Re（CO）3（L）系列配合物的成键和结构

借助于G03W程序包,对系列氨基羧酸分子的羰基铼配合物进行了结构优化,并对其中的相关能量、键长、键角、布局数等进行了研究.计算结果表明:各配合物相对于羰基铼中间体均具有一定的稳定性;配体分子结构中含有杂环或者较多数目杂原子时,有形成相对更稳定配合物的趋势;配体分子结构中应含有适宜的间隔体,否则需经较大的结构扭转或局部原子的拥挤方可形成相应配合物.     

The catalytic performance study of polymerized ionic liquid synthesized in different conditions on alkylation of o‐Xylene with styrene

In this work, a series of novel acidic polymerized ionic liquids were used as heterogeneous catalyst for alkylation of o‐Xylene with styrene. And the effect of the amount of initiator and the type of acid used for ion exchange on catalyst structure and the catalytic performance of catalysts for alkylation were studied thoroughly. The experiment results show: when the percentage of the amount of initiator in the total material is 3%, the polymerized ionic liquid catalyst MPM‐SO₃H‐[C₃V][SO₃CF₃] has the most uniform with a specific surface area of 97.30 m²/g and a pore volume of 0.35 cm³/g. Benefiting from the unique structure features, MPM‐SO₃H‐[C₃V][SO₃CF₃] manifested an excellent catalytic performance for alkylation of o‐Xylene with styrene, along with the conversion of styrene was 96.8% and the yield of 1‐Phenyl‐1‐ortho‐xylene ethane was 94.7%. Therefore, this work provides a novel reference to the synthesis of polymerized ionic liquids and clearly explains the advantage of novel acidic polymerized ionic liquids on alkylation.     

Morphology–luminescence correlations in europium-doped ZnO nanomaterials

In order to investigate the correlations of morphologies and optical properties, different morphologies of Eu-doped ZnO were synthesized by different methods. Specifically, the structure of SiO₂/ZnO:Eu nanoflower was synthesized for the first time and has not been reported previously. One percent was chosen as the Eu doping concentration. The relations of the morphology, diameter, and uniformity with the PL intensity were examined. The PL intensity of ZOE samples has a close relationship with the morphology. The PL intensity order of the different morphologies of ZnO:Eu is as follows: nanorod arrays > thin film > nanospheres > nanoparticles > nanoflowers > nanorods. The PL intensity of nanomaterials is larger, if the diameter of the nanomaterials is larger. However, the size of diameter is not the most important reason. It was found that the sample uniformity plays a key role on ZnO:Eu PL intensity. ZnO:Eu with small particle diameters may have strong photoluminescence intensity, if the nanoparticles are uniform.     

多项式环中单项式理想的分解

利用单项式理想生成元的性质,给出了一类特殊单项式理想(生成元是变量的纯幂)的幂的分解表达式,这不仅拓宽了我们对多项式理论内容的认识,而且这样的分解表达式提供了这类单项式理想正则度(Castelnuovo-Mumford regularity)计算的方法.     

对数平均和双参数广义Muirhead平均之间的比较

本文讨论了两个不同正实数x和y的对数平均L(x,y)=(x-y)/(logx-logy)与双参数广义Muirhead平均M(a,b;x,y)=[(x~ay~b+x~by~a)/2]~(1/(a+b))之间的比较,得到了如下三个结论:(11)若(a,b)∈D_1∪E_1∪L_0,则M(a,b;x,y)L(x,y);(2)若(a,b)∈D_2∪E_2,则M(a,b;x,y)L(x,y);(3)若(a,b)∈D_3∪E_3,则存在x_1,y_1,x_2,y_2,使得M(a,b;x_1;y_1)L(x_1,y_1)和M(a,b;x_2,y_2)L(x_2,y_2).其中D_1={(a,b)∈R~2:a+b≠0,ba,ω_1(a,b)≤0,ω_2(a,b)≤0},E_1={(a,b)∈R~2:a+b≠0,ba,ω_1(a,b)≤0,ω_2(a,b)≤0},D_2={(a,b)∈R~2:ab≤0,ba,ω_1(a,b)≥0},E_2={(a,b)∈R~2:ab≤0,ba,ω_1(a,b)≥0},D_3={(a,b)∈R~2:ba0,ω_1(a,b)0)∪{(a,b)∈R~2:ba0,ω_1(a,b)=0,ω_2(a,b)0}∪{(a,b)∈R~2:ba,ab≤0,ω_1(a,b)0,ω_2(a,b)0},E_3={(a,b)∈R~2:ab0,ω_1(a,b)0}∪{(a,b)∈R~2:ab0,ω_1(a,b)=0,ω_2(a,b)0}∪{(a,b)∈R~2:ab,ab≤0,ω_1(a,b)0,ω_2(a,b)0},L_0={(a,b)∈R~2:a=b≠0},ω_1(a,b)=(a+b)[3(a-b)~2-(a+b)],ω_2(a,b)=(a+b)[2(a-b)~2+1]-3(a~2+b~2).     

钯纳米粒子的形貌可控合成与催化性能

借助于一种全新的表面活性剂N,N-dimethyloctadecylammonium bromide acetate sodium（OTAB-Na）,成功实现了对小尺寸钯纳米粒子微结构的控制。通过对合成条件的微扰,高度均匀且分散性良好的枝化结构和凹面体结构的钯纳米粒子被成功地制备。催化测试（利用氨硼烷作为氢化试剂来还原4-硝基苯酚为4-胺基苯酚）发现,钯纳米粒子的催化活性与其微观纳米结构相关,其中枝化结构的钯纳米粒子表现出了更为突出的催化性能。     

电喷雾电离源测定印刷线路板阵列离子阱的分析性能

电喷雾电离源(ESI)测定了印刷线路板材料制成的四通道PCB矩形离子阱中一个通道的的分析性能。结果表明,质谱峰检测到的离子信号的种类和强度明显受到离子动能的影响。当离子动能低于18 eV,则得到的质谱峰主要为精氨酸Arg离子(m/z 175.2),增加其离子动能则Arg离子(m/z 175.2)易碎裂,发生脱胍基、脱水等反应。在正弦波的射频模式下测定了离子质量隔离和离子质量选择激发,以SWIFT缺口频率为50～60 kHz,75～85 kHz和130～145 kHz分别隔离了m/z 175.2,117.3和71.8的离子;用频率为55、80和135 kHz的正弦波(振幅为1.0 V)选择激发弹出了m/z 175.2,117.3和71.8的离子。在氦气气氛下,频率为102 kHz正弦波可以使得Arg离子(m/z 175.2)发生碎裂,得到m/z 157.2,130.3和117.3碎片离子。电流积分法的测定结果表明,在256 kHz共振激发时离子测定效率为46.3%,在边界弹出时,离子测定效率约为9.7%。     

Biomimetic synthesis of calcium carbonate with different morphologies under the direction of different amino acids

Using three different amino acids (AAs) as organic matrices, including the highly nonpolar hydrophobic l-valine, the positively charged l-arginine and the less polar uncharged l-serine, calcium carbonate (CaCO₃) with different morphologies and polymorphs were synthesized by a facile gas diffusion reaction based on biomimetic strategy. Compared with the control cubic calcite obtained in the absence of AAs, the product from l-valine was cubic calcite aggregates assembled by nano-platelets. The product from l-arginine was spherical vaterite aggregates assembled by spherical nanoparticles. The product from l-serine was the mixture of cubic calcite and spherical vaterite. The structures and properties of the side chains of the AAs exerted the significant effects on the nucleation and growth of the CaCO₃. The formation mechanisms of the CaCO₃ in the presence of AAs are preliminarily discussed. The results suggest that the polymorphs and morphologies of the inorganic nanomaterials might be easily adjusted through the careful selection of the organic matrices.     

基于烟酰腙Schiff碱的Cu(Ⅱ)和Ni(Ⅱ)配合物的合成、晶体结构和性质

采用缓慢挥发法合成了2个烟酰腙类Schiff碱配合物[Cu(Py)(HL¹)]₂ (1)和[Ni(L²)₂] (2), 其中, H₃L¹=2, 4-二羟基苯甲醛缩烟酰腙, HL²=2-乙酰基吡啶缩烟酰腙。采用元素分析、红外光谱、紫外光谱、荧光光谱和热重分析以及X-射线单晶衍射分析进行 了表征。结果表明, 1和2的晶体均属单斜晶系, P2₁/c空间群;1的晶胞参数a=0.739 86(12) nm, b=1.903 7(3) nm, c=1.154 86(19) nm, β=105.090(3)°, V=1.570 5(4) nm³;该化合物是中心对称的双核配合物, 每个Cu(Ⅱ)离子都处于畸变四方锥配位环境;结构基 元通过π-π相互作用和O-H…N氢键形成三维超分子。2的晶胞参数a=2.034 0(5) nm, b=1.183 2(3) nm, c=1.020 7(3) nm, V=2.456 1(11) nm³;中心离子Ni(Ⅱ)的配位数为6, 它处于畸变八面体配位环境。配合物有很高的热稳定性, 分解温度分别为315 ℃ (1)和358 ℃ (2)。     

Enantioselective Reduction of Prochiral Ketones with NaBH4/Me2SO4/(S)-Me-CBS

The enantioselective reduction of prochiral ketones with NaBH₄/Me₂SO₄/(S)-Me-CBS is described. Borane is generated in situ via the reaction of NaBH₄ with Me₂SO₄ in tetrahydrofuran, which is as efficient as the commercial one. Such in situ–generated borane reagent was applied to reduce prochiral ketones in the presence of chiral oxazaborolidine catalyst directly. The corresponding chiral secondary alcohols were obtained with excellent enantiomeric excesses (93–99% ee) and good to excellent yield (80–99%).