基于LC-MS/MS的咖啡酰奎宁酸异构体鉴别方法研究

该文对单咖啡酰奎宁酸和二咖啡酰奎宁酸的位置异构体分别进行液相色谱分析和不同碰撞能下的二级质谱分析,并对其质谱裂解规律进行了研究。结果发现,单咖啡酰奎宁酸的母离子377和子离子163在不同碰撞能下其强度发生显著变化,通过377/163的强度比值可区分其位置异构体。377/163比值大小依次为3-O-咖啡酰奎宁酸、4-O-咖啡酰奎宁酸、5-O-咖啡酰奎宁酸。二咖啡酰奎宁酸的母离子539和子离子377、163在不同碰撞能下其强度发生显著变化,通过539/377、377/163的强度比值可区分其位置异构体。539/377比值大小依次为4,5-O-二咖啡酰奎宁酸、3,4-O-二咖啡酰奎宁酸、3,5-O-二咖啡酰奎宁酸。377/163比值大小依次为3,5-O-二咖啡酰奎宁酸、4,5-O-二咖啡酰奎宁酸、3,4-O-二咖啡酰奎宁酸。基于Agilent Poroshell 120 SB-Aq C_(18)色谱柱,不同梯度下咖啡酰奎宁酸位置异构体的洗脱顺序均为5-O-咖啡酰奎宁酸、4-O-咖啡酰奎宁酸、3-O-咖啡酰奎宁酸、3,4-O-二咖啡酰奎宁酸、3,5-O-二咖啡酰奎宁酸和4,5-O-二咖啡酰奎宁酸。通过色谱保留特征和质谱裂解规律对金银花中咖啡酰奎宁酸的位置异构体实现了准确鉴别。     

基于多靶点分子对接筛选金银花治疗非酒精性脂肪肝成分研究

整合多靶点分子对接和反向靶点预测技术探究金银花治疗非酒精性脂肪肝(NAFLD)物质基础及潜在机制。借助TCMSP、ETCM数据库并挖掘文献收集金银花成分,以PPARα、PPARδ及FXR受体为靶标,运用分子对接筛选金银花中活性化合物,反向靶点预测活性化合物潜在靶点,构建蛋白互作网络并进行生物功能和通路富集。11种金银花活性成分对3个靶标的亲和力高于阳性对照,野漆树苷与PPARα的结合能力最强,3,5-二-O-咖啡酰奎宁酸甲酯与PPARδ和FXR结合能力最强。初步获得金银花治疗NAFLD主要成分为黄酮类和酚酸类,其中野漆树苷、3,4-二-O-咖啡酰奎宁酸甲酯、3,5-二-O-咖啡酰奎宁酸甲酯、异绿原酸B发挥主要作用。筛选出的成分主要通过PI3K-Akt、MAPK和胰岛素信号通路特异地作用于肝、脂肪细胞和肝癌细胞发挥治疗NAFLD的作用。本研究基于多靶点分子对接技术筛选金银花治疗NAFLD活性成分,提示金银花酚酸类成分具有进一步开发成药物的潜力,为后续进一步研究开发治疗NAFLD的创新药物提供一定的理论基础。     

反相高效液相色谱法同时测定咖啡豆中的6种酚酸类化合物

建立了同时测定咖啡豆中6种酚酸类化合物(咖啡酸、3-咖啡酰奎尼酸、4-咖啡酰奎尼酸、5-咖啡酰奎尼酸、3,5-二咖啡酰奎尼酸、4,5-二咖啡酰奎尼酸)的反相高效液相色谱测定方法。采用Kromasil C18柱(200 mm×4.6 mm, 5 μm),以乙腈和0.1%甲酸水溶液为流动相进行梯度洗脱,二极管阵列检测器检测,45 min内可对6种目标物进行同时检测,且各化合物都能达到基线分离。经测定,样品中6种酚酸类化合物的加标回收率为90.76%～104.73%,相对标准偏差为0.7%～3.9%。该法简便、快速、灵敏度高,适用于咖啡豆中6种酚酸类化合物的同时分析以及咖啡豆原料与制品的质量控制和综合评价。     

少花斑鸠菊中苯丙素类化合物的结构鉴定

利用DiaionHP-20、ToyopearlHW-40、MCI-GelCHP-20、SephadexLH-20、RP18、硅胶等柱色谱法对海南少花斑鸠菊(Vernonia chunii)中的化学成分进行分离纯化,根据理化性质和光谱方法(1HNMR、13CNMR、DEPT、1H-1HCOSY、HSQC、HMBC、ESI-MS、IR)鉴定化合物的结构。从中分离鉴定了7个苯丙素类化合物:3,2′-二-(3,4-二羟基苯基)-5,3′-二羟基-6,7-骈二氢吡喃-3,4-二氢苯骈吡喃酮(Ⅰ)、1,3-二咖啡酰基奎宁酸(Ⅱ)、1,5-二咖啡酰基奎宁酸(Ⅲ)、1-(3,4-二甲氧基苯基)-2,3-二羟甲基-6,7-二甲氧基-1,2,3,4-四氢萘(Ⅳ)、绿原酸(Ⅴ)、咖啡酸(Ⅵ)、阿魏酸(Ⅶ)。其中Ⅰ为新化合物,另外6个化合物为首次从该植物中分离得到。     

高效液相色谱法测定兰紫解毒颗粒中5种主要成分

建立高效液相色谱法同时测定兰紫解毒颗粒中绿原酸、3,5-二-O-咖啡酰奎宁酸、苦参碱、氧化苦参碱和(R,S)-告依春含量的方法。取0.1 g兰紫解毒颗粒样品,用体积分数为75%的甲醇溶液超声提取30 min,取适量样品溶液上机测定;采用ACQUITY UPLCHSS T3 C₁₈柱(150 mm×2.1 mm,1.8μm)作为分析柱,柱温为25℃,以乙腈-0.1%磷酸水溶液作为流动相梯度洗脱,洗脱流量为0.25 mL/min,进样体积为1μL。绿原酸、3,5-二-O-咖啡酰奎宁酸、苦参碱、氧化苦参碱和(R,S)-告依春的质量浓度在0.407 6～42.529 2μg/mL范围内与色谱峰面积线性关系良好,相关系数为0.999 6～0.999 8,方法检出限为0.001～0.014μg/mL。样品平均加标回收率为97.85%～100.35%,测定结果的相对标准偏差为1.05%～2.93%(n=6)。该方法简单、高效、准确、稳定,可同时测定兰紫解毒颗粒中5种主要成分的含量。     

藤黄化学成分的研究

传统中药藤黄通过各种色谱方法分离纯化, 得到15个化合物, 根据其理化性质和光谱方法鉴定其结构分别为: 2α-羟基-3β-乙酰氧基白桦酯酸(1), 10α-羟基表藤黄酸(2), 藤黄酸(3), 异藤黄酸(4), gambogin (5), gambogoic acid B (6), desoxymorellin (7), isomorellin (8), gambogenic acid (9), isogambogenin (10), gambogellic acid (11), desoxygambogenin (12), morellic acid (13), isomorellic acid (14), 30-hydroxygambogic acid (15). 其中化合物1和2为新化合物.     

绿原酸的导数极谱法测定

绿原酸的导数极谱法测定李自林郑筱梅（重庆师范学院化学系４０００４７）王琰（重庆建筑大学基础科学系）关键词绿原酸导数极谱法中图分类号Ｏ６５７．１４绿原酸即３－咖啡酰奎宁酸，是咖啡酸和奎宁酸形成的酯。它是金银花的主要成分，具有清热解毒，抗菌消炎的作用。除...     

高效液相色谱同时测定注射用双黄连(冻干)中六种活性成分含量

建立了高效液相色谱(HPLC)同时测定注射用双黄连(冻干)中绿原酸、咖啡酸、4,5-二咖啡酰奎宁酸、黄芩苷、黄芩素和汉黄芩素的含量的方法。采用Agilent TC-C_(18)色谱柱(250×4.6 mm,5mm),以乙腈―0.25%(wt)冰醋酸为流动相,梯度洗脱,流速1.0 m L/min,检测波长350 nm,柱温35℃。结果表明,六种成分基本分离,线性关系良好,平均回收率在99.72%~101.56%之间。本方法准确、简便、重现性好,可以实现注射用双黄连(冻干)多成分质量控制。     

油酸酰胺基季铵盐Gemini表面活性剂的制备及性能

以油酸酰胺丙基二甲基胺、1,3-二氯-2-丙醇、1,4-二溴-2-丁烯和1,4-二溴丁烷为原料,分别合成了3种不同连接基团的油酸酰胺基季铵盐阳离子Gemini表面活性剂GS-1、GS-2和GS-3.通过傅里叶变换红外光谱(FT-IR)和核磁共振波谱(1 H NMR)对其结构进行表征,并对其Krafft温度、表面活性、乳...     

N-芳基马来海枞酸单甲酯二酰亚胺位阻异构化反应及其动力学特性

在合成松香基手性试剂(4a~4f)的过程中,首次发现N-(1-萘基)-马来海枞酸二酰亚胺(4f)的位阻异构现象,而与其结构类似的N-苯基-马来海枞酸二酰亚胺(4a)、N-(2-羧基苯基)-甲酯化马来海松酸二酰亚胺(4b)、N-(2-硝基苯基)-甲酯化马来海松酸二酰亚胺(4c)、N-(2-氯苯基)-甲酯化马来海松酸二酰亚胺(4d)和N-[1-(2-氨基)-苯基]-甲酯化马来海松酸二酰亚胺(4e)则没有该位阻异构现象.化合物4a~4f的结构通过核磁共振、质谱和红外光谱等方法进行了表征.采用变温条件下的1H NMR谱图研究了化合物4f的位阻异构化动力学特性.     

苯并二噁唑系列聚合物的合成及表征

以4,6-二氨基-1,3-苯二酚盐酸盐为原料,分别和对苯二甲酸、1,4-萘二甲酸、2,6-萘二甲酸、2,5-噻吩二甲酸、4,4-′(1,2-二苯基乙烯)二甲酸在多聚磷酸介质中反应,合成单环的聚(1,4-亚苯基)苯并二噁唑(PBO)、稠环的聚(1,4-亚萘基)苯并二噁唑(1,4-PNBO)和聚(2,6-亚萘基)苯并二噁唑(2,6-PNBO)、杂环的聚(2,5-亚噻吩基)苯并二噁唑(PTBO)及含有两个苯环的聚-4,4′-亚(1,2-二苯乙烯基)苯并二噁唑(4,4′-PDPEBO).采用傅立叶红外光谱、热重分析、元素分析、特性黏数分析对系列聚合物进行了表征.研究结果表明PBO、1,4-PNBO、4,4-′PDPEBO、2,6-PNBO和PTBO 5种聚合物的耐热性能依次降低,特性黏数依次为25.40、16.76、20.63、15.38和14.63 dL/g.     

丁酸氯维地平降解杂质的合成

以4-(2,3-二氯苯基)-1,4-二氢-2,6-二甲基-3,5-吡啶二羧酸(2-氰基乙基)（甲基）酯(5)为起始原料,合成了丁酸氯维地平的5种降解杂质：4-(2,3-二氯苯基)-1,4-二氢-2,6-二甲基-3,5-吡啶二羧酸单甲酯(A), 4-(2,3-二氯苯基)-1,4-二氢-2,6-二甲基-3-吡啶羧酸甲酯(B), 4-(2,3-二氯苯基)-2,6-二甲基-3,5-吡啶二羧酸单甲酯(C), 4-(2,3-二氯苯基)-2,6-二甲基-3,5-吡啶二羧酸（丁酰氧基甲基）（甲基）酯(D)和4-(2,3-二氯苯基)-2,6-二甲基-3-吡啶羧酸甲酯(E)。其中A由5水解制得;B由A脱羧制得;C由5氧化后再经水解制得;D由C和丁酸氯甲酯缩合制得;E由C脱羧制得,化合物结构经¹H NMR和MS（ESI）确证。     

Synthesis of 1,4-dihydro-2-methyl-4-oxo-3-quinolineglyoxylic acid and related compounds

The synthesis of 1,4-dihydro-1-methoxy or ethyl -2-methyl-4-oxo-3-quinolineglyoxylic acid derivatives are described. α-Acetoxy-1,4-dihydro-1-hydroxy-2-methyl-4-oxo-3-quinolineacetic acid esters ( 7a, 7a ), which are key intermediates, were prepared by catalytic hydrogenation of 2-acetoxy-3-acetyl-4-hydroxy-4-(2-nitrophenyl) crotonic acid lactone ( 6 ) in methanol or ethanol.     

Solid-phase syntheses of heterocycles containing the 2-aminothiophenol moiety

Efficient and general procedures have been developed for the solid-phase preparation of substituted benzothiazoles (1), 3, 4-dihydro-1,4-benzothiazines (2), 3,4-dihydro-1,4-benzothiazine-1, 1-dioxides (3), 3,4-dihydro-3-oxo-1,4-benzothiazines (4), and 3, 4-dihydro-3-oxo-1,4-benzothiazine-1,1-dioxides (5). All five classes of compounds were prepared from a common intermediate, resin-bound 2-amino-4-carboxythiophenol, in a minimal number of steps. This intermediate was generated by (i) coupling 4-fluoro-3-nitrobenzoic acid onto Wang resin, or onto an amino acid bound to the resin, (ii) substitution of the aryl fluoride with a protected thiol, (iii) reduction of the nitro group, and (iv) removal of sulfur protection. Reaction with the appropriate substrates and reagents to effect cyclization gave the substituted core structures, which were modified further to introduce additional point(s) of diversity. Following cleavages from the solid support, the compounds were obtained in high initial purities and good isolated yields after purification.     

Development of a solid-phase extraction method for simultaneous extraction of adipic acid, succinic acid and 1,4-butanediol formed during hydrolysis of poly(butylene adipate) and poly(butylene succinate)

A solid-phase extraction (SPE) method was developed for the simultaneous extraction of dicarboxylic acids and diols formed during hydrolysis of poly(butylene succinate), PBS, and poly(butylene adipate), PBA. Four commercial non-polar SPE columns, three silica based: C8, C18, C18 (EC), and one resin based: ENV+, were tested for the extraction of succinic acid, adipic acid and 1,4-butanediol, the expected final hydrolysis products of PBS and PBA. ENV+ resin was chosen as a solid-phase, because it displayed the best extraction efficiency for 1,4-butanediol and succinic acid. Linear range for the extracted analytes was 1-500 ng/microl for adipic acid and 2-500 ng/microl for 1,4-butanediol and succinic acid. Detection and quantification limits for the analytes were between 1-2 and 2-7 ng/microl, respectively, and relative standard deviations were between 3 and 7%. Good repeatability and low detection limits made the developed SPE method and subsequent gas chromatography-mass spectrometry (GC-MS) analysis a sensitive tool for identification and quantification of hydrolysis products at early stages of degradation.     

Synthesis of 3-substituted 2-oxo-1,4-thiazines and evaluation of their protective effect against endotoxin shock in mouse.

5-Methyl-2,3-dioxo-2H,4H-1,4-thiazine (7) was obtained by the oxidation of 5-methyl-2H-1,4-thiazin-3(4H)-one (5) with m-chloroperbenzoic acid in MeOH, followed by acid hydrolysis of the resulting 2,2-dimethoxy-1,4-thiazine (6). 3-Chloro-2-oxo-1,4-thiazine (10), which was obtained from 7 by heating with phosphorous oxychloride, reacted with various nucleophiles to give 3-substituted 2-oxo-1,4-thiazines (11a--y). Some of these 2-oxo-1,4-thiazines, 11a--b, e, o and r--s, showed a protective effect against endotoxin shock in D-galactosamine-sensitized mice.     

Newbouldiaquinone and newbouldiamide: a new naphthoquinone-anthraquinone coupled pigment and a new ceramide from Newbouldia laevis

Newbouldiaquinone (1), a new naphthoquinone-anthraquinone coupled pigment and a new ceramide named newbouldiamide (2), have been isolated from Newbouldia laevis, besides the known compounds lapachol (3), canthic acid, oleanolic acid, 2-methyl-9,10-anthracenedione, 2-acetylfuro-1,4-naphthoquinone, 2,3-dimethoxy-1,4-benzoquinone, 2-(4-hydroxyphenyl)ethyl triacontanoate, beta-sitosterol and beta-sitosterol glucopyranoside. The structure elucidations of the isolated new compounds were performed on the basis of spectroscopic and chemical evidence. Preliminary studies showed that 1 is moderately antibacterial against Gram-positive Bacillus megaterium and that 3 has moderate herbicidal and antibacterial activities.     

具有类CsCl拓扑的CoⅡ配位聚合物的合成，结构与磁性

本工作在溶剂热条件下合成了2例以二核或三核CoⅡ为节点,具有八连接类CsCl拓扑的配位聚合物:[Co(na)(ina)]和[Co3(na)4(1,4-chdc)](Hna=nicotinic acid,Hina=isonicotinic acid,1,4-H2chdc=eyclohexane-1,4-dicarboxylic acid).磁性研究表明,2个配合物均呈现反铁磁行为.     

Diversity in magnetic properties of 3D isomorphous networks of Co(II) and Mn(II) constructed by napthalene-1,4-dicarboxylate

Two novel 3D isomorphous organic-inorganic hybrid frameworks, [M(1,4-napdc)]n ( M = Co(II), and Mn(II), ; 1,4-napdcH2 = napthalene-1,4-dicarboxylic acid) have been hydrothermally synthesized and structurally characterized, and the magnetic results exhibit metamagnetic behaviour (TC = 5.5 K), and a weak antiferromagnetic interaction, which are structurally correlated.     

Crystal engineering using anilic acids and dipyridyl compounds through a new supramolecular synthon

The anilic acids, 2,5-dihydroxy-1,4-benzoquinone (1a), 2,5-dibromo-3,6-dihydroxy-1,4-benzoquinone (bromanilic acid; 1b), 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid; 1c), and 2,5-dicyano-3,6-dihydroxy-1,4-benzoquinone (cyananilic acid; 1d), were cocrystallized with rigid organic ligands containing two pyridine rings, 2,4-bipyridine (2a), 4,4'-bipyridine (2b), 1,2-bis(2-pyridyl)ethylene (3a), 1,2-bis(4-pyridyl)ethylene (3b), 2,2'-dipyridylacetylene (4a), 3,3'-dipyridylacetylene (4b), and 4,4'-dipyridylacetylene (4c). Fourteen complexes 5-18 were obtained as single crystals, and their crystal structures were successfully determined by X-ray analysis. All complexes except those with 2a are 1:1 and are composed of an infinite linear or zigzag tape structure, the formation of which is ascribed to intermolecular O-H...N, N(+)-H...O, or N(+)-H...O(-) hydrogen bonds or a combination of these between the anilic acids and the dipyridyl compounds. In the complexes 5 and 6, no infinite tape structure is observed although the molecular units connected by a similar hydrogen-bonding pattern are formed. For the 1:1 complexes, we have found two types of stacking arrangements, segregated stacks (7, 9, 12-15, 18) and alternated ones (8, 10, 11, 16, 17). In the complexes of 1c with the series of dipyridylacetylenes 4 (14, 15, 17), the neutral, dication, and monocaction states are formed depending on the nitrogen positions, which can be attributed to the different basicity of the pyridyl groups.