Intramolecular excimer fluorescence,its solvent dependence,and photodimerization of 1,2-dianthrylethanes

Both 1,2-di(1-anthryl)ethane (I) and 1,2-di(9-anthryl) ethane (II) show two types of excimer fluorescence spectra under different conditions; one with peak at 460 nm (type-1) and the other with peak at 530 nm (type-2). Furthermore, the type-1 excimer emission shows a peculiar dependence upon the solvent polarity.     

Salting-out extraction technique for pretreatment in the liquid chromatographic determination of copper(II), aluminum(III), iron(III) and manganese(II) in biological samples

A solvent extraction method for the simultaneous determination of Cu, Al, Fe and Mn by reversed phase liquid chromatography is presented. The metal chelates with 5-chloro-8-quinolinol are extracted into an acetonitrile phase with tetrabutylammonium perchlorate and ammonium sulfate as salting-out agents, followed by LC separation and determination using an ODS column. The experimental parameters such as the composition of mobile phase and concentration of the salting-out agent for phase separation have been investigated. The mobile phase is a mixture of 3:1 (v/v) acetonitrile-0.02 mol l(-1) sodium acetate solution containing 5x10(-3) mol l(-1) 5-chloro-8-quinolinol. The proposed method has been applied to the trace analysis of Cu, Al, Fe and Al in bovine liver and citrus leaves.     

SPECT images using a multislice fan beam collimator

Several methods to improve the image resolution of single photon emission computed tomography (SPECT) occur to us. It is one method to use multislice fan beam collimators which have the parallel collimation along the cephalic-caudul axis of a patient and the conversing collimation within planes parpendicular to that axis. It is impossible to obtain corrective image when we used the algorithm which is commonly used for reconstruction of SPECT images. We proposed a reconstruction algorithm for multislice fan beam collimator in this paper. An interpolation method developed for fan beam type X-ray CT was modified to reconstruct images from SPECT with multislice fan beam collimator. This algorithm was confirmed by means of computer simulation studies. Beside improving the system resolution by effectively reducing the intrinsic resolution of the cameras, this collimator also increases the system sensitivity by utilizing a large fraction of the crystal area. We have thought that to use multislice fan beam collimator is beneficial for SPECT images.     

Water adsorption on a p(2x2)-Ni(111)-O surface studied by surface x-ray diffraction and infrared reflection absorption spectroscopy at 25 and 140 K

The adsorption of water molecules on an oxygen-predosed p(2x2)-Ni(111)-O surface was studied by surface x-ray diffraction and infrared reflection absorption spectroscopy (IRAS) at temperature of 25 and 140 K. Precise structures including adsorbed water, predosed oxygen, and substrate nickel atoms at these two temperatures were determined by x-ray structural analysis. It was found that water molecules adsorb on oxygen additive sites, forming a hydrogen bond at 25 K. A predosed 2x2 oxygen atom appears to accommodate one, two, or three water molecules at positions relating to threefold rotation symmetry. When the surface temperature was raised to 140 K, water molecules appear at an atop site of Ni. The distance between Ni and the oxygen atoms of a monomer water molecule was found to be 0.2241(22) nm. The adsorbed water molecule induces buckling and a lateral shift of the substrate nickel. The IRAS results provided evidence regarding the existence of two distinct adsorption sites. Water molecules in the low-temperature phase exhibit bands from both hydrogen-bonded nuOD and free OD stretchings, while those in the high-temperature phase lie flat with a molecular plane parallel to the surface.     

Controlled pyrolysis of polyethylene/polypropylene/polystyrene mixed plastics with high impact polystyrene containing flame retardant: Effect of decabromo diphenylethane (DDE)

The pyrolysis of polyethylene(PE)/polypropylene(PP)/polystyrene(PS) mixed with high impact polystyrene (HIPS-Br) containing decabromo diphenylethane (DDE) as a brominated flame retardant with antimony trioxide as a synergist was performed under controlled temperature programmed pyrolysis (two steps) conditions to understand the decomposition behaviour and evolution of brominated hydrocarbons from flame-retardant additives. The liquid products were extensively analyzed by gas chromatographs equipped with FID, ECD, MSD, TCD, AED and FT-IR. The solid residue samples were analyzed by powder X-ray diffraction and combustion followed by ion-chromatography. The controlled pyrolysis of PE/PP/PS/HIPS-Br significantly affected the decomposition behaviour of HIPS-Br and subsequently the formation of decomposition products. GC/ECD analysis confirmed that the brominated hydrocarbons were concentrated in step 1 liquid products leaving less brominated hydrocarbons in the step 2 liquid products, similar to the decabromo diphenyl ether flame retardant containing mixed plastics. The yield of liquid products in step 1 from 3P/DDE-Sb(5) was 5 wt% and from 3P/DDE-Sb(0) was 2.4 wt%. The presence of antimony in the DDE containing plastics affected the yield of liquid, gas and residue products. ECD analysis showed that the presence of antimony increased the Br containing hydrocarbons and step 1 has 3-4 times higher brominated compounds than step 2 hydrocarbons in both the samples.     

Development of a static headspace gas chromatographic/mass spectrometric method to analyze the level of volatile contaminants biodegradation

Volatile compound biodegradation analysis usually requires the time-consuming step of extraction of the analytes from the matrix using organic solvents or costly radioactive-compounds. Thus, it is desirable to have a simple and fast technique to generate a good evaluation of bacterial biodegradation. The goal of this research was to develop a methodology on the basis of static headspace-gas chromatography/mass spectrometry (HS-GC/MS) to evaluate the level of volatile contaminant biodegradation. The effects of the following parameters were studied: temperature and time of equilibration. The biodegradation experiments were carried out with bacteria inoculation in mineral media in presence of volatile hydrocarbon compounds (toluene, p-xylene, nonane and naphthalene). Autoclaved inoculates were used as control and reference sample. The optimal headspace conditions were observed when the vials were heated at 80 degrees C for 20 min, the syringe at 81 degrees C and an injection volume of 0.4 mL was used. This methodology has the advantage of being relative free from matrix effects.     

Quantum chemical study of Lewis acid catalyzed allylboration of aldehydes

The reaction rate enhancement in the reaction of allylboronate with benzaldehyde in the presence of AlCl3 has been studied theoretically. B3LYP calculations find a relatively high activation barrier for the reaction of pinacol allylboronate with benzaldehyde in the absence of the Lewis acid. The reaction paths that go through the transition states coordinated by an AlCl3 molecule at one of the two oxygen atoms in the boronate give significantly lower values of activation energy. An analysis of electron populations and orbitals taking part in bond formation indicates that the AlCl3 molecule attached to the boronate oxygen atom strengthens the electrophilicity of the boron center, while it weakens the nucleophilicity of the C(gamma)-C(beta) bond. The result supports the electrophilic boronate activation mechanism proposed by Rauniyar and Hall on the basis of experiments and kinetic studies. In contrast, the reaction path in which AlCl3 is coordinated to the carbonyl oxygen of benzaldehyde shows a higher activation barrier, though the initial reactant complex is more stable than those in other reaction paths. The AlCl3 molecule reduces the reactivity of aldehyde by depressing the nucleophilicity of the sigma-type lone pair of electrons on the carbonyl oxygen, though the electrophilicity of the carbonyl pi orbital is strengthened to some extent. The significance of charge polarization within allylboronate in enhancing the reactivity of boron by the Lewis acid is discussed.     

Novel highly active FSM-16 supported molybdenum catalyst for hydrotreatment

FSM-16 (Folded Sheet Silica) supported catalysts could accommodate 12 wt% Mo (18% MoO(3)) as a monolayer with higher dispersion than any other silica support; these catalysts showed outstanding HDS and HYD activities compared to gamma-Al(2)O(3), amorphous silica, and other mesoporous silica supported catalysts.     

Optically switchable chelates: optical control and sensing of metal ions

This study introduces new concepts in the design, synthesis, and in vitro and in vivo characterization, manipulation, and imaging of organic chelates whose association with metal ions is rapidly and reversibly controlled by using light. Di- and tricarboxylic group bearing photochromes, nitrobenzospiropyran (nitroBIPS), undergo rapid and reversible, optically driven transitions between their spiro (SP) and fluorescent merocyanine (MC) states. The MC state of nitroBIPS-8-DA binds tightly to various metal ions resulting in specific shifts in absorption and fluorescence, and the dissociation constant for its Gadolinium complex in water is measured at approximately 5 microM. The metal-bound MC state is converted to the weaker-binding SP state with use of 543 nm light, while the SP to MC transition is complete with use of 365 or 720 nm (2-photon) light within several microseconds. Fluorescence imaging of the MC state of nitroBIPS-8-TriA was used to quantify the rate and efficiency of optical switching and to provide a real-time readout of the state of the optically switchable chelate within living cells.