1-取代-1H-1,2,3-三唑-4-甲酰胺类化合物的设计合成与生物活性

以吡唑酰胺类杀菌剂为模板,应用"生物等排原理"设计了1,2,3-三唑甲酰胺类具有等排结构的化合物,从丙炔酸出发合成内炔酰胺后,利用Cu(I)催化的1,3-偶极环加成反应,使其与叠氮化合物反应,快速合成了17个结构新颖的1-取代-1H-1,2,3-三唑-4-甲酰胺类化合物.当使用Cu/C催化时,中间体N-(3,4-二甲氧基苯基乙基)丙炔酰胺(4a)与2,2,2-三氟乙基叠氮(14)在三乙胺作添加剂的条件下,可以获得中等收率的偶联的1,2,3-三唑化合物17.所有目标化合物都通过核磁共振氢谱,元素分析或高分辨质谱的确认,并测试了其生物活性.结果表明,该类化合物虽无明显的杀菌活性,但在100μg/mL测试浓度下,化合物6a,6e,6k和61均表现出较好的除草活性.     

Studies on the interaction of achiral cationic pseudoisocyanine with chiral metal complexes

The effect of chiral metal complexes ([Co(en)(3)]I(3)·H(2)O, cis-[CoBr(NH(3))(en)(2)]Br(2), K[Co(edta)]·2H(2)O and [Ru(phen)(3)](PF(6))(2)) on the polymer-bound J-aggregates in aqueous mixtures of pesudoisocyanine (PIC) iodine and poly(acrylic acid, sodium)(PAAS) have been studied by UV-vis absorption, circular dichroism (CD) and fluorescence spectra. At low concentration, the PIC monomers could self-assemble to form supermolecules by binding to each of the COO(-) groups on the polymer chains through electrostatic interactions. After the addition of chiral metal complexes to the formed PIC-PAAS J-aggregates, we found that only the chiral multiple π-conjugated phenanthroline metal complexes could transfer their metal-centered chiral information to the formed J-aggregates. The chiral J-aggregates showed a characteristic induced circular dichroism (ICD) in the visible region of J-band chromophore, and the ICD signals depend on the absolute configuration, concentration of the chiral multiple π-conjugated metal complexes, as well as temperature. More interestingly, the supramolecular chirality of the polymer supported PIC J-aggregates could be memorized even after the addition of an excess opposite chiral complex enantiomers. This is in sharp contrast to the behavior in the high concentrated NaCl induced PIC-J aggregates, in which the optical rotation of a mixture of two enantiomers varies linearly with their ratio.     

A facile synthesis of anatase TiO2 nanosheets-based hierarchical spheres with over 90% {001} facets for dye-sensitized solar cells

Anatase TiO(2) nanosheets-based hierarchical spheres with over 90% {001} facets synthesized via a diethylene glycol-solvothermal route were used as photoanodes of dye-sensitized solar cells, which generated an energy conversion efficiency of 7.51%.     

pH-switchable inversion of the metal-centered chirality of metallabenzenes: opposite stereodynamics in reactions of ruthenabenzene with L- and D-cysteine

We report herein the first study on the chemical interaction between metallabenzenes and bioactive molecules. Due to its unique stereoelectronic activities, a phenanthroline-derived ruthenabenzene [Ru{CHC(PPh(3))CHC(PPh(3))CH}Cl(C(12)H(8)N(2))(PPh(3))]Cl(2) (1) selectively binds cysteine in aqueous solution at physiological pH and then undergoes a dynamic inversion of configuration at the Ru center. The structure of the L-cysteine-binding product of 1 has been determined by means of X-ray diffraction. The replacement of the L-cysteine with the D form results in an inverted stereodynamic effect. Furthermore, the inversion process of the Ru-centered configuration could be conveniently controlled by a simple pH adjustment. This is attributed to the significant influence of a special intramolecular electrostatic interaction on the dynamic epimerization process of the cysteine-binding product.     

The adsorption behaviours of Pt adatom on pristine and defective bilayer graphene

The structural stability and electronic property of metal Pt atom anchors on two typical substrates (including the pristine and defective bilayer graphene, PBG and DBG) are studied using the first-principles calculations. For the PBG sheets, the Pt atom at the bridge site of bottom layer has only one stable adsorption, which is more stable than other sites of the top layer. For the DBG sheets, the doped Pt below defective site has the larger adsorption energy than that of the upper one. Compared to the isolated graphene films, the Pt(111) substrate-supported graphene systems have effect on the adsorption energies of Pt adatom to some extent, but it does not affect the most preferable configurations. Moreover, the diffusion pathways and energy barriers of Pt adatom on PBG and DBG substrates are comparatively investigated. For the DBG sheets, the Pt dopant has smaller diffusion barrier on upper layer than that of the intercalation process through the defective site. Therefore, the Pt dopant prefers to diffuse on the top layer and then forms the metal impurity. This work provides valuable information on understanding the formation process and intercalation mechanism of metal adatom on graphene sheets.     

CO oxidation over BC3 nanosheet: a theoretical study

ABSTRACT

Metal-free catalysts have attracted more attention due to their highly active in catalytic oxidation reactions. The electronic structure and catalytic property of BC₃ sheet are investigated by using first-principles calculations. It is found that the BC₃ sheet as the active surface can effectively regulate the adsorptive stability of reactive gases. Besides, the possible reaction processes for CO oxidation on the BC₃ sheet are comparably analysed through different reaction mechanisms, which include the Eley–Rideal (ER), Langmuir–Hinshelwood (LH) and termolecular Eley–Rideal (TER). In the CO oxidation reactions, the decomposition of O₂ molecule as the starting state (0.40?eV) is an energetically more favourable process than those of other processes, the Eley–Rideal (ER) reactions (2O_ads+2CO→CO₂) are more prone to take place with lower energy barriers (3 sheet. These results provide an important guidance on exploring the highly efficiency metal-free catalyst for CO oxidation.     

新型键合纤维素手性固定相的制备及其拆分性能评价

键合型多糖手性固定相因具有化学稳定性高和溶剂耐受性好的特点而受到研究者的极大关注。采用施陶丁格（Staudinger）反应将6-叠氮-6-脱氧纤维素-3,5-二氯苯基氨基甲酸酯键合到氨丙基硅胶上得到一种新的键合型手性固定相（ImCel）,研究了其手性分离性能,并探讨了非常规流动相（如氯仿、四氢呋喃等）的影响。结果表明,在20对手性化合物中,17对在合适的流动相下得到基线分离。ImCel在正相条件下的分离性能优于反相条件,且在含氯仿的流动相中仍对手性化合物表现出良好的分离能力。在分离一系列芴甲氧羰基（fmoc）-氨基酸衍生物时,ImCel与键合6-叠氮-6-脱氧纤维素-3,5-二甲基苯基氨基甲酸酯的手性固定相表现出互补性,出现了固定相改变引起的对映体洗脱反转现象。本研究丰富了键合型多糖手性固定相的种类和合成方法,为开发新的键合型手性固定相提供了参考。     

功能化高分子磁性载体的制备及选择性吸附稀土离子

悬浮聚合法制备含四氧化三铁微粒的甲基丙烯酸羟乙酯聚合物, 再由环氧化和氨基化反应得到功能化高分子磁性载体(FPMC), 采用酸渗实验、红外光谱和X-光电子能谱(XPS)等对产物进行性能表征;研究FPMC对RE3+离子( RE=La, Eu, Y)的选择性吸附作用, 进而探讨稀土离子浓度对载体FPMC吸附效果的影响.     

超高压氦增压系统研制

主要介绍了超高压氦增压系统的工作原理、设计原则和加工方法,讨论了各功能部件的选择与高压密封设计,同时指出了在使用超高压氦增压系统时应当注意的问题。在系统建成后,通过手动、自动控制分步增压和保压实现了最高300 MPa的超高压氦气输出,相应的高压漏率达到(3.5～5.0)×10-7Pa.m3/s。对系统主要性能参数进行了考核,并将其与3种同类增压装置的相应参数进行了比较,结果表明该系统设计合理、性能优越并且安全可靠。该系统将主要应用于惯性约束微球靶充氘氚系统的各项性能测试。     

A THREE-VALUE-SEGMENTATION METHOD OF COAL CONTAINING INCLUSION BASED ON GRAY DISTRIBUTION OF COMPUTED TOMOGRAPHY IMAGE1)

煤体CT图像阈值分割是其三维真实结构重构的前提. 基于单轴压缩状态下煤体的CT图像,提出了一种基于图像灰度分布的孔隙度计算方法, 结合灰度直方图,利用实测孔隙度反推法对煤体CT图像进行了裂隙--煤基质--煤杂质三值化,同时与 最大类间方差法和最大熵法的三值化结果进行了对比分析. 结果表明, 最大熵法对于煤基质和煤杂质不能较好区分; 最大类间方差法对于图像微小区域灰度的突变(裂隙的产生)敏感性低,无法有效区分裂隙与煤基质; 本文改进的灰度直方图法避免了最大类间方差法和最大熵法的劣势,具有较好的图像三值化效果,且煤基质与煤杂质间的阈值基 于实验结果得到,具有更高的可信度和准确度.