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61.
Electrode reactions followed by very fast chemical reactions are considered. A simple approach, in which steady state and linear concentration profiles in the reaction layer are assumed, is proposed for the simulation of these processes when the substrate is not present in large excess. When the substrate/depolarizer mole ratio is less than one, two well-separated peaks are detected; under such conditions, working curves that enable the corresponding second-order homogeneous rate constant to be evaluated can be derived by the finite-difference simulation technique. The method is applied to elucidation of the reduction of the tetrakis(triphenylphosphine)nickel(I) complex in the presence of hydrogen ions in acetonitrile at ?30°C. 相似文献
62.
Cyclohexanone and cycloheptanone can be enantioselectively functionalized in the 3-position with up to 92% ee and 87% ee, respectively, by the base-promoted dimerization of the corresponding enones using 3,4,5-tribenzyloxybenzyl cinchoninium bromide, as a new effective catalyst. 相似文献
63.
For a topological space X and a point x ∈ X, consider the following game—related to the property of X being countably tight at x. In each inning n ∈ ω, the first player chooses a set A n that clusters at x, and then the second player picks a point a n ∈ A n ; the second player is the winner if and only if \(x \in \overline {\left\{ {{a_n}:n \in \omega } \right\}} \).In this work, we study variations of this game in which the second player is allowed to choose finitely many points per inning rather than one, but in which the number of points they are allowed to choose in each inning has been fixed in advance. Surprisingly, if the number of points allowed per inning is the same throughout the play, then all of the games obtained in this fashion are distinct. We also show that a new game is obtained if the number of points the second player is allowed to pick increases at each inning. 相似文献
64.
The self-directed growth of organic molecules on silicon surfaces allows for the rapid, parallel production of hybrid organic-silicon nanostructures. In this work, the formation of benzaldehyde- and acetaldehyde-derived nanostructures on hydrogen-terminated H-Si(100)-2x1 surface is studied by scanning tunneling microscopy in ultrahigh vacuum and by quantum mechanical methods. The reaction is a radical-mediated process that binds the aldehydes, through a strong Si-O covalent bond, to the surface. The aldehyde nanostructures are generally composed of double lines of molecules. Two mechanisms that lead to double line growth are elucidated. 相似文献
65.
[Structure: see text] Gronert (J. Org. Chem. 2006, 71, 1209) has challenged the importance of hyperconjugation in determining C-H bond dissociation enthalpies (BDEs) in alkanes. Electron paramaganetic resonance spectra of H3CCH2*, (H3C)2CH*, and (H3C)3C* show significant positive spin on their beta-H3C groups' hydrogens. A 55%/45% partitioning of these spins between hyperconjugation and spin polarization mechanisms linearly correlates with the C-H BDEs in methane, ethane, propane, isobutane and propene. Hyperconjugation is an important factor determining alkane C-H BDEs. 相似文献
66.
Chiara Lavarello Sebastiano Barco Martina Bartolucci Isabella Panfoli Emanuele Magi Gino Tripodi Andrea Petretto Giuliana Cangemi 《Molecules (Basel, Switzerland)》2021,26(14)
Liquid-chromatography coupled to high resolution mass spectrometry (LC-HRMS) is currently the method of choice for untargeted metabolomic analysis. The availability of established protocols to achieve a high confidence identification of metabolites is crucial. The aim of this work is to describe the workflow that we have applied to build an Accurate Mass Retention Time (AMRT) database using a commercial metabolite library of standards. LC-HRMS analysis was carried out using a Vanquish Horizon UHPLC system coupled to a Q-Exactive Plus Hybrid Quadrupole-Orbitrap Mass Spectrometer (Thermo Fisher Scientific, Milan, Italy). The fragmentation spectra, obtained with 12 collision energies, were acquired for each metabolite, in both polarities, through flow injection analysis. Several chromatographic conditions were tested to obtain a protocol that yielded stable retention times. The adopted chromatographic protocol included a gradient separation using a reversed phase (Waters Acquity BEH C18) and a HILIC (Waters Acquity BEH Amide) column. An AMRT database of 518 compounds was obtained and tested on real plasma and urine samples analyzed in data-dependent acquisition mode. Our AMRT library allowed a level 1 identification, according to the Metabolomics Standards Initiative, of 132 and 124 metabolites in human pediatric plasma and urine samples, respectively. This library represents a starting point for future metabolomic studies in pediatric settings. 相似文献
67.
Kapusta Dmitry P. Firsov Denis A. Khrenova Maria G. Grigorenko Bella L. Nemukhin Alexander V. 《Structural chemistry》2019,30(2):481-488
Structural Chemistry - In this work, we focus on some structural aspects of enzyme catalysis by modeling effects of the electrostatic potential created by the solvation water shells on properties... 相似文献
68.
Aurora Modica Marco Di Bella Maria Francesca Alberghina Maria Brai Dorotea Fontana 《Natural product research》2019,33(7):987-996
AbstractThe subject of this present work is a group of nine historical pictures shot in Palermo by the Sicilian photographer E. Interguglielmi in 1912. They are nine matte-collodion prints mounted on the original cardboard supports and all of them show foxing stains affecting the paper surface. In order to characterise the chemical composition of the supports and investigate foxing spots, non-destructive and micro-destructive analysis were carried out. X-rays fluorescence (XRF) analysis was used to characterise the elemental composition of all the mounting boards, allowing a comparison between the foxing spots and non-affected areas. Laser-Induced Breakdown Spectroscopy was used to investigate the presence of lower atomic number elements, not detectable by XRF, while SEM imaging allowed the investigation of surface appearance and nature of original paper samples from the cardboards. 相似文献
69.
Stephen J. Mihailov Dan Grobnic Robert B. Walker Christopher W. Smelser Gino Cuglietta Tom Graver Alexis Mendez 《Optics Communications》2008,281(21):5344-5348
Bragg gratings are written with ultrafast 800 nm radiation and a phase mask through the polyimide polymer coatings of commercially available high NA fibres that are both unloaded and loaded with high pressure hydrogen gas. For polyimide coated fibres with very high germanium core concentrations, index modulations greater than 1 × 10−4 are induced. Stable core index modulations 60% of their original value were present after 115 h at 500 °C. 相似文献
70.