Mössbauer and ESR study of pyridine-inactive phthalocyanineiron (II) in zeolite supercage

Pyridine-treated phthalocyanineiron (II) (FePc) was synthesized in a NaY-zeolite supercage. Mössbauer spectra indicated the presence of pyridine-inactive FePc without any change of Mössbauer parameters. The relative yield of the inactive complex was not simply dependent on the amount of iron doped and the temperature during reduction for preparation. Spin-spin interaction may have broadened the ESR signal at g=6 for FePc in zeolite, suggesting that the FePc molecules are located close together in zeolite. It is postulated that two types of FePc in zeolite particle were formed, in accordance with the reactivity of FePc to pyridine adduct formation.     

Novel high birefringence dibenzothiophenylacetylene liquid crystals

We have designed, synthesized and evaluated dibenzothiophenylacetylene homologues as new heterocyclic molecules which were expected to have high δα values and short wavelength UV absorption spectra. The dibenzothiophenyl acetylene homologues exhibited wide nematic phase ranges and had very high extrapolated δn of over 0.6 and directly measured values of 0.5. The compounds with two dibenzothiophenyl rings were colourless, so that we have succeeded in obtaining colourless super-high δn liquid crystals. We have also analysed the contribution of the transition band to the refractive indices and the birefringence. From the analysis, the main origins of δn for compounds 1 and 2 are lower MOs than the HOMO and this results in the compatibility of large δn and lack of colour. The dibenzothiophenylacetylene compounds behaved according to our design expectations.     

流体力学半径对估算胶体微球聚集速率常数的影响

胶体粒子聚集速率常数实验值远低于理论值一直是被普遍关注的问题.聚集速率常数的理论推导是基于粒子的几何半径来考虑的,但决定粒子扩散速率及聚集速率的应该是粒子的流体力学半径(大于几何半径),因而它是使聚集速率常数实验值低于理论值的因素之一.影响流体力学半径的因素很多,其中,带电粒子在溶液中因表面存在双电层,会明显增大流体力学半径,造成聚集速率减慢.而双电层的厚度又随溶液中离子强度的不同而改变.本工作在聚集速率的公式中引入了修正因子,即几何半径与其流体力学半径之比,以修正由于用几何半径代替流体力学半径带来的误差.其中几何半径和流体力学半径可以分别用扫描电镜(SEM)和动态光散射(DLS)来测定.以两种粒径的聚苯乙烯带电微球为例,考察了在不同离子强度下,该误差的大小.结果发现,对于半径为30 nm的微球,用流体力学半径计算的慢聚集速率常数比理论值偏低约8%.该误差随离子强度增加而减少.对于快聚集情况,流体力学半径对聚集速率基本没有影响.     

Ionic strength and pH dependence of binding constants of Am(III)- and Eu(III)-humates

Binding constants of Eu(III)- and Am(III)-complexes with soil-derived humic acid were determined by solvent extraction at various pH and ionic strength. Based on the dependence of binding constants on pH and ionic strength, stabilities of the humate complexes in land water and seawater were estimated. Speciation calculation based on the binding constants indicated that Am(III) could combine with humic substances in natural water system.     

Multitracer study on the effect of humate formation on the adsorption behavior of metal ions on kaolinite and silica gel

The multitracer technique was applied to elucidate of influence of humate formation on adsorption behavior of ultratrace elements. Dissolved fractions of Co, As, Rb, Sr, Y, Zr, Ba, Ce, Eu, Gd, Tb, Yb, Lu, Hf, Re and Pt in contact with kaolinite or silica gel were determined simultaneously either in the presence or absence of humic acid, which was partly adsorbed on the solid. Percentage of dissolved fraction of rare earth elements was identical to that of humic acid, indicating high stability of the rare earth-humate complex. Hydrolysis was the most important factor controlling the behavior of Zr and Hf. Both hydrolysis and humate complexation influenced the adsorption of Co, Sr, Ba and Pt, whereas neither affected the distribution of As, Rb and Re.     

Synthetic magnetic opals

We present studies of novel nanocomposites of BiNi impregnated into the structure of opals as well as inverse opals. Atomic force microscopy and high resolution elemental analyses show a highly ordered structure and uniform distribution of the BiNi filler in the matrix. These BiNi-based nanocomposites are found to exhibit distinct ferromagnetic-like ordering with transition temperature of about 675 K. As far as we know there exists no report in literature on any BiNi compound which is magnetic.     

Association of cesium with ferric components in altered flood basalt

Cesium content in eleven positions of a continental basalt with a columnar joint was determined by means of neutron activation analysis. Concentration of cesium is about four times higher at the altered portions of the fracture than at the unaltered. Water and Fe³⁺ content determined by gravimetry, Mössbauer spectroscopy, and inductively coupled plasma optical emission spectroscopy were also correlated with cesium concentration, suggesting accumulation of cesium with ferric components. Such processes may be important for estimating the behavior of radiocesium in the environment.