羊耳菊中咖啡酰基奎宁酸类化学成分研究北大核心CSCD

采用正相硅胶色谱柱、Sephadex LH-20以及制备HPLC等色谱方法对羊耳菊进行分离纯化,并通过理化常数和波谱数据鉴定其化学结构。深入研究羊耳菊干燥全草的咖啡酰基奎宁酸类化学成分。从羊耳菊中分离得到8个咖啡酰基奎宁酸类化合物,分别为1,5-O-二咖啡酰基奎宁酸（1）、1,3,5-O-三咖啡酰基奎宁酸（2）、3,5-O-二咖啡酰基奎宁酸甲酯（3）、3,4-O-二咖啡酰基奎宁酸甲酯（4）、3,4-O-二咖啡酰基奎宁酸乙酯（5）、4,5-O-二咖啡酰基奎宁酸乙酯（6）、3,5-O-二咖啡酰基奎宁酸（7）、3,4-O-二咖啡酰基奎宁酸（8）。化合物1-3为从该植物中首次分离得到,4-6从该属植物中首次分离得到。     

蹄叶橐吾根的化学成分研究

从蹄叶橐吾（Ligularia fischeri）的根中分离得到13个化合物,通过波谱学等方法鉴定为2-hydrox-platyphyllide（1）,liguhodgsonal（2）,nsujapone（3）,6’-亚油酰基田-胡萝卜苷（4）,Luped（5）,6,7-二羟基香豆素（6）,3-谷甾醇（7）,胡萝卜苷（8）,（25,3S,4R,12E）-N-[2’-（R）-羟基二十二碳酰基]-1,3,4-三羟基-2-氨基-二十碳-12-烯（9）,单硬脂酸甘油酯（10）,α-羟基二十四烷酸（11）,1,3-二棕榈酸甘油酯（12）,二十七烷醇（13）。其中化合物1—6为首次从该种植物中分离得到。     

蜘蛛香化学成分的研究北大核心CSCD

研究蜘蛛香Valerianajatamansi的化学成分,为选择控制其质量的化学成分提供依据。应用色谱技术分离纯化得到9个化合物,根据化合物的理化性质和波谱数据鉴定其分别为橙皮苷（1）,5-O-咖啡酰基奎宁酸（2）,3,4-O-二咖啡酰基奎宁酸（3）,4,5-O-二咖啡酰基奎宁酸（4）,3-O-咖啡酰基奎宁酸甲酯（5）,3-O-咖啡酰基奎宁酸（6）,原儿茶酸（7）,咖啡酸（8）,松脂素（9）。其中化合物2,7为首次从该种植物中分离得到,化合物3—5为首次从该属植物中分离得到。     

魔芋中脑苷脂类化合物的分离与结构鉴定

首次从魔芋中分离出由特殊羟基脂肪酰基构成的脑苷脂类化合物.通过光谱和化学方法鉴定为1-O-β-D-吡喃葡萄糖-(2S,3R,4E,8Z)-2-(2'R-羟基脂肪酰基)-正十八碳-4,8-二烯鞘胺醇.其中羟基脂肪酰基主要由2-羟基-正十六酰基,2-羟基-正十八酰基,2-羟基-正二十酰基,2-羟基-正二十二酰基,2-羟基-正二十四酰基组成.     

滇南红厚壳的化学成分

从滇南红厚壳（Calophyllum polyanthum Wall.et Choisy)的果实乙醇提取物中分离得到2个新化合物－滇南红厚壳内酯A（calopolyanolide A,1),滇南红厚壳内酯B（calopolyanolide B,2)以及3个已知化合物calanolide E2(3),voleneol(4)和没食子酸（gallic acid,5)。经波谱学鉴定了2个新化合物的结构分别为：6,6－二甲基－12α-(2α,3α-H）-12α-（2－甲基－3－羟基丁酰基）－8b－羟基－4－苯基－吡喃并－二氢香豆素;6,6－二甲基－12a-(2α,3β-H）-12a-(2-甲基－3－羟基丁酰基）－8b－羟基－4－苯基－吡喃并－二氢香豆素。     

朱红栓菌提取物抗氧化、抗肿瘤活性评价及相关化学成分分析

采用石油醚、乙酸乙酯、乙醇浸提朱红栓菌 Trametes cinnabarina 子实体干粉,得到不同极性提取物;采用清除DPPH 自由基、羟自由基、超氧阴离子自由基能力,测定提取物的体外抗氧化活性;MTT法检测提取物对人肝癌细胞株HepG2细胞增殖的抑制作用。结果表明,朱红栓菌石油醚、乙酸乙酯、乙醇提取物均具有一定的抗氧化、抗肿瘤活性;各提取物在浓度为4-5mg/mL时,对DPPH自由基、羟自由基和超氧阴离子自由基清除能力大小依次为乙酸乙酯提取物>乙醇提取物>石油醚提取物;乙酸乙酯提取物对3种自由基的最高清除率分别为60.23%、74.49%、63.84%。各提取物对人肝癌细胞株HepG2细胞增殖抑制作用大小依次为乙酸乙酯提取物>乙醇提取物>石油醚提取物;乙酸乙酯提取物的抑制率最高达55.93%。采用硅胶和凝胶等柱色谱方法结合核磁、波谱和质谱等技术对乙酸乙酯提取物的化学组分进行分析,共分离纯化出11种化合物,分别鉴定为：麦角甾醇（1）,邻苯二甲酸二丁酯（2）,对羟基苯甲酸甲酯（3）,麦角甾-7,22,二烯-3-酮（4）,1-[(12E,16E)-12,16-二十碳二烯酰基]-2-[(E,E)-7,11-十八碳二烯酰基]-3-硬脂酰基甘油（5）,cinnabarin（6）,过氧麦角甾醇（7）,尿嘧啶（8）,甘露醇（9）,腺嘌呤核苷（10）,豆甾-7,22-二烯-3β,5α,6β-三醇（11）。除化合物6外均为首次从朱红栓菌子实体中分离得到。研究结果为开发利用朱红栓菌子实体提供了科学依据。     

毛头鬼伞子实体化学成分及抗糖尿病活性初探

从毛头鬼伞子实体中萃取得到乙醇、乙酸乙酯、石油醚3种有机提取物,采用α-葡萄糖苷酶活性抑制实验对3种有机提取物的抗糖尿病活性进行评价,结果显示,乙酸乙酯提取物对α-葡萄糖苷酶有较强的抑制活性。采用柱层析技术从乙酸乙酯提取物中分离纯化出10种化合物,经核磁等方法鉴定为：（1）顺,顺-9,12-十八(碳)二烯酸;（2）顺式-9-十八烯酸;（3）(22E,24R)-麦角甾烷-5,7,22-三烯-3β醇;（4）3β-5α-6α-22E-麦角甾-7,22-双烯-3,5,6-三醇-6-亚油酸酯;（5）3β-5α-6α-22E-麦角甾-7,22-双烯-3,5,6-三醇-6-油酸酯;（6）邻苯二甲酸二异丁酯;（7）对羟基苯乙醇;（8）4-羟基苯乙基乙酸酯;（9）3-(4-羟基-3-甲氧苯基)败脂酸;（10）N-反式-3,4亚甲二氧基肉桂酰基-3-甲氧基酪胺。对分离化合物的α-葡萄糖苷酶活性抑制实验结果显示,N-反式-3,4亚甲二氧基肉桂酰基-3-甲氧基酪胺对α-葡萄糖苷酶具有较强的抑制活性,其IC₅₀值为4.17mg/mL。     

恶臭假单胞菌SJTE-1中转化17β-雌二醇的3-酰基-ACP还原酶的鉴定与功能研究

[目的]假单胞菌SJTE-1可高效转化17β-雌二醇,但是催化该转化的酶尚不清楚。本文鉴定了该菌株的一个新的3-酮酰基-ACP还原酶（ANI01589.1）,并对其进行了功能研究。[方法]首先,我们克隆了该3-酰基-ACP还原酶的编码基因,在大肠杆菌BL21（DE3）菌株中进行了异源表达;利用金属离子亲和层析法,纯化获得了重组蛋白。体外检测了重组蛋白的活性与酶学性质,并利用高效液相色谱法（HPLC）测定了该酶的催化产物。[结果]3-酮酰基-ACP还原酶可被17β-雌二醇诱导表达,重组蛋白纯化量可达19.6 mg/L。蛋白序列比对结果表明,该蛋白包含短链脱氢酶/还原酶（SDR）的2个共有区域和多个保守残基。该酶以NAD⁺为辅助因子,将17β-雌二醇转化为雌酮;其K_m值为0.071 mmol/L,k_cat值为2.4±0.06/s^-1,5 min内可转化超过95.8%的雌二醇。该酶的最佳反应温度为42℃,最佳pH为8.0。不同二价离子对该酶的活性影响不同,Mg²⁺和Mn²⁺可增强其酶活性。[结论]这一假单胞菌SJTE-1来源的3-酮酰基-ACP还原酶可高效催化17β-雌二醇的转化,该酶可能在该菌株的雌激素代谢过程中起到重要作用。     

低浓度内皮素-1对活性氧抑制肺表面活性物质脂质合成的保护

在离体肺组织培养模型上观察低浓度（1～100pmol/L）内皮素-1（endothelin-1,ET-1）对活性氧所致肺表面活性物质（pulmonary surfactant,PS）脂质合成障碍及PS脂质主要组分磷脂酰胆碱合成限速酶CTP;磷酸胆碱二胞苷酰基转移酶（pulmonary surfactant,PS）脂质合成障碍及PS脂质主要组分磷脂酰胆碱合成限速酶CTP;磷酸胆碱二胞苷酰基转移酶（phosphorylchoine cytidylyltransferase,CCT）活性的影响。结果显示：（1）黄嘌呤-黄嘌呤氧化酶超氧阴离子生成系统呈剂量依赖性地降低肺组织^3H-胆碱的掺入量;（2）ET-1可减轻活性氧所致^3H-胆碱掺入量的减少和肺组织丙二醛含量的增高;但对肺组织超氧化物歧化酶、过氧化氢酶及总抗氧化能力无明显影响;（3）ET-1可分别提高和降低肺组织细胞微粒体和细胞浆的CCT活性,并可减轻活性氧所致肺微粒体CCT活性的降低。结果表明,低浓度ET-1具有保护肺微粒体的CCT活性、减轻氧化性肺损伤所致PS合成障碍的作用,其保护机制并非通过影响肺组织内部抗氧化系统而实现。     

酰基供体结构对褶皱念珠茵脂肪酶（CRL）催化芳香仲醇动力学拆分立体选择性的影响

研究仲醇的酶催化动力学拆分机制,发现酰基供体的结构是影响酶催化动力学拆分选择性的一个重要因素。通过实验发现了一类用于仲醇动力学拆分（KR）的优秀酰基供体——长链有机酸的对氯苯酚酯,并将这种酰基供体成功用于褶皱念珠菌脂肪酶（CRL）催化的仲醇动力学拆分过程。在1-苯乙醇的动力学拆分（KR）过程中,随着对氯苯酚有机酸酯供体中酰基部分碳原子数的增加,产物的对映体过量值（e．e.p值）也在不断地提高。当碳原子数≥5,转化率达到50％时,产物的叫．。值仍能保持大于99％。这样的规律也适用于其他的仲醇拆分过程,当选择对氯苯酚戊酸酯作为酰基供体用于其他仲醇的动力学拆分过程时,可以实现仲醇的高效拆分,反应6h转化率达到50％,产物的对映体过量值e．e．p为100％。     

A new flavanone sulfonate and other phenolic compounds from Fumana montana

The phytochemical study of ethyl acetate and n-butanol extracts of Fumana montana Pomel yielded a new flavanone sulfonate named naringenin-8-sulfonate (1), in addition to nine known compounds including two flavonols; tellimoside (2) and isoquercetrin (3), two flavanols; (−)-gallocatechin (4) and (−)-epigallocatechin (5), one benzophenone glucoside; iriflophenone-2-O-β-glucoside (6), one phenolic glucoside; (−)-rhododendrin (7) and three benzoic acid derivatives; p-hydroxybenzoic acid (8), gallic acid (9) and methyl gallate (10). It should be noted that this is the first report of compounds (2) and (6) in Cistaceae family. The structures of the isolated compounds were determined by comprehensive 1D and 2D NMR analysis, mass spectrometry, IR and by comparison with literature data.     

A new neolignan glucoside from hairy roots of Cichorium intybus

A new neolignan glucoside was isolated from hairy roots of Cichorium intybus. Its structure was determined as (7S, 8R)-3′-demethyl-dehydrodiconiferyl alcohol-3′-O-β-glucopyranoside based on a combination of 1D and 2D NMR techniques and CD data. In addition, further water soluble constituents, including four known phenolic compounds and one known sesquiterpene lactone glucoside, were isolated from the same source.     

Methyl gallate and its 3-glucoside promote rooting in bean cuttings

Methyl gallate stimulated adventitious root formation in cuttings of bean (Phaseolus vulgaris L.). This polyphenol was quickly metabolized into 3-glucosyl methyl gallate to such an extent that 4 h after application no methyl gallate was detected. The isolated glucoside when supplied exogenously at 0.5 mM also enhanced rooting; the effect was 2-fold greater than that of methyl gallate. The glucoside persisted in the cuttings for 72 h after treatment. Because methyl gallate is rapidly transformed to a stable glucoside, we suggest that the root stimulation effect could be ascribed to its glucoside.     

Two New Phenolic Glycosides from Viburnum cylindricum ( Caprifoliaceae)

从水红木( Viburnum cylindricum ) 植物中分离出2 个新化合物, 1- phloroglucinyl- ( 6-methybutyryl )-B-D- glucopyranoside命名为cylindrin A ( 1) , 1- [ 4- ( 3- hydroxy-l propyl ) ]- pyrocatechol- ( 6-methybutyryl )-B-D- glucopyranoside, 命名为cylindrin B ( 2) , 以及7 个已知化合物tachioside ( 3) , syingic acid-4-B-D- glucopyran oside ( 4) , 1-B-D-glucopyranosyloxy-3-methoxy-5- hydroxybenzene ( 5 ) , 4- hydroxy- 3-methoxypheno-l 1-O-B-D- glucoside ( 6 ) , 4-hydroxy- 2, 6- dimethoxypheno-
l 1-O-B-D- glucoside ( 7) , phlorogluc ino-l 1-O-B-D-glucoside ( 8 ) , 1-B-D- glucosyloxy-2- ( 3-methoxy- 4- hydroxyphenyl) propane- 1, 3- diol ( 9) . 它们的结构经波谱方法得到鉴定。3~ 9 为首次从该种植物中分离得到。     

苏铁蕨的化学成分

从蕨类植物苏铁蕨(Brainea insignis)中分离得到1个新的苯乙烯基吡喃酮苷,利用波谱技术鉴定了其结构。此外,还得到了1个已知的苯乙烯基吡喃酮苷和4个其它已知化合物。同时,还测定了分离得到的两个苯乙烯基吡喃酮苷化合物的DPPH自由基清除活性。     

仙茅苷丙——仙茅根茎的新酚苷成分

从仙茅(CurculigoorchioidesGaertn.)根茎中分离得到4个化合物,分别为curculigoside(1)、curculigosideB(2)、curculigosideC(3)和2,6-dimethoxylbenzoicacid(4)。其中,化合物3为一个新的酚苷类成分,命名为仙毛苷丙,用现代波谱方法(1H-NMR、13C-NMR、2D-NMR和ESI-MS)鉴定其化学结构为5-羟基-2-O-b-D-吡喃葡萄糖基苄基-3'-羟基-2',6'-二甲氧基苯甲酸酯。     

Synthesis and antiviral activity of substituted quercetins

Influenza viruses are important pathogens that cause respiratory infections in humans and animals. In addition to vaccination, antiviral drugs against influenza virus play a significant role in controlling viral infections by reducing disease progression and virus transmission. Plant derived polyphenols are associated with antioxidant activity, anti-carcinogenic, and cardio- and neuro-protective actions. Some polyphenols, such as resveratrol and epigallocatechin gallate (EGCG), showed significant anti-influenza activity in vitro and/or in vivo. Recently we showed that quercetin and isoquercetin (quercetin-3-β-d-glucoside), a glucoside form of quercetin, significantly reduced the replication of influenza viruses in vitro and in vivo (isoquercetin). The antiviral effects of isoquercetin were greater than that of quercetin with lower IC(50) values and higher in vitro therapeutic index. Thus, we investigated the synthesis and antiviral activities of various quercetin derivatives with substitution of C3, C3', and C5 hydroxyl functions with various phenolic ester, alkoxy, and aminoalkoxy moieties. Among newly synthesized compounds, quercetin-3-gallate which is structurally related to EGCG showed comparable antiviral activity against influenza virus (porcine H1N1 strain) to that of EGCG with improved in vitro therapeutic index.     

Iridoids,monoterpenoid glucoindole alkaloids and flavonoids from Vinca major

A new secoiridoid glucoside, vinmajoroside (1), was isolated from the leaves of Vinca major L. along with 11 known compounds belonging to the secoiridoid ((7α)-7-O-methylmorroniside, 2), iridoid (loganin, loganic acid and 7-O-p-coumaroylloganin), monoterpenoid glucoindole alkaloid (5 (S)-5-carboxyvincoside and strictosamide), flavonoid (rutin, kaempferol 3-O-rutinoside and robinin), lignan (syringaresinol 4-O-β-glucopyranoside) and phenolic acid (chlorogenic acid) groups. The structure elucidation of the isolates was accomplished by extensive 1D and 2D-NMR experiments as well as ESI-MS. Secoiridoids and lignan were encountered for the first time in the genus Vinca.     

Potentiometric and (1)H NMR studies of complexation of Al(3+) with (-)-epigallocatechin gallate, a major active constituent of green tea.

The acid dissociation of (-)-epigallocatechin gallate (abbreviated as egcg) and its complexation with Al(3+) were studied by potentiometric titrations, and were compared with those of (-)-epicatechin (ec) and (-)-epigallocatechin (egc). In Al(3+)-ec and Al(3+)-egc reaction systems, [Al(LH(-2))](+), [Al(LH(-2))(OH)](0), and [Al(LH(-2))(2)](-) are formed, as reported for Al(3+)-catechin (c). Reactions between Al(3+) and egcg at pH <4.1 yield AlLH(-2) and AlLH(-3) species. The 1H NMR studies have shown that two hydroxyl groups of the gallate (D) ring are deprotonated and coordinated to an Al(3+) ion in [Al(egcgH(-2))](+). The AlLH(-3) species of egcg is supposed to be formulated as [Al(egcgH(-3))](0) in which one hydroxyl group of the pyrogallol (B) ring and two hydroxyl groups of the D ring are deprotonated; an Al(3+) ion is coordinated to two oxygen atoms of the D ring and one oxygen atom from the B ring of the neighboring chelate molecule, resulting in the formation of a polymeric structure. In the Al(3+) complex of egcg, the gallate group forms major coordinate bonds and results in solution properties that are different from those of ec, egc and c which have no gallate group.     

Characterisation of the phenolic profile of Boerhaavia diffusa L. by HPLC-PAD-MS/MS as a tool for quality control

Phenolic acids and flavonols of nine leaf and three root samples of Boerhaavia diffusa L., collected at different locations and subjected to several drying procedures, were characterised by reversed-phase HPLC-PAD-ESI/MS for the first time. Ten phenolic compounds were identified: 3,4-dihydroxy-5-methoxycinnamoyl-rhamnoside, quercetin 3-O-rhamnosyl(1-->6)galactoside (quercetin 3-O-robinobioside), quercetin 3-O-(2"-rhamnosyl)-robinobioside, kaempferol 3-O-(2"-rhamnosyl)-robinobioside, 3,5,4'-trihydroxy-6,7-dimethoxyflavone 3-O-galactosyl(1-->2)glucoside [eupalitin 3-O-galactosyl(1-->2)glucoside], caffeoyltartaric acid, kaempferol 3-O-robinobioside, eupalitin 3-O-galactoside, quercetin and kaempferol. Quantification was achieved by HPLC-PAD and two phenolic patterns were found for the leaves, in which quercetin 3-O-robinobioside or quercetin 3-O-(2"-rhamnosyl)-robinobioside was the major compound. Caffeoyltartaric acid was only present in the root material where it represented the main phenolic constituent. The results obtained demonstrated that the geographical origin (particularly the nature of the soil), but not the drying process, influences the phenolic composition.