四氨酯化合物的合成及其对液体双酚A环氧树脂的流变控制及固化性能的影响

利用羟基(-OH)和异氰酸酯基(-NCO)的简易反应合成了含4个氨酯键(-NHCOO-),两端基为十六碳烷链(-C16H33)的四氨酯化合物,并用作液体双酚A环氧的流变改性剂。利用傅里叶红外(FTIR)、差示量热扫描仪(DSC)、偏光显微镜和扫描电镜(SEM)对四氨酯化合物及其环氧复配物进行了表征分析。通过流变仪、动态力学分析仪(DMA)及万能试验机等对环氧复配物的流变性及其固化物性能进行了研究。结果表明,四氨酯化合物借助氢键作用和范德华力可在液体环氧基体中自组装形成合适及可控的分子聚集体形态,从而实现对液体环氧复配物流变性的有效控制。5%的四氨酯化合物可使环氧复配物拥有与含10%工业用气相二氧化硅(RY200)的环氧复配物一样的触变性。同时,四氨酯化合物的相变特性使其环氧复配物的流变性具有热可逆性。另外,环氧固化性能受四氨酯化合物影响较小。

氨酯化合物对聚碳酸1,2-丙二酯的同时增韧和增强研究

采用非异氰酸酯路线合成了1,6-六亚甲基二氨基甲酸羟异丙酯(BPU),分子量为320.利用熔融共混方法制备了聚碳酸1,2-丙二酯(PPC)/BPU共混物.研究发现BPU与PPC间有较好的相容性,随着BPU含量的增加,共混体系的起始热分解温度(Td,5%)可分别增加24～33℃,共混物韧性也显著提高,断裂伸长率最大可增至53.4%,为纯PPC的4倍,且共混物的强度和模量仍维持在较高的数值;BPU含量不超过10 wt%时,可以同时实现共混体系的增韧和增强.剪切屈服和银纹化是PPC/BPU体系得以增韧的最主要机理,而空洞化现象起辅助作用.

N,N-二取代甘氨酸酯的ESI-MS/MS研究

应用多级质谱(+)ESI-MS/MS考察了八种N,N-二取代甘氨酸酯化合物的质谱行为,并对其质谱裂解途径进行解析,为表征该类化合物提供了依据。

The Type of Catalyst to Physical Properties of Soy-Based Polyurethane

Flexible Polyurethane （PU） foam is the material most widely used among urethanes. The foams were synthesized via the reaction of soy polyol, mixtures of isocyanates MDI：TDI （80：20）, in the presence of water （blowing agent） with molding process. This experiment was to analyze the physical properties of soy polyol and elaborate the principle of catalyst within the synthesis. The use of liquid and solid catalyst on the polyol synthesis results in significant cellular morphology and properties of polyurethane foam. It is found that the PU which was synthesized using bentonite catalyst has an irregular form of cell morphology, and it has higher density than using sulphuric acid catalyst.

Inhibition of protein tyrosine phosphatase 1B activity by triterpenes isolated from Aceriphyllum rossii

An organic layer prepared from the seed of Aceriphyllum rossii was studied to identify the active compounds for protein tyrosine phosphatase 1B（PTP1B） inhibition.Bioassay guided fractionation resulted in the isolation of PTP1B inhibitory activity of triterpenes（1-4）.These four compounds were identified as aceriphyllic acid C（1）,aceriphyllic acid D（2）,aceriphyllic acid E（3） and aceriphyllic acid F（4）.The isolated 1-4 compounds inhibited PTP1B with IC50 values ranged from（2.1±1.5） μmol/L to（11.2±2.5） μmol/L.Kinetic analysis of PTP1B inhibition by aceriphyllic acid C（1） and aceriphyllic acid D（2） suggested that oleanane-type triterpenes inhibited PTP1B activity in a mixed-type manner.

Inhibition of protein tyrosine phosphatase 1B by triterpenes isolated from Potentilla discolor Bge

Seven oleanene triterpenes were isolated from the roots of Potentilla discolor Bge and their structures were identified as 3-oxoolean-12-en-27-oic acid（1）, gypsogenic acid（2）, 3α-hydroxyolean-12-en-27-oic acid（3）, 3β-hydroxyolean-12-en-27-oic acid（4）, aceriphyllic acid A（5）, aceriphyllic acid A methyl ester（6）, and oleanolic acid（7）. Compounds 1–7 inhibited protein tyrosine phosphatase 1B（PTP1B） activity, with IC50 values ranging from（7.5±0.5） to（22.7±0.5） μmol/L. Among the isolates, compounds 1, 2, 3 and 7 from the Potentilla discolor Bge were found to exhibit selective PTP1 B inhibitory activity.

Effects of compound 209 on colorectal cancer cell HT-29 in vivo and in vitro

Compound 209 is a newly synthesized dithiocarbamate derivative with antiproliferation activity in vitro, however, its antitumor effect in vivo and the underlying mechanisms have yet to be identified. We explored the antitumor effect of compound 209 and the possible mechanisms for its inhibition of the growth of HT-29 xenograff tumor and proliferation of HT-29 cells. Cell proliferation was evaluated with SRB assay in vitro. The results showed that compound 209 had significant antiproliferation activity on HT-29 cells. Furthermore, the xenograff HT-29 nude mouse model was used to study the antitumor effect of compound 209 in vivo. We found that compound 209 significantly inhibited tumor growth and did not cause loss of body weight or leukocytopenia. Analysis by flow cytometry indicated that compound 209 arrested HT-29 cell cycle in G~ phase. Western blotting analysis suggested that compound 209 increased the expression of p27, cyclin E, CDK2, cyclin D1 and CDK4. These results demonstrated the antitumor effect of compound 209 and its potential use as an anticancer drug.

Enhanced antitumor effect of TM208 in combination with 5-fluorouracil in H_(22) transplanted mice

4-Methylpiperazine-l-carbodithioc-acid-3-cyano-3,3-diphenylpropyl ester hydrochloride（TM208）,a newly synthesized dithiocarbamate derivative,exhibits antitumor effect in vivo with low toxicity.However,the antitumor effect of TM208 in combination with drugs in clinical use for cytotoxic chemotherapy has not been identified.In our study,the antitumor effects and toxicities of TM208 in combination with cisplatin（DDP）,cyclophosphamide（CTX） and 5-fluorouracil（5-Fu）,respectively,were evaluated in vivo using a transplanted solid-type hepatocarcinoma H_（22） mice model.The results suggested that 5-Fu（5 mg/kg/2d） potentiated the antitumor effect of TM208（100 mg/kg/d） with significantly higher tumor inhibition rates（P0.01） and a slight elevation of toxicity;however,DDP and CTX in combination with TM208 did not exhibit similar enhanced antitumor effect.For further investigation,we found that the TM208 and 5-Fu combination therapy led to G_2/M cell cycle arrest of tumor cells in vivo by downregulating the protein expression of cyclin Bl,cdc2,cdk7,and upregulating the expression of p21 and p53.The protein expression levels of cyclin Dl and cyclin E were also downregulated in tumor cells treated with TM208 and 5-Fu,while those of cdk4 and cdk2 remained unchanged.The change of mRNA expression level of cdc2 was consistent with that of its protein in each group,while the mRNA expression of cyclin B1 remained unchanged among each group.These results demonstrated the dosage regimen of TM208 for combination therapy and could serve as evidence for clinical use of TM208 as an antineoplastic drug.

IC5, a dithiocarbamate derivative, inhibits colon cancer cell proliferation in vitro and colitis-associated colorectal carcinogenesis in vivo

Colorectal cancer （CRC） is one of the leading causes of cancer-related deaths, and inflammatory bowel diseases and dysregulated cell proliferation play important roles in colorectal carcinogenesis. Therefore, inhibition of inflammatory signaling and cell proliferation is used as a major strategy for chemoprevention of CRC. In the present study, it was found that IC5, a dithiocarbamate derivative, could inhibit the proliferation of LoVo human colon cancer cells in a concentration-dependent manner, with an IC50 of 22 gM. The anti-proliferation effect of IC5 was accompanied by a significant cell cycle arrest in G2/M phase. Further study revealed that IC5 significantly inhibited NF-~B signaling in LoVo cells, suggesting that IC5 could inhibit inflammatory responses. We then evaluated the in vivo efficacy of IC5 to inhibit colitis-associated colorectal carcinogenesis using an azoxymethane （AOM）/dextran sodium sulfate （DSS） mouse model. AOM/DSS treatment resulted in a CRC incidence of 58.3%, while the incidences were decreased to 37.5% and 25% in mice orally administered with 50 and 100 mg/kg IC5, respectively. In addition, IC5 also reduced the plasma levels of alanine aminotransferase and asparatate aminotransferase. Taken together, these results suggested that IC5 could prevent colitis-associated colorectal carcinogenesis, and more attention should be paid to it as a cancer chemopreventive agent in further investigation.

Enantioselective synthesis of β-amino esters bearing a quinazoline moiety via a Mannich-type reaction catalyzed by a cinchona alkaloid derivative

The cinchona alkaloids catalyzed the direct asymmetric Mannich reactions of 1, 3-dicarbonyl compounds with acyl imines to produce novel β-amino ester derivatives containing a quinazoline moiety. The adducts were isolated with high enantiomeric excess （up to 99%）.