1,2,4-三氮唑酰基硫脲的合成及生物活性

采用亚结构连结法设计合成了6种未见文献报道的标题化合物，它们的结构经元素分析、IR、，^1HNMR和MS确证，并进行了初步的生物活性测试，结果表明部分化合物具有良好的植物生长调节活性或除草性。     

Low-temperature SEM for detection of fungicide activity

Low-temperature scanning electron microscopy (LTSEM) combined with cryopreparation methods provided images of well-preserved biological surfaces and structures on a routine basis. Fractures of wheat leaves revealed epidermal and parenchymatous cells and masses of fungal hyphae growing in intercellular spaces. Freeze-fractured plant cells contained haustoria of the brown rust fungus Puccinia triticina. Extrahaustorial matrices were clearly distinguishable and at infection sites granular material was found. Activity of the triazole fungicide cyproconazole was mainly directed towards fungal hyphae and sporogenic tissue, resulting in a stronger branching and swelling of hyphal tips and collapse of fungal cells. Cryofixation methods combined with the use of a cryopreparation unit (Balzers SCU 020) were more reliable in interpreting the observed biological events through easier discrimination between evidence and artefacts. More advantages in the use of the cryopreparation unit are described in detail.     

含1,2,4-三氮唑类杀菌剂的研究进展

综述了国内外含 1 ,2 ,4 -三氮唑类杀菌剂的研究进程 ,讨论了结构与活性的关系 ,总结了 1 ,2 ,4 -三氮唑类杀菌剂的应用现状及存在问题 ,提出了一些改进措施与建议。     

7-苄氨基-9,10-二氢-1,2,4-三氮唑并[4,3-a]喹啉衍生物的合成及环合反应的探讨

以6-氨基-3,4-二氢-2(1H)-喹啉酮为起始原料,经缩合、还原、硫代、环合等反应合成了5个7-苄氨基-9,10-二氢-1,2,4-三氮唑并[4,3-a]喹啉衍生物。产物的结构经核磁共振谱和质谱确证。     

三氮唑合铬(Ⅲ)配合物应激下三角帆蚌生化指标及营养组分的变化

本文以1,2,3-三氮唑-4,5-二羧酸为配体诱导合成了一种新型细胞小片处理剂—三氮唑合铬配合物,并对其结构进行了表征分析。采用体外模拟应激方式,探讨了三氮唑合铬配合物对三角帆蚌生化指标和营养组分的影响情况。结果表明:三氮唑铬配合物在浓度2.5 μg/g和10 μg/g时可以促进三角帆蚌蛋白质合成,在浓度40 μg/g时可以促进蛋白质代谢和增强碱性磷酸酶活性;三氮唑合铬配合物应激后,三角帆蚌体内的牛磺酸和不饱和脂肪酸相对含量显著提高(p<0.05);而且血清生化指标、氨基酸组分、脂肪酸组分之间分别存在一定相关性。由此表明,三氮唑合铬配合物能够促进三角帆蚌伤口愈合,促进珍珠质分泌,有助于珍珠的形成,同时能提高其免疫活性,从而提高珍珠的产量和质量。     

两种富氮稠环型1，2，5-噁二唑类含能盐的合成及性能

以5,6-二肼基-［1,2,5］噁二唑并［3,4-b］吡嗪（1）为原料合成了5,5''-（肼-1,2-二亚基亚胺）双（5,7-2H-［1,2,5］噁二唑并［3,4-e］［1,2,4］三唑并［4,3-a］吡嗪-8（4H）-亚胺）高氯酸盐（2）和5,5''-（二氮烯-1,2-二亚基）双（［1,2,5］噁二唑并［3,4-e］［1,2,4］三唑并［4,3-a］吡嗪-8（7H）-亚胺）硝酸盐（3）两种富氮含能盐。采用核磁共振（NMR）、傅里叶红外光谱（FT-IR）、元素分析（EA）、X-射线单晶衍射（XRD）等多种手段对含能离子盐2和3的结构进行了表征,利用差示扫描量热法（DSC）研究其热分解行为,运用BAM标准测试方法获得摩擦感度和撞击感度,同时基于等键反应方程与EXPLO5软件预测其爆轰性能。结果表明,化合物2和3的晶体均属于单斜晶系,分别属于Pn 和P2₁/n空间群,二者的晶体结构中阳离子部分具有良好的平面性,晶体堆积图中观察到了大量氢键。化合物2和3的热分解温度分别为154 ℃和130 ℃,理论爆速分别为7722 m·s^-1和8008 m·s^-1,理论爆压分别为26.3 GPa和28.4 GPa,摩擦感度均为360 N,撞击感度均大于40 J。化合物2和3在爆轰性能、摩擦感度、撞击感度性能上均优于传统炸药TNT。     

Harmicens,Novel Harmine and Ferrocene Hybrids: Design,Synthesis and Biological Activity

Cancer and malaria are both global health threats. Due to the increase in the resistance to the known drugs, research on new active substances is a priority. Here, we present the design, synthesis, and evaluation of the biological activity of harmicens, hybrids composed of covalently bound harmine/β-carboline and ferrocene scaffolds. Structural diversity was achieved by varying the type and length of the linker between the β-carboline ring and ferrocene, as well as its position on the β-carboline ring. Triazole-type harmicens were prepared using Cu(I)-catalyzed azide-alkyne cycloaddition, while the synthesis of amide-type harmicens was carried out by applying a standard coupling reaction. The results of in vitro biological assays showed that the harmicens exerted moderate antiplasmodial activity against the erythrocytic stage of P. falciparum (IC₅₀ in submicromolar and low micromolar range) and significant and selective antiproliferative activity against the MCF-7 and HCT116 cell lines (IC₅₀ in the single-digit micromolar range, SI > 5.9). Cell localization experiments showed different localizations of nonselective harmicene 36 and HCT116-selective compound 28, which clearly entered the nucleus. A cell cycle analysis revealed that selective harmicene 28 had already induced G1 cell cycle arrest after 24 h, followed by G2/M arrest with a concomitant drastic reduction in the percentage of cells in the S phase, whereas the effect of nonselective compound 36 on the cell cycle was much less pronounced, which agreed with their different localizations within the cell.     

三唑类抗真菌药物伏立康唑的合成

以氟代乙酸乙酯为原料,经缩合、溴代、加氢、拆分等反应合成了具有光学活性的抗真菌药物伏立康唑。中间体氟代丙酰基乙酸乙酯(FPEA)的合成条件是:n(氟乙酸乙酯):n(丙酰氯)=1．10:1,回流反应4 h,收率32％;6-乙基-5-氟嘧啶-4(3H)酮(EFPO)的合成条件是:n(FPEA):n(甲脒乙酸盐)=1:1．18,在0℃反应1 h,收率51．9％;6-乙基-4-氯-5-氟嘧啶(CEFP)的合成条件是:n(EFPO):n(POCl3)=1:2．2,回流反应3 h,收率82．8％;6-(1-溴乙基)-4-氯-5-氟嘧啶(CBFP)的合成:n(CEFP):n(NBS)=1:1．15,回流反应12 h,收率78％;(2R,3S／2S,3R)-3-(4-氯-5-氟嘧啶-6-基)-2-(2,4-二氟苯基)-1-(1H-1,2,4-三唑-1-基)丁-2-醇盐酸盐的合成条件:n(CBFP):n(氟康唑)=1．0:1．0,控制反应温度低于5℃,反应2 h,收率67．5％,将上述中间体盐用40％NaOH溶液调pH=11,经后处理得到伏立康唑白色结晶,收率74％。题述化合物经元素分析、1H NMR、FT-IR确证了结构,总收率1．3％。     

3—芳基—5—巯基—1,2,4—均三唑合成及其生物活性研究

以芳香羧酸为原料，经酯化，肼解等多步反应合成了８种３－芳基－５－巯基－１，２，４－均三唑。研究了该类化合物的生物活性。