Influence of the characteristics of soil and fly ash on the supercritical carbon dioxide extraction of dioxins.

Several investigations on the extraction of dioxins from soil and fly ash with supercritical fluid have been reported; however, few of them describe the influence of components on the extraction. We extracted dioxins from eight samples with different values of organic carbon content and surface area with supercritical CO(2) at a temperature of 463 K, a pressure of 40 MPa, and using 10% toluene as an entrainer. We researched the influence of the characteristics of soil and fly ash on supercritical CO(2) extraction of dioxins. The results revealed that the extraction efficiencies of PCDD/DFs and PCBs were high for all soil samples, while that of fly ash samples decreased with the increase in organic carbon content and surface area. The extraction efficiencies of dioxins from four standard samples, activated carbon, humic acid, alumina, and florisil, were also examined. The results revealed that the extraction efficiencies were strongly influenced by activated carbon like components present in the samples.     

A highly sensitive spectrophotometric determination of beryllium with chromal blue G and cetyltrimethylammonium chloride

Chromal blue G in the presence of cetyltrimethylammonium chloride is proposed for the spectrophotometric determination of microgram amounts of beryllium. The sensitivity of color reaction between beryllium and chromai blue G has been greatly increased by the sensitizing action of cetyltrimethylammonium chloride (_626nm = 93,000). Beer's law is obeyed over the range 0.012–0.12 ppm of beryllium. Full color development occurs in 20 min at pH 5.5 and at 626 nm. The mole ratio of beryllium and chromai blue G in the complex is estimated to be 1:2. The proposed method is very sensitive and selective for determination of beryllium when EDTA is used as a masking agent.     

High magnetic field solid‐state NMR analyses by combining MAS,MQ‐MAS,homo‐nuclear and hetero‐nuclear correlation experiments

A general strategy of structural analysis of alumina silicate by combining various solid‐state NMR measurements such as single pulse, multi‐quantum magic angle spinning, double‐quantum homo‐nuclear correlation under magic angle spinning (DQ‐MAS), and cross‐polarization hetero‐nuclear correlation (CP‐HETCOR) was evaluated with the aid of high magnetic field NMR (800 MHz for ¹H Larmor frequency) by using anorthite as a model material. The high magnetic field greatly enhanced resolution of ²⁷Al in single pulse, DQ‐MAS, and even in triple‐quantum magic angle spinning NMR spectra. The spatial proximities through dipolar couplings were probed by the DQ‐MAS methods for homo‐nuclear correlations between both ²⁷Al–²⁷Al and ²⁹Si–²⁹Si and by CP‐HETCOR for hetero‐nuclear correlations between ²⁷Al–²⁹Si in the anorthite framework. By combining various NMR methodologies, we elucidated detailed spatial correlations among various aluminum and silicon species in anorthite that was hard to be determined using conventional analytical methods at low magnetic field. Moreover, the presented approach is applicable to analyze other alumina‐silicate minerals. Copyright © 2012 John Wiley & Sons, Ltd.     

Semiempirical Pm3 Quantum Mechanics Calculations of Carbohydrate Crystals

ABSTRACT

Miniature crystal models of six small carbohydrates were examined using the PM3 semiempirical quantum mechanics method. The minicrystal structures, consisting of 27 sugar residues, were optimized by the combined procedure of partial optimization and reconstruction of the model, while maintaining the original crystal symmetries. All of the minicrystals were successfully optimized without exhibiting a great increase in an energy at any reconstruction step. Some minicrystals showed a prolonged behavior of optimization cycles. A major source of structure change appeared to arise from hydroxyl group rotations wherein the largest movements mostly occurred in an early optimization stage. No significant deformations in geometry of either residues or hydrogen bonds were observed in the final minicrystal structures. The thermodynamic values calculated for the optimized minicrystals were in reasonably good agreement with the literature data. The present study indicated that the PM3 semiempirical method successfully predicted the basic features of intermolecular hydrogen bonding involved in a condensed system.     

A sensitive and quantitative technique for detecting autophagic events based on lysosomal delivery

We sought to develop a sensitive and quantitative technique capable of monitoring the entire flux of autophagy involving fusion of lysosomal membranes. We observed the accumulation inside lysosomal compartments of Keima, a coral-derived acid-stable fluorescent protein that emits different-colored signals at acidic and neutral pHs. The cumulative fluorescent readout can be used to quantify autophagy at a single time point. Remarkably, the technique led us to characterize an autophagy pathway in Atg5-deficient cells, in which conventional LC3-based autophagosome probes are ineffective. Due to the large Stokes shift of Keima, this autophagy probe can be visualized in conjunction with other green-emitting fluorophores. We examined mitophagy as a selective autophagic process; time-lapse imaging of mitochondria-targeted Keima and GFP-Parkin allowed us to observe simultaneously Parkin recruitment to and autophagic degradation of mitochondria after membrane depolarization.     

Two-photon pumping of random lasers by picosecond and nanosecond lasers

We experimentally demonstrated two-photon pumping of random lasers using picosecond and nanosecond pump lasers. The picosecond laser pumping experiment was performed with 400 ps laser pulses at 770 nm, and the gain media was a Coumarin 480D dye solution doped with TiO₂ nanoparticles. Onset of laser action was observed at a pump laser pulse energy below 500 μJ. The nanosecond laser pumping experiment was performed with 7 ns laser pulses at 1064 nm, and the gain media was a Rhodamine 640 dye solution doped with TiO₂ nanoparticles. Onset of laser action was observed at a pump laser energy ∼18 mJ. Our results suggest that there exists an optimal pulse duration of the pumping laser in two-photon pumped random lasing that leads to minimum photodamage of the gain media and still keeps a high pumping efficiency. PACS 33.50.Dq; 42.55.Mv; 42.55.Zz     

Pulsed-field ionization electron spectroscopy and conformation of copper-diammonia

Copper-diammonia, Cu(NH3)2, and its deuterated species, Cu(ND3)2, are produced in supersonic molecular beams and studied by pulsed-field ionization zero electron kinetic energy photoelectron spectroscopy and ab initio calculations. Structural isomers with a copper atom binding to an ammonia dimer or two ammonia molecules are obtained by the calculations. By comparing the experimental measurements to the theoretical calculations, the neutral and ionic forms of copper-diammonia are determined to be in a doubly bound linear conformation in their ground electronic states. The adiabatic ionization potentials of Cu(NH3)2 and Cu(ND3)2 are measured as 29,532 (5) and 29,313 (5) cm(-1), respectively. The metal-ligand symmetric stretching frequencies are measured to be 436 cm(-1) for Cu+-(NH3)2 and 398 cm(-1) for Cu+-(ND3)2, and the metal-ligand bending frequencies 75,139 cm(-1) for CuCu+-(NH3)2 and 70125 cm(-1) for CuCu+-(ND3)2. Moreover, the dissociation energy of Cu(NH3)2-->CuNH3+NH3 is determined to be 11(3) kcal mol(-1) through a thermodynamic relationship.