钯催化1,3-丁二烯羧酯化合成3-戊烯酸甲酯

以1,3-丁二烯、CO和甲醇为原料,进行羧酯化反应合成3-戊烯酸甲酯是Altam路线生产己内酰胺绿色工艺的关键步骤.将Pd与三齿N-杂环配体或双膦配体组成的催化体系用于1,3-丁二烯的羧酯化反应中,其中乙酸钯/2,6-二(3,5-二甲基吡唑基)吡啶催化剂表现出中等的催化活性,在150oC,p(CO)=6.0MPa的优化条件下反应6h,1,3-丁二烯转化率为78.8%,3-戊烯酸甲酯选择性达92.2%(TON=226);而乙酸钯/2,2′-二(二苯基膦基)苯醚催化体系的活性更高,在优化反应条件下,1,3-丁二烯转化率达90.4%,3-戊烯酸甲酯选择性为91.6%(TON=181).在200oC及类似的羧酯化反应条件下,1,3-丁二烯发生二聚反应,其转化率为99%以上,二聚产物4-乙烯基-1-环己烯选择性高于96%.

Synthesis of cyclic carbonates from epoxides and CO_2 in acetonitrile via the synergistic action of BMIMBr and electrogenerated magnesium

Using 1-butyl-3-methyl-imidazolium bromide （BM1MBr） as the supporting electrolyte and magne- sium as the sacrificial anode, a new and highly efficient electrochemically catalytic route was devel- oped for the synthesis of cyclic carbonates from epoxides and CO2. Based on the cooperative action of BMIMBr and an electrogenerated magnesium salt obtained under a N2 atmosphere, CO2 reacted with a wide range of epoxides to readily generate cyclic carbonates in moderate to excellent yields under mild conditions.

Microbubble ultrasound contrast agent with three esters and carboxylic methyl cellulose as main shell materials: Its preparation and imaging evaluation

Objective: To study on the preparation process of a new surfactant-based microbubble ultrasound contrast agent and to evaluate its contrast effects in vivo. Methods: Microbubble ultrasound contrast agent with three ester surfactants and other additives as its shell materials was prepared by sonication. Sulfur hexafluoride was adopted as the inner gas of the microbubbles. New methods through the combination of optical microscope and some softwares were used to measure the size distribution and the concentration of the microbubbles. Some parameters such as the pH value of the phosphate buffer, quantity of the carboxylic methyl cellulose in the shell materials, selection of the ultrasound power and process time, were studied. Six hybirded dogs were used to verify the in vivo contrast imaging of the contrast agent using second harmonic power Doppler modality. Safety and persistent time of the agent inner animal body were also investigated. Results: Ultrasound contrast agent prepared in the experiment had an average microbubble diameter of 3.95 microns with concentration of 3.6×109 microbubbles per millilitre. Carboxylic methyl cellulose was found as an important shell material which had obviously effect on the microbubble stability and production even with a little quantity. The buffer pH value also had a key role on the microbubble formation and the final production. When the buffer pH value reached 7.4, there was no microbubble produced. Under the approximate microbubble production, process time could be shorten with the increasing ultrasound power. The obvious ultrasound contrast imaging effects were detected in the dog's heart chamber and liver as well as kidney using only one millilitre agent when diluted. The agent was found safe to the dogs. At the same time, persistent time of the agent was found over 20 min in the dog's body. Conclusion: The new ultrasound contrast agent prepared in the experiment has high microbubble production and concentration, narrow microbubble size distribution ranging in several microns, well stability, little dosage needed in the contrast, well safety to the dogs and long persistent time, obvious contrast imaging effect in the dog's heart chamber, kidney and liver. These experiment data indicate that the new ultrasound contrast agent with three ester surfactants and carboxylic methyl cellulose as its main shell materials can be further developed for clinical purposes.

Synthesis of Dimethyl-2,6-Naphthalene Dicarboxylate by Esterification Catalyzed by Sodium Tungstate

The process of synthesis of dimethyl-2,6-naphthalene dicaboxylate from esterification of 2,6-naphthalene dicarboxylic acid (2,6-NDCA) by methanol using sodium tungstate as catalyst was investigated. The orthogonal tests method was used for optimizing the process factors. The effects of reaction temperature, mass percentage of catalyst, reaction time and mass ratio of methanol to 2,6-NDCA on the 2,6-NDCA conversion were investigated. It was found that all the four factors had significant effect on the conversion. The optimum reaction conditions were reaction temperature 215 ℃,mass percentage of catalyst 3%, reaction time 3 h, mass ratio of methanol to 2,6-NDCA 6∶1. The 2,6-NDCA conversion at above condition was 92.80%.

Soluble Expression in Escherichia Coli and Purification of Human Carboxylesterase 1

Objective: To achieve an optimized method for soluble expression of human carboxylesterase 1(hCE-1) in escherichia coil and purification by Ni2+-NTA agarose affinity chromatography, to get improved protein yield and purity for further development of hepatocellular carcinoma(HCC) diagnosis ELISA kits. Methods: The best antigen epitopes of hCE1 were predicted by comparing secondary structure, flexible regions, hydrophilicity, antigenic index surface probability of residues. Afterwards,pET-42a(+) with a His-tag and a GST-tag was applied to form recombinant plasmid pET-42a(+)/hCE1, which facilitated purification when using Ni2+-NTA agarose affinity chromatography. Protein quality was measured by SDS-PAGE and BCA protein assay.Western-blot identification was also performed to ensure the correct expression of hCE1protein. Results: The residues from 500 to 567 near C-terminal of hCE1 protein were considered the best epitopes which exhibited high hydrophilicity and high surface probability and relatively flexible secondary structure and low homology compared with hCE2 and hCE3. His-hCE1 500-567 fusion protein was achieved by IPTG-inducted expression with an expected mass of 42 kDa. After purification, the final product was specially identified, which reached over 95% purity and more than 10 mg/L of microbial culture. In Western blot, the purified fusion protein was recognized by anti-hCE1monoclonal antibody, along with previous sequencing validation, which demonstrated the correct preparation of soluble hCE1 protein. Conclusion: This is an efficacious and affordable strategy to generate fusion hCE1 of high quality in E coli, which facilitates preparation of hCE1 monoclonal antibody and further HCC diagnosis research.