准经典轨线方法对Ca+CD3Ⅰ→CaⅠ+CD3同位素效应的动力学研究

在扩展Lond-Eyring-Polanyi-Sato(LEPS)势能面上,采用准经典轨线方法对反应Ca+CD3I→CaI+CD3进行了动力学计算,并讨论了该反应的同位素效应.在同位素效应作用下,产物CaI的振动态分布向低振动态转移,反应体系的散射截面在低碰撞能和高碰撞能处有较小的变化.同时,受到反应物的质量因子变化的影响,产物转动取向值减少,产物转动取向增强.仅有产物的角分布受同位素效应的影响不明显.     

Synthesis, Crystal Structure and Chemical Bonding of a New Binary Lu-Sn Phase: Lu11Sn10

A new tetragonal phase of Lu11Sn10 is obtained from high temperature reaction of the pure elements in a welded tantalum tube. Its crystal structure was established by single-crystal X-ray diffraction. Lu11Sn10 crystallizes in the tetragonal space group I4/mmm (No.139) with a=11.2953(18), c=16.424(4), V=2095.5(7)3 , Z=4, Mr=3111.57, Dc=9.863 g/cm3 , μ=62.897 mm-1, F(000)=5124, and the final R=0.0348 and wR=0.0894 for 706 observed reflections with I>2σ(I). The structure of Lu11Sn10 may be derived from the Ho11Ge10 structural type. It is isostructural with Dy11Sn10 , featuring a three-dimensional (3D) framework composed of [Sn4] squares and [Sn2] dimers interlinked via Sn-Sn bonds with two types of one-dimensional (1D) tunnels along the c-axis, which are occupied by isolated Sn atoms, [Sn2] dimers and all the Lu atoms. Band structure calculation based on density functional theory method indicates that Lu11Sn10 is metallic.     

Liquid crystalline behaviour of hydrazide derivatives containing alkoxyazobenzene

Two series of dissymmetric hydrazide derivatives containing alkoxyazobenzene with nitro terminal group and octyloxy terminal group, N-4-alkoxyphenyl-N′-4-((4-nitrophenyl)azophenyl) benzohydrazide (Bn-NO₂, n indicates the number of carbon atoms) and N-4-octyloxyphenyl-N′-4-((4-octyloxyphenyl)azophenyl) benzohydrazide (B8-B8), were designed and synthesised, and their liquid crystalline properties were investigated by means of differential scanning calorimetry, polarised optical microscopy and wide-angle X-ray diffraction. It was found that B8-B8 with octyloxy terminal chains displayed monolayer smectic C phase, whereas Bn-NO₂ with nitro terminal group displayed SmA_d phase, and intermolecular hydrogen bonding was confirmed as the driving force. In addition, the effect of hydrogen bonding, dipole–dipole interactions and steric hindrance effect on the liquid crystalline structures were also discussed.     

火焰原子吸收法直接测定铅酸蓄电池用硫酸中铁

建立了火焰原子吸收光谱法直接测定H2SO4中Fe的方法。采用蓄电池用H2SO4样品直接配制标准加入法系列溶液,用火焰原子吸收光谱法直接测定蓄电池用H2SO4中的Fe含量。在选定的仪器测定条件下,采用标准加入法所测得的蓄电池用H2SO4中的Fe含量与国标法所测得的结果相比较无显著性差异,检出限为0.060μg/mL(n=13),1.00μg/mL Fe标准溶液平行测定13次,所得吸光度的相对标准偏差为3.3%(n=13)。本法可应用于H2SO4样品中Fe的测定。     

化学发光分析与高效液相色谱联用检测酪氨酸

在强碱性条件下,KMnO4氧化酪氨酸产生自由基,自由基氧化Luminol产生强化学发光,酪氨酸浓度与相对发光强度呈线性关系。选用C18反相色谱柱、CH3OH、KH2PO4混合液为流动相,酪氨酸能很好分离。基于此,建立CL-HPLC检测酪氨酸的新方法,线性范围为1.2×10-3～5.0×10-2g/L、线性相关系数为0.9994、RSD为2.37%、检测限为3.3×10-4g/L。方法已于检测实际样品氨基酸口服液,并与UV光度法,结果一致。本文探讨了酪氨酸增强KMnO4-Luminol化学发光机理。     

聚吡咯/海藻酸钠纳米球的制备及其应用于高性能超级电容器

用海藻酸钠作为结构导向剂,通过原位氧化聚合吡咯法制备了聚吡咯/海藻酸钠(PPy/SA)纳米球.聚吡咯/海藻酸钠纳米球的形貌和结构通过扫描电镜(SEM)、X射线衍射(XRD)和傅里叶变换红外(FTIR)光谱进行表征.材料的电化学性能通过循环伏安法和恒电流充放电方法进行测试.电化学测试表明,聚吡咯/海藻酸钠纳米球在1 mol L-1KCl电解液中,电流密度为1 A g-1时其比电容高达347 F g-1.与纯聚吡咯相比较,聚吡咯/海藻酸钠纳米球具有更优异的循环稳定性能.     

Sb,Bi,Zr,Si元素微量掺杂对荧光粉YAG∶Ce发光性能的影响

采用高温固相法分别合成了Sb³⁺,Bi³⁺,Zr⁴⁺,Si⁴⁺共掺杂的YAG:Ce黄色荧光粉。研究了YAG:Ce黄色荧光粉的发光强度随元素种类以及微量掺杂浓度的变化情况及相关机理。结果显示,随着元素Sb³⁺,Bi³⁺,Zr⁴⁺,Si⁴⁺掺杂浓度的增加,发射峰强度均表现出先增大后减小的趋势。Sb³⁺,Bi³⁺与Ce³⁺之间存在多极子相互作用的共振传递及晶格修复作用,当Sb³⁺,Bi³⁺掺杂浓度分别为0.5和0.1 mmol时发射峰强度达到最大值,分别提高了35.5%和44.8%。在YAG:Ce中由于Zr⁴⁺,Si⁴⁺的电荷补偿作用,促进Ce⁴⁺→Ce³⁺的转化,从而提高了YAG:Ce的发光强度。Zr⁴⁺,Si⁴⁺掺杂浓度分别在0.3和7 mmol时达到最大值,分别提高了27.4%和31.2%。由荧光粉颗粒形貌可知,Sb³⁺,Bi³⁺,Zr⁴⁺,Si⁴⁺元素的微量掺杂能促使晶粒长大,并且近似球型,导致发光强度有明显的提高。     

微波辅助合成石墨烯/氧化镍复合材料及其表征

本文通过微波辅助的方法,快速而有效地在热膨胀石墨烯(RG)的缺陷上原位合成氧化镍纳米颗粒,形成石墨烯/氧化镍复合材料(RG/NiO)。利用X-射线衍射(XRD),拉曼光谱(Raman),傅里叶变换红外(FTIR),扫描电镜(SEM),透射电镜(TEM),热重-差热(TGA-DSC)对所制备样品的结构、形貌和NiO含量在复合材料中的含量进行表征。结果表明,热膨胀石墨烯层数约7~8层,层间距约为0.35nm,缺陷多,在水热和微波处理后抗氧化性明显变差。复合材料中氧化镍颗粒平均粒径为25nm,均匀而密集地分散在石墨烯平面上,同时在复合材料中的含量为19.8%。     

An efficient synthesis of 3-(N-piperidinemethyl)-2,2,5,5-tetramethyl-1-oxy-3-pyrroline,a promising radioprotector for cancer radiotherapy

Nitroxides can ameliorate the toxic effects of radiation during cancer therapy. Nitroxides are paramagnetic and can be used in magnetic resonance imaging (MRI) and electron paramagnetic resonance imaging (EPRI) to monitor in vivo oxidative stress status. Compound 5 (3-(N-piperidinemethyl)-2,2,5,5-tetramethyl-1-oxy-3-pyrroline) was found to be the most effective nitroxide radioprotector. An efficient synthesis for this promising radioprotector was developed.     

A simple and economic method for accurate determination of the energy peak efficiency of 208 keV γ-ray of 237U based on 241Pu/237U secular equilibrium

A new method is developed for the determination of energy peak efficiency of 208 keV γ-ray of ²³⁷U based on ²⁴¹Pu/²³⁷U secular equilibrium. Plutonium solution was purified to remove Am with Dowex 1 × 2 anion exchange chromatography and the concentration of ²⁴¹Pu in the purified solution was determined using ²⁴²Pu isotope-dilution mass spectrometry on an inductively-coupled plasma mass spectrometry. The solution can be used as calibration source for the determination of energy peak efficiency of 208 keV γ-ray of ²³⁷U after 48 days. The method was validated for a planar HPGe detector at the 12 mm above the detector surface. The results showed that this is a simple and economic method for determining the energy peak efficiency of gamma detectors for 208 keV γ-ray of ²³⁷U.