希土烯丙基化合物的研究——Ⅷ.镝、钬、铒、镱和镥的2-甲基烯丙基化合物的合成

用无水希土氯化物与2-甲基烯丙基氯化镁及四甲基乙二胺,0℃下,在四氢呋喃中反应,加乙醚后可得到五个含2-甲基烯丙基的重希土元素的化合物。经元素分析、红外光谱和质谱分析的鉴定,确定该化合物的组成为Ln(C₄H₇)₂Cl₅Mg₂(tmed)₂。     

草酸锰分解过程的机理函数判别和动力学研究

用等温热重和线性升温热重分析法研究了草酸锰热分解过程,提出了判断其机理函数的3步判别法。经实验和理论分析证明,该反应受随机成核和晶核随后生长的过程(A_3a机理)支配,其活化能E=103.95 kJ/mol,频率因子A=4.448×10~8min~(-1).动力学补偿效应为IgA=0.09661E-1.2856     

DNA intercalating studies of [Ru(bpy)<Subscript>2</Subscript>HPIP]<Superscript>2+</Superscript> with intramolecular hydrogen bond ligand based on introduction of copper ion

The effects of copper ion on the interaction of [Ru(bpy)₂HPIP]²⁺(bpy = 2,2′-bipyridine, HPIP = 2-(2-hydroxyphenyl) imidazo [4,5-f] [1, 10] phenanthroline) with DNA have been investigated by electronic absorption spectroscopy and fluorescence spectroscopy. HPIP ligand of the complex with an intramolecular hydrogen bond can bind Cu²⁺ in the absence of DNA, as revealed by the absorbance and fluorescence decrease for [Ru(bpy)₂HPIP]²⁺. The resultant heterometallic complex binds to DNA via intercalation of HPIP into the DNA base pairs and its DNA-binding ability is stronger than [Ru(bpy)₂HPIP]²⁺ itself. The DNA bound [Ru(bpy)₂HPIP]²⁺ cannot bind Cu²⁺ at low Cu²⁺ concentration and the intramolecular hydrogen bond in HPIP is located inside the DNA helix. While the Cu²⁺ concentration is relative high, Cu²⁺ can quench the fluorescence of DNA bound [Ru(bpy)₂HPIP]²⁺. The quenching reason is proposed.     

四（对羟基苯基）卟啉—硅胶固定相的合成及在核苷酸分析中的应用

以大孔微硅胶作基体，经γ－氨丙基三乙氧基硅烷活化与间隔臂氯代环内烷反应后，再与预先合成的四（对羟基苯基）卟啉配体键合，构成电荷转移型亲和色谱固定相。以ＰＨ＝７．０的磷酸盐缓冲溶液作流动相，成功实现对一些核苷酸的高效液相亲和色谱分离。     

The analysis of salen complexes by fast atom bombardment mass spectrometry and atmospheric pressure chemical ionization mass spectrometry

Fast atom bombardment (FAB) mass spectrometry provides useful structural information about salen complexes and salen-based oxo transfer catalysts that are not appreciably soluble in organic solvents. It was discovered that initial dissolution of these complexes in trifluoroacetic acid was crucial for producing good FAB mass spectra. Trifluoroacetic acid helps dissolve the salen-based catalysts, concentrates the analyte molecules at the matrix surface, and most importantly, suppresses the reduction process, which is a well-known phenomenon when protic matrices are used. The best FAB matrices for these catalysts were found to be thioglycerol and “magic bullet.” However, dechlorination occurred under the acid conditions for complexes containing iron chloride and manganese chloride. Demetalation also occurred for nickel-containing oxo transfer salen-based complexes. When the salen-based complexes are soluble in LC solvents, they can be analyzed easily by atmospheric pressure chemical ionization (APCI) mass spectrometry without the employment of relatively nonvolatile matrices. In addition, APCI/MS provides much more sensitive detection for manganese-salen complexes when compared with FAB results. No dechlorination or demetalation were observed when a negative ion mode APCI was employed. To our knowledge, this is the first time that an intact molecule of this type of complex has been observed by mass spectrometry.     

在硅磷酸镧中Ce^3＋离子对Tb^3＋离子的敏化

实验表明在La2O3·0.01SiO2·0.95P2O5基质中Ce^3 对Tb^3 有强的敏化作用。254nm紫外光激发下温度对Tb^3 激活的Ce^3 、Tb^3 共激活试样的发射强度的Ce^3 、Tb^3 共激活的试样Tb^3 的^5D4→^7F6:5:4跃迁的发射强度随湿度的变化。计算了Ce^3 到Tb^3 的能量传递效率。初步探讨了Ce对Tb的能量传递机理。     

Structural Study of Silica Xerogel Composites Containing Pd Aggregates

Composites containing Pd aggregates dispersed in amorphous silica are of interest from both a fundamental and applied point of view because of their attractive catalytic properties. The silica powders added with palladium, prepared by the sol-gel method, were studied using X-ray diffraction, and IR- and UV-Vis-spectrophotometry. Silica xerogel samples were prepared using a ethanol/H₂O/TEOS molar ratio of 4:11.6:1 and loaded with sodium tetrachloropalladate. The silica xerogel microstructure of the powders was studied as a function of annealing temperature. Attention was paid to the evolution of the glass matrix as well as the palladium aggregates in the SiO₂ matrix. We found in our samples partial crystallization of the glass matrix in form of quartz and cristobalite phases with palladium oxide and metallic palladium phase at 1000^∘C. The Rietveld refinement method was used in order to determine the percentage of the phase contents.     

Rapid Fabrication of Hollow SiO2 Spheres with Novel Morphology

The hydrolysis of tetraethoxysilane (TEOS) occurred on the surface of poly(methyl methacrylate) (PMMA) microshperes immediately after these microshperes were prepared in TEOS. Micron-sized hollow SiO2 spheres were obtained by calcination of the coated PMMA microshperes. It was found that the final hollow spheres were constituted by small SiO2 particles.     

Chiral tris(oxazoline)/Cu(II) catalyzed coupling of terminal alkynes and nitrones

Novel chiral iPr-tris(oxazoline)/Cu(ClO4)2 x 6H2O catalyzed coupling of terminal acetylenes and nitrones to afford cis-disubstituted beta-lactams is described; the choice of base proves essential to both the diastereoselectivity and the enantioselectivity.     

1-(α-萘乙酰基)-4-芳酰基氨基硫脲及3-(α-萘亚甲基)-4-芳酰基-1,2,4-三唑琳-5-硫酮的合成

许多酰氨基硫脲类衍生物有抗病毒、抗细菌、抗肿瘤等功效,我们曾经通过5-(α-萘)-2H-四唑-2-乙酰肼与芳酰异硫氰酸酯缩合得一系列新的酰氨基硫脲和相关的杂环衍生物,观察到它们在很低的浓度下就有调节小麦芽鞘生长的功能。Kothari等用α-萘乙酰肼与芳基异硫氰酸酯缩和制得一系列1-(α-萘乙酰基)-4-芳基氨基硫脲及