Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004     

Concentrations of hazardous heavy metals in environmental samples collected in Xiamen, China, as determined by vapor generation non-dispersive atomic fluorescence spectrometry.

Non-dispersive atomic fluorescence spectrometry (NDAFS) coupled with vapor generation (VG) sample introduction was applied to the determination of the concentrations of hazardous heavy metals, such as arsenic, cadmium, lead and mercury, in seawater, soils and total airborne particulate matter (PM) collected around the Xiamen area in China. Almost 100% sample introduction efficiency was achieved by using thiourea and ascorbic acid for the pre-reduction of As(V) to As(III), K3Fe(CN)6 and tartaric acid for pre-oxidation of Pb(II) to Pb(IV), and masking the interferences arising from the co-existing transition metals to As, Cd, Hg and Pb during their vapor generation process. Moreover, a novel sample pretreatment device was developed to avoid the loss of mercury, lead, cadmium and arsenic during sample pretreatment. With such methods, the detection limit (DL) of arsenic, cadmium, lead and mercury was down to 0.08, 0.03, 0.05, 0.01 ng mL(-1) (3sigma), respectively. The relative standard deviations (RSD, n = 11) for arsenic, cadmium, lead and mercury at 10 ng mL(-1) were 0.9%, 1.6%, 1.3% and 2.0%, respectively. The concentrations of hazardous heavy metals in the environmental samples collected in Xiamen, China are in the range from 0.02 +/- 0.001 ng mL(-1) in seawater to 15.3 +/- 0.2 microg g(-1) in soils. Besides flame/GF-AAS and ICP-AES/MS, VG-NDAFS should be another choice for the determination of hazardous heavy metals in environmental samples.     

Determination of tyrosine traces by adsorption voltammetry of its copper (II) complex

The electrochemical behavior of the copper-tyrosine complex has been studied by linear-sweep adsorption voltammetry. In 0.02 mol/L Na₂HPO₄ buffer solution (pH=9.6), the complex can be adsorped on a hanging mercury drop electrode and reduced at a peak potential of about –0.42 V (vs. SCE). The secondary derivative peak height is linear proportional to the concentration of tyrosine in the range 1.0×10^–7–5.0×10^–5 mol/L. The detection limit is 5×10^–8 mol/L.Project supported by the Provincial Science Foundation of Shandong Province     

Ba（n，x）~（134）Cs，~（134）Ba（n，2n）~（133）Ba，

用中子活化法相对于５４Ｆｅ（ｎ，Ｐ）５４Ｍｎ反应，在１３．５０—１４．８０ＭｅＶ中子能区测量了Ｂａ（ｎ，ｘ）１３４Ｃｓ，１３４Ｂａ（ｎ，２ｎ）１３３Ｂａ，１４０Ｃｅ（ｎ，２ｎ）１３９Ｃｅ，１４２Ｃｅ（ｎ，２ｎ）１４１Ｃｅ和２３Ｎａ（ｎ，２ｎ）２２Ｎａ的反应截面．并将所测的结果和其他作者的结果进行了比较，中子能量是用９０Ｚｒ（ｎ，２ｎ）８９ｍ＋ｇＺｒ反应和９３Ｎｂ（ｎ，２ｎ）９２ｍＮｂ反应截面比法测定的。     

Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

The study of lithium fast ion conductors of Li3xLa0.67−xScyTi1−2yNbyO3 system

Perovskite-type lithium fast ion conductors of Li_3xLa_0.67−xSc_yTi_1−2yNb_yO₃ system were prepared by solid state reaction. X-Ray powder diffraction shows that perovskite solid solution form in the ranges of x=0.10, y≤0.10. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of the order of 10⁻⁴ S·cm⁻¹ and 10⁻⁵ S·cm⁻¹ at 25 °C respectively. The compositions have low bulk activation energies of about 17 kJ/mol in the temperature ranges of 298 – 523 K and total activation energies of about 37 kJ/mol in the temperature ranges of 298 – 523 K.     

Effect of end groups on complexation kinetics between cyclodextrins and guest polymers

α‐Cyclodextrin (α‐CD) has been complexed with various poly(ethylene glycol) (PEG) derivatives in aqueous solution. It has been found that the end groups of PEG derivatives affect the complexation kinetics greatly, but have only a little influence on the thermodynamic behavior. By increasing the hydrophobicity of end groups, the complexation speeds up rapidly. On the other hand, the bulky end groups slow down the threading of polymeric guests into the cavity of CD. By changing the hydrophobicity and the size of end groups, the complexation rate can be adjusted in the range of several orders of magnitudes, which should be quite useful in the design of new supramolecular systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2050–2057, 2006     

Theoretical and numerical analysis on multispectral bioluminescence tomography

Recently, molecular imaging has been rapidly developed to studyphysiological and pathological processes in vivo at the cellularand molecular levels. Among molecular imaging modalities, opticalimaging has attracted a major attention for its unique advantages.In this paper, we establish a mathematical framework for multispectralbioluminescence tomography (BLT) that allows simultaneous studiesof multiple optical reporters. We show solution existence, uniquenessand continuous dependence on data as well as the limiting behaviourswhen the regularization parameter approaches zero or when thepenalty parameter approaches infinity. Then, we propose twonumerical schemes for multispectral BLT and derive error estimatesfor the corresponding solutions.     

Crystal and molecular structure of (μ-p-CH3C6H4C2S) (μ-n-C3H7S)Fe2(CO)6Co2(CO)6

The crystal and molecular structure of the complex containing cobalt-carbon and iron-sulfur cluster cores, (μ-p-CH₃C₆H₄C₂S) (μ-n-C₃H₇S)Fe₂(CO)₆Co₂(CO)₆, has been determined by X-ray diffraction method. The crystals are triclinic, space group P&1bar;, with a — 9.139(2), b=9.610(1), c-17.183(2) Å, α = 84.36(1), β-89.45(1), γ=88.15(1)°, V-1501.0 ų; Z=2, D_c=1.74 g/cm³. R=0.072, Rw=0.081. The results of the structure determination show a cobalt-carbon cluster core formed through the reaction of (μ-p-CH₃C₆H₄C₂S)(μ-n-C₃H₇S)Fe₂(CO)₆ with Co₂(CO)₈. In the cobalt-carbon cluster core, the bond length of the original C≡C lengthened to 1.324 Å which is close to the typical value of carbon-carbon double bond. The groups connecting the carbons of the cluster core are in cis position and lie on the opposite side of cobalt atoms. In this complex, the conformation of —SC₃H₇ is e-type, while that of —SC₂C₆H₄CH₃ is a-type.     

Mass‐lumping or not mass‐lumping for eigenvalue problems

In this article we analyze the effect of mass‐lumping in the linear triangular finite element approximation of second‐order elliptic eigenvalue problems. We prove that the eigenvalue obtained by using mass‐lumping is always below the one obtained with exact integration. For singular eigenfunctions, as those arising in non convex polygons, we prove that the eigenvalue obtained with mass‐lumping is above the exact eigenvalue when the mesh size is small enough. So, we conclude that the use of mass‐lumping is convenient in the singular case. When the eigenfunction is smooth several numerical experiments suggest that the eigenvalue computed with mass‐lumping is below the exact one if the mesh is not too coarse. © 2003 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 19: 653–664, 2003