SSZ-13分子筛上甲醇转化过程中甲氧基物种的生成与活性研究

本文使用固体核磁共振（NMR）技术研究了SSZ-13分子筛上甲醇制烯烃反应过程中表面甲氧基物种的生成以及反应活性.通过二维¹³C-²⁷Al HMQC NMR方法确证了甲醇在分子筛骨架Brønsted酸位上生成的甲氧基物种,以及在Lewis酸位上生成的另外一种表面甲氧基物种.¹³C NMR结合气相色谱-质谱（GC-MS）实验结果表明,这两种甲氧基物种在甲醇制烯烃反应中均具有较高的反应活性,既可以导致烃池物种的生成,也可以参与烃池反应生成碳氢化合物.     

Comprehensive performance of a ball-milled La0.5Pr0.5Fe11.4Si1.6B0.2Hy/Al magnetocaloric composite

Due to the hydrogen embrittlement effect, La(Fe,Si)₁₃-based hydrides can only exist in powder form, which limits their practical application. In this work, ductile and thermally conductive Al metal was homogeneously mixed with La_0.5Pr_0.5Fe_11.4Si_1.6B_0.2 using the ball milling method. Then hydrogenation and compactness shaping of the magnetocaloric composites were performed in one step via a sintering process under high hydrogen pressure. As the Al content reached 9 wt.%, the La_0.5Pr_0.5Fe_11.4Si_1.6B_0.2H_y/Al composite showed the mechanical behavior of a ductile material with a yield strength of ~44 MPa and an ultimate strength of 269 MPa accompanied by a pronounced improvement in thermal conductivity. Due to the ease of formation of Fe-Al-Si phases and the several micron and submicron sizes of the composite particles caused by ball milling process, the magnetic entropy change of the composites was substantially reduced to ~1.2 J/kg· K-1.5 J/kg· K at 0 T-1.5 T.     

固体高分辨~(13)C NMR研究γ线辐照对结晶聚乙稀聚集态结构的影响

结晶聚乙烯(PE)经~(60)Coγ线辐照后,用固体高分辨~(13)C NMR CP/DD/MAS方法观测解析了辐射效果与具有片晶结构的结晶相,结晶—橡胶状无定形界面相以及橡胶状无定形相的聚集态结构的关系。考察了各相中的~(13)C核自旋—晶格弛豫和自旋-自旋弛豫行为及辐照对其影响。得到辐照后产生交联,破坏,相转变及晶型变化等有意义的结果,对PE的辐照效应和机制的探讨提供了核磁共振的新实验证据。     

Substituent effect investigation of 3‐(2, 4‐dichlorophenyl)‐1‐(4′‐X‐phenyl)‐2‐propen‐1‐one. Part 1. Correlation analysis of 13C NMR chemical shifts

A series of substituted chlorinated chalcones namely, 3‐(2,4‐dichlorophenyl)‐1‐(4′‐X‐phenyl)‐2‐propen‐1‐one, have been synthesized, X being H, NH₂, OMe, Me, F, Cl, CO₂Et, CN, and NO₂. Dual substituent parameter (DSP) models of ¹³C NMR chemical shift (CS) have revealed that π‐polarization concept could be utilized to explain the reverse field effect at CO, the enhanced substituent field effect at CO, C‐2, and C‐5, and the decreased sensitivity of substituent field effect at C‐6. Chlorine atoms dipole direction at the benzylidene ring either enhances or reduces substituent effect depending on how they couple with the substituent dipole at the probe site. The correlation of ¹³C NMR CS of C‐2, C‐5, and C‐6 with σ and σ indicates that chlorine atoms in the benzylidine ring deplete the ring from charges. Both MSP of Hammett and DSP of Taft ¹³C NMR CS models give similar trends of substituent effects at C‐2, C‐5, and C‐6. However, the former fail to give a significant correlation for CO and C‐6 ¹³C NMR CS. MSP of σ_q and DSP of Taft and Reynolds models significantly correlated ¹³C NMR CS of C_β. MSP of σ_q fails to correlate C‐1′ ¹³C NMR CS. Investigation of ¹³C NMR CS of non‐chlorinated chalcones series: 3‐phenyl‐1‐(4′‐X‐phenyl)‐2‐propen‐1‐one has revealed similar trends of substituent effects as in the chlorinated chalcones series for C‐1′, CO, C_α, and C_β. In contrast, the substituent effect of the non‐chlorinated chalcone series at C‐2, C‐5, and C‐6 did not correlate with any substituent constant. Copyright © 2010 John Wiley & Sons, Ltd.     

Magnetoelastic properties of Nd6Fe13Cu intermetallic compound

Magnetoelastic properties of Nd₆Fe₁₃Cu intermetallic compound are reported. To study the magnetoelastic behaviour of this compound, the thermal expansion as well as the longitudinal (λ_l) and transverse (λ_t) magnetostriction were measured by using the strain gauge method in the selected temperature range of 80-500 K under applied magnetic fields up to 1.5 T. An anomaly and invar-type effects are observed in the linear thermal expansion and α(T) curves at the Néel temperature. The linear spontaneous magnetostriction decreases sharply by approaching the Néel temperature and also shows the short-range magnetic ordering effects when antiferromagnetic-paramagnetic transition occurs. In the low field region, the absolute values of the anisotropic magnetostriction are small and then start to increase with applied magnetic field. Each isofield curve of the anisotropic magnetostriction passes through a minimum and then approaches to zero with increasing temperature. This magnetostriction compensation arises from the difference in the magnetoelastic coupling constants of the sublattices in this compound.     

Fast volumetric spatial-spectral MR imaging of hyperpolarized C-labeled compounds using multiple echo 3D bSSFP

Purpose

The goal of this work was to develop a fast 3D chemical shift imaging technique for the noninvasive measurement of hyperpolarized ¹³C-labeled substrates and metabolic products at low concentration.

Materials and Methods

Multiple echo 3D balanced steady state magnetic resonance imaging (ME-3DbSSFP) was performed in vitro on a syringe containing hyperpolarized [1,3,3-2H3; 1-¹³C]2-hydroxyethylpropionate (HEP) adjacent to a ¹³C-enriched acetate phantom, and in vivo on a rat before and after intravenous injection of hyperpolarized HEP at 1.5 T. Chemical shift images of the hyperpolarized HEP were derived from the multiple echo data by Fourier transformation along the echoes on a voxel by voxel basis for each slice of the 3D data set.

Results

ME-3DbSSFP imaging was able to provide chemical shift images of hyperpolarized HEP in vitro, and in a rat with isotropic 7-mm spatial resolution, 93 Hz spectral resolution and 16-s temporal resolution for a period greater than 45 s.

Conclusion

Multiple echo 3D bSSFP imaging can provide chemical shift images of hyperpolarized ¹³C-labeled compounds in vivo with relatively high spatial resolution and moderate spectral resolution. The increased signal-to-noise ratio of this 3D technique will enable the detection of hyperpolarized ¹³C-labeled metabolites at lower concentrations as compared to a 2D technique.     

新型萘酰亚胺衍生物的13C NMR研究

报道了四种新的萘酰亚胺衍生物的¹³C NMR谱. 应用¹H、¹³C、DEPT、HMQC、HMBC 等谱确定了这四种化合物的分子结构,并对全部谱峰进行了归属,探讨了分子结构对¹³C NMR化学位移的影响.     

The first Chevalley–Eilenberg Cohomology group of the Lie algebra on the transverse bundle of a decreasing family of foliations

In [L. Lebtahi, Lie algebra on the transverse bundle of a decreasing family of foliations, J. Geom. Phys. 60 (2010), 122–133], we defined the transverse bundle V^k$V^k$ to a decreasing family of k$k$ foliations _Fi$F_i$ on a manifold M$M$. We have shown that there exists a (1,1)$(1,1)$ tensor J$J$ of V^k$V^k$ such that J^k≠0$J^k\ne 0$, J^k+1=0$J^{k+1}=0$ and we defined by _LJ(V^k)$L_J\left(V^k\right)$ the Lie Algebra of vector fields X$X$ on V^k$V^k$ such that, for each vector field Y on V^k$V^k$, [X,JY]=J[X,Y]$[X,JY]=J[X,Y]$.     

Influences of laser remelting on microstructure of nanostructured Al2O3-13 wt.% TiO2 coatings fabricated by plasma spraying

The effects of laser remelting on microstructure of nanostructured Al₂O₃-13 wt.% TiO₂ ceramic coatings prepared by plasma spraying with agglomerated powders were studied. The microstructure of the feedstock, as-sprayed and laser-remelted coatings were investigated by using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffractometry (XRD). The results indicate that the plasma-sprayed ceramic coating consists of both fully melted regions and partially melted regions. The totally ceramic coating, especially the fully melted regions, has a typical plasma-sprayed lamellar-like structure as the conventional coating, and has some pores. According to the difference of microstructures, the partially melted regions can be divided into liquid-phase sintered regions (a three-dimensional net or skeleton-like structure: Al₂O₃-rich submicron particles embedded in the TiO₂-rich matrix) and solid-phase sintered regions (remained nanoparticles). The lamellar defect of the as-sprayed coating is erased, and the compactness of the coating is improved significantly after laser remelting. The laser-remelted region composed of fine equiaxed grains, which are different from the conventional column-like crystals along the direction of the heat current. Due to the rapid solidification of laser remelting process, there are still some nanoparticles in the remelted region because of an insufficient time for grains growth.