Reaction pathways for model II–VI precursors: A computational study

A computational study of the reactions of model II–VI precursors, MH₂ (M=Zn, Cd, Hg) and H₂E (E=O, S, Se, Te), is reported. The present computations yield several results of relevance to OMVPE of II–VI materials from MR₂/ER precursors. Adduct formation is feasible at low temperatures, in line with recent experiments, but not at higher temperatures common in II–VI OMVPE. Calculations suggest that adducts are most likely to form after elimination has resulted in replacement of hydride with hydroxide ligands (in our model) or alkyl with alkoxide ligands (in larger models). The overall reaction MH₂+2 H₂E→M(EH)₂ is generally more favorable, kinetically and thermodynamically, for lighter metals and heavier elements. On the basis of calculated thermodynamic and kinetic quantities, we conclude that the preferred pathway from reactants (MH₂+2 H₂E), except for M=Hg and E=Te, to an M(EH)₂ intermediate is by way of a 1:2 adduct (or a similar portion of the potential energy surface in the absence of a bound adduct) followed by two successive H₂ eliminations, in preference to the alternative in which adduct formation and H₂ elimination occur in succession. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 71: 47–56, 1999     

Ultrathin Ti3C2 nanowires derived from multi-layered bulks for high-performance hydrogen evolution reaction

One-dimensional ultrathin nanowires（NWs） offer a great deal of promising properties for electrochemical energy storage and conversion due to their nanoscale confinement effect and high surface-to-volume ratios. It is highly desirable to precisely design and synthesize ultrathin Ti₃C₂ NWs in the aspect of size,crystalline structure and composition. Here, we report a simple alkalization strategy to design the ultrathin Ti₃C₂ NWs for hydrogen evolution re...     

5-Nitrotetrazol and 1,2,4-Oxadiazole Methylene-Bridged Energetic Compounds: Synthesis,Crystal Structures and Performances

A new structural type for melt cast materials was designed by linking nitrotetrazole ring with 1,2,4-oxadiazole through a N-CH₂-C bridge for the first time. Three N-CH₂-C linkage bridged energetic compounds, including 3-((5-nitro-2H-tetrazol-2-yl) methyl)-1,2,4-oxadiazole (NTOM), 3-((5-nitro-2H-tetrazol-2-yl)methyl)-5-(trifluoromethyl)-1,2,4 -oxadiazole (NTOF) and 3-((5-nitro-2H-tetrazol-2-yl)methyl)-5-amine-1,2,4-oxadiazole (NTOA), were designed and synthesized through a two-step reaction by using 2-(5-nitro-2H-tetrazole -2-yl)acetonitrile as the starting material. The synthesized compounds were fully characterized by NMR (¹H, ¹³C), IR spectroscopy and elemental analysis. The single crystals of NTOM, NTOF and NTOA were successfully obtained and investigated by single-crystal X-ray diffraction. The thermal stabilities of these compounds were evaluated by DSC-TG measurements, and their apparent activation energies were calculated by Kissinger and Ozawa methods. The crystal densities of the three compounds were between 1.66 g/cm³ (NTOA) and 1.87 g/cm³ (NTOF). The impact and friction sensitivities were measured by standard BAM fall-hammer techniques, and their detonation performances were computed using the EXPLO 5 (v. 6.04) program. The detonation velocities of the three compounds are between 7271 m/s (NTOF) and 7909 m/s (NTOM). The impact sensitivities are >40 J, and the friction sensitivities are >360 N. NTOM, NTOF and NTOA are thermally stable, with decomposition points > 240 °C. The melting points of NTOM and NTOF are 82.6 °C and 71.7 °C, respectively. Hence, they possess potential to be used as melt cast materials with good thermal stabilities and better detonation performances than TNT.     

Synthesis of Energetic 7-Nitro-3,5-dihydro-4H-pyrazolo[4,3-d][1,2,3]triazin-4-one Based on a Novel Hofmann-Type Rearrangement

Rearrangement reactions are efficient strategies in organic synthesis and contribute enormously to the development of energetic materials. Here, we report on the preparation of a fused energetic structure of 7-nitro-3,5-dihydro-4H-pyrazolo[4,3-d][1,2,3]triazin-4-one (NPTO) based on a novel Hofmann-type rearrangement. The 1,2,3-triazine unit was introduced into the fused bicyclic skeleton from a pyrazole unit for the first time. The new compound of NPTO was fully characterized using multinuclear NMR and IR spectroscopy, elemental analysis as well as X-ray diffraction studies. The thermal behaviors and detonation properties of NPTO were investigated through a differential scanning calorimetry (DSC-TG) approach and EXPLO5 program-based calculations, respectively. The calculation results showed similar detonation performances between NPTO and the energetic materials of DNPP and ANPP, indicating that NPTO has a good application perspective in insensitive explosives and propellants.     

高效液相色谱圆二色检测技术在手性化合物分析中的应用

对近年来高效液相色谱圆二色检测技术在手性化合物分析中的应用进展进行综述,简单介绍了高效液相色谱圆二色检测器的原理和特点,着重介绍了非手性色谱条件下圆二色检测技术在手性化合物对映体纯度测定、复杂基质中手性化合物分析以及在手性化合物绝对构型测定中的应用,并讨论了它的应用前景。     

激光辐照对MgB2超导体电子结构的影响

研究了光辐照对MgB2超导体电子结构的影响。对MgB2超导体进行不同时间的激光照射后,利用正电子湮没技术对光照样品进行了研究,根据正电子寿命谱参数的变化情况,对光辐照后MgB2超导体样品中缺陷及电子结构的变化进行了讨论。实验表明:MgB2超导体中的平均电子浓度对激光的照射十分敏感,并随光照时间的增加而增加。     

Cationic photopolymerization of ambifunctional monomers

Certain metal-catalyzed hydrosilations have been found to occur in a highly regioselective manner which makes them useful for the preparation of unique classes of ambifunctional monomers. These monomers bear two chemically different functional groups within the same molecule. By selection of the appropriate functional groups it is possible to design monomers in which the functional groups react independently, copolymerize, or polymerize by different mechanisms. This article describes some recent results of the synthesis and polymerization of several novel types of ambifunctional monomers.     

Effects of Airflow Ultrafine-Grinding on the Physicochemical Characteristics of Tartary Buckwheat Powder

Five different ultrafine milled flours (UMFs) were prepared from Tartary buckwheat via airflow ultrafine-grinding at different grinding pressures. The airflow ultrafine-grinding resulted in marked differences in particle size (from 100 to 10 μm). The UMFs were all brighter in appearance (higher L*) than Tartary buckwheat common flour (TBCF). Illustrated by the example of 70 °C, the UMFs were also found to have a greater water holding capacity (from 4.42 g/g to 5.24 g/g), water solubility (from 12.57% to 14.10%), and water solubility index (from 5.11% to 6.10%). Moreover, as the particle sizes reduced, the moisture content decreased (from 10.05 g/100 g DW to 7.66 g/100 g DW), as did the total starch content (from 68.88 g/100 g DW to 58.24 g/100 g DW) and the protein content (from 13.16% to 12.04%). However, the grinding process was also found to have negative effects on the mineral content of the Tartary buckwheat. Additionally, several substantial variations were found in their hydration properties along with grinding pressure changes in the differently ground UMFs. Consequently, fine Tartary buckwheat powders of a bright yellow color, with superior food processing properties, were prepared in this study by airflow ultrafine-grinding.     

交流示波极谱基础研究(Ⅳ)——切口的性质

用修正的Micka公式,从理论上描述了交流示波极谱图上切口的性质,用实验进行了验证。