New regioisomeric naphthol–thiazole based ‘turn-on’ fluorescent chemosensor for Al

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.     

The concerted and stepwise chemisorption mechanisms of isothiazole and thiazole on Si(100)?2?��?1 surface

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.     

Polarization of multiple scattered light in planetary atmospheres from solution of the coupled linear integral equations derived for mixed rayleigh-isotropic scattering

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.     

Gold(III) six-membered N^C^N pincer complexes: synthesis, structure, reactivity and theoretical calculations

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.     

Approximate and exact technique for multidimensional radiation transport in a plane parallel atmosphere; Application to the 4.3 μm auroral arc

We develop an integral equation formulation for the solution of multidimensional radiation transport problems in a plane-parallel atmosphere. The formulation is applied to a nominal case of a 4.3 μm auroral arc. The accuracy of a computation-saving, approximate method is investigated.     

Geochemical characterization of miocene core sediments from Shahbazpur gas-wells (Bangladesh) in terms of elemental abundances by instrumental neutron activation analysis

Journal of Radioanalytical and Nuclear Chemistry - Geochemical characterization of Shahbazpur structure (Bengal Foredeep) in terms of elemental abundances obtained from INAA are presented by...     

Which Hydrogen Atom of Toluene Protonates PAH molecules in (+)-Mode APPI MS Analysis?

A previous study (Ahmed, A. et al., Anal. Chem. 84, 1146–1151( 2012) reported that toluene used as a solvent was the proton source for polyaromatic hydrocarbon compounds (PAHs) that were subjected to (+)-mode atmospheric-pressure photoionization. In the current study, the exact position of the hydrogen atom in the toluene molecule (either a methyl hydrogen or an aromatic ring hydrogen) involved in the formation of protonated PAH ions was investigated. Experimental analyses of benzene and anisole demonstrated that although the aromatic hydrogen atom of toluene did not contribute to the formation of protonated anthracene, it did contribute to the formation of protonated acridine. Thermochemical data and quantum mechanical calculations showed that the protonation of anthracene by an aromatic ring hydrogen atom of toluene is endothermic, while protonation by a methyl hydrogen atom is exothermic. However, protonation of acridine by either an aromatic ring hydrogen or a methyl hydrogen atom of toluene is exothermic. The different behavior of acridine and anthracene was attributed to differences in gas-phase basicity. It was concluded that both types of hydrogen in toluene can be used for protonation of PAH compounds, but a methyl hydrogen atom is preferred, especially for non-basic compounds.      

Proton N.M.R. lineshape in nematic microdroplets

The dependence of the proton N.M.R. absorption spectrum on nematic director configuration and molecular self-diffusion in nematic submicrondroplets is analysed. The lineshape is evaluated numerically for radial and bipolar director configuration. The motional averaging is taken into account by means of a numerical simulation of the molecular diffusion which induces slow molecular reorientations due to non-uniform orientational ordering in the droplet. This diffusion process strongly affects the absorption spectra of the radial configuration, whereas spectra of the bipolar configuration are only slightly influenced. The possibility of determinating the submicrometre nematic droplet structures using the proton N.M.R. lineshape is discussed.     

DFT study of response mechanism and selectivity of poly(3,4-ethylenedioxythiophene) towards CO2 and SO2 as gas sensor

Structural Chemistry - To evaluate the sensing ability of poly(3,4-ethylenedioxythiophene) (PEDOT) towards CO2 and SO2 gaseous molecules, an extensive quantum mechanical study has been carried out...