紫红曲中的麦角甾类化合物

研究紫红曲乙醇提取物中显示细胞毒活性的醋酸乙酯萃取部位的化学成分。利用正反相硅胶、凝胶Sephadex LH-20、结合闪式(Flash)柱色谱和制备高效液相色谱等多种色谱手段进行分离纯化,借助核磁和质谱等波谱学方法进行结构鉴定。从紫红曲乙醇提取物的醋酸乙酯萃取部位中分离鉴定了5个麦角甾类化合物,分别为:麦角甾-7,22-二烯-3β,5α,6β-三醇(1),(22E,24R)-麦角甾-7,22-二烯-6-酮-3β,5α,9α-三醇(2),(22E,24R)-23-甲基麦角甾-7,22-二烯-3β,5α,6β-三醇(3),(22E,24R)-23-甲基麦角甾-7,22-二烯-6-酮-3β,5α,9α-三醇(4),麦角甾-4,6,8(14),22-四烯-3-酮(5)。上述5个化合物均为首次从紫红曲中分离得到。除化合物1外,其余化合物均为首次从红曲菌属中发现。在体外MTT法的细胞毒活性测试中,所筛选的化合物在10×10-6mol/L浓度下均未显示细胞毒的活性。     

大王棕内生真菌次级代谢产物的研究

通过高效液相色谱法,正相硅胶柱色谱法、凝胶柱色谱法等分离方法对大王棕内生真菌的次级代谢产物进行分离纯化,再应用NMR和MS等现代波谱分析方法对其进行结构鉴定,从中首次分离鉴定了6个化合物,分别为1’,2’-epoxy-3’,4’-didehydropenicillide.;丁二酸;3β-羟基-5α,8α-过氧化麦角甾-6,22-二烯;ergosta-7,22-dien-3β,5α,6α-triol;3β-羟基-麦角甾-5,7,22-三烯;4-羟基苯乙酸。     

水皮子蘑菇不同极性提取物中组分的分离与鉴定

对五台山传统食用菌水皮子蘑菇(落叶杯伞Clitocybe phyllophila(Pers.)P. Kumm.)的化学成分进行研究。通过凝胶、硅胶柱色谱等方法从落叶杯伞的子实体中提取分离得到10个单体化合物,应用现代色谱技术以及波谱分析方法,结合化学方法,对单体化合物的结构鉴定为邻苯二甲酸二丁酯(1)、棕榈酸(2)、麦角甾醇(3)、麦角甾醇过氧化物(4)、十八烷酸(5)、苯甲酸(6)、脲(7)、麦角甾-7,22-二烯-3β,5α,6β-三醇(8)、白桦酯醇(9)、3-吡啶甲酸(10)。该10种化合物均为首次从落叶杯伞中分离得到。

     

西藏林芝地区野生黑木耳的化学成分

通过正相硅胶柱色谱、中压反相柱色谱、凝胶柱色谱、TLC及HPLC等技术从西藏黑木耳中分离、纯化得到7个单体化合物,通过MS、NMR并结合文献报道确定其结构,其中包含6麦角甾醇类化合物,分别为(22E,24R)-麦角甾-7,22-二烯-3β,5α,6β-三醇(1yy2),(22E,24R)-麦角甾-5,7,22-三烯-3β-醇(Lyy3),3β,5α,9α-三羟基-7,22-(22E,24R)-麦角甾二烯-6-酮(Lyy4),5α,8α-环氧-(22E,24R)-麦角甾-6,22-二烯-3β-醇(Lyy5),5α,8α-环氧-(22E,24R)-麦角甾-6,9(11),22-三烯-3β-醇(Lyy6),(22E,24R)-麦角甾-7,22-二烯-3β,5α,6α,9α-四醇(Lyy7);剩余一个为5-羟甲基-2-异丙-1-醇-2,3-二氢苯并呋喃(Lyy1)。这7个化合物均为首次从黑木耳中分离得到的单体化合物。     

盐生海芦笋来源真菌Penicillium stoloniferum发酵产物抗肿瘤活性成分研究

采用活性追踪的方法,对一株盐生海芦笋来源真菌Penicillium stoloniferum发酵产物中的抗肿瘤活性成分进行分离和鉴定。利用常压硅胶柱层析、Sephedex LH-20、半制备HPLC等分离方法从中分离得到8个单体化合物,通过理化性质分析及波谱学方法鉴定其化学结构分别为：麦角甾-7,9(11),22-三烯-3-醇、麦角固醇、菠菜甾醇、5α,8α-环二氧-(22E,24R)-23-甲基麦角甾-6,22-二烯-3β-醇、色氨酸-苯丙氨酸-环二肽、苯丙氨酸、邻苯二甲酸正丁酯、邻苯二甲酸异丁酯;以SRB法评价化合物的抗肿瘤活性,5α,8α-环二氧-(22E、24R)-23-甲基麦角甾-6,22-二烯-3β-醇、邻苯二甲酸正丁酯、邻苯二甲酸异丁酯对小鼠乳腺癌P388细胞具有强的细胞毒活性,IC50值分别为14、34、46μg/mL,其他化合物没有活性。     

两种生产工艺藤椒油产品挥发性成分对比分析

采用顶空-气相色谱-质谱法对两种生产工艺藤椒油产品的挥发性成分进行分析,并结合NIST14质谱数据库检索定性,峰面积归一法定量。结果显示:传统油浸法和超临界CO₂萃取法藤椒油产品中共鉴定出33种挥发性成分,共有的挥发性成分有16种,主要的挥发性成分(相对含量≥4.5%)有4种(右旋萜二烯、芳樟醇、桧烯和月桂烯);传统油浸法特有的挥发性成分有6种(β-榄香烯、1-石竹烯、大根香叶烯、α-石竹烯、辛醛和癸醛),超临界CO₂萃取法特有的挥发性成分有11种(3-甲基-2-丁烯腈、5-氰基-1-戊烯、左旋-β-蒎烯、α-松油烯、反式-β-罗勒烯、3,3-二甲基己醇、乙酸-4-松油烯醇酯、苯乙酸甲酯、(E,E)-2,4-己二烯醛、(+)-香茅醛和1-甲基-异己酸)。烯类和醇类化合物是藤椒油产品挥发性成分的主要种类,但其相对含量存在差异;超临界CO₂萃取法藤椒油产品的挥发性成分中含有微量的酸类化合物(1-甲基-异己酸)。该研究结果可为改善生产加工工艺和提高藤椒油产品品质提供理论依据。     

西林火姜姜油树脂的成分分析

以西林火姜干姜片为原料,通过索氏提取分别制备石油醚姜油树脂（ginger oleoresin extracted by petroleum ether,PEGO）和无水乙醇姜油树脂（ginger oleoresin extracted by absolute ethanol,AEGO）并研究其成分组成。结果显示：PEGO和AEGO经GC-MS分别鉴定出46、38种挥发性成分,主要为姜烯、β-倍半水芹烯,α-法呢烯、β-红没药烯、α-姜黄烯、α-柠檬醛、β-柠檬醛、β-水芹烯、桉叶油醇、2-茨醇等萜烯类化合物和6-姜酚、6-姜烯酚、8-姜烯酚等难挥发性姜辣素化合物。另外,还检测出丰富的脂肪酸、总酚、黄酮和甾醇等非挥发性成分,脂肪酸均主要为棕榈酸、亚油酸、羊脂酸、月桂酸、硬脂酸、低羊脂酸、豆蔻酸、反油酸、油酸等,不饱和脂肪酸以亚油酸和油酸为主,其中亚油酸含量均高达20%以上;PEGO和AEGO总酚含量分别为118.61±1.55、105.36±1.09 mg GAE/g;黄酮含量分别为15.72±0.51、13.36±0.03 mg RE/g;总甾醇含量分别为4.86±0.02、3.54±0.07 mg/g,且组成均为菜油甾醇、豆甾醇、β-谷甾醇。研究表明,西林火姜姜油树脂含有丰富的营养物质、风味物质和活性物质,并且提取溶剂对姜油树脂的物质组成和含量都具有一定影响。     

四种食用菊花主要成分分析

采用滴定法、紫外分光光度法、高效液相色谱法对4种食用菊花SYJ1、SYJ2、SYJ3和SYJ4主要化学成分(氨基酸、可溶性糖、可溶性蛋白、总黄酮、抗坏血酸、绿原酸、槲皮素和黄芩苷)进行含量测定。采用水蒸气蒸馏法提取食用菊花中的挥发油,用气相色谱-质谱法对其挥发油化学成分进行鉴定,并用峰面积归一化法测其相对含量。结果表明:食用菊SYJ3中主要化学成分含量较高,其氨基酸、可溶性糖、可溶性蛋白、总黄酮、抗坏血酸、绿原酸、槲皮素和黄芩苷含量分别为15.69、65.03、39.72、156.97、69.95、1.96、3.13和17.62 mg·g^-1。4种食用菊花挥发油成分数量分别为37个、33个、25个和38个,最主要成分为α-蒎烯、1,8-桉叶油素、双环(2.2.2)癸烷-2-烯-5-酮、2,6,6-三甲基-双环(3.1.1)-庚-2-烯-4-醇-乙酯、β-榄香烯、(-)-β-石竹烯和α-荜澄茄烯。不同品种食用菊花主要化学成分含量及挥发油种类和含量差异显著(p<0.05)。     

矢车菊素-3-葡萄糖苷与四种乳蛋白相互作用的研究

采用荧光光谱法、傅里叶红外光谱法和圆二色谱法,研究矢车菊素-3-葡萄糖苷(cyanidin 3-O-glucoside,C3G)与α-酪蛋白、β-酪蛋白、乳清蛋白和β-乳球蛋白的相互作用。结果表明,C3G对上述四种乳蛋白都产生了荧光静态猝灭作用,在溶液中C3G与乳蛋白相互结合摩尔比约为1:1,且由热力学参数判定C3G与α-酪蛋白结合的分子间作用力为氢键与范德华力,而与β-酪蛋白、乳清蛋白和β-乳球蛋白结合主要靠静电引力。通过比较C3G与α-酪蛋白、β-酪蛋白、乳清蛋白和β-乳球蛋白相互作用的荧光猝灭率(84%、74%、77%、75%);温度分别为298、318、338 K时的结合常数(423.448、362.994、28.655×10⁴ L/mol;9.524、8.056、8.308×10⁴ L/mol;9.262、6.940、7.889×10⁴ L/mol;30.440、11.830、17.262×10⁴ L/mol);结合距离(2.17、2.66、2.18、2.19 nm),由此得出α-酪蛋白与C3G结合最紧密。傅里叶红外光谱和圆二色谱分析显示,C3G的加入使得α-酪蛋白的α-螺旋增加,β-折叠和转角降低;β-酪蛋白的α-螺旋、β-折叠和转角均增加;乳清蛋白的α-螺旋、β-折叠和转角均无明显变化;β-乳球蛋白的α-螺旋降低,β-折叠和转角增加。C3G对四种乳蛋白均有较强的结合能力,可以使其构象发生变化。     

生姜精油的提取及GC-MS分析

本研究以生姜为原料,以生姜精油得率为评价指标,通过单因素和响应面试验确定了最佳提取条件,最后通过气相色谱质谱联用仪(GC-MS)对提取得到的生姜精油进行分析鉴定。结果表明,粉碎粒径、液料比和蒸馏时间可明显影响生姜精油的得率,水蒸气蒸馏法提取生姜精油的最佳条件为:粉碎粒径160目,液料比19:1 (mL/g),蒸馏时间118 min,此条件下生姜精油的得率为2.09%±0.01%。通过GC-MS对生姜精油进行分析,共鉴定出56种化合物,其中烯类物质39种,醇类10种,醛类3种,酯类2种,烷烃类1种,酮类1种,其主要成分为α-姜烯、β-倍半水芹烯、β-红没药烯、α-法尼烯、α-姜黄烯。     

猪苓中黄嘌呤氧化酶抑制剂的筛选分离及质谱分析

试验以猪苓为研究对象，综合利用遗传算法-BP神经网络数学模型、色谱和质谱等技术，建立快速筛选猪苓中黄嘌呤氧化酶抑制剂的新方法。首先，利用遗传算法-BP神经网络数学模型优化猪苓中麦角甾醇的提取工艺；其次，以黄嘌呤氧化酶为生物靶分子，应用超滤质谱技术，筛选猪苓中潜在的黄嘌呤氧化酶抑制剂，同时，应用分子对接技术验证超滤实验的准确性；最后，以活性筛选为导向，利用高速逆流色谱技术分离猪苓中黄嘌呤氧化酶抑制剂。结果显示：猪苓中麦角甾醇的最佳提取工艺为乙醇体积分数80%、液料比16 mL/g、提取时间1.4 h、提取次数3次，在此条件下，麦角甾醇得率为2.31%；从猪苓中筛选并分离出4个纯度均在90%以上的黄嘌呤氧化酶抑制剂，其抑制效果强弱顺序为猪苓酮A>猪苓酮B>麦角甾-4,6,8(14),22-四烯-3-酮>麦角甾-7,22-二烯-3-酮。该方法快速、灵敏，为猪苓抗痛风药理作用的进一步研究提供了一定的理论基础。     

The individual lipid compositions produced by Cunninghamella sp. Salicorn 5, an endophytic oleaginous fungus from Salicornia bigelovii Torr.

An endophytic oleaginous fungus Salicorn 5 has been isolated from Salicornia bigelovii Torr. and characterized as Cunninghamella sp. based on its morphological characteristics and ITS1-5.8S-ITS2 gene sequence analysis. The individual lipid compositions produced by Salicorn 5 were isolated and determined to be (1) oleic acid, (2) linoleic acid, (3) γ-linolenic acid (GLA), (4) 2,3-dihydroxypropyl oleate, (5) 2,3-dihydroxypropyl stearate, (6) 1,3-diolein, (7) 1,2-diolein, (8) 1,3-2-oleyl,2-stearoyl triacylglycerol, (9) ergosterol peroxide, (10) stigmasta-7,22-diene-3β,5α,6α-triol, (11) stigmasterol, and (12) ergosterol. The chemical structures of these compounds were determined by a combination of electrospray ionization mass spectrometry (ESI–MS) and nuclear magnetic resonance (NMR) analysis, as well as a comparison with data from the literature. Analysis of the fatty acids showed that they were composed predominantly of polyunsaturated fatty acids (PUFAs), including oleic acid (35.57 %), linoleic acid (21.58 %), palmitoleic acid (16.31 %), and linolenic acid (13.28 %), whereas stearic acid, palmitoleic acid, myristic acid, arachidic acid, and eicosenoic acid were found in lower amounts. These results could therefore provide a useful platform for fully exploring the potential application of oleaginous fungus Salicorn 5, and optimizing of the fermentation conditions for producing the PUFAs and high-value GLA, as well as providing further insight into the relationship between endophytes and their hosts.     

远东疣柄牛肝菌化学成分分析

目的：研究远东疣柄牛肝菌子实体的化学成分。方法：采用Sephadex LH-20凝胶色谱柱和硅胶色谱柱进行分离纯化,通过波谱数据和理化常数鉴定化合物的结构。结果：从远东疣柄牛肝菌中分离鉴定出11 种化合物：5-（L）-羰基-四氢吡咯-2-甲酸甲酯（A）、5-（L）-羰基-四氢吡咯-2-甲酸（B）、腺苷（C）、尿嘧啶核苷（D）、α-甲基-D-呋喃核糖（E）、（2R,3R）-2,3,4-三羟基丁酸（F）、2,2,5,5-四甲基四氢呋喃（G）、D-阿拉伯糖酸-1,4-内酯（H）、2-乙酰胺基-1,6-脱水-2-脱氧-D-吡喃型葡萄糖（I）、2-乙酰胺基-1,6-脱水-2-脱氧-D-吡喃型半乳糖（J）和麦角甾-7,22-二烯-3β,5α,6β-三醇（K）。结论：化合物A、B和E～J为首次从远东疣柄牛肝菌中分离得到的化合物。     

Cholesterol Oxides in Swedish Foods and Food Ingredients: Fresh Eggs and Dehydrated Egg Products

Cholesterol oxides were enriched from lipid extracts of fresh and dehydrated egg yolk products by chromatography on Lipidex and TEAP-Lipidex. Appropriate fractions from TEAP-Lipidex were analyzed by capillary GLC as their TMS derivatives. At the detection limit level, ca 0.2 ppm in total lipids, no cholesterol oxides could be detected in fresh egg yolk. Similarly, spray dried egg yolk powder contained only traces of cholesterol oxides when fresh or stored for 2 months at 4°C. Prolonged storage gave lipid extracts which contained variable levels (0.2–12 ppm) of known oxidation products, viz., cholest-5-ene-3β, 7α-diol, cholest-5-ene-3β, 7β-diol, 5,6α-epoxy-5α-cholestan-3β-ol, 5,6 β-epoxy-5 β-cholestan-3β-01, cholest-5-ene-3β, 20α-diol, 3 β-hydroxycholest-5-en-7-one. Traces or small quantifiable amounts of cholest ?5-ene-3β, 25-diol and 5α-cholestane-3β, 5, 6β-triol were observed in some samples at longer storage periods.     

Cholesterol Oxides in Swedish Foods and Food Ingredients: Milk Powder Products

Cream-, whole milk-and skim milk powders had 1.6, 2.0, and 18.9 mg cholesterol/g fat, respectively. About 90% of the cholesterol was unesterified. Analyses of fresh spray-dried whole-and skim milk powders from “low and medium heat” conditions and fresh roller-dried whole milk powder from “low heat” conditions contained less than 0.1 ppm cholesterol oxides in lipids. However, spray-dried whole-and skim milk powders from “high heat” conditions had substantial levels of some important cholesterol oxides. Skim-milk powders, stored in big sacks for 11–37 months and small consumer packages for 2–23 months, contained variable amounts of 5, 6α-epoxy-5β-cholestan-3β-ol (0.3–4.0 ppm), 5,6β-epoxy-5α-cholestan-3β-ol(0.7–10.40ppm), cholest-5-ene-3β,7α-diol(0.5–16.2 ppm), cholest-5-ene-3β,7β-diol(1.3–20.8 ppm), cholest-5-ene-3β,20α-diol(0.6–2.7 ppm), cholest-5-ene-3,25-diol(0.3–0.8 ppm), 5α-cholestane-3β,5,6β-triol(1.3–2.5 ppm) and 3-hydroxy-cholest-5-en-7one(1.8-24.9 ppm).     

莱菔子化学成分的分离与鉴定

目的：研究莱菔子化学成分,探索生品莱菔子的物质基础。方法：采用大孔吸附树脂HP-20、聚苯乙烯型大孔吸附树脂（MCI gel）、ODS、硅胶及LiChroprep RP-18等色谱技术进行分离纯化,运用光谱学方法对得到的化合物进行结构鉴定。结果：从莱菔子甲醇提取物中分离鉴定了16?个化合物：顺-13-二十二碳烯酸（1）、豆甾-4-烯-3-酮（2）、（22E,24R）-麦角甾-5,22-二烯-3β-醇（3）、豆甾-5-烯-3β-醇（4）、反-阿魏酸甲酯（5）、反-芥子酸甲酯（6）、β-豆甾醇-3-O-β-D-葡萄糖苷（7）、α-D-吡喃半乳糖基-（1-6）-α-D-吡喃葡萄糖基-（1-2）-β-D-呋喃果糖苷（8）、β-D-呋喃果糖基-α-D-（6-芥子酰基）葡萄糖苷（9）、β-D-（3-芥子酰基）呋喃果糖基-α-D-葡萄糖苷（10）、β-D-（3-芥子酰基）呋喃果糖基-α-D-（6-芥子酰基）葡萄糖苷（11）、β-D-（3,4-二芥子酰基）呋喃果糖基-α-D-（6-芥子酰基）葡萄糖苷（12）、异鼠李素-3-O-β-D-葡萄糖苷（13）、异鼠李素-3,4’-O-β-D-二葡萄糖苷（14）、异鼠李素-3-O-β-D-葡萄糖-7-O-α-L-鼠李糖苷（15）、3’-O-甲基-（－）-表儿茶素-7-O-β-D-葡萄糖苷（16）。结论：化合物2、3、7～10、13～16为首次在该植物中得到。     

A new glucitol from an endophytic fungus Fusarium equiseti Salicorn 8

An endophytic fungus Salicorn 8 was isolated from Salicornia bigelovii Torr. and identified as Fusarium equiseti based on internal transcribed spacer gene (ITS) sequence analysis. A new glucitol, diglucotol (1), together with five known compounds, cerebroside C (2), Nb-acetyltryptamine (3), 3β,5α,9α-trihydroxy-(22E,24R)-ergosta-7,22-dien-6-one (4), cerevisterol (5) and ergosterol peroxide (6), was isolated from the culture of Salicorn 8. The chemical structures of these compounds were elucidated by extensive spectroscopic analysis and on the basis of their chemical reactivities. This work describes for the first time the isolation of these compounds from F. equiseti. Compound 1 exhibited weak antiproliferative activities toward MCF-7, MDA-MB-231 and Caco-2 cancer cells with EC₅₀ values of 97.56, 92.35 and 99.39 μM, respectively, whereas compound 5 showed high levels of inhibitory activities against MCF-7, MDA-MB-231 and Caco-2 cancer cells with EC₅₀ values of 32.4, 41.5 and 37.56 μM, respectively. Compound 6 exhibited less potent inhibitory activities than 5 against MCF-7, MDA-MB-231 and Caco-2 cancer cells with EC₅₀ values of 64.5, 52.4 and 77.56 μM, respectively. All of the other compounds were found to be inactive.     

Cholesterol oxides in processed meats

Methods for the extraction of cholesterol oxides from meats were studied. A dry column technique for the extraction of sterols was found to be more rapid and convenient than conventional chloroform-methanol extraction. An overall yield of 32·0% and 23·6% for radiolabelled cholesterol and cholesterol oxides, respectively, was obtained after dry column extraction, saponification and chromatography on a silica arrestant column, Florisil?-AgNO(3) column and silica Sep-Pak? column. The overall extraction efficiency of ten meat samples was 22·3 ± 1·7 %. Cholesterol oxides present in measurable amounts included 5-cholesten-3β, 19-diol, 5-cholesten-3β-ol-22-one, the α and β epimers of 5-cholesten-3β, 7-diol and cholestan-3 β, 5α, 6β-triol in some of the meat samples analyzed, but, for the majority of samples, no detectable amounts of known cholesterol oxides were found. Most of the meats, however, contained unidentified components that are non-polar with respect to cholesterol.