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。     

Epigenetic Manipulation Induces the Production of Coumarin‐Type Secondary Metabolite from Arthrobotrys foliicola

Pursuing epigenetic manipulation approach in fungi led to the isolation of an unusual coumarin metabolite from fungi. An addition of the histone deacetylase inhibitor, suberohydroxamic acid (SBHA), to the culture medium of Arthrobotrys foliicola induced production of the coumarin‐type secondary metabolite represented by a single intensive peak in the HPLC profile of the ethyl acetate extract. The compound which was identified as 4‐ethyl‐7‐hydroxy‐8‐methyl‐2H‐chromen‐2‐one ( 1 ) was isolated from nature for the first time. Moreover, the investigation on the remaining part of the HPLC profile led to the separation of 6‐ethyl‐2,4‐dihydroxy‐3‐methylbenzaldehyde ( 2 ) and ten 2,5‐diketopiperazine compounds ( 3 – 12 ). The structures of isolates were deduced by their mass and NMR spectroscopic data. The coumarin‐type secondary metabolite ( 1 ) with peculiar smell induced by epigenetic stimulation is found for the first time in the Arthrobotrys species and the family Orbiliaceae. We evaluated 1 for the cytotoxic, anti‐inflammatory, anti‐allergic and nematocidal activities, however, it was found inactive.     

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.