以香豆素为母体的荧光探针的合成、离子识别及拟合计算研究

设计合成了含噻唑和腙结构的香豆素类钴离子荧光探针分子CCo,其结构用1HNMR和13CNMR进行了表征,考察了其光谱性能和电化学性能,并对其结构进行了拟合计算研究。CCo在常见金属离子(Cd2+、Co2+、Na+、Mn2+、Fe3+、Pb2+、Hg2+、Cu2+、Zn2+、Cu+、K+、Mg2+、Ag+、Ni2+、Cr3+)中能够选择性地识别Co2+。滴加Co2+后探针吸收光谱红移60 nm,荧光光谱蓝移75 nm。探针分子溶液在三电极系统及四丁基高氯酸胺作电解质下能用于Hg2+的检测。通过拟合计算进一步验证了探针吸收光谱峰值与实验值一致。     

四正丁基溴化铵催化合成香豆素的研究

以水杨醛和醋酸酐为原料,无水碳酸钾为催化剂来合成香豆素。研究了四正丁基溴化铵的活化作用、四正丁基溴化铵的用量、反应温度以及反应时间对香豆素产率的影响。结果表明：用四正丁基溴化铵作活化剂,香豆素的产率由原来的61.3%提高到84.3%。最佳反应条件：n（水杨醛）∶n（四正丁基溴化铵）=1∶0.04,反应温度160℃,反应时间4h,香豆素的产率可达85.1%。     

气相色谱-串联质谱法测定香精香料中的香豆素和黄樟素

采用乙醇超声提取,丙酸苯乙酯为内标进行定量,气相色谱-离子阱串联质谱法测定香精香料中香豆素和黄樟素的含量。选取香豆素的母离子和子离子分别为 m/z 146和 m/z 118,黄樟素的母离子和子离子分别为 m/z 162和 m/z 131,内标丙酸苯乙酯选择 m/z 104为定量离子。结果表明,香豆素和黄樟素在0.05~5 mg/L范围内呈良好线性关系（r>0.995）,方法的检测限(S/N=3)香豆素为0.004 mg/L、黄樟素为0.002 mg/L,加标回收率为90.0%～131.2%。该方法操作简单、快速、灵敏度高,适用于香精香料中香豆素和黄樟素的快速检测。     

7-羟基-4-甲基香豆素的合成研究

以间苯二酚和乙酰乙酸乙酯为原料,有机酸和固体超强酸作为催化剂,合成了7 -羟基-4-甲基香豆素.实验结果表明:间苯二酚、乙酰乙酸乙酯物质的量比为1:1,催化剂对甲苯磺酸用量为1.5％（物质的量百分比）,85℃下反应2h,产率较高为85.1％.     

New Coumarin Derivatives and Other Constituents from the Stem Bark of Zanthoxylum avicennae: Effects on Neutrophil Pro-Inflammatory Responses

Three new coumarin derivatives, 8-formylalloxanthoxyletin (1), avicennone (2), and (Z)-avicennone (3), have been isolated from the stem bark of Zanthoxylum avicennae (Z. avicennae), together with 15 known compounds (4–18). The structures of these new compounds were determined through spectroscopic and MS analyses. Compounds 1, 4, 9, 12, and 15 exhibited inhibition (half maximal inhibitory concentration (IC₅₀) values ≤7.65 µg/mL) of superoxide anion generation by human neutrophils in response to formyl-l-methionyl-l-leucyl-l-phenylalanine/cytochalasin B (fMLP/CB). Compounds 1, 2, 4, 8 and 9 inhibited fMLP/CB-induced elastase release with IC₅₀ values ≤8.17 µg/mL. This investigation reveals bioactive isolates (especially 1, 2, 4, 8, 9, 12 and 15) could be further developed as potential candidates for the treatment or prevention of various inflammatory diseases.     

Synthesis and in vitro Anticancer Activity of Zinc(II) Phthalocyanines Conjugated with Coumarin Derivatives for Dual Photodynamic and Chemotherapy

The combination of photodynamic therapy and chemotherapy is a promising strategy to overcome growing problems in contemporary medicine, such as low therapeutic efficacy and drug resistance. Four zinc(II) phthalocyanine–coumarin conjugates were synthesized and characterized. In these complexes, zinc(II) phthalocyanine was used as the photosensitizing unit, and a coumarin derivative was selected as the cytostatic moiety; the two components were linked via a tri(ethylene glycol) chain. These conjugates exhibit high photocytotoxicity against HepG2 human hepatocarcinoma cells, with low IC₅₀ values in the range of 0.014–0.044 μM . The high photodynamic activities of these conjugates are in accordance with their low aggregation tendency and high cellular uptake. One of these conjugates exhibits high photocytotoxicity and significantly higher chemocytotoxicity. The results clearly show that the two antitumor components in these conjugates work in a cooperative fashion. As shown by confocal microscopy, the conjugates can localize in the mitochondria and lysosomes, and one of the conjugates can also localize in the cell nuclei.     

Substituted imino and amino derivatives of 4-hydroxycoumarins as novel antioxidant,antibacterial and antifungal agents: Synthesis and in vitro assessments

A series of imino and amino derivatives of 4-hydroxycoumarins were synthesised and evaluated for antioxidant potential, through different in vitro models such as (DPPH) free radical-scavenging activity, linoleic acid emulsion model system, reducing power assay and phosphomolybdenum method. Also, antimicrobial activity of obtained coumarins was evaluated against 13 bacteria and eight fungi. All prepared compounds possessed good antioxidant activity and among them a p-nitrophenol derivative with IC₅₀ at 25.9 μM possessed radical-scavenging activity which was comparable to BHT. Observed data for antibacterial activity indicated strong activity of all tested amino derivatives, while imines showed better antifungal properties.     

基于香豆素-茚满二酮共轭物的硫醇比色探针

基于硫醇对α,β-不饱和双键的亲核加成,设计合成了一种香豆素-1,3-茚满二酮加合物的比色硫醇探针.硫醇与探针发生迈克尔加成,打断了分子内的共轭体系,阻止了香豆素向缺电子的1,3-茚满二酮基团的分子内电荷转移,引起了吸收光谱上的蓝移和溶液颜色的变化(由紫蓝色变为无色).研究结果表明:在DMSO-PBS buffer(0.01M,pH=7.4,9∶1,v/v)体系中,探针1能够用于半胱氨酸(Cys),同型半胱氨酸(Hcy)和还原型谷胱甘肽(GSH)的高选择性裸眼识别,Cys的检出限为6.9×10-7mol/L.     

香豆素衍生物基荧光型水性聚氨酯的制备及性能

采用“一步法”,以异佛尔酮二异氰酸酯(IPDI)、聚己二酸新戊二醇酯(PNGA)、二羟甲基丙酸(DMPA)为原料,用荧光剂7-氨基-4-三氟甲基香豆素(AFC)对预聚体进行封端,在IPDI、PNGA、DMPA、AFC摩尔比为1:0.45:0.30:0.15条件下,制备出一种具有长期贮存稳定性的新型荧光型水性聚氨酯乳液(WPU-AFC)。其结构通过FTIR和UV证实;同时系统地讨论了空间位阻,温度以及AFC含量等因素对乳液荧光性能的影响。结果表明,制备的WPU-AFC的荧光强度主要受“结构荧光猝灭”影响而不是“浓度荧光猝灭”影响;随着温度的升高,WPU-AFC和AFC的荧光强度均降低;相同条件下,WPU-AFC的荧光强度与AFC相比均有明显增强;此外,随着AFC分子中苯并吡喃环刚性结构在聚氨酯主链的引入,胶膜的热稳定性明显提高。     

SDS对香豆素在SB-16胶束增溶行为影响

为了模拟药物香豆素在十二烷基硫酸钠(SDS)和十六烷基磺基甜菜碱(SB-16)复配体系中的分配规律,采用分子动力学的方法模拟了香豆素分子(C-343)在SB-16水溶液中的增溶行为,在上述溶液的基础上又继续添加了表面活性剂SDS,并研究了SDS对香豆素在SB-16胶束增溶行为影响。研究结果表明,在298 K,101.3 kPa下的平衡条件下,C-343可以自发地增溶到SB-16球形胶束中。SDS分子的烷基尾链部分插入到SB-16球形胶束内部,并在SB-16表面形成一层疏水基团在内,亲水基团在外的SDS分子薄层。C-343分子在SDS分子的疏水作用和静电作用下,从SB-16胶束内部逐步迁移至SDS胶束的外层表面上。从理论证实了添加表面活性剂可以对药物分子在胶束溶液中的增溶与释放过程进行有效控制,以期为该类体系的试验研究提供理论依据。