Stereo- and enantioselective determination of pesticides in soil by using achiral and chiral liquid chromatography in combination with matrix solid-phase dispersion

The separation of enantiomers and diastereomers of 8 commonly used pesticides was investigated by liquid chromatography (LC) using a Chiralcel OD column (cellulose tris-3,5-dimethylphenylcarbamate as the chiral stationary phase) and a Pirkle-type Chirex 3020 column (urea derivative from the reaction of (R)-1-(alpha-naphthyl)ethylamine with (S)-tert-leucine, chemically bonded to 3-aminopropylsilanized silica as the chiral stationary phase). The pesticides studied included one organophosphorus insecticide (phenthoate), 3 triazole fungicides (uniconazole, diniconazole, and propiconazole), and 4 pyrethroids (fenpropathrin, beta-cypermethrin, beta-cyfluthrin, and alpha-fenvalerate). The enantiomers were separated within 20 min with a resolution of > or = 1.5 using a mixture of n-hexane and 2-propanol as the mobile phase for all the pesticides studied except propiconazole, for which only the 2 diastereomers were baseline separated. This method allows determination of the enantiomers or stereoisomers of the above pesticides in soil. The strategy was as follows: (1) First, the total concentration(s) of the enantiomer pair(s) of a chiral pesticide in soil was (were) determined by a newly developed matrix solid-phase dispersion (MSPD) procedure, followed by silica-based LC quantification. The recoveries ranged from 76.5 to 93.6% with relative standard deviations of 6.0%. (2) Second, the enantiomeric ratio(s) (ER(s)) of the chiral pesticide was (were) determined by LC with a chiral stationary phase after fractionation of the MSPD extract by silica-based LC. The determined ERs or stereoisomeric ratio(s) (SR(s); for propiconazole, only the SR of the 2 diastereomers was determined) in soil samples spiked with the above 8 racemic pesticides agreed with those of the corresponding standard solutions. (3) Third, based on the total concentrations and the corresponding ERs, the concentration of each enantiomer in soil was calculated. The proposed method is rapid, precise, and sensitive, and is appropriate for the investigation of the stereo- and enantioselective degradation of pesticides in environmental media.     

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 of novel mesoporous silica spheres with starburst pore canal structure

Novel spherical mesoporous silica materials with uniform diameters and starburst mesopore structures were synthesized by a simple one-step procedure with ethanol as the co-solvent in dilute aqueous solution and their formation mechanism was proposed. The arrangement of the pore canal and the diameter of the sphere could be tailored by altering the concentration of ethanol.     

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.     

耐硫催化剂上合成混合醇的研究

通过改进制备方法和添加助剂，用浸渍－热分解法制得了具有高活性和高选择性的MoS2-K-C型耐硫低碳混合醇催化剂。在8.0-11.0MPa,290-340℃，6000-12000h^-1,H2 S 浓度为100ppm 左右的条件下，在直流反应器中对催化剂进行了性能测试，结果表明，醇得率为0.14-0.47gROH(gcat·h)^-1，选择性为89-98%。同时，考察了操作条件对催化剂性能的影响。1042h的试验，证明催化剂具有很好的稳定性。     

电场作用下苏氨酸的电流特性研究

制备了以液态苏氨酸为沟道材料的四端有机场效应晶体管,观测了其随着栅极电压的不同呈现出源漏两极之间不同的电学特异现象;还观测了苏氨酸在外电场作用下,阻抗随着源漏之间电压频率变化的关系,提出一个极性液体模型解释了其导电机理。     

La2O3-Mo5Si3/MoSi2复合材料的高温氧化行为

研究了0．8％La2O3-MosSi3／MoSi2复合材料在1200℃空气中的高温氧化行为。结果表明：0．8％稀土和MoSi3的加入，使材料的抗氧化性能降低。MosSi3含量越高，材料的抗氧化性能越差。当MosSi3含量低于30％时，在氧化初始阶段，质量变化呈直线下降，随着氧化的进行，氧化逐渐增重，材料表面形成较致密的SiO2阻止了材料的进一步氧化，使得氧化增重较小。而0．8％La2O3-40％Mo5Si3／MoSi2复合材料却出现了“粉化”现象。0．8％La2O3．MosSi3／MoSi2复合材料抗氧化性能的降低，归因于Mo5Si3差的抗氧化性和材料致密度的降低；另外，稀土和Mo5Si3的加入，细化了材料的晶粒，使晶界面积增加，加速了氧在晶界中的扩散，促进了材料的氧化。     

Yb:GdVO4晶体的缺陷研究

Yb：GdVO4晶体是一种很好的激光材料，但缺陷会对晶体的激光性能产生严重影响，开展对该晶体的缺陷研究有助于提高晶体质量。采用提拉法生长了面25mm×20mm，掺杂浓度为2％的Yb：GdVO4晶体；分析了晶体的结构及其对晶体解理性的影响；采用化学腐蚀法，以盐酸、氢氟酸为腐蚀剂，对晶体的主要晶面进行了化学腐蚀实验，通过其腐蚀坑形貌对晶体中的位错和晶界进行了研究；对晶体进行了高分辨X衍射实验，结果表明晶体中存在镶嵌块结构；开裂及散射颗粒也为晶体中较常见缺陷。分析了缺陷的成因并提出了预防措施。     

Synthesis of polypiperazine-amide thin-film membrane on PPESK hollow fiber UF membrane

A new interfacial polymerization (IP) procedure is developed in order to synthesize polypiperazine-amide thin-film membrane on the inner surface of poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber ultrafiltration (UF) membrane.A hollow fiber composite membrane with good performance was prepared and studied by FT-IR and scanning electron microscopy.     

Stable, reproducible nanorecording on rotaxane thin films

Stable, reversible conductance transitions and memory effects were observed in solid-state rotaxane-based Langmuir-Blodgett (LB) thin films. Taking advantage of the switching property, we have achieved reproducible nanometer-scale recording dots on rotaxane LB films via voltage application using a scanning tunneling microscope probe. The stable and easily controlled conductance switching makes the rotaxanes a hopeful candidate for nanorecording.