Nucleophilic reactivities of indoles

The kinetics of the coupling of indole (1a), N-methylindole (1b), 5-methoxyindole (1c), and 5-cyanoindole (1d) with a set of reference benzhydryl cations have been investigated in acetonitrile and/or dichloromethane. The second-order rate constants for the reactions correlate linearly with the electrophilicity parameter E of the benzhydryl cations. This allows the determination of the reactivity parameters, N and s, characterizing the nucleophilicity of 1a-d according to the linear free enthalpy relationship log k(20 degrees C) = s(N + E) (Acc. Chem. Res. 2003, 36, 66). The nucleophilicity parameters thus defined describe nicely the reactions of 1a-d with 4,6-dinitrobenzofuroxan (2), a neutral superelectrophilic heteroaromatic whose electrophilicity (E) has been recently determined. On this ground, the kinetics of the coupling of 2 with a large variety of indole structures have been studied in acetonitrile, leading to a ranking of this family of pi-excessive carbon nucleophiles over a large domain of the nucleophilicity scale N. Importantly, two linear and parallel correlations are obtained on plotting the measured N values versus the pK(a)(H(2)O) values for protonation at C-3 of 5-X-substituted indoles and 5-X-substituted 2-methylindoles, respectively. This splitting reveals that the presence of the 2-methyl group causes steric hindrance to the approach of 2 from the adjacent C-3 position of an indole structure. The N vs pK(a)(H(2)O) correlation for 5-X-substituted indoles is used for a rapid determination of the C-3 basicity of indoles whose acidity constants cannot be measured through equilibrium studies in strongly acidic aqueous media.     

Thickness effect on the structural and optical constants of stibnite thin films prepared by sulfidation annealing of antimony films

This paper deals with some physical properties of antimony sulphide Sb₂S₃ thin films obtained by an annealing process in sulphur vapors at 300 °C of Sb thermal evaporated thin films deposited on glass substrate. The crystal structure and surface morphology were investigated by both XRD and AFM techniques. This structural study shows that Sb₂S₃ thin films were well crystallized in orthorhombic structure and some parameters such as the lattice parameter, crystallite size, microstrain and degree of preferred orientation have been reported and correlated with the effect of crystallite size. On the other hand, the refractive index and the extinction coefficient were discussed in terms of the Forouhi–Bloomer model. The optical band gap was found to range from 1.75 to 2.23 eV. Finally, the analysis of the optical parameters extracted from the Urbach–Martienssen and Forouhi–Bloomer models lead to some explanations of the correlations between the structural properties in terms of the crystallite size and optical ones.     

Nucleophilicity parameters of enamides and their implications for organocatalytic transformations

The kinetics of the reactions of eleven substituted enamides with benzhydrylium ions (diarylcarbenium ions) were determined in acetonitrile solution. The second-order rate constants follow the correlation log k(2) (20 °C)=s(N)(E+N), which allowed us to derive reactivity parameters N and s(N). With 4.6相似文献   

Calculation of self-absorption coefficients of calcium resonance lines in the case of a CaCl2–water plasma

The resonance escape factors for the lines emitted by a neutral calcium atom Ca I at 4226.73 Å and of ionic calcium Ca II at 3933.66 Å and at 3968.47 Å are calculated assuming a Voigt profile and in the case of CaCl₂–water plasma. The dependence of the escape factor on the optical thickness ?₀ from the line center which itself depends on the two main spectral line shape broadening mechanisms (pressure and Doppler effects) are considered. The variation of the resonance escape factors with the temperature, the CaCl₂ molar proportion and the size of the plasma are also investigated. This calculation is useful for the application of Laser-Induced Breakdown Spectroscopy in the quantitative analysis of elemental composition. Its application allows us to reduce the non-linearities in the relation between resonance lines intensities of calcium in our case and its concentration.     

Mixed micellization and surface properties of non-ionic/cationic surfactants

We investigate the surface properties of aqueous binary mixtures of our cationic surfactant O-dodecyl-N,N′-diisopropylisourea hydrochloride (ISO-DIC C₁₂) with commercially available nonionic surfactant polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether (TritonX-100) at different temperatures (288 to 303?K). The micellization behavior of the binary systems is studied by determining the surface tension and other important physicochemical parameters, such as the critical micelle concentration (CMC), surface tension at the CMC(γ_cmc), Krafft Temperature (T_K), maximum excess concentration (Γ_max), minimum surface area per molecule (A_min), surface pressure at the CMC (П_cmc), and the adsorption efficiency (pC20) at the air/water interface. The study has additionally covered the calculation of thermodynamic parameters of micellization, including the standard Gibbs free energy, the standard enthalpy, the standard entropy, the free energy, and the Gibbs free energy of adsorption at air/water interface. The CMC values of the binary systems determined by experimental data are used to evaluate the micellar composition in the mixed micelle, the interaction parameter β and the activity coefficients f₁(ISO-DIC C₁₂) and f₂ (polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether) using the theoretical treatment proposed by Clint and Rubingh. Our results reveal that the proposed binary systems possess enhanced surface activity compared to those of the individual surfactants.     

Filtering of continuous-time Markov chains

This paper discusses finite-dimensional optimal filters for partially observed Markov chains. A model for a system containing a finite number of components where each component behaves like an independent finite state continuous-time Markov chain is considered. Using measure change techniques various estimators are derived.     

On a Partially Observed Illness-Death Model

A biological population with N individuals assumed to be healthy is monitored over time. A portion of these individuals die from natural causes while other may get infected with a disease and become sick. A number of the sick individuals will then die from natural causes and other may die from the disease. A stochastic model for the various transitions ‘healthy, sick, death’, is studied where it is assumed that the only observed states are deaths. Based on these information, optimal filters for the number of individuals in each state are derived. This revised version was published online in August 2006 with corrections to the Cover Date.     

On Abstract Third-Order Differential Equation and Its Applications

Acta Mathematica Sinica, English Series - In this paper, we consider an abstract third-order differential equation and deduce some results on the maximal regularity of its strict solution. We...     

Efficiency of purchasing and selling agents in markets with quality uncertainty: The case of illicit drug transactions

Since Akerlof’s theory of lemons, economists have viewed quality uncertainty as an informational advantage for sellers. Drawing on frontier techniques, we propose in this paper a simple method for measuring inefficiency of both sellers and buyers in markets for goods with different levels of quality. We apply a non-parametric robust double-frontier framework to the case of illicit substance markets, which suffer from imperfect information about drug quality for purchasers and to a lesser extent for sellers. We use unique data on cannabis and cocaine transactions collected in France that include information about price, quantity exchanged and purity. We find that transactional inefficiency does not really benefit either dealers or purchasers. Furthermore, information influences the performance of agents during market transactions.