New palladium(II) and platinum(II) complexes with 9-aminoacridine: structures, luminiscence, theoretical calculations, and antitumor activity

The new complexes [Pd(dmba)( N10-9AA)(PPh 3)]ClO 4 ( 1), [Pt(dmba)( N9-9AA)(PPh 3)]ClO 4 ( 2), [Pd(dmba)( N10-9AA)Cl] ( 3), and [Pd(C 6F 5)( N10-9AA)(PPh 3)Cl] ( 4) (9-AA = 9-aminoacridine; dmba = N,C-chelating 2-(dimethylaminomethyl)phenyl) have been prepared. The crystal structures have been established by X-ray diffraction. In complex 2, an anagostic C-H...Pt interaction is observed. All complexes are luminescent in the solid state at room temperature, showing important differences between the palladium and platinum complexes. Complex 2 shows two structured emission bands at high and low energies in the solid state, and the lifetimes are in agreement with excited states of triplet parentage. Density functional theory and time-dependent density functional theory calculations for complex 2 have been done. Values of IC 50 were also calculated for the new complexes 1- 4 against the tumor cell line HL-60. All of the new complexes were more active than cisplatin (up to 30-fold in some cases). The DNA adduct formation of the new complexes synthesized was followed by circular dichroism and electrophoretic mobility. Atomic force microscopy images of the modifications caused by the complexes on plasmid DNA pB R322 were also obtained.     

Coibamide A, a potent antiproliferative cyclic depsipeptide from the Panamanian marine cyanobacterium Leptolyngbya sp

Coibamide A (1) is a new, potent antiproliferative depsipeptide which was isolated from a marine Leptolyngbya cyanobacterium collected from the Coiba National Park, Panama. The planar structure of 1 was elucidated by a combination of NMR spectroscopy and mass spectrometry. Exhaustive 1D and 2D NMR spectroscopy included natural abundance 15N and variable temperature experiments; mass spectrometry included TOF-ESI-MSn and FT-MSn experiments. Chemical degradation followed by chiral HPLC- and GC-MS analyses was used to assign the absolute configuration of 1. This highly methylated cyclized depsipeptide exhibited an unprecedented selectivity profile in the NCI 60 cancer cell line panel and appears to act via a novel mechanism.     

用于NSH紫外滤光片的长桥式聚倍半硅氧烷防潮膜

以双环己基甲烷4,4’-二异氰酸酯与3-氨丙基三乙氧基硅烷反应制备了具有长桥链结构的聚倍半硅氧烷前驱体. 利用制备的前驱体在碱性条件下水解缩聚制备了桥式聚倍半硅氧烷溶胶, 并对硫酸镍(NSH)紫外滤光片镀膜. 通过FT-IR, 29Si MAS NMR和N2吸附-脱附表征对凝胶结构进行了分析, 用SEM和AFM对薄膜的表面形貌进行了研究, 通过一定湿度(70%)下NSH滤光片光学性质的变化观察了薄膜的防潮性能. 结果表明, 这种桥式聚倍半硅氧烷薄膜是致密无孔的, 能够对NSH滤光片起到很好的防潮保护.     

多氯代吩噁嗪热力学性质的密度泛函理论研究

在B3LYP/6-31G*水平上对135个多氯代吩噁嗪(PCPXs)系列化合物进行了全优化和振动分析计算, 得到各分子在298.15 K, 1.013×105 Pa标准状态下的热力学性质. 设计等键反应, 计算了PCPXs系列化合物的标准生成热(Δf )和标准生成自由能(Δf ), 研究了这些参数与氯原子的取代位置及取代数目(NPCS)之间的关系, 结果表明: 熵( )、Δf , Δf 与NPCS之间有很强的相关性. 根据异构体标准生成自由能的相对大小, 从理论上求得异构体的相对稳定性. 以Gaussian 03程序的输出文件为基础, 采用统计热力学程序计算了PCPXs化合物在200 K至1800 K的摩尔恒压热容(Cp,m), 并用最小二乘法求得Cp,m与温度之间的相关方程, 发现Cp,m与T, T－1和T－2之间有着很好的相关性.     

1-脱氢松香酰基-3-取代硫脲以及5-(脱羧脱氢松香-4-基)-3-芳氨基- 1H-1,2,4-三唑化合物的合成与生物活性

以广西的优势资源松香为原料, 脱氢松香酸与亚硫酰氯、硫氰化钾分别在回流条件下反应6 h和1.5 h, 得到脱氢松香酰异硫氰酸酯, 产率52%; 然后与胺在加热回流条件下反应1.5 h, 得到11种1-脱氢松香酰基-3-取代硫脲4, 产率63%～94%; 4a～4f 分别与水合肼在搅拌下回流反应3～6 h, 得到6种5-(脱羧脱氢松香-4-基)-3-芳氨基-1H-1,2,4-三唑化合物5, 产率70%～94%; 所有化合物的结构均经IR, 1H NMR, 13C NMR和元素分析确认. 初步生物活性测试表明, 4e, 4f, 4j, 5b对枯草杆菌抑菌率较高, 特别是4j在浓度为50 mg/L时就达到较好效果; 4b, 4h, 4i, 5e在100 mg/L时对大肠杆菌的抑菌效果较好.     

新型α1受体拮抗剂先导化合物的寻找(I): 5-氯-2-(4-(芳氧烷基)哌嗪-1-基)苯并噁唑类化合物的设计、合成及生物活性研究

为寻找用于治疗良性前列腺增生的新型α1受体拮抗剂, 以本研究组发现的2-[(4-(2-(2-氯苯氧基)乙基)哌嗪-1-基)甲基]-5-甲基苯并噁唑(wb5c)为先导化合物, 结合已构建的α1-AR拮抗剂药效团模型, 通过骨架改造, 设计出以苯并噁唑-2-基哌嗪为母核的目标物, 然后以5-氯-2-氨基酚和取代苯酚为原料, 经缩合、卤代、氨化、Williamson醚合成、取代等反应共合成11个新目标化合物, 结构经ESI-MS, 1H NMR, IR及HRMS确证. 初步药理活性实验表明, 目标物具有中等强度α1受体拮抗活性, 符合我们提出的三元素药效团模型. 5-氯-2-[4-(芳氧烷基)哌嗪-1-基]类化合物是一类新的具有潜在开发价值的α1受体拮抗剂.     

化学气相反应法制备不同碳基体表面SiC涂层组织结构分析

采用化学气相反应法, 以同种工艺分别在石墨和C/C复合材料表面制备了SiC涂层, 借助X射线衍射仪(XRD)、扫描电镜(SEM)及能谱分析等手段分析了涂层的微观结构, 研究了不同碳基体对SiC涂层结构和表面形貌的影响, 并初步对比考察了涂层的高温抗氧化性能. 结果表明: 制备的SiC涂层整体致密, 与基体结合良好, 但存在明显的结构差异. 石墨表面制得的SiC涂层呈梯度分布, 涂层主要由致密外层及过渡内层组成, 而C/C复合材料表面制得的SiC涂层仅由致密外层组成; 在1823 K的空气氧化氛围中, 与C/C复合材料SiC涂层试样相比, 石墨SiC涂层试样表现出更好的高温抗氧化性能, 经30 h氧化及7次循环热震实验后, 涂层试样的氧化失重率仅为0.182%.