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1.
《Journal of Saudi Chemical Society》2020,24(10):754-764
A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λmax = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k1 versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k1) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = sN (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. . 相似文献
2.
A likelihood-based method for haplotype association studies of case-control data with genotyping uncertainty 总被引:1,自引:0,他引:1
ZHU Wensheng & GUO Jianhua School of Mathematics Statistics Northeast Normal University Changchun China 《中国科学A辑(英文版)》2006,49(1):130-144
This paper discusses the associations between traits and haplotypes based on Fl (fluorescent intensity) data sets. We consider a clustering algorithm based on mixtures of t distributions to obtain all possible genotypes of each individual (i.e. "GenoSpec-trum"). We then propose a likelihood-based approach that incorporates the genotyping uncertainty to assessing the associations between traits and haplotypes through a haplotype-based logistic regression model. Simulation studies show that our likelihood-based method can reduce the impact induced by genotyping errors. 相似文献
3.
F.E. SalmanN. Shash H. Abou El-HadedM.K. El-Mansy 《Journal of Physics and Chemistry of Solids》2002,63(11):1957-1966
AC conductivity and dielectric studies on vanadium phosphate glasses doped with lithium have been carried out in the frequency range 0.2-100 kHz and temperature range 290-493 K. The frequency dependence of the conductivity at higher frequencies in glasses obeys a power relationship, σac=Aωs. The obtained values of the power s lie in the range 0.5≤s≤1 for both undoped and doped with low lithium content which confirms the electron hopping between V4+ and V5+ ions. For doped glasses with high lithium content, the values of s≤0.5 which confirm the domination of ionic conductivity. The study of frequency dependence of both dielectric constant and dielectric loss showed a decrease with increasing frequency while they increase with increasing temperature. The results have been explained on the basis of frequency assistance of electron hopping besides the ionic polarization of the glasses. The bulk conductivity increases with increasing temperature whereas decreases with increasing lithium content which means a reduction of the V5+. 相似文献
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Electrical impedance measurements of Na3H(SO4)2 were performed as a function of both temperature and frequency. The electrical conductivity and dielectric relaxation have been evaluated. The temperature dependence of electrical conductivity reveals that the sample crystals transformed to the fast ionic state in the high temperature phase. The dynamical disordering of hydrogen and sodium atoms and the orientation of SO4 tetrahedra results in fast ionic conductivity. In addition to the proton conduction, the possibility of a Na+ contribution to the conductivity in the high temperature phase is proposed. The frequency dependence of AC conductivity is proportional to ωs. The value of the exponent, s, lies between 0.85 and 0.46 in the room temperature phase, whereas it remains almost constant, 0.6, in the high-temperature phase. The dielectric dispersion is examined using the modulus formalism. An Arrhenius-type behavior is observed when the crystal undergoes the structural phase transition. 相似文献
7.
Stephen Butkewitsch 《Applied Surface Science》2006,252(23):8277-8286
The present study showed that sulfonated poly(styrene-ethylene/butylenes-styrene) (S-SEBS) triblock copolymer ionomers can be made to exhibit dielectric constants on the order of a hundreds thousand. Although they are too lossy at this point to use as dielectric materials in capacitors or as electrostrictive Maxwell effect transducer materials because of their high hydrogen ion conductivity, the results of these initial dielectric studies as a function of ion content were used to try to understand the effects of a polar plasticizer, water, on dielectric properties of the acid form of this ionomer. This was done before moving on to more tightly bound ions (rather than the hydrogen ions of the sulfonic acid groups used here) and to other polar, less mobile plasticizers (which also interact strongly with the ionic dipoles). The discovery of such high dielectric constants suggested the possibility that low dielectric loss versions of this type of polymer, as well as other members of the class known as ionomers, might find future applications as extremely high dielectric constant materials in capacitors or transducers. Experimental results for films with degrees of sulfonation on the order of 10% or more showed dielectric constants on the order of ?′ ∼ 100,000 but dielectric loss tangents near D = tan δ ∼ 0.3, when the materials were exposed to high humidity conditions. Experiments to determine the effects of water content on the material's dielectric response showed that water can easily move into and out of the films studied and that this transport behavior is strongly correlated to the relative humidity of the environment and to the degree of sulfonation. Water content, in this case, was thus the primary consideration when attempting to understand the observed high dielectric constants in films with degree of sulfonation greater than 5.5%. However, vacuum-dried films were, also, examined and observed to exhibit a dielectric constant on the order of 2 until the degree of sulfonation was greater than 11%. Above this value, the dielectric constant increased by approximately 100% to a value on the order of 4. 相似文献
8.
A series of low density polyethylene systems has been studied with respect to structural evolution and short-term dielectric breakdown behaviour. All materials were based upon a single polymer, that is commonly used in high voltage applications, but with different additives. In all three of these systems, multiple melting transitions were observed, as a result of molecular fractionation effects during crystallization. In the virgin polymer, a space-filling banded spherulitic morphology was found to develop at low temperatures (102 °C and below) whereas, at higher temperatures, only a few isolated axialites were observed. Inclusion of the antioxidant resulted in greatly increased nucleation densities, such that, at low temperatures, no evidence of spherulitic organisation remained. At higher temperatures, sheaf-like lamellar aggregates developed, which were much smaller and much more numerous than in the case of the virgin polymer. Further addition of dicumyl peroxide (DCP) resulted in the rapid formation of a crosslinked network at 200 °C. Some crosslinking also occurred at 150 °C, but over a much longer timescale. Where extensive crosslinking occurred prior to crystallization, the resulting gel inhibited structural development, such that only a few small, isolated sheaves were able to form at 102 °C. In view of the principal application area of this material, the breakdown strength of each of the above systems was then measured and the whole data set was analysed statistically. When structural factors were considered alongside the statistics, no clear trends emerged to indicate that either the compositional or morphological variations were reflected in the short-term electrical failure processes. 相似文献
9.
1 INTRODUCTION Carbon nanotubes have many potential applica- tions due to their unique structures and properties[1~4]. Physicists have been studying their electrical, me- chanical and other properties since their discove- ries[5, 6]. Recently, chemists are interested in carbon nanotubes because their properties can be altered by chemical functionalization[7~14], and these functiona- lized nanotubes can undergo further chemical trea- tment. So the potential application range of such na- … 相似文献
10.
Studies of thickness and temperature dependencies of the dielectric susceptibility of nitrobenzene interlayers formed on conductive substrates were carried out. The obtained data were processed under the assumption of the existence of dimers (with opposite directions of molecular dipole moments) in orientationally ordered wall-adjacent layers. The results were treated on the basis of Lifshits theory. 相似文献