Crown-containing butadienyl dyes 8. Structures and complexation of chromogenic dithia-15(18)-crown-5(6) ethers

The structures of new butadienyl dyes of the benzothiazole series containing the dithia-15-crown-5 (2a) or dithia-18-crown-6 (2b) fragments were established by X-ray diffraction. Complexation of dyes 2a,b with Hg²⁺, Pb²⁺, Cd²⁺, Ag⁺, Zn²⁺, and alkaline-earth cations in aqueous-acetonitrile solutions was studied by spectrophotometry. At a high percentage of water in solutions (P _w ≈ 50%), these dyes have a very low ability to bind Pb²⁺ cations (logK < 2) and virtually do not bind Cd²⁺, Zn²⁺, and alkaline-earth cations. At the same time, these dyes form stable 1: 1 complexes with Hg²⁺ and Ag⁺ cations at all P _w. The stability constants of complexes with the Ag⁺ cation increase with increasing P _w because the free energy of hydration of this cation is much lower than the free energy of solvation in acetonitrile. In the P _w range from 0 to 75%, the stability constants of the complexes of dyes 2a,b with the Hg²⁺ cation are larger than those of the corresponding complexes with the Ag⁺ cation by more than four orders of magnitude. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 90–96, January, 2006.     

H-quadrupolar coupling-based analysis of stereochemical and regiochemical memory in the Pd-catalysed allylic alkylation of iso-cinnamyl type substrates employing the chiral monophosphine ligands ‘MOP’ and ‘MAP’

The reaction of iso-cinnamyl acetate with NaC(Me)(CO₂Me)₂, catalysed by Pd-‘MOP’ (MOP=2-methoxy-2′-diphenylphosphino-1,1′-binaphthalene) is known to proceed with a regiochemical memory effect that results in the predominant generation of the branched alkylation product. The analogous reaction employing ‘MAP’ as ligand (MAP=2-N,N-dimethylamino-2′-diphenylphosphino-1,1′-binaphthalene) proceeds with ‘normal’ regioselectivity to generate predominantly the linear isomer of product. A ²H-NMR based analysis, employing quadrupolar coupling in a chiral liquid crystal matrix, has been developed to facilitate the simultaneous study of the regiochemical and stereochemical outcome of the reaction of both enantiomers of iso-cinnamyl ester substrates in ²H-labelled but racemic samples. The analysis allows the comparison of relative rates of two competing isomerisation processes occurring in the π-allyl intermediates in the Pd-catalysed reaction, one of which facilitates asymmetric induction, the other resulting in loss of regiochemical memory. It is demonstrated that the two processes are partially coupled and that this then limits the attainment of high global enantiomeric excess in the branched product to reactions that proceed with low regiochemical retention. A key factor for the observation of high regiochemical memory is found to be the nucleophilicity of the malonate anion and the electrophilicity of the Pd-π-allyl intermediate with reduction in the reactivity of either partner resulting in the onset of substantial loss of memory.     

一种新颖有机-无机杂化配位聚合物[(C10H16N)2（Pb2I6）·2DMF·H2O]n的自组装合成和晶体结构(英)

A novel coordination polymer [(C₁₀H₁₆N)₂（Pb₂I₆）·2DMF·H₂O]_n (C₁₀H₁₆N=N-butyl-2-Methy-Pyridinium) was synthesized by the reaction of Pb(NO₃)₂ with C₆H₁₀NI at room temperature in DMF solvent and structurally characterized by means of X-ray single diffraction. The title compound crystallizes in triclinic system, space group P1 with a=1.1237(2) nm, b=1.25330(16) nm, c=0.808 00(12) nm, α=102.523(4)°, β=92.475(5)°, γ=95.712(10)°, V=1.102 9(3) nm³, Z=1, D_c=2.470 Mg·m^-3, F(000)=738, chemical formula C₂₆H₄₈N₄O₃Pb₂I₆ and M_r=1 640.46, μ（MoKα）=11.849 mm^-1, the final R=0.057 8 and wR=0.166 5 for 3716 observed reflections with I > 2σ(I). The title compound consists of cations ([(C₁₀H₁₆N)⁺] and anion chain(PbI₃^-),they are combined by static attracting forces in the crystal. DMF and H₂O locate between the organic and inorganic moiety. CCDC: 210812.     

1570例学龄前儿童血铅水平调查

为了解顺德伦教学龄前儿童血铅水平及铅中毒发病情况 ,以便及时采取有效措施 ,根据整群分层随机抽样 ,检测了本区学龄前儿童血铅水平 ,并进行了流行病学分析。结果表明 ,本次调查学龄前儿童 1 5 70例 ,血铅水平为 (1 0 8 6± 79 8) μg/L ,儿童铅中毒患病率为 5 0 76% ;男童血铅水平及铅中毒患病率都高于女童 ,但无明显统计学差异 (P >0 0 5 ) ;年龄越大血铅水平相对越高 ,铅中毒患病率也越高 ,并存在明显差异 (P <0 0 1 )。提示顺德伦教学龄前儿童血铅水平及铅中毒患病率维持在较高水平 ,应及时采取有效措施 ,防治儿童铅中毒。     

钇对Nd-Fe-Al-Ni非晶合金热稳定性与晶化行为的影响

采用差示扫描量热法（DSC）、X射线衍射（XRD）和透射电镜（TEM）研究了Y对Nd-Fe-Al-Ni非晶合金热稳定性和晶化行为的影响。结果表明,淬火态的Nd60Fe20Al10Ni10-xYx（x=0,2）合金基本为非晶组织同时还含有少量的淬态相,Y的加入抑制了淬态相的析出。加入Y后,非晶合金的晶化开始温度和晶化峰值温度都向高温方向移动,证明其热稳定性提高。Y的加入改变了合金的晶化方式和最终晶化产物,使非晶基体中析出的晶化相更加弥散圆整细小。并且Y具有在化学上钝化氧杂质的作用,从而抑制了氧的有害作用。利用Kissinger方程获得了Nd60Fe20Al10Ni8Y2非晶合金的晶化开始和晶化峰值激活能分别为1.21和1.16 eV。     

Inhibition of Pb-Leaching from Lead Crystal Glass by Coating with Films Prepared by the Sol-Gel Method

The chemical durability of lead glass tumblers (24% PbO) in a 4% (v/v) acetic acid solution before and after coating with sol-gel derived SiO2 films was assessed to determine the extent of reduction in Pb-leaching that can be achieved. It was found that by coating the internal surface of the glass tumblers with 1 ml of 10% TEOS solutions at 100°C and densifying the coating formed at 500°C for 1 h, it was possible to reduce Pb-leaching to about one quarter of that of the uncoated glass.     

两种含锌化合物对慢性染铅大鼠海马NADPH-d阳性神经元影响的比较

为探讨硫酸锌(ZnSO4)和牛磺酸锌(TZC)拮抗铅对学习记忆的损害的不同，采用NADPH-黄递酶(NADPH-d)组化，观察了饮用含0.2g／L醋酸铅(PbAc)饮水和含不同剂量(5．0，15．0g／kg)ZnSO4、(5．9、17．7g／kg)TZC饲料喂养的大鼠海马一氧化氮合酶(NOS)活性的变化。结果表明，各补锌组均不同程度地缓解铅致NOS活力减低，铅 低TZC组、铅 高ZnSO4组和铅 低ZnSO4组大鼠海马神经元的NOS活性明显高于染铅组，其中铅 低TZC组的保护作用最显著，而铅 高TZC组的NOS活性明显低于对照组，而接近染铅组水平。结论是锌对抗铅的毒性作用与锌的化学结合形式、锌的剂量密切相关。     

X-ray emission spectroscopy with EPMA applied to high Tc Superconductors using new spectrometer crystals

The High Temperature Superconductors are characterized by a very anisotropical structure and by typical arrangements of Cu- and O-atoms within CuO₂-planes. In studying the electronic structure of these compounds there is a strong demand for high resolution valence band spectroscopy. Using an electron probe microanalyzer we study the X-ray emission of O-K_ga and Cu-L emerging from polycrystalline YBa₂Cu₃O₇ and Tl₂Ba₂Ca₂Cu₃O₁₀. The O-K emission band is analyzed using a chlinochlore crystal in (001) orientation (2d = 28.4 Å). For the Cu-L emission band we use a beryl crystal in (10¯10) orientation (2d = 15.9 Å). Furthermore, orientation dependent X-ray emission spectroscopy of single-crystalline YBa₂Cu₃O₇ and Tl₂Ba₂Ca₁Cu₂O₈ specimens was performed. We present the partial O-K spectra which represent the O-2p ( = x, y, z) electronic densities of states of the valence band and compare them with calculated data.     

预取向液晶单体光聚合反应

通过表面摩擦、施加外电场(或磁场)和应力剪切等手段使液晶单体取向后进行光聚合反应是制备高度取向、高度均匀和高度透明高分子液晶膜的重要方法。它在高分子非线性光学材料、导电商分子材料和光纤涂层等领域中具有广泛的应用前景。     

超细粉Pb0.75Ca0.25[(Ni1/3Nb2/3)0.08Ti0.912Mn0.008]O3的制备与表征

报道了用化学共沉淀法制备掺杂Ca、Ni、Nb、Mn钛酸铅超细陶瓷粉末的方法。制得的粉料化学式为:Pb_0.75Ca_0.25[(Ni_1/3Nb_2/3)_0.08Ti_0.912Mn_0.008]O₃,粒径小于0.1μm,所有的掺杂元素均能定量掺入。