1,2-聚丁二烯分子运动的~(13)C-NMR研究——Ⅱ.分子运动的温度依赖性

本文用200MHz脉冲傅利叶变换波谱仪测定了1,2-聚丁二烯样品在不同温度下的~(13)C-T_(19)NOE,线宽和化学位移等~(13)G自旋弛豫参数,研究了1,2-聚丁二烯分子运动的温度依赖性.结果发现,在-10—-30℃之间,样品中各碳核的NOE和谱线宽度随温度变化的曲线斜率增加,表明此时长程链运动冻结;各碳核nT_1随温度的变化均在-45℃左右出现极小值.     

乙烷脱氢与逆水煤气变换耦合制乙烯反应--助剂对Fe/SiO2催化剂活性的影响

研究了乙烷脱氢与逆水煤气变换耦合制乙烯反应中助剂对Fe/SiO2催化剂活性的影响。结果表明，添加氧化物助剂有利于反应，Fe-Mn／K^ -SiO2催化剂显示较高的活性和选择性，在740℃时，乙烷转化率和乙烯选择性分别为37．3％和98．6％。二氧化碳的作用是消除积炭以及与氢反应以提高乙烷的脱氢反应转化率。XPs表明催化剂表面存在 3价铁和 4价锰物种。     

Heterocyclic analogs of 5,12-naphthacenequinone. 2. Synthesis of 4,11-dihydroxynaphtho[2,3-f]indazole-5,10-dione and its n-methyl derivatives

On methylating 4,11-dimethoxynaphtho[2,3-f]indazole-5,10-dione with methyl iodide in the presence of base a mixture is formed of its 1-and 2-methyl derivatives. Demethylation of the methoxy groups of the starting material and of the products of its alkylation leads to the formation of 4,11-dihydroxynaphtho[2,3-f]indazole-5,10-dione (pyrazoloquinizarine) and its 1-and 2-methyl derivatives. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 691–696, May, 2006.     

铁系无铬型CO高温变换催化剂的谱学研究

用Ｍｏｓｓｂａｕｅｒ谱，ＸＲＤ及ＴＥＭ技术对铁系无铬型催化剂的前驱态、母体及还原态在不同工艺条件下的生成及晶相结构的微变过程进行了研究。确证了水合四氧化三铁Ｆｅ３－ｘＯ４·ｎＨ２Ｏ和γ－Ｆｅ２Ｏ３晶态的形成，并探讨了晶相参数微变引起晶体结构的差异导致的催化活性的变化。在Ｆｅ３－ｘＯ４·ｎＨ２Ｏ中ＳＢ／ＳＡ比值为２，ｘ值接近于０时催化活性最高。     

Polycyclic Phosphorus Sulfide Compounds containing Chiral Amido or Imido Substituents

Reactions of α‐P₄S₃I₂ with (S)‐ or racemic‐RNH₂ (R = CH(Me)Ph) have given solutions containing exo, exo‐ or endo, exo‐α‐P₄S₃(NHR)₂, α‐ or β‐P₄S₃(μ‐NR), or P₄S₂(μ‐NR), as the first compounds with polycyclic phosphorus sulfide skeletons to contain chiral substituents. The expected diastereomers have been characterised by complete analysis of their ³¹P{¹H} NMR spectra, and relative configuration has been assigned in most cases. Considerable diastereomeric differences in coupling constants and chemical shifts were found.     

Experimental and theoretical study of <Superscript>13</Superscript>C shielding tensors in new-style molybdenum complex

¹³C 2D-PASS spectra of two new cis-dioxo catecholatomolybdenum complexes (NH₂CH₂NH₂CHCH₂)₂(H⁺)₃[Mo^vO ₂(C₆H₄O₂)₂] and (NH₂CH₂CH₂CH₂NH₂)₂(H⁺)₃[Mo^(v)O₂ (C₂H₂O₂)₂] have been obtained by solid-state nuclear magnetic resonance (NMR), in which the spinning sidebands were well-separated. The principal components of the ¹³C shielding tensors were extracted by theoretically fitting the intensities of ¹³C spinning sidebands. The effects of counter cations on ¹³C chemical shift isotropy and shielding tensor of cis-dioxo catecholatomolybdenum complex anion [Mo ^(v)O₂(C₆H₄O₂)₂]³⁻ were studied, comparing the ¹³C CSA of those carbon sites in complex anions with that of the counter cations. Based on the known structure of the molybdenum complex crystal, theoretical values of ¹³C shielding tensors were calculated by the ainitio GIAO method, in comparison with the experimental results.     

Quantum mechanics and relativity: attempt at a new start

The approach which led Louis de Broglie to the assertion, for particles with nonzero rest mass, of the two correlated relationsp =h/ andW =mc ² =hv, is reexamined. A modified approach is then developed. This leads to a set of mutually coherent new relations with respect to which de Broglie's relationsp =h/ andW =mc ² =hv appear as certain approximations. The mentioned set of new relations entails the prediction of specific effects which can be verified experimentally. If it is confirmed, this set of new relations might constitute the germ of a theory able to accomplish a veritable unification of relativity and microphysics.     

用软件定标技术扩展EM－360L核磁共振谱仪的温度适应范围

利用计算机控制和数据处理技术对进口核磁共振谱仪加以改造，使其测试所需要的环境温度由原来的恒温降至室温。其精度保持不变，硬件方案捷可靠，软件利用一个标准样品的已知参数来校正系统的刻度单位，算法采用动态的可调刻度单位标定其它样品的测试结果，取得了较为理想的效果。     

Activity of Co?Mo catalysts supported on alumina modified with La2O3

Catalytic activity in the water-gas shift (WGS) reaction was measured over Co−Mo sulfides supported on alumina modified with La₂O₃. Increasing concentration of La₂O₃ up to 15% provides better catalytic performance and higher sorption capacity of ammonia.