白及内生菌Penicillium oxalicum的化学成分
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摘要
对从中药白及新鲜药材中分离得到的一株内生菌草酸青霉菌Penicillium oxalicum进行固体发酵40 d后得到发酵产物,将发酵产物采用75%乙醇渗漉提取后,用乙酸乙酯萃取,并利用硅胶柱色谱、Sephadex LH-20凝胶、HPLC等方法进行成分分离.从中分离得到15个单体化合物,经质谱、核磁共振等波谱方法鉴定为α-亚麻酸甲酯(1)、亚油酸甲酯(2)、benzoic acid(3)、4-hydroxybenzaldehyde(4)、ganodermasides D(5)、dankasterone A(6)、calvasterol B(7)、cyclo-(Pro-Phe)(8)、penioxalicin(9)、5α-麦角甾-7,22-二烯-3β,5,6β-三醇(10)、cis-4-hydroxyscytalone(11)、3,4-dihydroxyphenylaceticacidmethylester(12)、protocatechuicacid(13)、cyclo-(4-S-hydroxy-R-proline-R-isoleucine)(14)、cyclo-L-(4-hydroxyprolinyl)-L-leucine(15).其中化合物1以及4-15均为首次从P. oxalicum中分离得到.本研究结果可促进白及及其内生菌资源的开发利用.(图1参32)
To study the isolation and elucidation of chemical constituents of Penicillium oxalicum, an endophytic fungus was isolated from Bletilla striata(Thunb.) Reichb. f. After solid state fermentation for 40 days, secondary metabolites were percolated by ethanolwater(75:25, V/V), extracted with ethyl acetate, and purified by column chromatography methods including silica gel, Sephadex LH-20, and high-performance liquid chromatography. A total of 15 compounds were isolated. Their structures were elucidated through extensive spectroscopic analyses as follows: α-methyl linolenic acid(1), methyl linoleate(2),benzoic acid(3), 4-hydroxybenzaldehyde(4), ganodermasides D(5), dankasterone A(6), calvasterol B(7), cyclo-(Pro-Phe)(8),penioxalicin(9), 5α-ergoside-7,22-diene-3β,5,6β-triol(10), cis-4-hydroxyscytalone(11), 3,4-dihydroxyphenylacetic acid methyl ester(12), protocatechuic acid(13), cyclo-(4-S-hydroxy-R-proline-R-isoleucine)(14), and cyclo-L-(4-hydroxyprolinyl)-L-leucine(15). Among these, compounds 1 and 4-15 were isolated from P. oxalicum for the first time.
To study the isolation and elucidation of chemical constituents of Penicillium oxalicum, an endophytic fungus was isolated from Bletilla striata(Thunb.) Reichb. f. After solid state fermentation for 40 days, secondary metabolites were percolated by ethanolwater(75:25, V/V), extracted with ethyl acetate, and purified by column chromatography methods including silica gel, Sephadex LH-20, and high-performance liquid chromatography. A total of 15 compounds were isolated. Their structures were elucidated through extensive spectroscopic analyses as follows: α-methyl linolenic acid(1), methyl linoleate(2),benzoic acid(3), 4-hydroxybenzaldehyde(4), ganodermasides D(5), dankasterone A(6), calvasterol B(7), cyclo-(Pro-Phe)(8),penioxalicin(9), 5α-ergoside-7,22-diene-3β,5,6β-triol(10), cis-4-hydroxyscytalone(11), 3,4-dihydroxyphenylacetic acid methyl ester(12), protocatechuic acid(13), cyclo-(4-S-hydroxy-R-proline-R-isoleucine)(14), and cyclo-L-(4-hydroxyprolinyl)-L-leucine(15). Among these, compounds 1 and 4-15 were isolated from P. oxalicum for the first time.
引文
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3 Tatsuzawa F,Saito N,Shigihara A,Honda T,Toki K,Shinoda K,Yukawa T,Miyoshi K.An acylated cyanidin-3,7-diglucoside in the bluish flowers of Bletilla striata[J].Jap Soc Hortic Sci,2010,79(2):215-220
4徐帮,邹坤,郭玲芝,刘呈雄,程凡.中华剑角蝗共生真菌Penicillium oxalicum中苯并吡喃酮二聚体类化合物的研究[J].天然产物研究与开发,2014,26(4):517-520[Xu B,Zou K,Guo LZ,Liu CX,Cheng F.Dimeric naphthopyrones from Penicillium oxalicum,a fungus residing in Acrida cinerea[J].Nat Prod Res Dev,2014,26(4):517-520]
5杨小姣,邹坤,尉小琴,程凡,覃慧林,贺海波,徐帮,涂璇.中华剑角蝗内生真菌Penicillium oxalicum次级代谢产物Secalonic acid A的分离及毒性实验研究[J].三峡大学学报(自然科学版),2015,37(5):105-109[Yang XJ,Zou K,Wei XQ,Cheng F,Qin HL,He HB,Xu B,Tu X.Experimental study of separation and toxicity of secalonic acid A,a kind of secondary metabolites from Penicilliun oxalicum.a fungus residing in Acrida Cinerea Gut[J].J Chin Three Gorges Univ(NatSci Ed),2014,37(5):105-109]
6孙玉林,陈茵,徐新亚,张晓勇,郑智慧,农旭华,鲍洁,漆淑华.海洋真菌Penicillium oxalicum SCSGAF 0023的次生代谢产物及其抗污损和酶抑制活性研究[J].天然产物研究与开发,2013,25(1):1-6+59[Sun YL,Chen Y,Xu XY,Zhang XY,Zheng ZH,Nong XH,Bao J,Qi SH.Secondary metabolites of marine-derived fungus Penicillium oxalicum SCSGAF 0023 and their antifouling and enzyme-inhibitory activities[J].Nat Prod Res Dev,2013,25(1):1-6+59]
7曾浩洋,阿布拉江·克依木,刘艳,闫祝炜,彭秧.宽裂龙蒿地上部分化学成分研究[J].中草药,2013,44(9):1096-1100[Zeng HY,Keyume ABLJ,Liu Y,Yan ZW,Peng Y.Chemical constituents from aerial parts of Artemisia dracunculus var.turkestanica[J].Chin Tradit Herbal Drugs,2013,44(9):1096-1100]
8 Huh S,Kim YS,Jung E,Lim J,Jung KS,Kim MO,Lee,J,Park D.Melanogenesis inhibitory effect of fatty acid alkyl esters isolated from Oxalis triangularis[J].Biol Pharm Bull,2010,33(7):1242-1245
9季宇彬,郑婷,尹姣定.中国南海海绵Cinachyrella sp.的化学成分研究[J].中国海洋药物,2018,37(2):7-12[Ji YB,Zheng T,Yin JD.Chemical constituents from Chinese marine sponge Cinachyrella sp.[J].Chin J Mar Drugs,2018,37(2):7-12]
10 Wei HX,Fang XW,Xie XS,Zhang SP,Jiang Y,Wu SH.Secondary metabolites of a soil-derived Streptomyces kunmingensis[J].Chem Nat Compd,2017,53(4):794-796
11 Weng YF,Lu J,Xiang L,Matsuura A,Zhang Y,Huang QM,Qi JH.Ganodermasides C and D,Two new anti-aging ergosterols from spores of the medicinal mushroom Ganoderma Lucidum[J].Biosci Biotechnol Biochem,2011,75(4):800-803
12 Amagata T,Tanaka M,Yamada T,Doi M,Minoura K,Ohishi H,Yamori T,Numata A.Variation in cytostatic constituents of a sponge-derived gymnascella dankaliensis by manipulating the carbon source[J].J Nat Prod,2007,70:1731-1740
13 K awa ha r a N,Sek it a S,Sat a ke M.Two steroid s f rom calvat ia cyathiformis[J].Phytochem,1995,38(4):947-950
14周婷婷,谢春兰,张改云,杨全.深海放线菌Streptomyces sp.WP6次生代谢产物的研究[J].广东药学院学报,2016,32(3):282-285[Zhou TT,Xie CL,Zhang GY,Yang Q.Study on the secondary metabolites from a deep-sea-derived actinomycete Streptomyces sp.WP6[J].J Guangdong Pharm Univ,2016,32(3):282-285]
15 Bian XQ,Bai J,Hu XL,Wu X,Xue CM,Han AH,Su GY,Hua HM,Pei YH.Penioxalicin,a novel 3-nor-2,3-seco-labdane type diterpene from the fungus Penicillium oxalicum TW01-1[J].Tetrahedron Lett,2015,56:5013-5016
16 Iorizzi M,Minale L,Riccio R,Lee JS,Yasumoto T.Polar steroids from the marine scallop Patinopecten yessoensis[J].J Nat Prod,1988,51(6):1098-1103
17 Huang R,Wang T,Xie XS,Ma KX,Fang XW,Wu SH.Secondary metabolites from an endophytic fungus Nigrospora sp.[J].Chem Nat Compd,2016,52(4):697-699
18 Zhang ZZ,Xiao BH,Chen Q,Lian XY.Synthesis and biological evaluation of caffeic acid 3,4-dihydroxyphenethyl ester[J].J Nat Prod,2010,73(2):252-254
19冯卫生,张志广,李孟,张靖柯,赵璇,郑晓珂,匡海学.北葶苈子化学成分研究[J].中国药学杂志,2018,53(1):16-19[Feng WS,Zhang ZG,Li Meng,Zhang JK,Zhao X,Zheng XK,Kuang HX.Chemical constituents from the seeds of Lepidium apetalum Willd[J].Chin Pharm J,2018,53(1):16-19]
20 Cronan JJM,Davidson TR,Singleton FL,Colwell RR,Cardellina JH.Plant growth promoters isolated from a marine bacterium associated with Palythoa sp.[J].Nat Prod Lett,1998,11(4):271-278
21 Mellouli L.Purification and structure determination of four bioactive molecules from a newly isolated Streptomyces sp.TN97 strain[J].Process Biochem,2006,41(7):1506-1513
22韩军花.植物甾醇的性质、功能及应用[J].国外医学(卫生学分册),2001,28(5):285-291[Han JH.The nature,function and application of plant sterols[J].Foreign Med Sci(Hygiene),2001,28(5):285-291]
23 Ovenden SPB,Nielson JL,Liptrot CH,Willis RH,Tapiolas DM,Wright AD,Motti CA.A new diketopiperazine,cyclo-(4-S-hydroxy-R-prolineR-isoleucine),from an australian specimen of the sponge Stelletta sp.[J].Mar drugs,2011,9(11):2469-2478
24 Kim HY,Park HM,Lee CH.Mass spectrometry-based chemotaxonomic classification of Penicillium species(P.echinulatum,P.expansum,P.solitum,and P.oxalicum)and its correlation with antioxidant activity[J].J Microbiol Methods,2012,90(3):327-335
25 Fran?ois T,Lambert SM,Michel JDP,Gaby NME,Fabrice FB,ZachéN,Henri AZP,Chantal M.Composition,radical scavenging and antifungal activities of essential oils from 3 Helichrysum species growing in Cameroon against Penicillium oxalicum a yam rot fungi[J].Afr J Agric Res,2010,4(7):121-127
26 Liu B,Wang HF,Zhang LH,Liu F,He FJ,Bai J,Hua HM,Chen G,Pei YH.New compound with DNA Topo I inhibitory activity purified from Penicillium oxalicum HSY05[J].Nat Prod Res,2015,29(23):2197-2202
27 Chen G,Jiang Z,Bai J,Wang H,Zhang S,Pei Y.Isolation,structure determination,in vivo/vitro assay and docking study of a xanthone with antitumor activity from fungus Penicillium oxalicum[J].Rec Nat Prod,2015,9(2):184-189
28 Sant amar ina M P,Rosello J,Llacer R.A nt agonistic activit y of Penicillium oxalicum Corrie and Thom,Penicillium decumbens Thom and Trichoderma harzianum Rifai isolates against fungi,bacteria and insects in vitro[J].Rev Iberoam Micol,2002,19(2):99-103
29 Gao L,Wang LS,Jiang XK,Qu YB.Linker length and f lexibility induces new cellobiohydrolase activity of PoCel6A from Penicillium oxalicum[J].Biotechnol J,2015,10(6):899-904
30 Liao HP,Sun SW,Wang P,Bi WL,Tan SY,Wei Z,Mei XL,Liu DY,Raza W,Shen QR,Xu YC.A new acidophilic endo-β-1,4-xylanase from Penicillium oxalicum:cloning,purification,and insights into the inf luence of metal ions on xylanase activity[J].J Ind Microbiol Biotechnol,2014,41(7):1071-1083
31 Su LH,Zhao S,Jiang SX,Liao XZ,Duan CJ,Feng JX.Cellulase with high beta-glucosidase activity by Penicillium oxalicum under solid state fermentation and its use in hydrolysis of cassava residue[J].World JMicrobiol Biotechnol,2017,33(2):1-11
32 Xu QS,Zheng XQ,Huang MP,Wu M,Yan YS,Pan JM,Yang Q,Duan CJ,Liu JL,Feng JX.Purification and biochemical characterization of a novelβ-fr uctofuranosidase from Penicillium oxalicum with transfructosylating activity producing neokestose[J].Process Biochem,2015,50(8):1237-1246
2 Park JE,Woo KW,Choi SU,Lee JH,Lee KR.Two new cytotoxic spirostane-steroidal saponins from the roots of Bletilla striata[J].Helv Chim Acta,2014,97(1):56-63
3 Tatsuzawa F,Saito N,Shigihara A,Honda T,Toki K,Shinoda K,Yukawa T,Miyoshi K.An acylated cyanidin-3,7-diglucoside in the bluish flowers of Bletilla striata[J].Jap Soc Hortic Sci,2010,79(2):215-220
4徐帮,邹坤,郭玲芝,刘呈雄,程凡.中华剑角蝗共生真菌Penicillium oxalicum中苯并吡喃酮二聚体类化合物的研究[J].天然产物研究与开发,2014,26(4):517-520[Xu B,Zou K,Guo LZ,Liu CX,Cheng F.Dimeric naphthopyrones from Penicillium oxalicum,a fungus residing in Acrida cinerea[J].Nat Prod Res Dev,2014,26(4):517-520]
5杨小姣,邹坤,尉小琴,程凡,覃慧林,贺海波,徐帮,涂璇.中华剑角蝗内生真菌Penicillium oxalicum次级代谢产物Secalonic acid A的分离及毒性实验研究[J].三峡大学学报(自然科学版),2015,37(5):105-109[Yang XJ,Zou K,Wei XQ,Cheng F,Qin HL,He HB,Xu B,Tu X.Experimental study of separation and toxicity of secalonic acid A,a kind of secondary metabolites from Penicilliun oxalicum.a fungus residing in Acrida Cinerea Gut[J].J Chin Three Gorges Univ(NatSci Ed),2014,37(5):105-109]
6孙玉林,陈茵,徐新亚,张晓勇,郑智慧,农旭华,鲍洁,漆淑华.海洋真菌Penicillium oxalicum SCSGAF 0023的次生代谢产物及其抗污损和酶抑制活性研究[J].天然产物研究与开发,2013,25(1):1-6+59[Sun YL,Chen Y,Xu XY,Zhang XY,Zheng ZH,Nong XH,Bao J,Qi SH.Secondary metabolites of marine-derived fungus Penicillium oxalicum SCSGAF 0023 and their antifouling and enzyme-inhibitory activities[J].Nat Prod Res Dev,2013,25(1):1-6+59]
7曾浩洋,阿布拉江·克依木,刘艳,闫祝炜,彭秧.宽裂龙蒿地上部分化学成分研究[J].中草药,2013,44(9):1096-1100[Zeng HY,Keyume ABLJ,Liu Y,Yan ZW,Peng Y.Chemical constituents from aerial parts of Artemisia dracunculus var.turkestanica[J].Chin Tradit Herbal Drugs,2013,44(9):1096-1100]
8 Huh S,Kim YS,Jung E,Lim J,Jung KS,Kim MO,Lee,J,Park D.Melanogenesis inhibitory effect of fatty acid alkyl esters isolated from Oxalis triangularis[J].Biol Pharm Bull,2010,33(7):1242-1245
9季宇彬,郑婷,尹姣定.中国南海海绵Cinachyrella sp.的化学成分研究[J].中国海洋药物,2018,37(2):7-12[Ji YB,Zheng T,Yin JD.Chemical constituents from Chinese marine sponge Cinachyrella sp.[J].Chin J Mar Drugs,2018,37(2):7-12]
10 Wei HX,Fang XW,Xie XS,Zhang SP,Jiang Y,Wu SH.Secondary metabolites of a soil-derived Streptomyces kunmingensis[J].Chem Nat Compd,2017,53(4):794-796
11 Weng YF,Lu J,Xiang L,Matsuura A,Zhang Y,Huang QM,Qi JH.Ganodermasides C and D,Two new anti-aging ergosterols from spores of the medicinal mushroom Ganoderma Lucidum[J].Biosci Biotechnol Biochem,2011,75(4):800-803
12 Amagata T,Tanaka M,Yamada T,Doi M,Minoura K,Ohishi H,Yamori T,Numata A.Variation in cytostatic constituents of a sponge-derived gymnascella dankaliensis by manipulating the carbon source[J].J Nat Prod,2007,70:1731-1740
13 K awa ha r a N,Sek it a S,Sat a ke M.Two steroid s f rom calvat ia cyathiformis[J].Phytochem,1995,38(4):947-950
14周婷婷,谢春兰,张改云,杨全.深海放线菌Streptomyces sp.WP6次生代谢产物的研究[J].广东药学院学报,2016,32(3):282-285[Zhou TT,Xie CL,Zhang GY,Yang Q.Study on the secondary metabolites from a deep-sea-derived actinomycete Streptomyces sp.WP6[J].J Guangdong Pharm Univ,2016,32(3):282-285]
15 Bian XQ,Bai J,Hu XL,Wu X,Xue CM,Han AH,Su GY,Hua HM,Pei YH.Penioxalicin,a novel 3-nor-2,3-seco-labdane type diterpene from the fungus Penicillium oxalicum TW01-1[J].Tetrahedron Lett,2015,56:5013-5016
16 Iorizzi M,Minale L,Riccio R,Lee JS,Yasumoto T.Polar steroids from the marine scallop Patinopecten yessoensis[J].J Nat Prod,1988,51(6):1098-1103
17 Huang R,Wang T,Xie XS,Ma KX,Fang XW,Wu SH.Secondary metabolites from an endophytic fungus Nigrospora sp.[J].Chem Nat Compd,2016,52(4):697-699
18 Zhang ZZ,Xiao BH,Chen Q,Lian XY.Synthesis and biological evaluation of caffeic acid 3,4-dihydroxyphenethyl ester[J].J Nat Prod,2010,73(2):252-254
19冯卫生,张志广,李孟,张靖柯,赵璇,郑晓珂,匡海学.北葶苈子化学成分研究[J].中国药学杂志,2018,53(1):16-19[Feng WS,Zhang ZG,Li Meng,Zhang JK,Zhao X,Zheng XK,Kuang HX.Chemical constituents from the seeds of Lepidium apetalum Willd[J].Chin Pharm J,2018,53(1):16-19]
20 Cronan JJM,Davidson TR,Singleton FL,Colwell RR,Cardellina JH.Plant growth promoters isolated from a marine bacterium associated with Palythoa sp.[J].Nat Prod Lett,1998,11(4):271-278
21 Mellouli L.Purification and structure determination of four bioactive molecules from a newly isolated Streptomyces sp.TN97 strain[J].Process Biochem,2006,41(7):1506-1513
22韩军花.植物甾醇的性质、功能及应用[J].国外医学(卫生学分册),2001,28(5):285-291[Han JH.The nature,function and application of plant sterols[J].Foreign Med Sci(Hygiene),2001,28(5):285-291]
23 Ovenden SPB,Nielson JL,Liptrot CH,Willis RH,Tapiolas DM,Wright AD,Motti CA.A new diketopiperazine,cyclo-(4-S-hydroxy-R-prolineR-isoleucine),from an australian specimen of the sponge Stelletta sp.[J].Mar drugs,2011,9(11):2469-2478
24 Kim HY,Park HM,Lee CH.Mass spectrometry-based chemotaxonomic classification of Penicillium species(P.echinulatum,P.expansum,P.solitum,and P.oxalicum)and its correlation with antioxidant activity[J].J Microbiol Methods,2012,90(3):327-335
25 Fran?ois T,Lambert SM,Michel JDP,Gaby NME,Fabrice FB,ZachéN,Henri AZP,Chantal M.Composition,radical scavenging and antifungal activities of essential oils from 3 Helichrysum species growing in Cameroon against Penicillium oxalicum a yam rot fungi[J].Afr J Agric Res,2010,4(7):121-127
26 Liu B,Wang HF,Zhang LH,Liu F,He FJ,Bai J,Hua HM,Chen G,Pei YH.New compound with DNA Topo I inhibitory activity purified from Penicillium oxalicum HSY05[J].Nat Prod Res,2015,29(23):2197-2202
27 Chen G,Jiang Z,Bai J,Wang H,Zhang S,Pei Y.Isolation,structure determination,in vivo/vitro assay and docking study of a xanthone with antitumor activity from fungus Penicillium oxalicum[J].Rec Nat Prod,2015,9(2):184-189
28 Sant amar ina M P,Rosello J,Llacer R.A nt agonistic activit y of Penicillium oxalicum Corrie and Thom,Penicillium decumbens Thom and Trichoderma harzianum Rifai isolates against fungi,bacteria and insects in vitro[J].Rev Iberoam Micol,2002,19(2):99-103
29 Gao L,Wang LS,Jiang XK,Qu YB.Linker length and f lexibility induces new cellobiohydrolase activity of PoCel6A from Penicillium oxalicum[J].Biotechnol J,2015,10(6):899-904
30 Liao HP,Sun SW,Wang P,Bi WL,Tan SY,Wei Z,Mei XL,Liu DY,Raza W,Shen QR,Xu YC.A new acidophilic endo-β-1,4-xylanase from Penicillium oxalicum:cloning,purification,and insights into the inf luence of metal ions on xylanase activity[J].J Ind Microbiol Biotechnol,2014,41(7):1071-1083
31 Su LH,Zhao S,Jiang SX,Liao XZ,Duan CJ,Feng JX.Cellulase with high beta-glucosidase activity by Penicillium oxalicum under solid state fermentation and its use in hydrolysis of cassava residue[J].World JMicrobiol Biotechnol,2017,33(2):1-11
32 Xu QS,Zheng XQ,Huang MP,Wu M,Yan YS,Pan JM,Yang Q,Duan CJ,Liu JL,Feng JX.Purification and biochemical characterization of a novelβ-fr uctofuranosidase from Penicillium oxalicum with transfructosylating activity producing neokestose[J].Process Biochem,2015,50(8):1237-1246
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