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1.
Forryan CL Klymenko OV Brennan CM Compton RG 《The journal of physical chemistry. B》2005,109(16):8263-8269
Understanding the mechanisms of solid-liquid systems is fundamental to the development and operation of processes for the production of agrochemicals and pharmaceuticals. The use of a strong inorganic base in an organic solvent, typically, potassium carbonate in dimethylformamide, is often used to facilitate the formation of a required anionic organic nucleophile. In this paper, the dissolution kinetics of potassium carbonate in dimethylformamide at elevated temperatures is studied in the presence of ultrasound, as revealed via monitoring of the deprotonation of 2-cyanophenol by dissolved K2CO3. Two independent experimental methods were employed; the loss of 2-cyanophenol was detected electrochemically at a platinum microdisk working electrode, and the formation of the 2-cyanophenolate anion was monitored via UV/visible spectroscopic analysis. The results were modeled by fitting the experimental data to a theoretical model for the surface-controlled dissolution of solid particles. The dissolution rate constant, k, for the dissolution of K2CO3 in DMF was found to have a value of (1.3 +/- 0.2) x 10(-7) mol cm(-2) s(-1) at 100 degrees C, and the activation energy for the dissolution was 44.2 +/- 0.4 kJ mol(-1) over the temperature range of 70-100 degrees C studied. 相似文献
2.
Tippmann EM Platz MS Svir IB Klymenko OV 《Journal of the American Chemical Society》2004,126(18):5750-5762
Laser flash photolysis (LFP, 308 nm) of endo-10-halo-10'-N,N-dimethylcarboxamidetricyclo[4.3.1.0]-deca-2,4-diene (1Cl and 1F) releases indan and halocarbene amide (2Cl and 2F). Although the carbenes are not UV-vis active, they react rapidly with pyridine to form ylides (4Cl, 4F), which are readily detected in LFP experiments (lambda(max) = 450 nm). Dioxane decreases the observed rate of carbene reaction with pyridine in CF(2)ClCFCl(2). Small amounts of THF decrease the observed rate of reaction of carbene 2F with pyridine but increase the rate of reaction of carbene 2Cl with pyridine. LFP (266 nm) of dienes 1Cl and 1F in CF(2)ClCFCl(2) with IR detection produces carbenes 2Cl and 2F with carbonyl vibrations at 1635 and 1650 cm(-1), respectively. In dioxane or THF solvent, LFP produces the corresponding ether ylides (5Cl, 5F) by capture of carbenes 2Cl and 2F. The ylides have broad carbonyl vibrations between 1560 and 1610 cm(-1). The addition of a small amount of dioxane in CFCl(2)CF(2)Cl extends the lifetime of the carbene. This observation, together with the ether-induced retardation of the rates of carbene capture by tetramethylethylene and pyridine, is evidence for solvation of the carbene by dioxane. 相似文献
3.
Obernikhina Nataliya V. Kachaeva Maryna V. Kachkovsky Oleksiy D. Brovarets Volodymyr S. 《Chemistry of Heterocyclic Compounds》2022,58(8-9):412-420
Chemistry of Heterocyclic Compounds - For the estimation of the biological affinity of nitrogen-containing π-conjugated heterocyclic systems toward amino acid residues in proteins, the... 相似文献
4.
We find a set of necessary and sufficient conditions under which the weight ${w: E \rightarrow \mathbb{R}^{+}}$ on the graph G = (V, E) can be extended to a pseudometric ${d : V \times V \rightarrow \mathbb{R}^{+}}$ . We describe the structure of graphs G for which the set ${\mathfrak{M}_{w}}$ of all such extensions contains a metric whenever w is strictly positive. Ordering ${\mathfrak{M}_{w}}$ by the pointwise order, we have found that the posets $({\mathfrak{M}_{w}, \leqslant)}$ contain the least elements ρ 0,w if and only if G is a complete k-partite graph with ${k \, \geqslant \, 2}$ . In this case the symmetric functions ${f : V \times V \rightarrow \mathbb{R}^{+}}$ , lying between ρ 0,w and the shortest-path pseudometric, belong to ${\mathfrak{M}_{w}}$ for every metrizable w if and only if the cardinality of all parts in the partition of V is at most two. 相似文献
5.
Oleksiy O. Vakhnenko 《Journal of Nonlinear Mathematical Physics》2017,24(2):250-302
We summarize the most featured items characterizing the semi-discrete nonlinear Schrödinger system with background-controlled inter-site resonant coupling. The system is shown to be integrable in the Lax sense that make it possible to obtain its soliton solutions in the framework of properly parameterized dressing procedure based on the Darboux transformation. On the other hand the system integrability inspires an infinite hierarchy of local conservation laws some of which were found explicitly in the framework of generalized recursive approach. The system consists of two basic dynamic subsystems and one concomitant subsystem and it permits the Hamiltonian formulation accompanied by the highly nonstandard Poisson structure. The nonzero background level of concomitant fields mediates the appearance of an additional type of inter-site resonant coupling and as a consequence it establishes the triangular-lattice-ribbon spatial arrangement of location sites for the basic field excitations. Adjusting the background parameter we are able to switch over the system dynamics between two essentially different regimes separated by the critical point. The system criticality against the background parameter is manifested both indirectly by the auxiliary linear spectral problem and directly by the nonlinear dynamical equations themselves. The physical implications of system criticality become evident after the rather sophisticated canonization procedure of basic field variables. There are two variants of system standardization equal in their rights. Each variant is realizable in the form of two nonequivalent canonical subsystems. The broken symmetry between canonical subsystems gives rise to the crossover effect in the nature of excited states. Thus in the under-critical region the system support the bright excitations in both subsystems, while in the over-critical region one of subsystems converts into the subsystem of dark excitations. 相似文献
6.
基于前体聚合状态对碳材料进行分类以发展结构-性质关系(英文) 总被引:1,自引:0,他引:1
Modern carbon science lacks an efficient structure-related classification of materials. We present an approach based on dividing carbon materials by the aggregate state of the precursor. The common features in the structure of carbon particles that allow putting them into a group are discussed, with particular attention to the potential energy stored in the carbon structure from different rates of relaxation during the synthesis and prearrangement of structural motifs due to the effect of the precursor structure. 相似文献
7.
Photoinitiated radical carbonylation with [(11)C]carbon monoxide at low concentration was employed in syntheses of carbonyl-(11)C-labeled amides using alkyl iodides and amines as precursors. Eleven (11)C-amides were synthesized in up to 74% decay-corrected radiochemical yields with reaction times of 400 s and with up to 95% conversion of carbon monoxide. Starting with 26.3 GBq of [(11)C]carbon monoxide, 10.6 GBq of 1-cyclohexane [(11)C]carbonyl-4-phenyl-piperazine (15) was obtained within 35 min from the end of bombardment (33 microA) and with a specific radioactivity of 192 GBq/micromol at the same time point. The influence of solvents was investigated. The described procedure extends the range of accessible labeling methods. The method may also be useful for preparation of (13)C- and (14)C-substituted compounds. 相似文献
8.
Volodymyr D. Khavryuchenko Oleksiy V. Khavryuchenko Vladyslav V. Lisnyak 《固体与材料科学评论》2011,36(2):47-65
This article describes the genesis of amorphous silica under high-heat conditions from SiO2 molecules through protoparticles, primary particles, and aggregates to agglomerates using vibrational spectra and quantum chemical simulations data. The impact of small molecules (water, HCl, CO2) is also discussed. The article also explains the nature of the pyrogenic silica amorphism. 相似文献
9.
Nesterov DS Kokozay VN Jezierska J Pavlyuk OV Boča R Pombeiro AJ 《Inorganic chemistry》2011,50(10):4401-4411
The three novel heterometallic complexes [CuCo(III)Co(II)(2)(MeDea)(3)Cl(3)(CH(3)OH)(0.55)(H(2)O)(0.45)](H(2)O)(0.45) (1), [CuCo(III)Zn(2)(MeDea)(3)Cl(3)(CH(3)OH)(0.74)(H(2)O)(0.26)](H(2)O)(0.26) (2), and [CuCo(III)Zn(2)(MeDea)(3)Cl(3)(DMF)] (3) have been prepared using a one-pot reaction of copper powder with cobalt chloride (1) and zinc nitrate (2, 3) in a methanol (1, 2) or dimethylformamide (3) solution of N-methyldiethanolamine. A search of the Cambridge Structural Database shows that the tetranuclear asymmetric cores M(4)(μ(3)-X)(μ-X)(5) of 1-3 represent an extremely rare case of M(4)X(6) arrays. The magnetic investigations of 1 disclose antiferromagnetic coupling in a Co(II)-Cu(II)-Co(II) exchange fragment with J(Co-Cu)/hc = -4.76 cm(-1), J(Co-Co)/hc = -2.76 cm(-1), and D(Co)/hc = +34.3 cm(-1). Compounds 1-3 act as precursors for the mild peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone with overall yields up to 23%. The synthetic and structural features as well as the thermogravimetric behavior and electrospray ionization mass spectrometry data are discussed. 相似文献
10.
Russell G Evans Oleksiy V Klymenko Paul D Price Stephen G Davies Christopher Hardacre Richard G Compton 《Chemphyschem》2005,6(3):526-533
Measurements on the diffusion coefficient of the neutral molecule N,N,N',N'-tetramethyl-para-phenylenediamine and the radical cation and dication generated by its one- and two-electron oxidation, respectively, are reported over the range 298-348 K in both acetonitrile and four room temperature ionic liquids (RTILs). Data were collected using single and double potential step chronoamperometry at a gold disk electrode of micrometer dimension, and analysed via fitting to the appropriate analytical expression or, where necessary, to simulation. The variation of diffusion coefficient with temperature was found to occur in an Arrhenius-type manner for all combinations of solute and solvent. For a given ionic liquid, the diffusional activation energies of each species were not only closely equivalent to each other, but also to the RTIL's activation energy of viscous flow. In acetonitrile supported with 0.1 M tetrabutylammonium perchlorate, the ratio in diffusion coefficients of the radical cation and dication to the neutral molecule were calculated as 0.89 +/- 0.05 and 0.51 +/- 0.03, respectively. In contrast, amongst the ionic liquids the same ratios were determined to be on average 0.53 +/- 0.04 and 0.33 +/- 0.03. The consequences of this dissimilarity are considered in terms of the modelling of voltammetric data gathered within ionic liquid solvents. 相似文献