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31.
32.
The efficiency of the in-source collision-induced dissociation (in-source CID) technique for the structural characterization of microcystins (MCYSTs) was evaluated. Microcystins that did not contain arginine underwent facile fragmentation to produce characteristic product ions at relatively low cone voltage and could be fully characterized based on their mass spectra. On the other hand, cyclic peptides possessing arginine residues, such as MCYST-RR, -LR, -YR and nodularin, were considerably more stable under in-source CID conditions and required higher cone voltage to induce fragmentation. This behaviour is explained in terms of the mobile proton model for peptide fragmentation that can be used as an indication for the presence of arginine when unknown microcystins are analyzed. In-source CID was applied to the characterization of microcystins released into water from a Microcystis aeruginosa culture (UTCC299) (UTCC: University of Toronto Culture Collection of Algae and Cyanobacteria). Six microcystins were detected in extracts from UTCC299: I, [D-Asp(3)]MCYST-LR; II, MCYST-LR; III, isomer of MCYST-LR; IV, isomer of methyl MCYST-LR; V, [D-Asp(3), Glu(OCH(3))(6)]MCYST-LR; and VI, [D-Glu(OCH(3))(6)]MCYST-LR. In-source CID provided mass spectral patterns similar to those obtained by CID in the collision cell of the mass spectrometer but was more sensitive for the analysis of microcystins. 相似文献
33.
Dr. Benoit Colasson Dr. Thomas Devic Dr. Joël Gaubicher Dr. Charlotte Martineau-Corcos Prof. Philippe Poizot Dr. Vincent Sarou-Kanian 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(37):9589-9596
The synthesis and characterization of a polyrotaxanated covalent organic network (CON) based on the association between the viologen and pillar[5]arene (P[5]OH) units are reported. The mechanical bond allows for the irreversible insertion of n-type redox centers (P[5]OH macrocycles) within a pristine structure based on p-type viologen redox centers. Both redox units are active on a narrow potential range and, in water, the presence of P[5]OH greatly increases the electroactivity of the material. 相似文献
34.
In a recent post on the Seqfan list the third author proposed conjectures concerning the summatory function of odious numbers (i.e., of numbers whose sum of binary digits is odd), and of evil numbers (i.e., of numbers whose sum of binary digits is even). We prove these conjectures here. We will also study the sequences of “generalized” odious and evil numbers, and their iterations, giving in particular a characterization of the sequences of usual odious and evil numbers in terms of functional equations satisfied by their compositions. 相似文献
35.
Olivier Herbinet Benoit Husson Hervé Le Gall Frédérique Battin-Leclerc 《国际化学动力学杂志》2020,52(12):1006-1021
In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n-heptane, ethylbenzene, and n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1 100 K, and for a residence time of 2 s. Based on results previously obtained close to the atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions was compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C7 diones was found significantly enhanced at 10 bar compared with lower pressures. The oxidation of ethyl- and n-butylbenzenes was investigated at 10 bar for equivalence ratios of 0.5, 1, and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C8 fuels and of 19 products for the C10 one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities. 相似文献
36.
Christophe Lacave Toan T. Nguyen Benoit Pausader 《Journal of Mathematical Fluid Mechanics》2014,16(2):375-406
We investigate the influence of the topography on the lake equations which describe the two-dimensional horizontal velocity of a three-dimensional incompressible flow. We show that the lake equations are structurally stable under Hausdorff approximations of the fluid domain and L p perturbations of the depth. As a byproduct, we obtain the existence of a weak solution to the lake equations in the case of singular domains and rough bottoms. Our result thus extends earlier works by Bresch and Métivier treating the lake equations with a fixed topography and by Gérard-Varet and Lacave treating the Euler equations in singular domains. 相似文献
37.
Motivated by recent physics papers describing rules for natural network formation, we study an elliptic-parabolic system of partial differential equations proposed by Hu and Cai [13, 15]. The model describes the pressure field thanks to Darcy's type equation and the dynamics of the conductance network under pressure force effects with a diffusion rate D ≥ 0 representing randomness in the material structure. We prove the existence of global weak solutions and of local mild solutions and study their long term behavior. It turns out that, by energy dissipation, steady states play a central role to understand the network formation capacity of the system. We show that for a large diffusion coefficient D, the zero steady state is stable, while network formation occurs for small values of D due to the instability of the zero steady state, and the borderline case D = 0 exhibits a large class of dynamically stable (in the linearized sense) steady states. 相似文献
38.
Benoit Rigo Philippe Gautret Anne Legrand Samira El Ghammarti Daniel Couturier 《合成通讯》2013,43(18):2609-2615
Starting from the readily available N,O-bis trimethylsilyl pyroglutamate, an easy high yield one pot synthesis of ketone 1 was described. 相似文献
39.
Richard J.C. Brown Kim E. Jarvis Benoit A. Disch Sharon L. Goddard 《International journal of environmental analytical chemistry》2013,93(3):335-348
Three different types of simple and low-cost calibration material for the measurement of the metals content of ambient particulate matter (PM) on filters using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) have been compared: cellulose ester filters spiked with multi-element calibration solutions, pellets of compressed ambient particulate matter certified reference material (CRM), and powdered ambient particulate matter CRM adhered to a surface. Elements determined were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn, each at approximate levels of 1000?ng per filter. Blank filters spiked with multi-elemental standards were found to be significantly more reproducible and repeatable than materials based on powdered reference materials. However, a comparison of these spiked filters with real samples of ambient PM showed that the analytical sensitivities obtained per mass of analyte were significantly different. It is concluded that the spiked filters could act as very effective quality control standards correcting, to within 1%, drifts in LA-ICP-MS measurements of up to 10%, or as indirect calibration materials supported by additional measurements using traditional wet chemical techniques. 相似文献
40.
Dr. Nicolas Menard Prof. Dr. Olivia Reinaud Dr. Benoit Colasson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(2):642-653
A biomimetic strategy for the monofunctionalization of a calix[6]arene core is described. It is based on host–guest chemistry (mimicking the Michaelis–Menten adduct in enzymes) and allows the finely tuned pre‐organization of the substrate (an alkyne) with respect to the reactant (three azido groups introduced at the calixarene large rim). It is shown that the thermal Huisgen reaction implemented in this work proceeds under very mild conditions with total regioselectivity of the cycloaddition process. The scope of the reaction was explored and the results suggest that such a supramolecular strategy is quite versatile and could be applied to the selective functionalization of other cavitands bearing different recognition patterns. A detailed structural, thermodynamic, and kinetic study is also reported, highlighting interesting biomimetic features: The importance of the host–guest adduct strength, the high sensitivity of the reaction to the pre‐organization of the reactive partners (alkyne vs. azide), and a significant impact of the embedment on the transition state. The self‐coordination of the monofunctionalized products was also studied and an “endo/exo” switch of the internal side‐chain could be triggered by adding competitive ligands. 相似文献