Two new reactive and highly selective turn-on fluorescent chemosensors based on the position of ring annulation of the naphthalene–thiazole moiety for aluminum ions in ethanol, were synthesized and investigated. It was found that sensors 2 and 4 exhibited a remarkable enhancement of emission upon complexation with Al3+. A TD-B3LYP/6-31G(d,p) calculation was performed to characterize the nature of the fluorescence behavior of sensors 2 and 4 upon Al3+ complexation. The mechanism of fluorescence was based on the cation promoted hydrolysis of ester and subsequent complexation. The combination of experimental and computational analyses provides a more complete understanding of the molecular level origin of these types of unique photophysical properties. 相似文献
A new phenanthroindolizidine alkaloid, 3-O-demethyl tylophorinidine (VI), was isolated from the aerial (leaves and stem) parts of Tylophora indica and characterized using different spectral techniques. Gel chromatography and reverse phase preparative HPLC were used for sample purification. The new alkaloid, VI, was screened for anticancer activity against a panel of different cancer cell lines and it showed significant anticancer activity with IC50 value in the range of 0.89?C1.40 ??M. 相似文献
Protein allostery is a phenomenon involving the long range coupling between two distal sites in a protein. In order to elucidate allostery at atomic resoluion on the ligand-binding WW domain of the enzyme Pin1, multistate structures were calculated from exact nuclear Overhauser effect (eNOE). In its free form, the protein undergoes a microsecond exchange between two states, one of which is predisposed to interact with its parent catalytic domain. In presence of the positive allosteric ligand, the equilibrium between the two states is shifted towards domain–domain interaction, suggesting a population shift model. In contrast, the allostery-suppressing ligand decouples the side-chain arrangement at the inter-domain interface thereby reducing the inter-domain interaction. As such, this mechanism is an example of dynamic allostery. The presented distinct modes of action highlight the power of the interplay between dynamics and function in the biological activity of proteins. 相似文献
The surface reaction pathways of isothiazole and thiazole on Si(100)?2?×?1 surface were theoretically investigated using multireference wavefunctions. In the case of isothiazole, the Si?CN dative adduct turned out to be the major surface product. In contrast, a direct reaction competition between a concerted [4?+?2]CC cycloaddition and Si?CN dative adduct was found in the adsorption of thiazole. Therefore, it is concluded that the particular geometric arrangements of heteroatoms exhibit distinctly different initial surface reaction mechanisms. 相似文献
A set of coupled integral equations describing nonconservative multiple scattering for a mixed isotropic and Rayleigh single scattering phase function in inhomogeneous, plane-parallel planetary atmospheres is derived. The equations are applicable for the frequency redistributions MRE (monochromatic radiative equilibrium), CFR (complete frequency redistribution), or PFR (partial frequency redistribution). Solution of the equations permits one to calculate the intensity and degree of polarization in an arbitrary direction outside or inside the plane-parallel scattering medium. The equations are readily adaptable to more complicated geometries. Solutions for several cases are presented to demonstrate the versatility and validity of the method. These include a calculation of MRE pure Rayleigh scattering of sunlight in an optically-thick planetary atmosphere to demonstrate agreement with the results of Coulson(1)et al. (1960), calculations of the altitude profile of the degree of polarization of the earth's Ly-α 1216A and helium 584A dayglow, and the center to limb variation of the degree of polarization of the sunlight diffusely reflected from a distant planet such that the scattering is pure Rayleigh and conservative at the top of the planet's atmosphere, varying smoothly to conditions of nonconservative and pure isotropic scattering deep in the planet's atmosphere. Tables of functions that one might utilize (without resort to a digital computer) to obtain solutions in the escape function approximation are also given. 相似文献
In this paper we report results from some investigations on the use of ultrasonics in controlling hydrodynamic cavitation in the shear layer downstream of a sudden expansion. Control of this type of cavitation has been achieved by modulating the local pressure that was experienced by a nucleus present in the shear layer. This modulation was made possible by using a piezoelectric device, termed as Ultrasonic Pressure Modulator (UPM). The performance of UPM has been studied at different dissolved gas concentrations with electrolysis bubbles as nuclei. Control of cavitation due to natural nuclei has also been attempted. Efficiency of UPM, in reducing cavitation, was seen to be dependent on the driving frequency employed. Experimental and numerical studies have been conducted to bring out the physics behind this approach of cavitation control. Different measures of cavitation control have been identified and some possible applications of this method have also been outlined. 相似文献
Research on Chemical Intermediates - The synthesis of a new series of triazole-biscoumarin conjugates by using a molecular hybridization approach is described. The newly synthesized compounds... 相似文献
Lysozyme is widely used for the synthesis of nanomaterials (e.g., gold nanoparticle) to fluorescently sense metal ions. However, the effect of metal ions on the fluorescence of lysozyme is not studied yet. Herein, we have explored the interactions of lysozyme with different metal ions to develop a direct sensing platform for Fe(III). It has been observed that the fluorescence of lysozyme was slightly decreased in the presence of Cu(II), Hg(II), As(V), Co(II), Cd(II), Cr(II), Fe(II), Mn(II), Pb(II), and Zn(II), while a significant decrease in the lysozyme fluorescence was observed for Fe(III). The effect of thermal stability on the fluorescence quenching was also studied from 25 to 60 °C. In the present study, the lysozyme sensing probe was able to selectively and accurately detect 0.5–50 ppm of Fe(III) with a LOD of 0.1 ppm (1.8 µM) at 25 °C.
The first six-membered gold(III) N^C^N pincer complex was obtained in good yield, under very mild conditions, by transmetalation of [Hg(κC-N^C^N)Cl] (N^CH^N = 1,3-bis(pyridin-2-ylmethyl)benzene, HL(1)) with Na[AuCl(4)]. The X-ray crystal structure of [Au(N^C^N)Cl][PF(6)] showed that the fused six-membered metallacycles each exist in a strongly puckered boat conformation. As shown by the (1)H NMR spectra in various solvents, the same structure is also retained in solution: no inversion of the six-membered metallacycles is observed in DMSO up to 95 °C. This correlates well with a reaction barrier of 17.5 kcal/mole, as determined by quantum chemical calculations. The reactivity of the present pincer complex is compared to that of the analogous 1,3-bis(2-pyridyl)benzene, HL(2), derivative, which has five-membered fused metallacycles. Sharp differences are found in the reactions with phosphines, such as PPh(3) and dppe (1,2-bis-diphenylphosphino-ethane), and with silver salts. Theoretical calculations were carried out on the two pincer complexes in order to try to understand these differences, and we found that the gold-chlorine bond is significantly stronger in the case of the complex containing five-membered metallacyclic rings. 相似文献