One step Pd(0)-catalyzed synthesis, X-ray analysis, and photophysical properties of cyclopent[hi]aceanthrylene: fullerene-like properties in a nonalternant cyclopentafused aromatic hydrocarbon.

A simple procedure for the synthesis of cyclopentafused polycyclic aromatic hydrocarbons (CP-PAH) with Pd(PPh(3))(2)Cl(2) catalyst has been applied to the one-pot palladium(0)-catalyzed coupling of 9,10-dibromoanthracene (1) with 2-methyl-3-butyn-2-ol. Reactions carried out in refluxing benzene in the presence of CuSO(4)/Al(2)O(3) yielded 9,10-dialkynylanthracene 2a, alkynyl aceanthrylene 2b, and 2,7-disubstituted cyclopent[hi]aceanthrylene 2c in 13%, 23%, and 19% purified yields, respectively, with total conversions of 80-90%. Sealed tube reactions without copper at 110 degrees C improved the yield of 2c up to >75%. Single-crystal X-ray analyses of 2a and 2c reveal a three-dimensional hydrogen bonding network, producing a unique crystal packing. The packing structure of 2b is dominated by pi-pi stacking interactions between two aceanthrylene molecules. CP-PAHs 2b and 2c have potentially interesting fullerene-like photophysics. While the UV-vis and fluorescence spectra of 2a (Phi(F) = 0.87) show the characteristic vibronic structure of anthracene, the UV-vis spectra of ruby-red aceanthrylene 2b and greenish-black cyclopent[hi]aceanthrylene 2c extend well into the visible range. Isomers 2b and 2c showed no detectable fluorescence emission. Unlike fullerenes, compounds 2b and 2c are poor singlet oxygen sensitizers with measured (1)O(2) quantum yields of 0.02 and 0.06, respectively. As expected from a simple Hückel analysis, 2c has relatively low two-electron reduction potentials as determined by cyclic voltammetry.     

Thorium in human blood serum,clot, and urine comparison with ICRP excretion model

Neutron activation followed by a simple radio-chemical separation procedure was employed to determine the concentrations of thorium (²³²Th) in human blood serum, clot, and urine of normal subjects and three groups of occupationally exposed persons. The thorium concentrations in the blood serum, clot, and urine samples of the exposed groups were distinctly higher than those of the other study groups and were found to increase with increasing occupational length of the persons. Daily urinary excretion is correlated with serum thorium burden and it is estimated that the daily excreted thorium is about 15% of the thorium in the serum pool.     

Anti-apoptotic and neuroprotective effects of Tetramethylpyrazine following spinal cord ischemia in rabbits

Background  

Tetramethylpyrazine (TMP) is one of the most important active ingredients of a Chinese herb Ligusticum wallichii Franchat, which is widely used in many ischemia disorders treatments. However, the exact mechanism by which TMP protects the spinal cord ischemia/reperfusion (I/R) injury is still unknown. For this purpose, rabbits were randomly divided into sham group, control group and TMP group. After the evaluation of neurologic function, the spinal cords were immediately removed for biochemical and histopathological analysis. Apoptosis was measured quantitatively by the terminal transferase UTP nick end-labeling (TUNEL) method and confirmed by electron microscopic examination, the expression of Bax and Bcl-2 was immunohistochemically evaluated and quantified by Western blot analysis.     

A facile way for preparing tin nanoparticles from bulk tin via ultrasound dispersion

In this paper, we reported a facile and rapid process to prepare tin nanoparticles from bulk tin via ultrasound dispersion. The morphology and structure of synthesized tin nanoparticles were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS) and thermogravimetric analysis (TGA). The results show that the morphology of tin nanoparticles is spherical and the structure of tin nanoparticles has the same crystal structure as the bulk tin. In addition, the tribological property of tin nanoparticles as additives in oil is evaluated on a four-ball tester and the results show that tin nanoparticles exhibit good performance in wear.     

稀土元素的摩擦学研究发展概况

本文对稀土元素的摩擦学研究发展概况作了综述与讨论,主要涉及的是稀土金属及稀土无机化合物和稀土配合物作为润滑油、脂及润滑涂层的添加剂的摩擦学特性,并对稀土无机化合物的高温润滑特性、稀土金属及其化合物在高温涂层中的应用作了简要讨论,最后还提出了稀土的摩擦学研究中当前值得注意的几个重要课题。     

一些磷－氮型极压抗磨添加剂性能的研究

合成了一些磷－氮型极压抗磨添加剂烷基亚磷酸酯胺盐和氮杂环胺盐，并对其油溶性和润滑性等进行了试验研究。结果表明，磷－氮型极压抗磨添加剂的化学结构对其油溶性和极压抗磨性都有较大的影响：烷基链增长有助于油溶性的改善，氮杂环胺盐的油溶性更好；伯胺盐的抗磨性比仲胺盐和叔胺盐的都好，氮杂环胺盐的抗磨性更好；磷－氮型极压抗磨添加剂的减摩性明显比硫化烯烃、烷基亚磷酸酯和苯三唑十八胺的都好，有的在２５０℃时的摩擦系数仅约为０．０４．Ｘ射线光电子能谱和俄歇电子能谱分析发现，磷－氮型极压抗磨添加剂在摩擦表面形成了一种含氮富磷的化学反应膜。其中，元素磷是以磷酸铁的化合态形式存在，而元素氮则是以其原有的价态形式存在，这表明氮参与了整个摩擦过程。在试验研究和分析讨论的基础上，通过综合归纳还提出了磷－氮型极压抗磨添加剂的作用机理模式图。     

填充聚四氟乙烯对尼龙6摩擦磨损性能影响的研究

用Timken试验机考察了热压成形的PTFE填充尼龙6在干摩擦状态下的摩擦磨损性能及PTFE填充量、滑动速度和负荷对摩擦磨损的影响,并用X-光电子能谱仪(XPS)和电子探针(EPMA)研究了金属偶件摩擦表面转移膜的组成与形貌。结果表明,在给定的试验条件下,填充PTFE能够有效地改善尼龙6的摩擦磨损性能,PTFE的填充量在8～20％(vol)之间时的效果较好,8％PTFE填充尼龙6的PV值可比纯尼龙6的高1倍;填充PTFE的效用主要取决于转移膜的特性和PTFE在转移膜中的富集量。     

聚四氟乙烯对齿轮润滑成膜膏润滑性能的影响

作者以聚四氟乙烯(PTFE)为固体润滑剂填料对GM型齿轮润滑成膜膏进行了改进,并且研制出了两种新的成膜膏系列产品。经四球试验机、动静摩擦系数精密测定仪和SRV试验机评价的结果表明,添加PTFE的GM-2型成膜膏的承载能力和减磨性能都明显地比未添加的好;以PTFE为主要固体润滑剂填料的GM-3和MFC-1型两种润滑成膜膏也都具有良好的润滑性能,其中后者的性能与含PTFE的GM-2型成膜膏的接近。通过对摩擦轨迹的电子探针检测发现,PTFE在摩擦过程中于摩擦表面形成了转移膜,因而改善了润滑成膜膏的摩擦学性能。     

Improved ion optics for introduction of ions into a 9.4‐T Fourier transform ion cyclotron resonance mass spectrometer

Enhancements to the ion source and transfer optics of our 9.4 T Fourier transform ion cyclotron resonance (ICR) mass spectrometer have resulted in improved ion transmission efficiency for more sensitive mass measurement of complex mixtures at the MS and MS/MS levels. The tube lens/skimmer has been replaced by a dual ion funnel and the following octopole by a quadrupole for reduced ion cloud radial expansion before transmission into a mass‐selective quadrupole. The number of ions that reach the ICR cell is increased by an order of magnitude for the funnel/quadrupole relative to the tube lens/skimmer/octopole. Copyright © 2015 John Wiley & Sons, Ltd.     

Analysis of ethyl glucuronide and ethyl sulfate using aqueous normal‐phase chromatography with mass spectrometry

The use of aqueous normal‐phase chromatography is explored as a possible format for the analysis of the forensically significant compounds ethyl glucuronide and ethyl sulfate. Standard solutions of the two compounds are used to verify the retention capabilities of two stationary phases (diamond hydride and undecanoic acid). These results are then compared to data obtained on hair extracts to determine if any matrix effects exist with respect to both retention and peak shape. The undecanoic stationary phase is used for the establishment of calibration curves for quantitative analysis. These curves are utilized to determine the concentration of ethyl glucuronide in several hair samples tested.