烯丙基二异雪松基硼烷的制备及其与羰基化合物的不对称反应

本文以(-)-α-雪松烯为原料, 制备了烯丙基二异雪松基硼烷(Icd~2B-CH~2CH=CH~2). 该手性硼烷很容易与醛反应生成相应的烯丙基取代的手性仲醇, 光学产率在60%e.e.左右. 与潜手性酮反应的光学产率低于30%e.e..     

负载型纳米TiO2复合载体及其CoMo催化剂的酸性及孔特性的研究

总结了复载不同纳米尺度的复合载体及其CoMo催化剂的表面酸性及孔结构特性的表征结果。结果表明，负载型纳米TiO2与基载体γ-Al2O3存在着相互作用。当负载比较少量的纳米TiO2时，复合载体的总酸量随着TiO2含量的增加而增加，超过γ-Al2O3的酸量，但当 TiO2的含量比较高时复合载体的酸量又降低，纳米TiO2优先负载在γ-Al2O3的强酸中心位；负载了CoMo活性组分后酸量增加。不同粒径的纳米TiO2对复合载体和催化剂的酸分布没有明显影响，但对总酸量有影响。对不同尺度TiO2，随着TiO2负载量的增加以及负载金属活性组分的增加，表面积、孔容和最可几孔径均有不同程度的减少。     

Synthesis and Crystal Structure of (2S,2'S,4'R)-2-(1-Hydroxy-1-ethylpropyl)-1-[(1'-p-tosyl-4'-hydroxypyrrolidin-2'-yl)methyl]pyrrolidine

1 INTRODUCTION In recent years, chiral β-amino alcohols have attracted much attention due to their special bio- logical functions and catalytic activities. Chiral β- amino alcohol moieties are usually found not only in natural products (e.g., cinchona alkaloids, ephe- drine, toxal, etc.) with special biological activities[1, 2], but also critical structural segments of some syn- thesized biologically active compounds, such as adrenergic agonists or antagolist[3, 4] and inhibitors for HI…     

锂离子电池用多孔硅/石墨/碳复合负极材料的研究

在两步高能球磨和酸蚀条件下制得了多孔硅/石墨复合材料，并对其进行碳包覆制成多孔硅/石墨/碳复合材料。通过TEM，SEM等测试手段研究了多孔硅材料的结构。作为锂离子电池负极材料，电化学测试结果表明多孔硅/石墨/碳复合材料相比纳米硅/石墨/碳复合材料有更好的循环稳定性。同时，改变复合体配比、热解碳前驱物、粘结剂种类和用量也会对材料的电化学性能产生较大的影响。其中使用质量分数为10％的LA132粘结剂的电极200次循环以后充电容量保持在649.9 mAh·g^-1，几乎没有衰减。良好的电化学性能主要归因于主活性体-多孔硅颗粒中的纳米孔隙很好地抑制了嵌锂过程中自身的体积膨胀，而且亚微米石墨颗粒和碳的复合也减轻了电极材料的体积效应并改善了其导电性。     

1，4二环己基取代六元瓜环与Na(Ⅰ)自组装实体的合成与晶体结构

A novel complex of a new 1,4-dicyclohexyl cucurbituril(DCYQ[6]) with sodium(Ⅰ) ion was synthesized, and the crystal structure was determined by X-ray diffraction technique. In this self-assembled entity both the cavity interaction of DCYQ[6] included a nitrate anion and the portal interaction of the dipole carbonyls of DCYQ[6] with sodium cations lead to form self assembled molecular capsules. The crystal structure of the entity shows a packing of the self assembled molecular capsules connected by hydrogen bonds of water molecules. CCDC: 271400.     

Substituent effects on heats of formation, group interactions, and detonation properties of polyazidocubanes

We have calculated the heats of formation (HOFs) for a series of polyazidocubanes by using the density functional theory (DFT), Hartree-Fock, and MP2 methods with 6-31G* basis set as well as semiempirical methods. The cubane skeleton was chosen for a reference compound, that is, the cubane skeleton was not broken in the process of designing isodesmic reactions. There exists group additivity for the HOF with respect to the azido group. The semiempirical AM1 method also produced reliable results for the HOFs of the title compounds, but the semiempirical MINDO3 did not. The relationship between HOFs and molecular structures was discussed. It was found that the HOF increases 330-360 kJ/mol for each additional number of the azido group being added to the cubane skeleton. The distance between azido groups slightly influences the values of HOFs. The interacting energies of neighbor azido groups in polyazidocubanes are in the range of 2.3 approximately 6.6 kJ/mol, which are so small and less related to the substituent numbers. The average interaction energy between nearest neighbor --N3 groups in the most stable conformer of octaazidocubane is 2.29 kJ/mol at the B3LYP/6-31G* level. The relative stability related to the number of azido groups of the title compounds was assessed based on the calculated HOFs, the energy gaps between the frontier orbitals, and the bond orders of the C--N3 and C--C bonds. The predicted detonation velocity of hepta- and octa-derivatives is over 9 km/s, and the detonation pressure of them is ca. 40 GPa or over.     

吸附O的Cu(110)c(2×1)表面原子结构和电子态

采用第一性原理的密度泛函理论方法计算了清洁Cu(110)表面和吸附O原子的Cu(110) c(2×1)表面的原子结构, 结构弛豫和电子结构, 得到了各种表面结构参数. 分别计算了O原子在Cu(110)表面三个可能吸附位置吸附后的能量, 并给出了能量最低的吸附位置上各层原子的弛豫特性和态密度. 结果表明O吸附后的Cu(110)表面有附加列(added-row)再构的特性, O原子吸附在最表层铜原子上方, 与衬底Cu原子的垂直距离为0.016 nm, 以氧分子为能量基准的吸附能为－1.94 eV; 同时由于Cu 3d- O 2p态的杂化作用使得低于费米能级5.5~6.0 eV的范围内出现了局域的表面态. 计算得到清洁的和氧吸附的Cu(110)表面的功函数分别为4.51 eV和4.68 eV. 电子态密度的结果表明：在Cu(110) c(2×1) 表面O吸附的结构下, 吸附O原子和金属衬底之间的结合主要是由于最表层Cu原子3d态和O原子2p态的相互作用.     

Determination of 19-norandrosterone in CCQM-P68. NIST results using an isotope dilution liquid chromatography/tandem mass spectrometry method

The US National Institute of Standards and Technology (NIST) participated in an international interlaboratory study under the auspices of the Consultative Committee for Amount of Substance (CCQM) for the determination of 19-norandrosterone (19-NA) in urine, the principal metabolite of nandrolone and certain other synthetic testosterone substitutes banned for use by the World Antidoping Agency (WADA). Prior to this study, NIST developed a candidate reference measurement procedure based upon isotope dilution liquid chromatography/tandem mass spectrometry. This method was applied to a urine sample distributed to the participants in the study by the Australian National Measurement Institute, Pymble, Australia (NMIA). The NIST results were in very good agreement with those from the other participants, all of whom used methods based upon gas chromatography/mass spectrometry. All known significant sources of uncertainty were evaluated, resulting in a relative expanded uncertainty of less than 5% (coverage factor k = 2).     

N,N′‐Bis(2‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide and N,N′‐bis­(3‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide

The mol­ecules of N,N′‐bis­(2‐pyridylmeth­yl)ferrocene‐1,1′‐diyl­dicarboxamide, [Fe(C₁₂H₁₁N₂O)₂], contain intra­molecular N—H⋯N hydrogen bonds and are linked into sheets by three independent C—H⋯O hydrogen bonds. The mol­ecules of the isomeric compound N,N′‐bis­(3‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide lie across inversion centres, and the mol­ecules are linked into sheets by a combination of N—H⋯N hydrogen bonds and π–π stacking inter­actions between pyridyl groups.     

3-芳基-1-(吡啶-3-基)-2-(1H-1,2,4-三唑-1-基)-2-丙烯-1-醇的合成及生物活性研究

用硼氢化钠还原3-芳基-1-(吡啶-3-基)-2-(1H-1,2,4-三唑-1-基)丙烯酮, 合成了10个新型含吡啶基的三唑醇类化合物. 所有化合物均经核磁、元素分析确证. 生物活性测试结果表明, 部分化合物具有一定的杀菌活性及植物生长调节活性.