A supramolecular microfluidic optical chemosensor

A supramolecular microfluidic optical chemosensor (muFOC) has been fabricated. A serpentine channel has been patterned with a sol-gel film that incorporates a cyclodextrin supramolecule modified with a Tb(3+) macrocycle. Bright emission from the Tb(3+) ion is observed upon exposure of the (mu)FOC to biphenyl in aqueous solution. The signal transduction mechanism was elucidated by undertaking steady-state and time-resolved spectroscopic measurements directly on the optical chemosensor patterned within the microfluidic network. The presence of biphenyl in the cyclodextrin receptor site triggers Tb(3+) emission by an absorption-energy transfer-emission process. These results demonstrate that the intricate signal transduction mechanisms of supramolecular optical chemosensors are successfully preserved in microfluidic environments.     

A Novel Dimeric Eremophilane from Ligularia virgaurea spp. oligocephala

A novel dimeric eremophilane, ligulolide B, was isolated from the alcoholic extract of the whole plant of Ligularia virgaurea spp. oligocephala. The structure was elucidated by various spectroscopic methods including intensive 2D NMR techniques （^1H-^1H COSY, gHMQC, gHMBC and ^1H-^1H NOESY） and HR-ESI-MS.     

Determination of hexamethylene-based isocyanates in spray-painting operations. Part 1. Evaluation of a polyurethane foam sponge sampler

A polyurethane foam (PUF) sponge was mounted in a cassette sampler and evaluated as a sorbent for the collection of hexamethylene diisocyanate (HDI) monomer and HDI-based oligomers. Recovery studies indicated 112 +/- 34% average recovery of HDI monomer and 92 +/- 9% and 97 +/- 25% average recovery of HDI-based oligomers when using impregnated PUF sponges. The PUF sponge was also evaluated during actual spray-painting operations. In a series of side-by-side sampling events, an impinger filled with 1-(2-methoxyphenyl)piperazine (MOP) in toluene was compared directly with a cassette sampler containing a PUF sponge impregnated with MOP or 1-(9-anthracenylmethyl)piperazine (MAP) in dimethyl sulfoxide (DMSO). For the analysis of HDI-based oligomer, there is no significant difference (p < 0.05, n = 7) in the air concentration when sampling with either the PUF sponge cassette or the impinger. The results are significant because they indicate that a PUF sponge, which is more convenient than an impinger, may be used for the collection of HDI-based oligomer generated during spray-painting operations.     

Spectroscopic and photophysical properties of hexanuclear rhenium(III) chalcogenide clusters

The electronic, vibrational, and excited-state properties of hexanuclear rhenium(III) chalcogenide clusters based on the [Re(6)(mu(3)-Q)(8)](2+) (Q = S, Se) core have been investigated by spectroscopic and theoretical methods. Ultraviolet or visible excitation of [Re(6)Q(8)](2+) clusters produces luminescence with ranges in maxima of 12 500-15 100 cm(-)(1), emission quantum yields of 1-24%, and emission lifetimes of 2.6-22.4 microseconds. Nonradiative decay rate constants and the luminescence maxima follow the trend predicted by the energy gap law (EGL). Examination of 24 clusters in solution and 14 in the solid phase establish that exocluster ligands engender the observed EGL behavior; clusters with oxygen- or nitrogen-based apical ligands achieve maximal quantum yields and the longest lifetimes. The excited-state decay mechanism was investigated by applying nonradiative decay models to temperature-dependent emission experiments. Solid-state Raman spectra were recorded to identify vibrational contributions to excited-state deactivation; spectral assignments were enabled by normal coordinate analysis afforded from Hartree-Fock and DFT calculations. Excited-state decay is interpreted with a model where normal modes largely centered on the [Re(6)Q(8)](2+) core induce nonradiative relaxation. Hartree-Fock and DFT calculations of the electronic structure of the hexarhenium family of compounds support such a model. These experimental and theoretical studies of [Re(6)Q(8)](2+) luminescence provide a framework for elaborating a variety of luminescence-based applications of the largest series of isoelectronic clusters yet discovered.     

Preferential Interactions on Polystyrene Divinylbenzene Copolymeric Sorbents

The adsorption of picric acid, naphthalene-sulfonic acid, and toluenesulfonic acid onto a polystyrene divinylbenzene copolymeric sorbent in methanol-water systems at 25°C was studied by reverse-phase high performance liquid chromatography. The observed peak asymmetry and increase in capacity factor at high methanol concentrations in the mixture was attributed to preferential interactions of the solutes at the surface. The phenomena were not as pronounced for octadecyl silane bonded phases.     

On the applicability of the pseudo-second order equation to represent the kinetics of adsorption at solid/solution interfaces: a theoretical analysis based on the statistical rate theory

It is shown that the empirical pseudo-second order kinetic equation is a very efficient formula to correlate the kinetic data generated by applying theoretical expressions developed from the fundamental SRT (Statistical Rate Theory) approach to the interfacial transport. This is especially true when the most popular linear representation is used in which time/adsorbed amount is plotted vs. time. However, the commonly observed goodness of such linear plots does not necessarily speak for the applicability of the pseudo-second order kinetic equation. A reliable estimation, for instance, of the equilibrium adsorbed amount is possible only when a substantial part of a kinetic isotherms corresponds to the conditions close to equilibrium. Energetic surface heterogeneity increases the goodness of these linear regressions. Then, experimental errors have only little effect on the pseudo-second linear plots. This article is dedicated to Professor Mietek Jaroniec on the occasion of his 60^th birthday.     

Homoepitaxy on bulk ammonothermal GaN

In this work results of extensive characterization of homoepitaxial layers grown on truly bulk ammonothermal gallium nitride (GaN) substrates are presented. The 2-μm-thick layers were deposited using metalorganic chemical vapor deposition. The photoluminescence (PL) and reflectance results show very intensive, perfectly resolved excitonic structure in range of band-edge emission of gallium nitride. This structure consists of both lines related to free excitons emission and very narrow lines (full-width at half-maximum (FWHM) value of the order of 0.3 meV) related with excitons bound to neutral acceptor and different neutral donors. In high excitation condition the biexciton emission was observed. The luminescence is uniform in the whole sample surface range. High PL homogeneity corresponds with structural and microscopic measurements performed on these layers. It proves that ammonothermal GaN substrates with perfect crystalline properties enable to grow excellent quality, strain-free homoepitaxial layers.     

一类齐次对称多项式上的切比雪夫不等式

本文借助于控制不等式及数学归纳法，将著名的切比雪夫不等式推广到m次一般齐次对称多项式上(如文中定理及引理7)，并将此结果用于对称平均等．旨在展示证明解析不等式的一些有效的方法和技巧，同时为数学研究特别是高维几何研究提供一些新的有趣而有用的解析不等式．     

Characterisation of selenium compounds in rye seedling biomass using <Superscript>75</Superscript>Se-labelling/SDS-PAGE separation/γ-scintillation counting,and HPLC-ICP-MS analysis of a range of enzymatic digests

In the present study, selenium-enriched plant biomass was investigated to evaluate the ability of rye seedlings to take up, and assimilate, inorganic selenium. Two different analytical approaches were used. Electrophoretic separation (SDS-PAGE) of proteins extracted from ⁷⁵Se-labelled biomass was used to investigate the biotransformation of selenite into organic forms of the element. Ion-pair chromatography coupled with ICP-MS detection was chosen for the analysis of selenium species, enzymatically extracted from the plant biomass. The results of three enzymatic hydrolysis procedures and three sequential enzymatic extractions procedures are compared. The most effective single extraction was proteolysis (using protease type XIV), giving an overall extraction efficiency of 48%. However, for combinations of enzymes, the most effective was cellulase (Trichoderma viride) followed by sequential extraction of the solid pellet using protease type XIV, giving an extraction efficiency of 70%. The complementary data from the electrophoretic fractionation of proteins, and the HPLC separation of Se-species in the proteolytic digests, reveal the existence of large number of selenium-containing compounds in the rye seedling plant biomass. The results showed the complete biotransformation of inorganic selenium into organic forms during germination of the rye seedlings. HPLC-ICP-MS analysis of extracts from the plant biomass did not show the presence of selenate or selenite. At the time of this study, the lack of suitable organic-MS facilities meant that it was not possible to characterise them fully. However, the data does show that a combination of different enzymes, rather than just the commonly-used protease, should be considered when developing an extraction strategy for selenium in different food types to those already reported in the literature.