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71.
Petr Fryčák Jaromír Jirkovský Václav Ranc Petr Bednář Vladimír Havlíček Karel Lemr 《Journal of mass spectrometry : JMS》2012,47(6):720-726
Atmospheric pressure chemical ionization is known for producing unusual artifacts of the ionization process in some cases. In this work, processes occuring in atmospheric pressure chemical ionization/MS of orotic acid that afforded ions accompanying protonated and deprotonated orotic acid molecules in the spectra were studied. Two processes ran in parallel in the ion source: decarboxylation of neutral orotic acid and collision‐induced dissociation of its protonated or deprotonated form. A procedure discerning pre‐ionization decomposition and post‐ionization dissociation by manipulating ion source parameters was proposed. Experiments with isotopically labeled solvents confirmed ion–molecule reactions of the product of collision‐induced dissociation of protonated orotic acid with solvent molecules in the ion source and even under vacuum in the ion trap. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
72.
Fryčák P Jirkovský J Ranc V Bednář P Havlíček V Lemr K 《Journal of mass spectrometry : JMS》2012,47(6):720-726
Atmospheric pressure chemical ionization is known for producing unusual artifacts of the ionization process in some cases. In this work, processes occuring in atmospheric pressure chemical ionization/MS of orotic acid that afforded ions accompanying protonated and deprotonated orotic acid molecules in the spectra were studied. Two processes ran in parallel in the ion source: decarboxylation of neutral orotic acid and collision-induced dissociation of its protonated or deprotonated form. A procedure discerning pre-ionization decomposition and post-ionization dissociation by manipulating ion source parameters was proposed. Experiments with isotopically labeled solvents confirmed ion-molecule reactions of the product of collision-induced dissociation of protonated orotic acid with solvent molecules in the ion source and even under vacuum in the ion trap. 相似文献
73.
Summary: Aqueous acrylic dispersions of hydroxy-functionalised copolymer microgel particles crosslinked with allyl methacrylate were synthesized by emulsion polymerization. The microgels were investigated as reactive polymer fillers in mixtures with a water-borne film-forming dispersion. Properties of coatings cast from mixtures of aqueous dispersion of hard microgel particles and film-forming water-borne dispersion were investigated. The swelling behaviour of microgels in selected solvents (aliphatic ketones) as a function of microgel composition is discussed as well. It was found that the swelling ability of microgels decreased with growing degree of crosslinking. Microgels comprising copolymerised butyl methacrylate swelled less in aliphatic ketones than microgels without this comonomer. This work was focused mainly on the influence of microgels incorporated in the commercial solvent-borne acrylic binders on the properties of coatings. It was shown that the application of microgels that were redispersed in acetone did not affect the surface appearance and transparency of coatings. Moreover, the presence of microgel network precursors accelerated film curing at ambient temperature and improved the final hardness of coatings. 相似文献
74.
The work deals with numerical modelling of several turbulent 3D jet flows: steady impinging jet, steady free jet in cross–flow, synthetic free jet (unsteady) and synthetic impinging jet (unsteady). The numerical method is based on artificial compressibility method with dual time extension for unsteady cases. Space discretization uses cell–centered finite volume method with third order accurate upwind approximation for convection, the time discretisations are implicit. Turbulence is modelled using two–equation eddy viscosity models and by explicit algebraic Reynolds stress model (EARSM by Wallin and Hellsten). The results of first three cases are compared with measurements. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
75.
Jiří Hanika Jaromír Lederer František Nečesaný Walter Poslední Vratislav Tukač Václav Veselý 《Chemical Papers》2014,68(12):1701-1706
The reason for this investigation into the partial oxidation (POX) of high-boiling hydrocarbons with oxygen in the presence of water vapour was to ensure increased demand on hydrogen, which is essential for the deeper hydrorefining of petroleum oils to ensure better quality of motor fuels. The tests demonstrated the good performance of the pilot plant unit and also the reproducibility of the experiment. The investigation detected a significant impact of water vapour on the selectivity of the partial oxidation of high boiling-point hydrocarbons with regard to the composition of the exhaust gas. In addition, it was noted that the hydrogen content in the reaction product of the partial oxidation of the mixture of visbreaking distillate and residue diluted with pyrolysis fuel oil, achieved 50 %. The content of components in the gaseous product accorded well with a synthesis gas composition produced by the plant unit of the UNIPETROL RPA Co., designed and built under licence from the Shell Petroleum Co. 相似文献
76.
Iva Honzíčková Jan Honzíček Jaromír Vinklárek Zdeňka Padělková Martina Řezáčová Lucie Šebestová 《应用有机金属化学》2014,28(4):252-258
A series of new ring‐functionalized niobocene dichloride compounds (RCH2C5H4)2NbCl2 (R = MeOCH2, (CH2)5NCH2, 2‐MeOC6H4, 3‐MeOC6H4, 4‐MeOC6H4, 2,4‐(MeO)2C6H3, 3,4‐(MeO)2C6H3, 2,4,6‐(MeO)3C6H2, 3,4,5‐(MeO)3C6H2, 4‐FC6H4, 4‐Me2NC6H4) was synthesized and characterized by electron paramagnetic resonance. Three structures were determined by X‐ray diffraction analysis and revealed the expected bent metallocene structure with two cyclopentadienyl ligands and two chlorides coordinated to niobium in the oxidation state IV. Chlorides and the centroids of the η5‐bonded cyclopentadienyl rings define a distorted tetrahedron. The cytotoxicity study has demonstrated that substitution with methoxybenzyl groups can lead to highly active species, but the activity strongly varies with the number and positions of the methoxy groups in the benzene ring. The most active species under study – {2,4‐(MeO)2C6H3CH2C5H4}2NbCl2 – has a maximal inhibitory concentration value comparable with cisplatin. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
77.
The 1H and 13C NMR chemical shifts of cis- and trans-protopinium salts were measured and calculated. The calculations of the chemical shifts consisted of conformational analysis, geometry optimization (RHF/6-31G** method) and shielding constants calculations (B3LYP/6-31G** method). Based on the results of the quantum chemical calculations, two sets of experimental chemical shifts were assigned to the particular isomers. According to the experimental results, the trans-isomer is more stable and its population is approximately 68%. 相似文献
78.
The kinetics and mechanism of the degradation reactions of substituted phenyl N-hydroxycarbamates and their N-methyl and N-phenyl analogues have been studied at pseudo-first-order reaction conditions in aqueous buffers and sodium hydroxide solutions at 20 [degree]C and 60 [degree]C and at I= 1 mol[middle dot]l(-1). The dependence of log k(obs) on pH for phenyl N-hydroxycarbamates at pH < 9 and pH > 13 is linear with the unit slope; at pH 10-12 log k(obs) is pH independent. The Bronsted coefficient [small beta](lg) is about -1 (pH 7-13) and -1.53 (pH > 13) indicating that the degradation reaction of phenyl N-hydroxycarbamates follows an E1cB mechanism giving the corresponding phenol/phenolate and HO-N[double bond, length as m-dash]C[double bond, length as m-dash]O. The latter species undergoes further decomposition to give carbonate, nitrogen and ammonia as final products. In contrast to the phenyl N-hydroxycarbamates the N-methyl derivatives at pH 7-9 undergo degradation to the corresponding phenol/phenolate, carbonate and methylamine via a concerted mechanism ([small beta](lg) is about -0.75). The only exception is 4-nitrophenyl N-hydroxy-N-methylcarbamate in which the predominant break down pathway proceeds via the Smiles rearrangement to give sodium N-methyl-(4-nitrophenoxy)carbamate. At pH > 9 the reaction of N-hydroxy-N-methylcarbamates is kinetically complex: the dependence of absorbance on time is not exponential and it proceeds as a consecutive two-step reaction. N-Hydroxy-N-phenylcarbamate under the same conditions undergoes degradation to phenol, carbonate, aniline and azoxybenzene. 相似文献
79.
80.