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.     

氨基羧酸纤维分离富集-电感耦合等离子体原子发射光谱法测定多种痕量稀土元素

本文制备了氨基羧酸纤维滤纸片作为柱填充物，成功地分离和富集了地化样品中的多种稀土元素。富集后的稀土元素采用电感耦合等离子体原子发射光谱法测定，回收率为90％～109％。本文还对基体干扰及其消除进行了研究。     

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.     

Pd-Rh型国Ⅲ排放三效催化剂的研制

对满足欧Ⅲ排放限值的Pd-Rh型三效催化剂进行研究开发,测试了新鲜催化剂的空燃比特性和起燃温度特性,并与市场上的欧Ⅲ催化剂在同等条件下老化后的性能进行了比较.对研制的催化剂进行封装总成后,按照GB18352.3-2005标准进行了常温冷起动Ⅰ型和低温冷起动IV型试验,测试结果完全能满足该标准的限值要求.     

Synthesis and in vivo study of metallofullerene based MRI contrast agent

Gd@C₈₂(OH)₄₀ has been developed as a new generation of MRI contrast agent. But recently, it was found that Gd@C₈₂(OH) _x with a larger number of OH (x>36) would lead to cage break and hence, release of highly toxic Gd ions. We synthesized the more stable Gd@C₈₂(OH) _x with less OH-number, Gd@C₈₂(OH)₁₆, and studied its proton relaxivity and MRI images. The results indicate that Gd@C₈₂(OH)₁₆ also gives high proton relaxivity, even higher than that of (NMG)₂-Gd-DTPA. The bio-distribution indicated that Gd@C₈₂(OH)₁₆ tends to be entrapped in the liver and kidney and remained in tissue for about 2 hours. The results suggest that the more stable metallofullerene derivative Gd@C₈₂(OH)₁₆ can be the potential candidate of the new MRI contrast agent.     

杂原子Pb同晶取代Si－ZSM－12中的部分Si及其鉴定

杂原子Ｐｂ同晶取代Ｓｉ－ＺＳＭ－１２中的部分Ｓｉ及其鉴定赵修松，王清遐，李宏愿（中国科学院大连化学物理研究所，大连１１６０２３）关键词Ｐｈ－ＺＳＭ－１２，合成，表征ＺＳＭ－１２属丝光沸石类，具有一维线性非交叉孔道（０．５７×０．６１ｎｍ）［１，２］，...     

Regulation of lithospermic acid B and shikonin production in Lithospermum erythrorhizon cell suspension cultures

Cell suspension cultures of Lithospermum erythrorhizon produced a large amount of lithospermic acid B, a caffeic acid tetramer, as well as shikonin derivatives (each ca. 10% of dry wt.) when cultured in shikonin production medium M-9. Various culture factors for increasing the production of lithospermic acid B were investigated. Lithospermic acid B production was inhibited by 2, 4-D or NH4+, whereas it was stimulated by Cu2+. These regulatory patterns were similar to those for the production of shikonin derivatives in these cell cultures, suggestive of close relations and similar metabolic regulation between the production of these compounds. Cultivation under light illumination, however, showed that these metabolisms were independently regulated. In particular, blue light showed a stimulatory effect on lithospermic acid B production, while shikonin production was strongly inhibited, indicative of an effective condition for lithospermic acid B production.     

Macroporous poly(methyl methacrylate) produced by phase separation during polymerisation in solution

Polymethyl methacrylate (PMMA) sponges were obtained by polymerization in a solution with monomer/ethanol ratios up to 20:80. The material obtained after the elimination of the solvent present a homogeneous distribution of dispersed pores up to a monomer/ethanol ratio lower than 40:60. For higher ethanol contents in the reacting mixture, the morphology of the sponge corresponds to a network of PMMA microparticles, leaving large empty spaces leading to highly porous structure. The monomer/ethanol ratio during polymerization has a large influence on the porosity, thermal, and mechanical properties of the material and, for large solvent contents, on the size of the polymer microparticles.     

Mixed ligand system of cysteine and thioglycolic acid assisting in the synthesis of highly luminescent water-soluble CdTe nanorods

Highly luminescent water-soluble CdTe nanorods were prepared with the assistance of the mixed ligand system of cysteine and thioglycolic acid; the aspect ratio and photoluminescence of the CdTe nanorods could be controlled by the refluxing time.     

衬钽管石墨炉中小量氢气的影响及稀土基质激光晶体中铕的测定

通过纯氩中加入小量氢气,研究了保护气体对衬鉏管石墨炉分析性能的影响,结果表明,采用5％H_2-Ar作保护气体,可以显著提离衬鉏管的成品率,明显延长衬鉏管的使用寿命,使衬钽管的测定重现性得到改善,而对测定灵敏度没有明显影响。干扰试验表明,本方法可直接用于稀土基质激光晶体中铕的测定,分析结果与计算值基本一致。