Atomic radical—molecule reactions F + CH<Subscript>3</Subscript>C≡CH: mechanistic study

The reaction of atomic radical F with propyne has been studied theoretically using ab initio quantum chemistry methods and transition state theory. The potential energy surface was calculated at the CCSD(T)/aug-cc-pVDZ (single-point) level using the UMP2/6-311++G(d,p) optimized structures. Two reaction mechanisms including the addition–isomerization–elimination reaction mechanism and the directed hydrogen abstraction reaction mechanism are considered. For the hydrogen abstraction reactions, i.e., the most probable evolution pathway in the title reaction, the HF formation occurs via direct abstraction mechanism dominantly and the H atom picked up by the atomic radical F should come mostly from the methyl group of normal propyne. On the other hand, for the addition–isomerization–elimination mechanism, the most feasible pathway should be the atomic radical F attacking on the C≡C triple bond in propyne (CH₃C≡CH) to form a weakly-bound adduct A1 with no barrier, followed by F addition to the C≡C triple bond to form the low-lying intermediate isomer 5. Subsequently, isomer 5 directly dissociates to P3 H₂CCCHF + H via transition state TS₅/P3. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. Furthermore, based on the analysis of the kinetics of all channels through which the addition and abstraction reaction proceed, we expect that the competitive power of reaction channels may vary with experimental conditions for the title reaction. The present work will provide useful information for understanding the processes of atomic radical F reaction with other unsaturated hydrocarbons. This material is available from author via E-mail.     

Aggregation-driven growth of size-tunable organic nanoparticles using electronically altered conjugated polymers

A novel class of monodisperse conjugated polymer nanoparticles have been readily prepared by the facile reprecipitation of poly{1,3-bis[2-(3-alkylthienyl)]azulene} or poly{1,3-bis[2-(3-alkoxythienyl)]azulene}. The multicomponent poly(bithiophene-alt-azulene) macromolecules were efficiently self-assembled into a wide range of size-tunable nanoparticles from a few tens to five hundred nanometers via the hydrophobic and pi-stacking effects in the mixed chloroform/methanol solutions. Electronically altered polymer structures with different alkyl or alkoxy substitutes exhibited variable self-assembling behaviors to precisely tune the size and the optical/electronic properties of nanoparticles. A strong size dependence of continuous bathochromic absorption and significant enhanced emission were observed with the increase of particle size. A linear relationship between the absorption or fluorescence intensities and the particle size was demonstrated as well, and this is very useful to probe the intermolecular interactions and the size evolutions of conjugated polymer nanoparticles. After the size-dependent optical and electronic properties are created, they can be further optimized to improve the performance of materials prior to the use in novel organic nanodevices in a cost-effective way.     

Single Atoms of Iron on MoS2 Nanosheets for N2 Electroreduction into Ammonia

Efforts have been devoted to achieving a highly efficient artificial synthesis of ammonia (NH₃). Reported herein is a novel Fe-MoS₂ catalyst with Fe atomically dispersed onto MoS₂ nanosheets, imitating natural nitrogenase, to boost N₂ electroreduction into NH₃ at room temperature. The Fe-MoS₂ nanosheets exhibited a faradic efficiency of 18.8 % with a yield rate of 8.63 μg mg_cat.⁻¹ h⁻¹ for NH₃ at −0.3 V versus the reversible hydrogen electrode. The mechanism study revealed that the electroreduction of N₂ was promoted and the competing hydrogen evolution reaction was suppressed by decorating the edge sites of S in MoS₂ with the atomically dispersed Fe, resulting in high catalytic performance for the electroreduction of N₂ into NH₃. This work provides new ideas for the design of catalysts for N₂ electroreduction and strengthens the understanding about N₂ activation over Mo-based catalysts.     

新型除草剂及其杂质的LC-MS和GC-MS分析

High performance liquid chromatography (HPLC) and electrospray ionization mass spectrometry (ESI-MS) have been utilized to analyze the synthesized 2-(2-arylaminomethylphenoxy)pyrimidine derivatives, which are a new kind of environmentally benign herbicides and have passed the temporary pesticide registration. The identification of main product and impurities has been achieved according to the UV and mass spectra. Moreover, one impurity, introduced by the raw material in the last step of the synthetic route, was identified by GC-MS analysis. It can be concluded that the combination of chromatography and mass spectrometry, including LC-MS and GC-MS, provided a vital tool of the pesticide science.     

Thermodynamics and dynamics of metallic glass formers: their correlation for the investigation on potential energy landscape

Great progress has been made in basic features of the potential energy landscape (PEL) theoretically. The present work, however, attempts to cast new light on it from experimental aspects. By a survey of experimental data related to thermodynamics or dynamics of metallic glass-forming liquids, it is found that the increased rate of excitation of vibrational entropy at glass transition tends to increase the rate of generation of configurational part. Although for the type of metallic materials a generally positive relationship exists between the density of the energy minima at glass transition and the liquid fragility strength, just as expected, our main attention is paid to the phenomenon of the scattering of the slopes. Analysis shows that the phenomenon results from the different average height of energy barriers between minima near glass transition. Investigation on the PdNiP metallic system indicates that the mismatch entropy is a dominant factor in the barrier height: a large value of it results in low energy barriers. Our previous work on the AlNiCe system gives the support to this finding.     

Synthesis of high purity single-walled carbon nanotubes in high yield

A simple method for the synthesis of high purity single wall carbon nanotubes has been developed by using nickel formate as a precursor for the formation of nearly mono-dispersed nickel seed-nanoparticles as catalysts in the CVD growth process.     

模糊控制理论在发动机温度控制中的应用

以模糊控制理论为基础，针对发动机温度控制中存在的非线性等问题，分析了当前发动机温度控制系统，并提出了发动机温度模糊控制方案。试验表明，采用模糊控制器后，显著改善了发动机温度自动控制的效果．     

DWDM上25.344 Mbit/s光监控信息传送系统的设计

采用25.344 Mbit/s光监控信息传送技术可以更好地满足当前密集波分复用(DWDM)系统中不断增加的网络监控信息和附加业务的需要.文章首先介绍了25.344 Mbit/s光监控信息传送系统的技术方案,然后详细描述了其帧结构、码型设计以及硬件实现的框图,最后介绍了该技术的优点.     

粒子群算法在BRDF模型参数优化中的应用

根据粗糙样片1.06微米激光双向反射分布函数(BRDF)的实验数据,利用粒子群算法结合BRDF五参数模型,对不同样片表面的BRDF进行了统计建模,获得了对应样片BRDF模型的参数值与偏差.获得的BRDF优化统计模型与没有参与优化建模的实验数据也吻合良好,验证了建模结果的合理性与正确性.将粒子群算法与遗传算法进行了比较,表明无论是优化计算时间还是拟合的精度,前者都明显优于后者.