羟胺合成哌嗪类化合物的研究

本文讨论了以羟胺为原料环合得到哌嗪及其衍生物。筛选得到了镍、铜、铬、锌、锰／氧化铝载体催化剂，并通过试验得到了最佳反应条件，使哌嗪的收率达95％以上。并根据类似方法合成了2-甲基哌嗪和顺式-2，6-二甲基哌嗪。     

哌嗪的生产应用和市场

综述了哌嗪的合成技术和应用开发现状,分析了哌嗪的市场前景。     

Antibacterial activity and mechanism of piperazine polymer

Piperazine polymers poly(ethylenediaminetetraacetic dianhydride-co-piperazine) (PE) and MGF-Ct24E-modified poly(ethylenediaminetetraacetic dianhydride-co-piperazine) (PEM) showed good antibacterial activity. Considering their different applications, the effects of time, pH, and inoculation concentration of these antibacterials against Escherichia coli (E. coli) in unique environments were evaluated in this study. The results indicated that the MIC and MBC values of the polymers increased after the introduction of MGF-Ct24E into PE, but the two types of polymers still exhibited good antibacterial activity in a short time period under acidic conditions. In addition, we investigated the effect of the piperazine polymers on bacterial cell structure. It was clear that PE and PEM could destroy the bacterial cell wall, cell membrane and DNA, and their specific mechanism may be different. For PE, its carboxyl group could react with peptidoglycans on the E.coli cell wall to form holes on the bacterial surface, allowing PE to penetrate into the bacterial cell to damage DNA. For PEM, the alkaline MGF-Ct24E could adsorb E.coli and make it shrink, meanwhile, the PE component created small holes on the bacterial walls and membranes, and inserted into the bacteria to result in bactericidal effect. These findings reveal the potential usefulness of PE and PEM in biomedical applications.     

Gold immunochromatographic sensor for the rapid detection of twenty-six sulfonamides in foods

A gold immunochromatographic sensor (GICS) was developed for the rapid detection of 26 sulfonamides in honey samples.The sensor was based on a group-specific monoclonal antibody (mAb) that can recognize all 26 sulfonamides.Three haptens (hapten 1 with a thiazole ring,hapten 2 with a benzene ring,and hapten 3 with a straight carbon chain) were used for antigen preparation.With hybridoma technology,a group-specific mAb was screened with a 50％ maximal inhibitory concentration (IC50) against sulfathizole (STZ) and the other 25 analogues ranging from 0.08 to 90.18 ng/mL.Mono-dispersed gold nanoparticles were conjugated with the mAb to develop the lateral immunochromatographic strip.A labeled antibody concentration of 0.1 μg/mL and a coating antigen concentration of 0.2 μg/mL in the test line were chosen for strip preparation.Under optimized conditions,the visual limits of detection (vLOD) for the concentrations of STZ,sulfamethoxazole,sulfamethizole,sulfadiazine,sulfamerazine,sulfadimethoxine,sulfamonomethoxine,sulfameter,sulfamethoxypyridazine,and sulfachloropyridazine were 5,0.25,0.25,10,5,10,25,2.5,5,0.25,and 10 μg/kg,respectively.Scanner analysis in honey samples revealed good performance for detection of the 26 sulfonamides.Commercial honey samples were tested with the sensor and positive results were confirmed with high-performance liquid chromatography.The proposed strip sensor provides a convenient method for the rapid and reliable determination of sulfonamides pollutants in honey samples.     

盐酸曲美他嗪的合成

研究一种冠状动脉血管扩张剂盐酸曲美他嗪的合成方法。以六水哌嗪为起始原料,经酰化、Mannich反应、水解、成盐反应制得目标化合物。目标化合物的结构经熔点测定、红外及1 H-NMR谱确证,总收率为29.2%,经HPLC检测纯度为98.5%。该合成方法成本较低、操作简便、条件温和,适于工业生产。     

4,5,6,7-四氢吡唑并[1,5-a]哌嗪-3-甲酸乙酯的合成

以4-氯-3-氧代丁酸乙酯为原料,经与叔丁醇钾醚化、DMF-DMA缩合、水合肼环合、脱叔丁基、羟基氧化、还原氨化、分子内环合以及氢化脱苄等反应合成了标题化合物。并对其中关键的羟基氧化反应和分子内环化反应的工艺条件进行了优化,获得了较优的工艺条件:在羟基氧化反应中以二氧化锰为氧化剂、氯仿为溶剂;在分子内环化反应中以甲基磺酰氧基(OMs)为离去基团。目标化合物的总收率为39.5%,其结构经~1HNMR、~(13)CNMR、MS和元素分析进行了确定。     

微流控芯片联用高效液相色谱-荧光检测器同时测定肉类食品中4种磺胺类药物残留

目的 建立一种使用微流控芯片进行肉类食品前处理,并结合高效液相色谱-荧光检测器(high performance liquid chromatography-fluorescence detector, HPLC-FLD)同时测定肉类食品中4种磺胺残留的方法。方法 样品先用乙酸乙酯提取后,在微流控芯片中用2 mol/L盐酸溶液反萃取和正己烷脱脂,收集盐酸流出液100μL,与0.5 g/mL醋酸钠溶液按照1:1(V:V)混合,加入0.2 g/L荧光胺50μL进行衍生化反应,采用岛津ODS-3色谱柱进行分离,流动相为乙腈-2%乙酸水溶液。结果 4种磺胺完全分离且在0.01～1.00mg/L呈良好的线性关系,在50、100、200μg/kg3个添加水平下,平均回收率为72.1%～91.6%,相对标准偏差为4.7%～13.6%,方法检出限为1～5μg/kg。结论 该方法具有快速、方便、经济、除脂效果好、环保等优点,适合肉类食品中4种磺胺类药物残留分析,并且提供了一个新的样品前处理思路。     

哌嗪基单丁酰胺酸钙/锌的合成及对PVC热稳定性研究

以丁二酸酐、哌嗪、氯化钙、氯化锌为原料,通过两步反应制备了哌嗪基单丁酰胺酸钙/锌（PSACa/Zn）热稳定剂。采用元素分析、电感耦合等离子体原子发射光谱仪（ICP?OES）和傅里叶变换红外光谱仪（FTIR）对产品结构进行表征,通过刚果红试纸法、转矩流变仪法、热失重法考察了PSACa/Zn对PVC的热稳定性能,并筛选了PSACa和PSAZn的最佳配比。结果表明,PSACa和PSAZn对PVC的静态热稳定时间分别可达74.5、41.5 min,优于硬脂酸钙（CaSt₂）、硬脂酸锌（ZnSt₂）热稳定剂;PSACa和PSAZn复配使用时,以m_PSACa∶m_PSAZn=1∶1时性能最佳,对PVC静态热稳定时间可达92 min,动态热稳定时间可达905 s;发现PSACa/Zn对PVC的长期热稳定性良好。     

UV-C辐照降解水中磺胺类药物

采用C类紫外线或称为短波紫外线（即UV-C）辐照降解水中磺胺类药物,考察了磺胺类药物种类、UV光强、磺胺类药物初始浓度、反应液pH对降解效果的影响。结果表明UV-C辐照对磺胺嘧啶、磺胺甲基嘧啶和磺胺甲恶唑的降解过程均符合拟一级反应动力学。UV-C辐照技术对磺胺甲恶唑的去除率最高,在反应液pH为7,光强为142μW/cm^2,初始浓度为0.02mmol/L条件下,辐照30 min后磺胺甲恶唑去除率达到67.80%,而磺胺嘧啶和磺胺甲基嘧啶去除率仅15%左右。通过增大紫外光强和减小初始浓度,可提高反应速率和磺胺甲恶唑去除率。反应液pH对反应效果的影响显著,酸性条件更利于UV-C辐照降解磺胺甲恶唑。     

1,4-二硝基呋咱并[3,4-b]哌嗪(DNFP)的合成

设计合成了高能量密度材料1,4-二硝基呋咱并[3,4-b]哌嗪（DNFP）。即以N,N＇-二叔丁基乙二胺为起始原料,低温条件下与二氯乙二肟缩合环化生成1,4-二叔丁基哌嗪-2,3-二酮肟（PDO—tB）,而后在氢氧化钠的乙二醇溶液中高温反应脱水环化得1,4-二叔丁基呋咱并[3,4-b]哌嗪,经98％硝酸和硫酸的混酸体系硝解合成出DNFP,总收率32．6％,采用红外光谱、核磁共振谱、元素分析对DNFP和中间体结构进行了表征;改进了PDO—tB的合成工艺条件,加料方式由一次性加入改为缓慢滴加,并确定了适宜的冷浴温度为-18℃;研究了不同硝解体系对反应的影响,确定了适宜的硝解体系为硝硫混酸,硝解收率为61．7％。