PAMAM体型缩聚物的制备及其性能研究

以分子末端带有多官能度活泼端基的PAMAM等为原料 ,通过缩聚反应制备了一类新型体型缩聚物 .借助X射线光电子能谱仪 (XPS)对制备的体型缩聚物进行分析 ,利用其化学分析电子光谱 (ESCA)中碳元素价态的拟合数据判断体型缩聚反应进行的程度 ,数据表明酯基碳 (—COO)拟合峰已基本消失 ,说明其与氨基缩合反应转化为酰胺基 (—CON) ,且反应进行的比较彻底 .通过体型缩聚物在乙醇、正己烷、甲苯、氯仿、异丙醇、乙酸、甲酸、去离子水中进行溶胀试验 ,发现其在甲酸作为溶剂体系中的溶胀比出现最大值 ,根据溶度参数的意义估测体型缩聚物的溶度参数约为δ2 =2 7 6 (MJ m3) 1 2 (即甲酸的溶度参数 ) .对原料PAMAM以及制备的体型缩聚物进行DSC分析 ,发现制备体型缩聚物的玻璃化转变温度 (Tg)有了较大提高 ,从初始原料PAMAM的负值提高到 4 8℃左右 .     

用硼酸作催化剂一锅法合成双（二氢化嘧啶酮-4-基）苯

A simple effective synthesis of bis(dihydropyrimidinone-4-yl)benzene derivatives, using boric acid as catalyst,from isophthalic aldehyde or terephthalic aldehyde, 1,3-dicarbonyl compounds and urea or thiourea in glacial acetic acid was described. As the expansion of the classical Biginelli reaction, this method has the advantage of excellent yields 83%-94% and short reaction time 0.5-1.5 h.     

C2-symmetric bis(oxazolinato)lanthanide catalysts for enantioselective intramolecular hydroamination/cyclization

C(2)-symmetric bis(oxazolinato)lanthanide complexes of the type [(4R,5S)-Ph(2)Box]La[N(TMS)(2)](2), [(4S,5R)-Ar(2)Box]La[N(TMS)(2)](2), and [(4S)-Ph-5,5-Me(2)Box]La[N(TMS)(2)](2) (Box = 2,2'-bis(2-oxazoline)methylenyl; Ar = 4-tert-butylphenyl, 1-naphthyl; TMS = SiMe(3)) serve as precatalysts for the efficient enantioselective intramolecular hydroamination/cyclization of aminoalkenes and aminodienes. These new catalyst systems are conveniently generated in situ from the known metal precursors Ln[N(TMS)(2)](3) or Ln[CH(TMS)(2)](3) (Ln = La, Nd, Sm, Y, Lu) and 1.2 equiv of commercially available or readily prepared bis(oxazoline) ligands such as (4R,5S)-Ph(2)BoxH, (4S,5R)-Ar(2)BoxH, and (4S)-Ph-5,5-Me(2)BoxH. The X-ray crystal structure of [(4S)-(t)BuBox]Lu[CH(TMS)(2)](2) provides insight into the structure of the in situ generated precatalyst species. Lanthanides having the largest ionic radii exhibit the highest turnover frequencies as well as enantioselectivities. Reaction rates maximize near 1:1 BoxH:Ln ratio (ligand acceleration); however, increasing the ratio to 2:1 BoxH:Ln decreases the reaction rate, while affording enantiomeric excesses similar to the 1:1 BoxH:Ln case. A screening study of bis(oxazoline) ligands reveals that aryl stereodirecting groups at the oxazoline ring 4 position and additional substitution (geminal dimethyl or aryl) at the 5 position are crucial for high turnover frequencies and good enantioselectivities. The optimized precatalyst, in situ generated [(4R,5S)-Ph(2)Box]La[N(TMS)(2)](2), exhibits good rates and enantioselectivities, comparable to or greater than those achieved with chiral C(1)-symmetric organolanthanocene catalysts, even for poorly responsive substrates (up to 67% ee at 23 degrees C). Kinetic studies reveal that hydroamination rates are zero order in [amine substrate] and first order in [catalyst], implicating the same general mechanism for organolanthanide-catalyzed hydroamination/cyclizations (intramolecular turnover-limiting olefin insertion followed by the rapid protonolysis of an Ln-C bond by amine substrate) and implying that the active catalytic species is monomeric.     

用于彩色液晶显示器的色分离光栅的优化设计

利用光栅实现液晶显示器中的色分离可以提高液晶显示器对光能的利用率。为了提高光能利用率,对光栅台阶数进行了优化设计,经矢量衍射理论计算,优化后的多台阶色分离光栅的能量利用率达到了65.3%,与采用滤色片的方法相比,光能利用率提高了近一倍;与三台阶相比,光能利用率提高了9.3%。     

柠檬酸与乙酸酐混合溶液中分光光度法测定盐酸西布曲明

柠檬酸和乙酸酐混合溶液与盐酸西布曲明在80℃的水浴中加热30 min,反应后使溶液呈紫黑色,在330 nm波长处吸收最大,据此建立测定盐酸西布曲明的分光光度法.盐酸西布曲明的质量浓度在0.17～18.5 mg·L-1范围内遵守比耳定律,相关系数为0.998 9,表观摩尔吸光率为8.16×104L·mol-1·cm-1,检出限为61.5μg·L-1.用于曲美胶囊中盐酸西布曲明的测定,测定结果与高效液相色谱法结果相符,其相对标准偏差(n=6)值均小于0.5%.     

超高效液相色谱–串联质谱法测定鲜蛋中氟苯尼考残留量的不确定度分析

评定超高效液相色谱–串联质谱法测定鲜蛋中氟苯尼考残留量的不确定度。建立测定鲜蛋中氟苯尼考的不确定度数学模型,不确定度来源包括标准溶液的质量浓度、样品溶液体积量取、称样质量、重复性,对不确定度分量分别进行评定,合成不确定值。鲜蛋中氟苯尼考残留量为1.49 μg/kg时,其扩展不确定度为0.19 μg/kg(k=2,P=95%)。为科学评价实验结果的准确性提供依据,为评定其它相关检测方法的不确定度提供参考。     

线性代数中特征向量的一个应用

在线性代数中,特征向量在矩阵的对角化过程中起着重要作用.从一个引例出发,证明了:一个矩阵与对角矩阵可交换当且仅当它可以用以特征向量为列向量的两个矩阵表示.做为推论,如果对角矩阵对角线上的相同元素在相邻位置,那么与其可交换的矩阵只能是准对角矩阵.     

REGULARITY OF WEAK SOLUTIONS TO A CLASS OF NONLINEAR PROBLEM

We study the regularity of weak solutions to a class of second order parabolic system under only the assumption of continuous coefficients.We prove that the wea...     

固相萃取气相色谱法测定水果中克菌丹和灭菌丹

采用硅镁吸附剂和硅胶作为混合固相萃取的净化方法,建立了固相萃取气相色谱法同时测定水果中克菌丹和灭菌丹的分析方法。研究了多种固相萃取柱和不同洗脱溶剂对克菌丹和灭菌丹保留行为的影响,优化了固相萃取净化方法及样品提取方法的分析条件。用GC-ECD检测,两种农药在0.05～2.0mg/L浓度范围内呈线性关系,相关系数大于0.997。苹果中4个浓度克菌丹和灭菌丹的加标回收率分别在100%～111%和104%～113%之间,RSD在3.0%～7.2%和2.8%～4.2%之间。在菠萝、草莓、梨和橙子中,克菌丹的平均回收率和RSD分别在95.6%～112%和2.5%～7.5%之间;灭菌丹在82.5%～96.4%和3.3%～8.0%之间,克菌丹和灭菌丹的方法检出限分别为0.012mg/kg和0.0056mg/kg。     

涡轮叶栅前缘槽缝气膜冷却的数值模拟

应用FINE/TURBO软件包,求解三维雷诺平均N-S方程,对叶片前缘有两列冷却槽缝的气膜冷却流场进行了数值模拟,获得了不同吹风比下叶片表面静压分布与极限流线.在计算结果与实验数据良好符合的基础上,详细分析了槽缝冷却三维定常流场结构与槽缝附近的流动细节.研究结果表明,槽缝冷却对前缘压力分布影响较大,且在压力面引起较大的分离流动,不利于冷却.