流通池光度滴定法应用—络合反应中的质子释放数测定

用具有流通池的分光光度计作测定装置,建立了由平衡移动法测定络合反应中质子释放数的新方法。方法简单、快速,仅用一个标准溶液,适于在变更pH值范围内金属离子不发生水解和没有其他副反应的体系。     

Hydrogen transport through Pd-Ni alloy electrodeposited on Pd substrate

Hydrogen transport through a Pd-Ni alloy electrodeposited on a Pd substrate (Pd-Ni/Pd bilayer symmetric electrode) has been investigated using cyclic voltammetry and a.c. impedance spectroscopy combined with the electrochemical hydrogen permeation method. The permeation build-up current transients and the measured impedance spectra were analyzed using the time-lag method for the bilayer electrode and a complex non-linear least squares data-fitting method based upon the derived Faradaic admittance for the hydrogen absorption into and diffusion through the bilayer electrode under the permeable boundary condition, respectively. The value of the hydrogen diffusivity in the Pd-Ni layer was lower than that in the Pd layer. Furthermore, the values of the charge transfer resistance and equilibrium absorption constant for the Pd-Ni/Pd bilayer electrode were higher than those for the Pd single layer electrode. From the experimental results, the role of the thin Ni(OH)₂ film formed on the Pd-Ni layer surface in the hydrogen transport through the Pd-Ni/Pd bilayer electrode is discussed in terms of its passivating effect and extremely large hydrogen solubility. Received: 22 January 1997 / Accepted: 15 April 1997     

A rapid method for the determination of methoprene in tobacco by high performance liquid chromatography

Summary A rapid sample preparation procedure combined with a short reversed-phase HPLC separation for the quantitation of methoprene residue in tobacco samples is described. A ground tobacco sample of 0.5 g is mixed with 3 mL of 2-propanol. The mixture is extracted for twelve minutes with the aid of sonication at an elevated temperature (45–55°C) and then filtered through a 0.45 m disposable filter prior to injection on HPLC. No sample cleanup or solvent evaporation step is required. Chromatographic analysis is performed on a C-18 column and the analysis time is 12.5 minutes. The detection limit for methoprene in tobacco samples is one part per million (g/g).     

Synthesis of poly[arylene ether sulfone-b-vinylidene fluoride] block copolymers

A series of α,ω-dihydroxy polyarylene sulfones (PAES) were synthesized comprising bisphenol A (PAES1, M_n=1800, 4900, and 9500 daltons), 4,4^′-biphenol (PAES2, M_n=4100 daltons), and hexafluorobisphenol A (PAES3, M_n=3300 daltons). These were reacted with α,ω-dibromo poly(vinylidene fluoride) (PVDF, M_n=1200 daltons) prepared by telomerization, to yield block copolymers possessing rigid and flexible segments. Block copolymers were characterized by FTIR, NMR, GPC, DSC, TGA and TEM. In several cases the block copolymers exhibited distinct thermal transitions, i.e. T_m and T_g for PVDF and PAES segments, respectively. Where observable, T_g of PAES domains in the block copolymers occurred at a temperature lower than the corresponding PAES homopolymer due to the flexible nature of the surrounding PVDF domains. Block copolymers exhibited a similar thermal stability to the corresponding PAES homopolymers but higher stability than the PVDF homopolymer, and much higher still than α,ω-dibromo PVDF. TEM analyses indicate that phase separation of PAES and PVDF domains occurs on the nanometer scale.     

Dynamics of curved DNA molecules: prediction and experiment

We have developed a quantitative predictive model capable of describing the dynamics of migration of intrinsically curved DNA fragments on polyacrylamide gels. The model takes into account structural features of DNA, end-to-end distance, screening of hydrodynamic interactions, ionic strength of buffer, electrostatic persistence length, structural fluctuations of the macromolecule, counter condensation, and variation of dielectric constant and viscosity of water with MPD. In doing so, we have also addressed a decade old issue on the effect of the organic solvent 2-methyl-2,4-pentanediol on gel migration of phased A-tracts. We show here that A-tract-solvent interactions are less favored compared with A-tract-A-tract and solvent-solvent interactions.     

无亲水基团取代的四苯基卟吩类LB膜的制备与表征

拉制了4种无亲水基团的四苯基卟吩LB膜,用透射电镜、荧光寿命、荧光光谱和紫外-可见光谱测量表征了膜的形貌和结构,发现膜中卟吩主要以聚集体形式存在。     

Precise and accurate determination of the stoichiometry of CuInS2 semiconductor material by electrochemical methods

Summary CuInS₂ is one of the important I–III–VI₂ ternary compounds which has in recent years received increasing interest in semiconductor science. In this study an electrochemical method has been developed based on a limited amount of available sample (0.5–10mg) for the precise and accurate determination of CuInS₂ composition. After decomposition of the sample in concentrated HNO₃ under pressure, copper and indium were sequentially determined by constant potential coulometry, and sulfur (as sulfate) by amperometric titration. Various experimental parameters which ensure high precision and accuracy of the results were carefully evaluated and calibrated. The overall errors for the determination of copper, indium and sulfur in a 10 mg sample were found to be +0.10%, –0.12% and +0.16%, respectively, which fullfills the requirement for accurate stoichiometric assessment.

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Reproduzierbare und genaue Bestimmung der Stöchiometrie von CuInS₂-Halbleitermaterial mit Hilfe elektrochemischer Verfahren

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Presented at the 10th International Symposium on Microchemical Techniques, August 25–29, 1986, Antwerp, Belgium     

Predicting adsorption isotherms of low-volatile compounds by temperature programmed desorption: iodine on carbon

Equilibrium adsorption isotherms for low-volatile compounds are extremely difficult to measure. A simple technique using temperature programmed desorption (TPD) is proposed. It is demonstrated that the two parameters needed for constructing the Langmuir isotherm can be derived with data from the TPD technique alone. Thus, the Langmuir isotherms of iodine on AX-21 super-activated carbon were obtained with this technique. A series of TPD experiments for samples with different initial loadings of iodine were carried out by varying the heating rates which resulted in different peak desorption temperatures. The peak desorption temperature decreased as the initial loading was increased because of the re-adsorption effect. The Langmuir constant was derived from kinetic theory with the activation energy for desorption obtained from the experiment. The activation energy for desorption was 12.3 kcal/mol. The Langmuir constants determined by this technique were in comparable order of magnitude to the reported values for iodine on activated carbon. The saturation capacity of AX-21 for iodine could also be determined from the TPD data obtained from samples with different initial loadings. The estimated saturation capacity from the TPD experiment was 2.96 g I(2)/g AX-21, which was close to the experimentally measured saturation capacity of 3.25 g I(2)/g AX-21 for the same system.     

Pseudo[n,m]rotaxanes of Cucurbit[7/8]uril and Viologen‐Naphthalene Derivative: A Precise Definition of Rotaxane

Rotaxane is a kind of classic supramolecule, which is usually constructed from a number of macrocycles and one axis molecule. Herein, we have expanded the supramolecular structure of [n]rotaxane to offer a precise definition of (pseudo)[n,m]rotaxane for accurately describing the two kinds of (pseudo)rotaxanes structures, which are self‐assembled from cucurbit[7/8]uril (CB[7/8]) and viologen‐naphthalene derivative, respectively. Furthermore, these CB‐based pseudorotaxanes exhibit varied photophysical properties, stimuli‐responsive behavior triggered by competitive guest, and self‐sorting behavior.     

Study of Six Polycyclic Aromatic Hydrocarbons by Chemical Deoxygenation Microemulsion-Stabilized Room Temperature Phosphorimetry

Six polycyclic aromatic hydrocarbons (PAHs) are studied by chemical deoxygenation microemulsion-stabilized room temperature phosphorimetry with sodium sulfite as an oxygen scavenger and thallous nitrate as a heavy atom perturber in sodium dodecyl sulfate medium. Several factors influencing room temperature phosphorescence such as the concentration of sodium dodecyl sulfate, the heavy atom concentration, the pH, and the concentration of sodium sulfite are discussed and the quenching effect of NO₂⁻on room temperature phosphorimetry of PAHs was compared in the microemulsion and micelle media.