Studies On The Chemical Constituents And Biological Activities Of Angiopteris Caudatiformis And Asplenium Unilaterale

Ferns widely distributed in various areas throughout the world,particularly abundant in tropical and subtropical zones,belong to the oldest group of higher plants. Among them,more than 2,600 species exist in China,some of them are used as food or medicine since ancient times and recorded in "Shen Nong's Herbal Classic", "Compendium of Materia Medica" and "Traditional Chinese Medicine Dictionary" as herbal medicines with effects of clearing away heat and toxic materials,reducing edema,dispersing blood stasis,inhibiting bacteria,diminishing inflammation, detoxicating,expelling worms,treating allergy,improving memory and increasing coronary blood flow.However,most of ferns have not been subjected to chemical investigations except some of the species of Dryopteridaceae,Pteridaceae and Polypodiaceae.The chemical constituents of Angiopteris caudatiformis and Asplenium unilaterale,used as folk medicines in China,were investigated in this thesis.The rhizome of Angiopteris caudatiformis has been used as medicine for a long time in Dai and Tujia nationalities in China for the treatment of infectious diseases, such as enteritis,diarrhea and pulmonary tuberculosis.The fibrous roots are also used as medicine for the treatment of cough caused by lung-heat,venomous snake bite, furuncle,and traumatic hemorrhage.However,no phytochemical and pharmacological researches have been reported on this species.The chemical constituents of Angiopteris caudatiformis were investigated for the first time in this thesis and 21 compounds were isolated and identified by modern chromatography and spectral analysis,including 6 esters:angiopterlactone A(CP1), angiopterlactone B(CP2),osmundalactone(CP3),osmundalin(CP4),3,5- dihydroxy-γ-caprolactone(CPS),and ethyl thioglycolate(CP6);5 sterols:daucosterol (CP7),β-sitosterol(CPS),stigmasta-5,17(20)-dien-3-ol(CP9),stigmast-3-O-β-D-glucopyranoside (CP10),and 7-hydroxystigmast-4-en-3-one(CP11);4 sugars and glucosides:maltolβ-D-glucopyranoside(CP12),α-glucose(CP13),maltose(CP14) and ethyl-α-D-glucoside(CP15);2 fatty acids:palmic acid(CP16) and stearic acid (CP17);and 4 other compounds:malealdehyde(CP18),5-hydroxymethyl -2-furaldehyde(CP19),1-O-α-D-glucopyranosyl-(2S,3R,4E,8Z)-2-N-palmitoyloctadecasphinga -4,8-dienine(CP20) and 2,4-dihydroxypyrimidine(CP21).Among them,CP1 and CP2 are new compounds possessing unique dual-lactone skeletons,the others except compound CP4 and CP8 are isolated for the first time from the genus Angiopteris,and all compounds are isolated from this species for the first time.The antitumor and insect-antifeedant activities of the 5 lactones(CP1,CP2,CP3, CP4 and CP5) from Angiopteris caudatiformis were screened,with the result that CP1 exhibited good inhibiting effects for HeLa cells with IC₅₀=68.8μM.CP3(500 ppm) and CP4(1,000 ppm) showed moderate insect-antifeedant effects towards the larva of Plutella xylostella and Heliothis virescens.The whole herb of Asplenium unilaterale is a Uygur medicine in China with the effects of clearing away heat and toxic materials,inducing astringency,expelling wind, removing damness,invigorating and regulating Qi.It has been used for the treatment of diarrhea.However,few researches have been reported on its chemical constituents. In this thesis,systematical studies have been reported on the chemical constituents of A.unilaterale,and 29 compounds were isolated and identified by applying modern chromatography and spectral analysis,including 5 megastigmane glucosides: (Z)-4-(2,6,6-trimethylcyclohex-2-enylidene)butan-2-ol(CPS4),icariside B₂(CPS5) and citroside A(CPS6),(6R,9R)-3-oxo-α-ionol-9-O-β-D-glucopyranoside(CPS7), and 6S,9R-roseoside(CPSS);4 cumarins:6-methyl-2H-chromen-2-one(CPS9), 6,7-dihydroxy-2H-1-benzopyran-2-one(CPS10),gibepyrone D(CPS11);2 triterpenes:asplenic acid(CPS1) and lupan-3-one(CPS12);1 flavone:violanthin (CPS13);5 sterols:β-sitosterol(CPS14),daucosterol(CPS15),22,23-dimethylcholest-S-en-3-ol(CPS16),stigmasta-3,5-diene(CPS17) and asplenilol (CPS2);6 fatty alcohol or fatty acid compounds,1-tetratriacontanol(CPS18), 1-triacontanol(CPS19),carnaubic acid(CPS20),palmitic acid(CPS21),palmitic acid(CPS22),and methyl arachidate(CPS23);3 lactones:aspleniloide(CPS3), 5-hexylfuran-2(5H)-one(CPS24) and 4,5-dihydroxypentyl isobutyrate(CPS25);and 3 other compounds:tocopherylquinone(CPS26),2,4-(1H,3H)-pyrimidinedione (CPS27) and stachyose(CPS28).Among which,compounds CPS1,CPS2 and CPS3 were new and all of the compounds were isolated from the genus Asplenium for the first time.In addition,research advances about the genera Angiopteris and Asplenium were summarized in this thesis,which provide evidence for the further research and application of plants from the two genera.