Interaction of long chain alkylammonium cations with reduced charge montmorillonite

Reduced charge montmorillonites (RCM) were prepared using lithium thermal treatment. The sorption of octylammonium (OA), dodecylammonium (DDA) and hexadecylammonium ions (HDA) on differently charged samples were studied. The amounts of DDA and HDA sorbed on each RCM exceed the cation exchange capacity (CEC) but that of OA exceeds only the CEC of samples with the lowest CEC. The sorption is affected not only by the layer charge but also by the formation of collapsed interlayer spaces in the lowest charged montmorillonites. X-ray measurements confirmed the decrease of the layer charge after lithium thermal treatment and the layer charge heterogeneity in RCMs.     

Enhancement of photocurrent generation by honeycomb structures in organic thin films.

A light-emitting poly (distyryldimethylbenzene-co-triethylene glycol) rod-coil block copolymer was used to fabricate films with three-dimensionally ordered honeycomb structures by the breath-figure method. Photocurrent generation and photovoltaic performance are studied, and the dependence of photocurrent on applied electric field is investigated. Introducing the ordered porous structure significantly improves the photoelectric conversion behavior, because porous structures not only enhance the light-harvesting efficiency but also benefit charge separation and charge transfer. This phenomenon may have great prospects for enhancing the photovoltaic behavior of organic thin-film devices.     

锂离子电池负极合金CoSn和Cu-Sn的制备与表征

CoSn alloy and Cu-Sn samples were synthesized by H₂-reduction following solid-state reaction between Co(Ⅱ)， Cu(Ⅱ)， Sn(Ⅳ) and NaOH at ambient temperature. The samples were characterized by XRD， SEM. The results showed that CoSn alloy (80～200nm) is globe-shaped， ultrafine hexagonal material， and Cu-Sn alloy powder consists of two phases， i.e. Cu₆Sn₅ and Cu₃Sn. Cu-Sn powder has spherical morphology and the particle size is estimated to be 60～70nm. The electrochemical performances of CoSn alloy and Cu-Sn powder were studied using lithium-ions model cell Li/LiPF₆ (EC+DMC)/CoSn (or Cu-Sn). It was demonstrated the reversible discharge capacities for 10 cycles keep above 280mAh·g^-1 for nanophase Cu-Sn， and 60mAh·g^-1 for CoSn alloy. Differ-ential capacity plots showed that the reaction mechanisms of Cu-Sn with lithium were reversible.     

汞电极表面电荷的快速估算

本文报导了用交流示波极谱快速估算电极表面电荷的方法。该方法使用仪器简单,测量快速,操作简便,在吸附研究中很有用处。     

A modified simplex method for multifactor optimization of selectivity in gas chromatography

A computer-assisted advanced simplex method is presented for the simultaneous optimization of multifactor ( stationary phase loading, carrier gas flow rate and column temperature ) for separation of ten compounds in gas chromatography. A three factors factorial design was used. The method was based on a special polynomial established from fifteen preliminary runs, using resolution as the selection criterion, with connection to a general simplex method. Excellent agreement is found between the predicted data and the experimental results, and most of experiments required in the general simplex method can be omitted.     

Novel application of quantum chemical investigation in terms of substituent parameters: Statistical comparison of dual and single substituent parameter treatments

The correlation analysis of Mulliken charge (Q_M) calculated by using density functional theory (B3LYP/STO-3G) calculations of 1-(4-azido-5-hydroxymethyl-tetrahydro-selenophen-2-ylmethyl)-5-substituted-1H-pyrimidine-2,4-dione, were done by using mono substituent parameter (Hammett’s model), and dual substituent parameter (Taft’s, Reynolds’, and Swain’s models). The dual substituent parameter correlations of the Q_M data gave no significant improvement over single parameter correlations, the best correlation observed with the Taft’s Model as compared with the Swain’s and Reynolds’ Models, respectively. The correlation analysis of Mulliken charge can be used successfully to demonstrate the existence or absence of the interaction between the oxygen of the carbonyl group and selenium atom.     

单体极性对甲基丙烯酸甲酯/丙烯酸丁酯/甲基丙烯酸钠无皂乳液共聚合的影响

研究了少量甲基丙烯酸钠（ＮａＭＡ）存在下单体极性对甲基丙烯酸甲酯（ＭＭＡ）／丙烯酸丁酯（ＢＡ）无皂乳液共聚合的影响．单体极性降低，使粒径减小、聚合速率提高、乳液表面张力和粘度降低、粒子表面电荷密度增大、聚合物分子量提高．ＭＭＡ／ＮａＭＡ无皂乳液聚合物只呈现一个玻璃化温度Ｔｇ，ＢＡ／ＮａＭＡ无皂乳液聚合物呈现两个Ｔｇ，ＭＭＡ／ＢＡ比为２∶１～１∶２的ＭＭＡ／ＢＡ／ＮａＭＡ无皂乳液聚合物呈现四个Ｔｇ，这是由于粒子外面相对富含ＯＳＯ－３和ＣＯＯ－基聚合物的亚层溶解了较多的水，使ＢＡ向粒子中心扩散，ＭＭＡ向外扩散，造成组成差异和相分离而引起的．     

Tuning of the alpha-terthiophene radical cation coupling reaction using mixed micelles with varying charge density.

The photophysics and photochemistry of alpha-terthiophene (alphaT), compartmentalized in mixed nonionic/anionic micelles, have been investigated with focus on the influence of the micellar surface charge density on the formation of the radical coupling product alpha-hexathiophene (alphaH). By varying the ratio of nonionic-to-anionic surfactants, and assuming ideal mixing, the charge density of the mixed micelles was varied. From Poisson-Boltzmann calculations, performed using the cell model, the electrostatic potential and the counterion activity were estimated as a function of the distance from the micellar surface. Upon excitation, the triplet state of alphaT is formed, from which the alphaT radical cation can be formed by absorption of a second photon. The radical cation can form alphaH if it encounters another alphaT radical cation. Under the experimental conditions used, this implies that the alphaH formation only occurs if the compartmentalized radical cation is able to migrate from its host micelle to another micelle, either via the surrounding bulk or by fusion of two micelles followed by mixing of their contents before micellar fission. The formation yield of the radical cation depends on the charge density of the mixed micelle; a lower charge density, that is, an increased amount of nonionic surfactant, lowers the yield. The yield of the coupling product alphaH, however, does not follow the same trend. A maximum yield of alphaH is found at intermediate nonionic surfactant molar ratios. This behavior is understood in terms of the Poisson-Boltzmann simulation results and by comparing charge-density changes as a function of molar fraction with the changes in counterion activity. The alphaH yield is a result of the balance between an increased possibility of radical cation bulk migration and a lowered electrostatic stabilization of the radical.     

Dependence of the relative retention of organic compounds on the nature and pressure of the carrier gas and on the thickness of the PEG-20M film in the capillary column

The effects of the carrier gas nature and pressure on the relative retention values of organic compounds were studied using a series of capillary columns differing in the film thickness of the polar stationary phase (PEG-20M). Relative retention depends linearly on the carrier gas pressure. This dependence becomes more pronounced in the following order of carrier gases: helium < nitrogen < carbon dioxide. The limiting relative retention at a carrier gas pressure approaching zero rather than relative retention values measured experimentally (relative retention time, Kovats retention index,etc.) is an invariant characteristic of a compound subjected to chromatography. For the carrier gases studied, the limiting retention values almost does not depend on the nature of the carrier gas used. The limiting indicating the complex absorption-adsorption nature of these parameters. Dissolution of a carrier gas in the stationary liquid phase has an effect on the relative retention. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2177–2186, December, 1997.