Design of pure heterodinuclear lanthanoid cryptate complexes

Heterolanthanide complexes are difficult to synthesize owing to the similar chemistry of the lanthanide ions. Consequently, very few purely heterolanthanide complexes have been synthesized. This is despite the fact that such complexes hold interesting optical and magnetic properties. To fine-tune these properties, it is important that one can choose complexes with any given combination of lanthanides. Herein we report a synthetic procedure which yields pure heterodinuclear lanthanide cryptates LnLn*LX₃ (X = NO₃⁻ or OTf⁻) based on the cryptand H₃L = N[(CH₂)₂N CH–R–CH N–(CH₂)₂]₃N (R = m-C₆H₂OH-2-Me-5). In the synthesis the choice of counter ion and solvent proves crucial in controlling the Ln–Ln* composition. Choosing the optimal solvent and counter ion afford pure heterodinuclear complexes with any given combination of Gd(iii)–Lu(iii) including Y(iii). To demonstrate the versatility of the synthesis all dinuclear combinations of Y(iii), Gd(iii), Yb(iii) and Lu(iii) were synthesized resulting in 10 novel complexes of the form LnLn*L(OTf)₃ with LnLn* = YbGd 1, YbY 2, YbLu 3, YbYb 4, LuGd 5, LuY 6, LuLu 7, YGd 8, YY 9 and GdGd 10. Through the use of ¹H, ¹³C NMR and mass spectrometry the heterodinuclear nature of YbGd, YbY, YbLu, LuGd, LuY and YGd was confirmed. Crystal structures of LnLn*L(NO₃)₃ reveal short Ln–Ln distances of ∼3.5 Å. Using SQUID magnetometry the exchange coupling between the lanthanide ions was found to be anti-ferromagnetic for GdGd and YbYb while ferromagnetic for YbGd.

We present a synthetic strategy to prepare the first heterodinuclear lanthanide(iii) cryptate complexes. The cryptate design ensures that the complexes are stable in solution for days. The exchange coupling in YbYb, GdGd and YbGd is investigated.     

The topochemical 1,6-polymerization of a triene

The first topochemical 1,6-polymerization of a triene has been observed. The required supramolecular structure for this polymerization was achieved by the pi-pi stacking of the isonicotinate functionality. The crystal environment of this polymerization reaction controlled both the molecular and supramolecular structure of the polymer and allowed its structure to be determined by single-crystal X-ray diffraction.     

Radiolysis of 1-naphthol in aqueous solutions

The effects of absorbed doses, initial pH and 1-naphthol concentration onto its radiolysis in aqueous sulphuric and hydrochloric acids by gamma rays from ⁶⁰Co were investigated. Under the experimental conditions, 1-naphthol degradation yields increased with increasing the absorbed doses (0.3–3.0 kGy) and with decreasing the initial 1-naphthol concentration (20–1 ppm). It was found out that the hydrated electrons did not play any significant roles in 1-naphthol radiolysis, as the degradation yields were higher at pH₀ ~ 0.46 compared to those at pH₀ ~ 2.0–5.0. The corresponding radiolytic yields G(−1-naphthol) were (6.13 ± 1.00)) × 10⁻² and (5.11 ± 0.22) × 10⁻² μmol/J in sulphuric acids, (15.61 ± 3.85) × 10⁻² and (4.76 ± 0.48) × 10⁻² μmol/J in hydrochloric acids. 1-Naphthol degradation rates could be described by the kinetic equations of pseudo-first-order reactions. An empirical relation between the observed reaction constants k _D and the initial 1-naphthol concentrations was established, enabling to predict the absorbed doses required for a given treatment efficiency. Three products of 1-naphthol degradation were revealed using an HPLC/UV procedure.     

碱金属钾对Ni基催化剂纤维素水蒸气气化活性的影响

采用两段式催化气化方式研究了生物质热解气化过程中碱金属的挥发对Ni基催化剂活性的影响。实验结果表明,负载K盐的纤维素水蒸气催化气化过程中,K挥发后会在催化剂表面沉积,而少量K的存在和表面沉积不但能够提高镍基催化剂的抗积炭能力,而且有助于提高其催化活性,产生更多的氢气。然而纤维素中K的浓度过大,将会抑制Ni基催化剂的效果;K在催化剂上的沉积随催化剂循环次数的增加而增加,K的含量愈高,对催化剂的抑制效果愈明显,从而缩短了催化剂的使用寿命。     

A new route to triphenylpyridines utilizing ketoximes as building blocks via cascade reactions under iron‐organic framework catalysis

Iron‐based metal–organic framework VNU‐20 was utilized as a heterogeneous catalyst for cascade reactions between ketoximes and dibenzyl ether to produce 2,4,6‐triphenylpyridines. Additionally, benzyl alcohol and (dimethoxymethyl)benzene could be used as an alternative starting materials for the transformation. The oxidant exhibited a remarkable impact on the reactions, and di‐tert‐butylperoxide was the most appropriate candidate. The VNU‐20 displayed higher efficiency than many homogeneous and heterogeneous catalysts. The catalyst was reusable for the cascade reactions without a noticeable deterioration in catalytic activity. This transformation is new, and would offer alternative routes to triphenylpyridines utilizing ketoximes as building blocks.     

用于 EAST 上低杂波平行波数测量的磁探针设计与测试

针对EAST上2.45GHz低杂波，完成了低杂波平行波数测量磁探针的设计、仿真与测试。利用有限元仿真软件COMSOL Multiphysics 5.2对磁探针尺寸进行仿真优化，确定了单匝环、矩形缝以及陶瓷片厚度等影响磁探针耦合性能的关键尺寸。测试结果表明，该磁探针对2.45GHz低杂波有良好的耦合性能和鉴别波极化的能力，与仿真结果一致。研究结果为EAST装置上低杂波平行波数测量诊断系统的建立提供重要的参考依据，从而为进一步开展高密度低杂波电流驱动实验研究提供必要的实验数据。     

A systematic study of J/ψ suppression in cold nuclear matter

Understanding the effects of cold nuclear matter on J/ψ production is a key requirement for interpreting the J/ψ suppression reported in heavy-ion collisions. Based on a Glauber model, the J/ψ–nucleon inelastic cross section is determined from a statistical analysis of the J/ψ world data on nuclear targets. The global fit of all data gives σ_J/ψN = 3.4 ± 0.2 mb, significantly smaller than previous estimates, yet the χ² of the fit is pretty large, χ²/ndf=1.5. A similar value, σ_J/ψN = 3.5 ± 0.2 ± 1.7 mb, is obtained when the De Florian–Sassot modifications of the nuclear parton densities are included in the analysis, although we emphasise that the present uncertainties on gluon (anti-) shadowing do not allow for a precise determination of σ_J/ψN. Finally, the possible energy dependence of the J/ψ–nucleon inelastic cross section is investigated within this framework. No significant energy dependence of the J/ψ–N interaction is observed. PACS  25.75.-q; 14.40.Gx; 24.85.+p     

Ueber die analytische Bestimmung der wesentlichen Bestandtheile des metallischen Wolframs, Ferrowolframs und Wolframstahls, des Ferrochroms und Chromstahls, sowie des Ferroaluminiums und Aluminiumstahls, unter theilweiser Zugrundelegung neuer Aufschlussverfahren

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