a well-resolved spectrum. The chemical shift of metabolites in an NMR spectrum depends on the actual environment of nuclei during analysis, and some differences could therefore be expected between extracted and whole cell samples. The shift differences were small, and assignment from analysis of lipophilic extract could be used to identify peaks in the whole cell spectrum. HR MAS 13C-NMR therefore offers a possibility for broad-range metabolic profiling directly on whole cells, simultaneously detecting metabolites that are otherwise not detected in the same analytical set up and avoiding tedious extraction procedures. [source] Ortho effect and steric inhibition of resonance: basicities of methyl-substituted acetophenones,JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 10 2003Eva Otyepková Abstract The basicity of 12 methyl-substituted acetophenones was measured spectrophotometrically in 46,90 vol.% sulfuric acid. The acidity function was constructed and the pKa values were calculated by a new algorithm proposed by Pytela. The substituent effects were divided into polar and steric, assuming that the former are approximately equal in the ortho and para positions. Polar effects of the methyl group bring about stronger basicity as expected; the effect is more intense than the acid weakening in equally substituted benzoic acids. Steric effects of ortho methyl groups are base strengthening. This is not due to steric inhibition of resonance since the conformation remains planar in most derivatives. Two ortho methyl groups are necessary to distort the planarity; their steric effect is more than doubled compared with one methyl group. These results do not agree with the common idea of twisted conformations with gradually increasing twisting angle but are better rationalized by the existence of two groups of derivatives, planar and non-planar. Copyright © 2003 John Wiley & Sons, Ltd. [source] Molecular Dynamics of Podand Studied by Broadband Dielectric and Nuclear Magnetic Resonance Spectroscopies,,MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 19-20 2007Bakyt Orozbaev Abstract Nuclear magnetic resonance (NMR) and broadband dielectric spectroscopies (BDS) were used to analyze the molecular dynamics in P10.3H Podand. The temperature studies of NMR line and magnetic spin,lattice relaxation times accompanied by DS investigation enabled us to distinguish three main dynamical processes connected with the motions of the P10.3H Podand chains. In the low-temperature region the magnetic relaxation was associated with fast axial C3 rotation of methyl groups. Moreover, two other independent processes were observed and interpreted as (i) segmental motion of both oxyethylene and ethylene units, and (ii) the overall motion involved in the melting process. [source] FTIR Microanalysis and Phase Behaviour of Ethylene/1-Hexene Random CopolymersMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 14 2007Mariano Pracella Abstract Ethylene/1-hexene random copolymers with 1-hexene content in the range of 1,5 mol-%, synthesised in the presence of new heterogeneous catalyst systems based on bis-carboxylato and -bis-chloro-carboxylato titanium chelate complexes, have been characterised by FTIR microspectroscopy (FTIR-M), DSC calorimetry and X-ray scattering. The co-monomer content and sequence distribution in the various samples were determined by means of both FTIR-M and 13C NMR spectroscopy. The deformation bands of methyl groups in the region of 1,400,1,330 cm,1 were used for the structural analysis of these copolymers. The effect of composition on the crystallinity and phase transitions of copolymers was analysed both in 1,500,1,300 and 760,690 cm,1 frequency ranges as a function of the annealing temperature. A neat variation of the absorbance ratio of methyl band at 1,378 cm,1 was recorded between 110 and 130,°C corresponding to the melting range of the copolymer crystals. The crystallisation behaviour of the copolymers was examined by DSC in dynamic and isothermal conditions; the isothermal kinetics were analysed according to the Avrami model. A marked decrease in the bulk crystallisation rate, accompanied by changes in the nucleation and growth of crystals, was found with an increase in the co-monomer content. The melting behaviour of isothermally crystallised samples was also investigated and the melting temperatures of the copolymers at equilibrium conditions were related to the composition; the experimental data were consistent with the Flory exclusion model of side branches from the crystalline phase. The lowering of crystal growth rate in the copolymers has been accounted for by an increase in the free energy of formation of critical size nuclei due to the effect of the side branches. [source] | |||||||||||||||||||||||||||||||||||||