N-取代N′-苯基哌嗪类化合物与硫杂蒽酮体系光诱导电子转移引发聚合体系的研究

本工作对N-苯基-N'-乙基呱嗪作为酮/胺光引发体系中组分之一的作用机制进行了研究。发现该特殊的胺类化合物虽包括二甲基苯胺和三乙胺两个部分,但它和酮类相组合形成的光引发体系只有较低的尤引发速率。对上述现象进行了讨论,并通过加入酸类化合物使其中一个胺发生季胺盐化,用以改进光引发效率来进一步证实文中所讨论的机制。     

新型氮芥和卤代烷基哌嗪芳香醛的合成

通过对Vilsmeier反应、烷基化反应和氯化反应的改进提出了以简单易得的苯胺和苯基哌嗪为原料制备氮芥和哌嗪芳香醛的方法. 采用该改进的方法合成了8个氮芥和哌嗪芳香醛, 其中7个为新化合物. 它们的结构均经质谱、红外光谱、核磁共振谱和元素分析确证.     

哌嗪取代卟啉的合成、表征及其抗癌活性

设计并合成了6个具有抗癌活性的哌嗪取代卟啉化合物,分别为5,10,15,20-四[4-(4'-乙基哌嗪基)苯基]卟啉(TEPPH2,8a),5,10,15,20-四[4-(4'-丁基哌嗪基)苯基]卟啉(TBPPH2,8b),5,10,15,20-四[4-(4'-庚基哌嗪基)苯基]卟啉(THPPH2,8c),5,10,15,20-四[4-(4'-苯基哌嗪基)苯基]卟啉(TPhPPH2,8d),5-[4-(4'-乙基哌嗪基)苯基]-10,15,20-三苯基卟啉(EPTPPH2,8e)和5-[4-(4'-丁基哌嗪基)苯基]-10,15,20-三苯基卟啉(BPTPPH2,8f).这些卟啉化合物都由取代苯甲醛与吡咯缩合而成,每一个卟啉分子中含有一个或四个具有抗癌活性的取代哌嗪结构,结构经元素分析,MS,1H NMR,IR和UV-vis等表征.初步的生物活性研究表明,这些化合物具有一定的抗癌活性,因而在医学上可能具有潜在应用前景.     

Influence of pH on formation and stability of phosphatidylcholine/phosphatidylserine coatings in fused-silica capillaries

The effect of pH on the formation and stability of phospholipid coatings in fused-silica capillaries in electrophoresis was investigated. A liposome solution consisting of 3 mM of 80:20 mol% phosphatidylcholine/phosphatidylserine (PC/PS) in N-(2-hydroxyethyl)piperazine-N'-(2-ethanesulfonic acid) (HEPES) buffer was used as coating material. The coating was prepared by a method described earlier and five steroids were used as neutral model analytes. First, the effect of pH of the coating solution on the formation and stability of phospholipid coatings was studied at pH 6.5-8.5. The pH of the background electrolyte (BGE) solution (HEPES) was either kept constant at pH 7.4 or made similar to the pH of the liposome coating solution. Results showed that attachment of the coating on the fused-silica wall mostly depends on the protonation of amines of the phospholipids and HEPES. The ability of the phospholipid coating to withstand changes in pH was then investigated by coating at pH 7.5 and separating steroids with acetic acid, 3-(cyclohexylamino)-1-propanesulfonic acid (CAPS), HEPES, or glycine BGE, adjusted to pH between 4.5 and 10.8. The results showed that with use of BGE solution at pH 10.8, the separation of steroids was not successful and the electroosmotic flow was high because of leakage of the phospholipid coating during preconditioning of the capillary with BGE solution. There was no phospholipid leakage with a BGE solution of pH 4.5, indicating that the protonated form of the functional groups of PS and HEPES participating in the attachment of the phospholipid coating to the capillary play an essential role in the success of the coating.     

Assay of free ferulic acid and total ferulic acid for quality assessment of Angelica sinensis

Activity of Chinese Danggui (DG), the processed root of Angelica sinensis (Oliv.) Diels, is linked to the ferulic acid content but the stability of ferulic acid during extraction for medicinal use is not known. The stabilities of ferulic acid and coniferyl ferulate were evaluated in the extracts of DG using a variety of extraction solvents. These included various combinations and proportions of methanol, water, formic acid, 1 M aqueous hydrochloric acid and 2% sodium hydrogen carbonate (NaHCO3) in water. Coniferyl ferulate was found liable to hydrolyze into ferulic acid in neutral, strongly acidic and basic solvents, where heat and water could facilitate this hydrolysis. However, the hydrolysis was relatively resisted in weakly organic acid. Based on the stability evaluation, two new terms, namely: free ferulic acid and total ferulic acid, were suggested and defined. Free ferulic acid refers to the natural content of ferulic acid in herbs. Total ferulic acid means the sum of free ferulic acid plus the amount of related hydrolyzed components. Meanwhile, the high-performance liquid chromatographic (HPLC) method was developed to assay free ferulic acid and total ferulic acid in DG using methanol-formic acid (95:5) and methanol-2% NaHCO3 in water (95:5) as extraction solvents, respectively. Ten DG samples were investigated on their contents of free and total ferulic acid. The results indicated that the amount variety of free ferulic acid was larger than that of their counterparts, and the ratio of total ferulic acid to free ferulic acid was 4.07 +/- 2.73 (mean +/- SD, n = 10). The chemical assay of DG using total ferulic acid content would be a better choice to assess the herbal quality and was recommended.     

1,4-二硝基-2,3-二硝胺基哌嗪的合成

本文以乙二胺, 乙二醛和脲为原料, 通过Mannich反应, 合成出2,5,7,9-四氮杂双环[4.3.0]壬-8-酮盐酸盐(1); 化合物1 亚硝化给出2,5-二亚硝基-2,5,7,9-四氮杂双环[4.3.0]壬-8-酮(2); 硝化化合物2制得2,5,7,9-四硝基-2,5,7,9-四氮杂双环[4.3.0]壬-8-酮(3); 化合物3水解制得1,4-二硝基-2,3-二硝胺基哌嗪(4).     

A thermal study of Cu(II) compounds formed with piperazine derivatives

The thermal behaviour of some Cu(II) compounds formed with 1,4-disubstituted piperazine derivatives has been studied. The investigations were performed on a MOM 1500 derivatograph. The endothermic effects observed at 170–180°C are associated with the processes of dehydration and dehalogenation of the compounds, with general formula LH₂·CuCl₄·H₂O, whereL is the piperazine derivative. The residue at 600°C remains relatively constant.     

Influence of cyclodextrins on nitrosation of drugs

The World Health Organization issued a nitrosation procedure (NAP Test) which allows to carry out nitrosation under standard conditions. It has proved that the in vitro reaction rates of the fast nitrosatable drugs piperazine, cimetidine and ethambutol are not influenced by -, - and -cyclodextrin. On the contrary, -, -cyclodextrin and heptakis-2,6-di-O-methyl--cyclodextrin enhance the nitrosation of the slower nitrosatable 1-ephedrine and fencamfamine significantly. This possible reaction must be considered if nitrosatable drugs are formulated with cyclodextrins to be administered to human beings.     

Einige Neue N,S-Substituierte 2-Nitrodienverbindungen Aus Reaktionen Von Mono(p-fluorarylthio)substituierten Dienen Mit Aminen

2-Nitrodiene compound 1 was stirred with p-fluorothiophenol for a long time and compound 3 was obtained. Compound 1 gave bis(thio)substituted 2-nitrodiene compound 4 and tris(thio)substituted compound 5 with 2 moles of p-fluorothiophenol in the presence of NaOH in ethanol. The compounds 9a–g have been prepared from 8a–g and 3. Compound 7 was obtained from the reaction of mono(thio)substituted 2-nitrodiene with morpholine. Compound 3 gives 11a–d in the reaction with piperidines in CH₂Cl₂ (or ether). Compound 13a–b have been obtained from the reaction of compound 3 with primary amines 12a–b. Compound 3 gives 15 and 16 in the reaction with 2,5-dimethylpiperazine in CH₂Cl₂.