应用2D NMR技术研究羌活苷的结构

从传统中药羌活中分离得到1个香豆素类化合物,应用1D和脉冲梯度场反相2D NMR检测技术 (gCOSY, gNOESY, gHMQC, gHMBC) 研究了其结构,鉴定为6′-O-(反式阿魏酰基)-紫花前胡苷,命名为羌活苷（Forbesoside）. 本文对其碳氢NMR信号进行了全归属. 对从伞形花内酯衍生化为7-去甲基软木花椒素、紫花前胡苷元和6′-O-(反式阿魏酰基)-紫花前胡苷的NMR信号变化规律以及糖残基NMR信号归属方法进行了讨论和总结.     

二苄基丁内酯型木脂素类化合物光谱规律分析

对不同结构类型的二苄基丁内酯型木脂素类化合物的光谱特征（IR，UV，MS，¹H NM R，¹³C NMR，CD）进行了归纳和总结，本项工作将有助于二苄基丁内酯型木脂 素类化合物的结构鉴定.     

鹅不食草挥发油的抗炎镇痛活性

探究鹅不食草挥发油(VOCM)中具有抗炎镇痛作用的主要化学成分。用水蒸气蒸馏法提取VOCM;用硅胶柱色谱法分离VOCM;以大鼠足趾肿胀程度和小鼠耳肿胀程度为指标观察VOCM及其分离组分的抗炎作用;用热板试验评价VOCM及其分离组分的镇痛作用;用GC-MS分析VOCM及其各分离组分的化学组成。共分离VOCM得到4个组分分别记为VOCM1、VOCM2、VOCM3和VOCM4;VOCM、VOCM2和VOCM3对蛋清致大鼠足趾肿胀、二甲苯致小鼠耳肿胀和热板致小鼠疼痛有显著抑制作用;用GC-MS分别从VOCM和VOCM1-VOCM4中鉴定出42、18、11、6和9种化学成分。VOCM2和VOCM3的化学成分为VOCM的抗炎镇痛主要有效成分。     

类呋喃香豆素的合成与DNA的结合及细胞毒性研究

呋喃香豆素类化合物无紫外光辅助照射时抗肿瘤活性低,为提高其正常情况下的抗肿瘤活性,依据“最小嵌入”假说对其进行结构改造。把呋喃香豆素结构中的呋喃环拆分出来,使其与香豆素由原来稠环相并的结合方式转变为通过化学键相连,得到合成简化的类呋喃香豆素。利用DNA熔解曲线、吸收光谱、荧光发射光谱和粘度测试考察了这些类呋喃香豆素与DNA的相互作用。综合DNA溶解曲线、光谱法和粘度测试的结果,推测除目标产物5b是一DNA嵌入剂外,其他化合物嵌入DNA能力下降,5a以部分嵌入方式与DNA结合,5c和5d是通过极为少见、鲜有报道的“桥型结构”与DNA相结合。利用“罗丹明B蛋白染色法”考察了目标化合物的体外细胞毒性,测试结果显示,与对照品补骨脂素相比这些化合物对肿瘤细胞体外生长抑制作用明显增强,并且非经典嵌入结合的化合物活性增强更明显。该研究拓展了“最小嵌入”假说的应用范围,同时为呋喃香豆素类化合物结构改造提供了依据。     

虎皮楠中2个黄酮苷的波谱学研究

研究了虎皮楠中的抗氧化活性成分.应用D101大孔吸附树脂、Sephadex LH-20及制备型高效液相色谱进行分离,应用波谱学(UV,ESI-MS,1H NMR,13C NMR,1H-1H COSY,HSQC,HMBC等)方法进行结构鉴定.分离得到1个二氢黄酮苷类化合物和1个黄酮苷类化合物,确定了1H NMR,13C NMR信号的全归属,化合物1鉴定为5,4′-二羟基二氢黄酮-7-O-α-L-鼠李糖(1→2)-β-D-葡萄糖苷,化合物2鉴定为7,4′-二羟基异黄酮-8-C-β-D-葡萄糖碳苷.     

香豆素类化合物与人血清白蛋白结合常数的QSPR研究

以21种香豆素类化合物的结构参数、拓扑指数为描述符,借助逐步回归方法建立了多个香豆素类分子结构同其与人血清白蛋白作用的结合常数之定量结构-结合常数关系(QSPR)回归模型,获得了比较满意的结果.模型的分析结果表明,结合作用与香豆素分子的能量、Z向偶极、疏水性有关,对香豆素类药物的设计与筛选具有一定的指导作用.     

含全氟烷基香豆素衍生物的简易合成及结构表征

以含全氟烷基香豆素为原料合成了一系列含全氟烷基香豆素亚胺类化合物，通过对该类化合物的IR、MS、¹H NMR、¹³C NMR的分析，归属了各NMR谱线，对相关化合物进行了结构确证，同时对该类化合物的光物理行为进行了初步研究.     

Dictamdiol的1H NMR 和13C NMR数据全归属

通过二维核磁技术,尤其是HMBC、HMQC和NOESY实验对一个从白鲜皮中分离得到的柠檬苦素类化合物-dictamdiol的¹H NMR 和¹³C NMR数据进行了全归属,并对文献中归属的错误进行了纠正.     

土荆芥果实挥发油成分及抗氧化能力

对土荆芥果实挥发油成分及抗氧化能力进行研究。采用质谱技术与Kovats指数相结合对土荆芥果实挥发油化学成分进行分离鉴定;利用清除1,1-二苯基苦基苯肼(DPPH)自由基的方法,评价土荆芥果实挥发油的抗氧化能力。土荆芥果实挥发油中分离鉴定了11种组分,其相对含量占挥发油总质量的98.94%,含量较高组分是α-异松油烯(60.44%),驱蛔素(15.57%),对-聚伞花素(12.76%)和α-松油烯(4.51%)。清除DPPH自由基IC50为6.9053mg.mL-1。土荆芥果实挥发油主要成分是萜烯类化合物;并具有一定的抗氧化能力。     

2D NMR对荠菜中的一个黄酮苷进行结构解析

对荠菜中分离得到的一个黄酮苷类化合物2″-O-α-L-阿拉伯糖异荭草苷进行了分离和结构解析,为荠菜进一步的开发利用提供依据. 利用溶剂提取法和大孔树脂色谱、聚酰胺色谱、Sephadex LH-20及高效液相半制备色谱手段进行提取分离,并通过理化性质和波谱分析鉴定了该化合物的结构,采用二维核磁共振（2D NMR）技术对其¹H和¹³C化学位移信号进行了全归属.     

Luminescent analysis of photoinduced detoxification of substituted furocoumarins

We have studied the effect of two detoxifying factors (UV radiation from different sources and humic substances) on the toxicity of alcoholic solutions of substituted coumarins. The change in the characteristics of the substituted coumarins was monitored spectrophotometrically. The toxicity of solutions of the substituted coumarins was monitored using a bioluminescence test system. We have shown that efficient detoxification of an alcoholic solution of coumarins occurs as a result of addition of humic substances. We have observed a dependence of the detoxification both on the structure of the studied compounds and on the characteristics of the source. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 228–232, March–April, 2008.     

新型吡唑并[3,4-d]嘧啶-4-酮类衍生物的结构表征和镇痛活性

本文以2-氰基-3-乙氧基丙烯酸乙酯与3,4-二甲基苯肼为原料,通过多步反应合成了三种新型吡唑并[3,4-d]嘧啶-4-酮类衍生物（A~C）,通过核磁共振（NMR,包括¹H NMR、¹³C NMR）和液相色谱-质谱联用（LC-MS）技术表征确证了其结构,并完整归属了三种化合物的¹H NMR数据．对所合成的化合物1-(3,4-二甲基苯基)-6-甲基-5-[3-(哌啶-1-基)丙氧基]-1,5-二氢-4H-吡唑并[3,4-d]嘧啶-4-酮（A）,通过小鼠脑部质谱成像和福尔马林实验进行了初步的体内镇痛活性评价,我们发现化合物A能透过血脑屏障,并产生显著且剂量依赖的镇痛活性．本研究为以吡唑并[3,4-d]嘧啶-4-酮为骨架的镇痛药物的研发提供了结构和体内活性的基础研究数据．     

4种香豆素类化合物的结构和荧光光谱

采用量子化学中密度泛函理论(DFT)的B3LYP方法在6-311G基组下对4种香豆紊类化合物进行了构型优化,经振动分析,未出现虚频率。在此基础上用单激发态组态相互作用(CIS)方法在相同水平下分别计算了4种化合物气相的荧光光谱,所得计算值与实验值基本吻合。     

6─或8─脂代─7─氧香豆素与二氢呋喃香豆素的NMR，MS研究

对从重齿毛当归（ＡｎｇｅｌｉｃａｐｕｂｅｓｃｅｎｓＭａｘｉｍｆ．ｂｉｓｅｒｒａｔａＳｈａｎｅｔＹｕａｎ）根及根茎中分得的１２种６－或８－脂代－７－氧－香豆素和８种二氢呋喃香豆素衍生物进行了１Ｈ和１３ＣＮＭＲ分析研究．结合文献．做出规律性总结．运用２ＤＮＭＲ技术．对文献中当归醇类化合物碳谱中的个别错误归属给予了纠正，并首次探讨了此类化合物的ＭＳ裂解途径．     

6-或8-脂代-7-氧香豆素与二氢呋喃香豆素的NMR,MS研究

对从重齿毛当归(Angelica pubescens Maxim f.biserrata Shan et Yuan)根及根茎中分得的12种6-或8-脂代-7-氧-香豆素和8种二氢呋喃香豆素衍生物进行了¹H和¹³C NMR分析研究,结合文献,做出规律性总结.运用2D NMR技术,对文献中当归醇类化合物碳谱中的个别错误归属给予了纠正,并首次探讨了此类化合物的MS裂解途径.     

The effect of 4-hydroxycoumarin and umbelliferone on DPPC bilayers. Ultrasound study

The organisation of two coumarins, 4-hydroxycoumarin and 7-hydroxy- coumarin (umbelliferone) in dipalmitolyphosphatidylcholine (DPPC) was examined in the study. Ultrasound absorption technique was applied to study the effect of the presence in DPPC membranes of one of the coumarines on the parameters of phase transition. 4-hydroxycoumarin was found to change both phase transition temperature of this transition, and cooperativity more than umbelliferone. Different influence of these examined compounds is associated with their different location in the DPPC membrane, what results from different distribution of amphyphilness in molecules of both compounds.     

Attenuation of morphine-induced analgesia in mice by exposure to magnetic resonance imaging: separate effects of the static, radiofrequency and time-varying magnetic fields

Exposure of adult male mice to a magnetic resonance imaging (MRI) procedure has been shown to abolish the nocturnal analgesic responses observed following treatment with morphine. The field component(s) responsible for this inhibitory effect were examined by exposing mice to either the static, time-varying or rf magnetic field components associated with an MRI procedure. In the middle of the night portion of their day-night cycle, mice were exposed for 23.2 min to one of the above field components, intraperitoneally injected with morphine sulphate (10 mg/kg) and then exposed to the field conditions for another 23.2 min, after which analgesic responses were determined. Analgesia was quantitated by determining the length of time mice were content to be on a hot surface (50 degrees C) before they showed discomfort by licking their paws. It was observed that the time-varying magnetic field completely abolished, the rf field significantly reduced, while the static field component (0.15 T) had no evident effect on morphine-induced analgesia. These results indicate that the time-varying, and to a lesser extent the rf, fields associated with the MRI procedure inhibit morphine-induced analgesia in mice. These data also raise the possibility that exposure in humans to some of the magnetic field components associated with MRI may have clinically relevant effects on the actions of narcotic drugs such as morphine.     

Synthesis,Characterization and Photophysical Studies of Tricoumarin-Pyridines

A series of novel tricoumarin-pyridines have been synthesized by the reaction of 4-formyl coumarins and substituted 3-acetylcoumarin with ammonium acetate for the application in organic electronics as well as fluorescent dyes. The structures of all new compounds were confirmed and characterized by IR, ¹H NMR and ESI-Mass analysis. All the important photo physical prerequisites for organic electronic application such as strong and broad optical absorption, thermal stability were determined for the synthesized molecules. Optical properties were studied by UV-Vis absorption and fluorescence spectroscopy. Optical band gaps of the tricoumarin-pyridines were found to be 2.72–3.10 eV as calculated from their onset absorption edge. The tricoumarin-pyridines were thermally stable up to 290–370 °C as determined by thermogravimetric analysis (TGA). Photophysical studies indicate the synthesized materials are promising candidates for organic electronic applications.     

两种新香豆素分子的热力学和光谱性质

使用密度泛函理论方法在B3LYP /6-31++G**理论水平对两种香豆素a和b分子的几何结构、光谱、热力学性质进行理论计算研究,并基于Tomasi的极化统一场模型(PCM)讨论溶剂效应。结果显示,香豆素a和b分子在气相中的最低能量吸收波长分别为352和355 nm,溶剂及其极性大小对香豆素a最低能量吸收波长影响很小,但在溶剂作用下香豆素b分子的最低能量吸收波长红移7-10 nm,溶剂的极性对该波长影响较小。298 K标准压力下香豆素a和b分子的气态标准摩尔生成焓 分别为-1373.171和-1310.805 kJ.mol-1,标准摩尔生成自由能 分别为-1064.043和-1035.849 kJ.mol-1,标准摩尔熵 分别为763.910和742.150 J.mol-1.K-1.