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991.
Abella CA Benassi M Santos LS Eberlin MN Coelho F 《The Journal of organic chemistry》2007,72(11):4048-4054
Using direct infusion electrospray ionization mass and tandem mass spectrometric experiments [ESI-MS(/MS)], we have performed on-line monitoring of some reactions used to form Tr?ger's bases. Key intermediates, either as cationic species or as protonated forms of neutral species, have been intercepted and characterized. The role of urotropine as the methylene source in these reactions has also been accessed. Reaction pathways shown by ESI-MS(/MS) have been probed by gas-phase ion/molecule reactions, and an expanded mechanism for Tr?ger's base formation based on the mass spectrometric data has been elaborated. 相似文献
992.
Di Donna L Mazzotti F Napoli A Salerno R Sajjad A Sindona G 《Rapid communications in mass spectrometry : RCM》2007,21(3):273-278
Olive drupe tissues have been selected as a possible source of information about the secondary metabolism of oleaceae secoiridoids. The structures of a number of new microcomponents, detected and isolated by a combined high-performance liquid chromatography (HPLC)-fraction collector/ultraviolet electrospray ionization mass spectrometry (UV/ESI-MS) apparatus, can be inferred from the data obtained by high-resolution tandem mass spectrometry in a QqTOF instrument. Some of them (1, 2, 3 and 4) are closely correlated to oleuropein. Others, such as neo-nuzhenide (5) and 2'-hydroxyoleuropein (6), typical of other oleaceae families, have never been found in olive tissues. 相似文献
993.
Fileti EE Moraes PR Domingues L Riveros JM 《Journal of mass spectrometry : JMS》2007,42(10):1310-1318
The gas-phase methylenation reaction between CH(3)S(+)=CH(2) and alkylbenzenes, aniline, phenol and alkyl phenyl ethers, which yields [M + CH](+) and CH(3)SH, has been studied by Fourier transform ion cyclotron resonance (FT-ICR) techniques and computational chemistry at the DFT level. The methylthiomethyl cation is less reactive than methoxymethyl and, unlike the latter, is unreactive toward benzene. The calculations suggest that reaction with toluene should proceed primarily by addition at the para and ortho positions resulting in a benzyl-type ion. Reaction with aniline-2,3,4,5,6-d(5) reveals that elimination of CH(3)SD is kinetically favored by a factor of 5 over elimination of CH(3)SH. Experiments with C(6)H(6)ND(2) and theoretical calculations suggest that methylenation at the nitrogen atom is energetically favorable and likely, but the observed results may reflect some H/D scrambling, which occurs after attack at a ring position. By comparison, reaction with phenol-2,3,4,5,6-d(5) reveals that methylenation followed by elimination of CH(3)SD is kinetically favored by a factor of 3.8 over elimination of CH(3)SH. For phenol, the theoretical calculations suggest that attack by CH(3)S(+)=CH(2) at the para or ortho position is the only low-energy pathway for methylenation. However, a low-energy pathway for hydrogen scrambling is predicted by the calculations originating from the exit complex, [CH(3)SH(...) CH(2)=C(6)H(4)=OH](+), of reaction at a ring position. 相似文献
994.
Rotationally resolved fluorescence excitation spectra of the 0(0)(0) bands of the S1<--S0 electronic transitions of 2- and 5-methylpyrimidine (2MP and 5MP, respectively) have been observed and assigned. Both spectra were found to contain two sets of rotational lines, one associated with the sigma=0 torsional level and the other associated with the sigma=+/-1 torsional level of the attached methyl group. Analyses of their structure using the appropriate torsion-rotation Hamiltonian yields the methyl group torsional barriers of V6'=1.56 and V6'=8.28 cm(-1) in 2MP and V6'=4.11 and V6'=58.88 cm(-1) in 5MP. Many of the lines in both spectra are fragmented by couplings with lower lying triplet states. Analyses of some of these perturbations yield approximate values of the intersystem crossing matrix elements, from which it is concluded that the sigma=+/-1 torsional levels of the S1 state are significantly more strongly coupled to the T1 state than the sigma=0 torsional levels. 相似文献
995.
G.P. Costa A.H.A. Gonçalves L.A.V. Viana J.C.S. Soares F.B. Passos F.M.T. Mendes A.B. Gaspar 《Materials Today Chemistry》2021
Ruthenium catalysts supported on zinc-promoted amorphous-niobium mixed oxides were prepared, characterized, and studied in the additive-free partial hydrogenation of benzene reaction. The amorphous matrix of Nb2O5 was responsible for a highly active Ru/Nb2O5 catalyst, although less selective than those containing zinc. The ZnO-containing supports were prepared by wet impregnation technique, followed by incipient wetness of ruthenium chloride salt. The catalysts were characterized by textural analysis, X-ray fluorescence, X-ray diffraction, H2 chemisorption, temperature-programmed reduction (TPR), Scanning electron microscopy, H2 temperature-programmed desorption, and X-ray photoelectron spectroscopy (XPS) of the calcined-reduced samples. Chlorine retention was observed on zinc-containing samples. An unexpected ZnNb2O6 oxide phase, ascribed to a selectivity increase with less activity loss, was obtained for the supports at lower temperatures than those related on the literature. A very complex electronic environment of Ru- and Zn-containing species interactions was observed by TPR. The presence of surface-reduced (Ru0) and partially reduced (Ruδ+) Ru species observed by XPS justified well, respectively, the activity and selectivity achieved with every catalyst. The addition of water as a solvent resulted in very constant yield to cyclohexene, as expected, despite activity diminution due to low solubility of the reactants. 相似文献
996.
Leonardo Lupacchini Fabrizio Maggi Carlo Tomino Chiara De Dominicis Cristiana Mollinari Massimo Fini Stefano Bonassi Daniela Merlo Patrizia Russo 《Molecules (Basel, Switzerland)》2021,26(1)
(1) Background: Nicotine is implicated in the SARS-COV-2 infection through activation of the α7-nAChR and over-expression of ACE2. Our objective was to clarify the role of nicotine in SARS-CoV-2 infection exploring its molecular and cellular activity. (2) Methods: HBEpC or si-mRNA-α7-HBEpC were treated for 1 h, 48 h or continuously with 10−7 M nicotine, a concentration mimicking human exposure to a cigarette. Cell viability and proliferation were evaluated by trypan blue dye exclusion and cell counting, migration by cell migration assay, senescence by SA-β-Gal activity, and anchorage-independent growth by cloning in soft agar. Expression of Ki67, p53/phospho-p53, VEGF, EGFR/pEGFR, phospho-p38, intracellular Ca2+, ATP and EMT were evaluated by ELISA and/or Western blotting. (3) Results: nicotine induced through α7-nAChR (i) increase in cell viability, (ii) cell proliferation, (iii) Ki67 over-expression, (iv) phospho-p38 up-regulation, (v) EGFR/pEGFR over-expression, (vi) increase in basal Ca2+ concentration, (vii) reduction of ATP production, (viii) decreased level of p53/phospho-p53, (ix) delayed senescence, (x) VEGF increase, (xi) EMT and consequent (xii) enhanced migration, and (xiii) ability to grow independently of the substrate. (4) Conclusions: Based on our results and on evidence showing that nicotine potentiates viral infection, it is likely that nicotine is involved in SARS-CoV-2 infection and severity. 相似文献
997.
Jorge S. Almeida Lucilia A. Meira Maiara S. Oliveira Leonardo S. G. Teixeira 《X射线光谱测定》2021,50(1):2-8
An analytical method was proposed for the quantification of Cd, Pb, Mn, and Fe in ground coffee samples using energy dispersive X‐ray fluorescence (EDXRF) spectrometry. External calibration was possible using the coffee matrix itself as standards with samples previously analyzed by inductively coupled plasma optical emission spectrometry (ICP OES). The ground coffee samples were analyzed in the form of pellets, which were placed in the center of the EDXRF measuring cell for the determination of the analytes. The limits of detection were 62, 55, 86, and 76 μg/kg for Cd, Pb, Fe, and Mn, respectively. Good linearities were obtained for the calibration curves with coefficients of correlation (R) of 0.9959 for Cd, 0.9939 for Pb, 0.9929 for Fe, and 0.9909 for Mn. Precision, evaluated as the relative standard deviation (RSD) of 10 independent measurements of different cataloged samples with an approximate concentration of 400 μg/kg for each analyte, was between 6 and 14% (n = 10), demonstrating that the preparation of the samples in form of pellets was sufficient to perform analyses by EDXRF. The proposed method was applied in the determination of Cd, Pb, Fe, and Mn in ground coffee samples collected in Salvador, Bahia, Brazil. In a parallel comparative procedure, coffee samples were also analyzed by ICP OES after sample pretreatment by acid digestion. A paired Student's t test was carried out (confidence level of 95%, n = 5) and no significant difference was observed between the concentrations obtained by the proposed and comparative methods. 相似文献
998.
Mohan Giri Suman Baral Gopi Chandra Kaphle Nirmal Dangi Sudip Shiwakoti Leonardo Bardomero Paul Lashomb Walter Wilcox 《理论物理通讯》2021,73(3):35202-104
Using the Thomas-Fermi quark model,a collective,spherically symmetric density of states is created to represent a gas of interacting fermions with various degeneracies at zero temperature.Over a family of pentaquarks,uudcc,color interaction probabilities were obtained after averaging over all the possible configurations.Three different functions are developed for light,charm,and anti-charm quarks and are assumed to be linearly related by some proportionality constants.Interesting patterns of quark distributions are observed while analyzing the quark function consistency conditions for such constants. 相似文献
999.
Leonardo Rossi Cristián Huck-Iriart María Ana Castro 《Journal of Coordination Chemistry》2017,70(21):3633-3649
The reaction of dirhodium tetrakis(3,4,5-trialkoxy)benzoates Rh2(B3OCn)4 (n = 10, 14, and 18) with three different dinitrogenated axial ligands (Lax), namely tetrazine (tz), phenazine (phz), and 4,4′-bipyridine (bpy), gave rise to three homologous series of mesogenic coordination polymers, [Rh2(B3OCn)4]Lax. All of them exhibited thermotropic columnar mesophases that were of the hexagonal type for tz and phz and rectangular for bpy. The lighter n = 10 homologs of the three series are liquid crystals (LC) at room temperature. Their mesomorphic properties have been compared with those of the previously studied Lax = pyrazine series. Models for the supramolecular organization of the three polymeric series in their Col LC phases are proposed on the basis of their structural parameters, as measured by XRD and SAXS. The differences are interpreted in terms of different coordination features of the axial ligands. 相似文献
1000.
Ana P. H. Rodrigues Iaci M. Pereira Sâmara D. de Souza Camila S. Brey Gil Giovanna Machado Sandhra M. Carvalho Fabiano V. Pereira Paulo R. P. Paiva Luiz C. A. de Oliveira Patrícia S. de O. Patricio 《Cellulose (London, England)》2017,24(4):1731-1744
Collagen is an important biomaterial because it has many applications in the biomedical sector. However, the high hydrophilicity of collagen (COL) leads to easy swelling. Thus, controlling this property is highly desirable. In this work, cellulose nanocrystals (CNCs) dispersed in glycerol (GLI) were incorporated in the matrix collagen to tailor the hydrophilicity and mechanical properties. Study of the hydrophilicity of the bio-based nanocomposite was evaluated by contact angle measurement and thermogravimetric analysis. Mechanical analyses showed that CNCs are excellent reinforcing fillers to the collagen matrix. Synchrotron small-angle X-ray scattering was employed to investigate the nanostructures of COL/GLI/CNC nanocomposites and CNC water dispersion. CNC in concentrations up to 1 wt% presents an intermediate shape between a rod and a plane with a 9.34-nm radius of gyration (R g). Bio-based nanocomposites present two different structural levels with two types of particles with very different R gs. At the intermediate power-law regime, a large-scale mass fractal aggregate is observed. In the high-power-law regime, it is observed scattering from primary particles smaller than 1 nm. As the CNC concentration increases, the original particle distorts from a rod to a plate. The cytotoxicity assay indicates that the collagen and nanocomposites did not affect the cell viability of rat calvarial cells in vitro. 相似文献