Trace metal speciation measurements in waters by the liquid binding phase DGT device

The speciation measurements of trace metals by the diffusive gradients in thin-films technique (DGT) using a poly(4-styrenesulfonate) (PSS) aqueous solution as a binding phase and a cellulose dialysis membrane (CDM) as a diffusive layer, CDM-PSS DGT, were investigated and showed good agreement with computer modelling calculations. The diffusion coefficients of ethylenediaminetetraacetic acid (EDTA) complexes with Cd²⁺ and Cu²⁺ were measured and compared with those of the inorganic metal ions. CDM-PSS DGT device was tested for speciation measurement in sample solutions containing EDTA, tannic acid (TA), glucose (GL), dodecylbenzenesulfonic acid (DBS) and humic acid (HA) as complexing ligands forming organic complexes with varying stability constants. Lower percentages of DGT labile copper concentrations over total filterable copper concentrations obtained from the deployments in freshwater sites indicated that copper complexes with organic matter were basically not measured by the devices.     

多支链烷基苯磺酸钠水溶液的表面性质

用自制的四种高纯度多支链烷基苯磺酸钠,研究了支链结构对其表面性质的影响.结果表明,随支链烷基碳数增加,临界胶束浓度降低,标准吸附自由能DGadӨ更负;但是,饱和吸附量Γmax却随支链烷基碳数增加而减小,且临界胶束浓度时的表面张力γcmc随吸附量减小而降低,表现出与一般表面活性剂不同的变化趋势.从多支链烷基苯磺酸钠的分子结构特点,解释了随支链烷基碳数增加Γmax和γcmc的变化规律,探讨了分子的独占面积(as)对Γmax及γcmc的影响.     

甲烷氧化偶联Ti-La-Li系多元氧化物催化剂的表面碱性和表面活性氧种

利用ＣＯ２－ＴＰＤ方法考察了Ｔｉ－Ｌａ－Ｌｉ系多元氧化物催化剂的表面碱性，实验发现：Ｃ２选择性与表面碱强度呈顺变关系，而ＣＨ４转化率与ＣＯ２的脱附峰面积呈顺变关系。同时，利用ＸＰＳ，Ｏ２－ＴＰＤ等方法对该体系催化剂的表面活性氧种进行了表征与研究。结果表明：催化剂的表面晶格氧与Ｃ２选择性有关，表面吸附氧与甲烷转化（包括偶联和深度氧化）有关。Ｏ２－ＴＰＤ实验发现催化剂的表面存在三种氧。α（１００℃≤ｔ     

Self－assembly of Novel Hetero[3]rotaxane, [2]Rotaxanes and [2]Catenane

One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF₆ was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated.     

Synthesis and X-ray diffraction studies of chiral nickel(II), zinc(II), manganese(II), and cobalt(II) complexes with C 2-symmetric 2,6-bis[4′-(R)-ethoxyoxazolin-2′-yl]pyridine

Chiral nickel(II), zinc(II), manganese(II), and cobalt(II) complexes with C ₂-symmetric 2,6-bis[4′-(R)-ethoxyoxazolin-2′-yl]pyridine were prepared, the single crystal of nickel(II) complex, [Ni((R,R)-Et-Py-box)(H₂O)₂Cl]Cl ((R,R)-Et-Pybox is 2,6-bis[4′-(R)-ethoxyoxazolin-2′-yl]pyridine), was obtained and indicated by X-ray diffraction analysis. The nickel(II) complex crystallizes in the orthorhombic system, space group P2₁2₁2₁ with a = 7.7346(4) Å, b = 19.7133(13) Å, c = 25.8014(14) Å, V = 3934.1(4) ų, Z = 8, and R = 0.0526 against 7010 reflections with I > 2σ (I). A feature of interest was noted in the unit cell of the compound, where two types of molecules exist, which similarly have a distorted octahedral geometry but only slightly differ in the orientation of the coordinated atoms to the central Ni atom. These two types of molecules interact with each other by O-H…Cl hydrogen bonds, giving rise to one dimensional ribbon structure.     

Influence of demulsifiers of different structures on interfacial dilational properties of an oil-water interface containing surface-active fractions from crude oil

The influences of two commercial demulsifiers that have a straight chain and branch chain, respectively, on the dilational viscoelasticity of an oil-water interfacial film containing surface-active fractions from crude oil were investigated. The branch-chain demulsifier AE-121 could efficiently substitute surface-active fractions of different average molecular weights from the oil-water interface, while straight-chain SP-169 could only efficiently substitute those of large average molecular weight. It was apt to form a mix-adsorption layer with surface-active fractions of small average molecular weight. The results showed that the molecular size (or represented by average molecular weights) of the surface-active fractions was an important factor influencing the reciprocity of demulsifiers and surface-active fractions at the oil-water interface. This effect could be well explained by the difference between sizes of surface-active fraction molecules and vacancies between demulsifier molecules at the interface. The results of SDBS also proved this explanation.     

Transition metal complexes bearing 2,6-bis(imino)pyridyl: Synthesis,structure, ethylene polymerization/ oligomerization studies

A series of new complexes {2,6-bis[1-((2-methyl-4-methoxyphenyl)imino)ethyl]pyridine}Cl₂ [M=Fe(II) (2), Co(II) (3), Ni(II) (4), Cu(II) (5), Zn(II) (6)] have been synthesized. At 25°C, using 500 equiv of methylaluminoxane (MAO), the activities of Fe(II), Co(II) catalysts can reach 4.02 ×10⁶ g/mol-Fehatm for ethylene polymerization and 3.98×10⁵ g/mol-Cohatm for ethylene oligomerization. The effects of polymerization conditions such as reaction temperature, Al/M molar ratio and time on the activity of catalyst have been explored.     

Theoretical studies on vibrational spectra of some halides of Group IIB elements

The vibrational spectra of Group IIB elements halides MX2 and their dimers M2X4 (M=Zn(II), Cd(II) and Hg(II); X=F, Cl, Br and I) have been systematically investigated by ab initio RHF and B3LYP methods with LanL2MB, LanL2DZ and SDD basis sets. The optimized geometries, calculated vibrational frequencies are evaluated via comparison with the experimental data. The vibrational frequencies, calculated by these methods with different basis sets, are compared to each other too. The best results can be obtained by RHF/SDD method, with this method, the deviations for MX2 and Hg2X4 are <7%. Some vibrational frequencies of M2X4 that have not been experimentally reported are also predicted.     

On the complexity of following the central path of linear programs by linear extrapolation II

A class of algorithms is proposed for solving linear programming problems (withm inequality constraints) by following the central path using linear extrapolation with a special adaptive choice of steplengths. The latter is based on explicit results concerning the convergence behaviour of Newton's method to compute points on the central pathx(r), r>0, and this allows to estimate the complexity, i.e. the total numberN = N(R, ) of steps needed to go from an initial pointx(R) to a final pointx(), R>>0, by an integral of the local weighted curvature of the (primal—dual) path. Here, the central curve is parametrized with the logarithmic penalty parameterr0. It is shown that for large classes of problems the complexity integral, i.e. the number of stepsN, is not greater than constm log(R/), where < 1/2 e.g. = 1/4 or = 3/8 (note that = 1/2 gives the complexity of zero order methods). We also provide a lower bound for the complexity showing that for some problems the above estimation can hold only for 1/3.As a byproduct, many analytical and structural properties of the primal—dual central path are obtained: there are, for instance, close relations between the weighted curvature and the logarithmic derivatives of the slack variables; the dependence of these quantities on the parameterr is described. Also, related results hold for a family of weighted trajectories, into which the central path can be embedded.On leave from the Institute of Mathematics, Eötvös University Budapest, H-1080 Budapest, Hungary.