全 文 ：第 28卷第 3期
2008年 6月
林　产　化　学　与　工　业
ChemistryandIndustryofForestProducts
Vol.28 No.3
June2008
AlelopathyandChemicalComponentsof
ExtractfromGreenPeelofJuglans
mandshuricaMaxim.
　　收稿日期:2007-09-17
　　基金项目:哈尔滨市留学回国人员基金(2005AFLXJ005)
　　作者简介:孙墨珑(1961-),女 ,黑龙江哈尔滨人,教授 ,博士 ,从事植物提取物化学研究
　＊通讯作者:宋湛谦 ,中国工程院院士 ,研究员 ,博士生导师 ,从事生物质资源的化学改性和应用 ,特别是松脂资源的深加工利用。
SUNMo-long　　
SUNMo-long1 , SONGZhan-qian2＊ , FANGGui-zhen3
(1.ColegeofScience, NortheastForestryUniversity, Harbin150040, China;
2.InstituteofChemicalIndustryofForestProducts, CAF;KeyandOpenLab.on
ForestChemicalEngineering, SFA, Nanjing210042, China;3.CollegeofMaterial
ScienceandEngineering, NortheastForestryUniversity, Harbin150040, China)
Abstract:TheextractfromgreenpeelofJuglansmandshuricaMaxim.wasextractedbycommonmethodforstudyingits
allelopathyandanalyzingthechemicalcomponents.Resultsshowedthatthealcoholextractandtheethylacetatepartofalcohol
extract(separatedwithethylacetatefromalcoholextract)exhibitalelopathy(inhibitingseedgerminationandseedlinggrowth)
onBrassicachinesis, RaphanussativusandMedicagosativa.Theireffectswereextract-concentrationdependent, increasingwith
theincreaseofextractconcentration.ThechemicalcomponentsintheethylacetatepartofalcoholextractfromgreenpeelofJ.
mandshuricawereanalyzedbyGC-MS.ResultsshowedthatthemainchemicalcomponentsandtheirGCcontentsintheethyl
acetatepartofalcoholextractwere:5-hydroxy-1, 4-naphthalenedione(juglone) 31.20%, n-hexadecanoicacid 9.99%,
7-methoxy-1-tetralone 7.99%, 1, 5-naphthalenediol 7.15%, 2, 6-dimethoxy-phenol 4.36%, 4-butoxybenzaldehyde
3.23%, 5-(hydroxymethyl)-2-furancarboxaldehyde2.96%, 1, 3-dihydroxyacetonedimmer2.94%, glycerin2.77%, 1(3H)-
isobenzofuranone2.57%.Twenty-fourcompoundsintheethylacetatepartofalcoholextracthavebeenidentifiedwithtotalGC
contentof94.55%.
Keywords:greenpeelofJuglansmandshuricaMaxim.;allelopathy;componentanalysis
CLCnumbers:TQ91 　　　　　Documentcode:A　　　　　ArticleID:0253-2417(2008)03-0045-05
核桃楸外果皮提取物的化感作用及成分分析
孙墨珑 1 , 宋湛谦 2 , 方桂珍 3
(1.东北林业大学理学院 , 黑龙江 哈尔滨 150040;
2.中国林业科学研究院林产化学工业研究所;国家林业局林产化学工程重点开放性实验室 , 江苏 南京 210042;
3.东北林业大学 材料科学与工程学院 , 黑龙江 哈尔滨 150040)
摘　要:采用常规提取法浸提核桃楸外果皮的化感作用成分。研究结果表明 , 核桃楸外果皮乙醇提取物和乙酸乙酯萃取
相对 3种受体植物青菜 、萝卜和紫花苜蓿具有化感作用(抑制萌发和抑制生长作用)。 化感作用随提取物浓度增大而增
大。采用 GC-MS分析核桃楸外果皮乙醇提取物中乙酸乙酯萃取相的化学组成和相对含量。分析结果表明 ,核桃楸外果
皮乙醇提取物中乙酸乙酯萃取相的主要化学成分为 5-羟基-1, 4-萘醌(胡桃醌), GC含量 31.20%;正十六酸 , GC含量
9.99%;7-甲氧基-1-四氢萘酮 , GC含量 7.99%;1, 5-萘二酚 , GC含量 7.15%;2, 6-二甲氧基苯酚 , GC含量 4.36%;
4-丁氧基苯醛;GC含量 3.23%;5-羟甲基-2-呋喃醛 , GC含量 2.96%;二聚 1, 3-二羟基丙酮 , GC含量 2.94%;丙三
46　 林　产　化　学　与　工　业 第 28卷
醇 , GC含量 2.77%;1(3H)-异苯并呋喃酮 , GC含量 2.57%。
关键词:核桃楸外果皮;化感作用;成分分析
JuglansmandshuricaMaxim.isoneofthepharmaceuticalhardwoodinthenortheastandthenorthof
China[ 1] .ThechloroformandbenzeneextractsofgreenpeelofJ.mandshuricainhibitgermination, growth
andformationofchlorophylofRaphanussativus, Lactucasativa, Echinochloacrus-AaliandDigitariasangui-
nalis[ 2] .Theextractionsofflavonoidsandjuglonesfromleaves, barkandgreenpeelofJ.mandshuricatrees
werecariedoutbythreeextractingmethods, namelycommonmethod, refluxmethodandultrasonicmeth-
od[ 3] .ThealcoholextractandthechloroformpartofextractfromgreenpeelofJ.mandshuricahadinsecticidal
activitiesagainstlarvaeofLymantriadispar[ 4] .Jugloneisthemaintoxicsubstance, andthereareotheractive
substanceswithlowertoxicitiesinJ.mandshurica[ 5] .Alelopathyisdefinedasthedirectorindirectharmful
orbeneficialefectsofoneplantonanotherthroughtheproductionofchemicalcompoundsthatescapeintothe
environment.Alelopathyplaysanimportantroleinagricultureandforestecosystem[ 6] .Inthisstudy, we
observedthealelopathy(inhibitingseedgerminationandseedlinggrowth)ofthealcoholextractandtheethyl
acetatepartofalcoholextract(separatedwithethylacetatefromalcoholextract)extractedfromgreenpeelof
J.mandshuricaonplantspeciesandanalyzedthechemicalcomponentsoftheethylacetatepartofalcohol
extractbyGC-MS, withapurposeofprovidingthetheoreticalproofforexploitationandutilizationofinsecti-
cidalplantsandsimulatingthesynthesizingofbotanicalpesticides.
1　Materialsandmethods
1.1　Materialsandreagents
ThegreenpeelsamplesofJ.mandshuricawerecolectedfromMao′ershanExperimentStationofNorth-
eastForestryUniversity.TheseedsofBrassicachinesis, R.sativusandMedicagosativawereobtainedfrom
AgricultureInstituteofHeilongjiangProvince.Alcohol(95%, massfraction), petroleumether(30-60℃),
chloroformandethylacetate(alAR)wereused.
1.2　Extractionmethods
ThegreenpeelofJ.mandshuricawasextractedwith 95% alcoholbycommonmethod.Thealcohol
extractwasconcentratedwithvacuumdistilation, andseparatedsuccessivelywithpetroleumether, chloroform
andethylacetateaccordingtothepolardiference.Fivetestconcentrationsofextractsamplesweredesignedas
12.5, 6.25, 3.12 , 1.56and0.78g/Lforstudyingthealelopathy(inhibitingseedgerminationandseedling
growth)onB.chinesis, R.sativusandM.sativa.
1.3　Testmethodsofalelopathy
Fiftyseedsofeveryplantspecieswereputintothecontainerwithsubstratebutwithoutbacterial, andadd
5mLtestextractsamplesinthecontainerat24℃ with8 hiluminationeveryday.Theseedsofeveryplant
specieswereusedforeachtestconcentrationandthreerepeatswereplacedforeachconcentration.Thecontrol
containerwithsolventbutwithouttheextractwasusedinthetest[ 7] .Thenumbersofseedgerminationand
lengthofseedlinggrowth(alsolengthofgrowthofyoungroots)weremeasuredafter5days.Wedetermined
theefectsofalcoholextractofgreenpeelofJ.mandshuricaonseedgerminationandseedlinggrowthofB.
chinesis, R.sativusandM.sativabycalculatingtherateofseedgerminationandinhibitingrateofseedling
growth(alsoinhibitingrateofgrowthofyoungroots).
Thecalculationformulaoftherateofseedgermination(R)isexpressedasfolowing:
R=numbersoftestseedgermination/numbersofcontrolseedgermination×100%
Thecalculationformulaoftheinhibitingrateofseedlinggrowth(I)(alsoinhibitingrateofgrowthof
youngroots)isexpressedasfolowing:
第 3期 孙墨珑 ,等:核桃楸外果皮提取物的化感作用及成分分析 47　
I=lenthoftestseedlinggrowth/lenthofcontrolseedlinggrowth×100%
1.4　Analysismethodsofactivecomponents
ThechemicalcomponentsandrelativecontentsintheethylacetatepartofextractfromgreenpeelofJ.
mandshuricawereanalyzedbyGC-MS.Agilent6890 N-5973 inertmadeinUSAwasused.Theanalysisof
chemicalcomponentsandrelativecontentsisaccomplishedaccordingtothepeakareabyNist02 GC-MS
informationanddatabase.
ConditionsofGCwereasfolows:DB-17MScapilarycolumn, length 30m, radius0.25mm, film
0.25 μm, temperature260℃ ingaseousroom, withheliumgas, flowrate1mL/min, injectamount1μL,
originaltemperature50℃ for3min, elevated10℃/minto250℃for5min, GC-MSmaximumtemperature
290℃.ConditionsofMSwereasfolows:EIelectronenergyofionicresource70eV, temperatureofionic
resource230℃, scanrange15-260u。
2　Resultsanddiscussion
2.1　Alelopathyofthealcoholextractandtheethylacetatepartofalcoholextract
AlelopathyofthealcoholextractsandtheethylacetatepartofalcoholextractfromgreenpeelofJ.
mandshuricaonB.chinesis, R.sativusandM.sativaforfivedayswasshowninTable1.
Table1　AllelopathyofthealcoholextractsongreenpeelofJ.mandshurica %
plantspecies massconcn./(g·L-1)
rateof
seedgermination
alcoholextractethylacetatepart
inhibitingrateof
youngrootsgrowth
alcoholextractethylacetatepart
inhibitingrateof
seedlinggrowth
alcoholextractethylacetatepart
B.chinesis
control 100　　 100　　 0　 0　 0　 0　
0.78 73.3 78.5 48.8 46.8 48.8 43.8
1.56 63.3 71.4 70.2 72.2 74.3 65.7
3.12 54.2 58.5 79.8 81.3 83.3 74.7
6.25 35.7 37.1 92.3 91.8 94.8 85.3
12.5 　6.7 　5.7 100　　 100　　 100　　 92.2
R.sativus
0.78 83.2 86.1 37.3 39.7 42.2 33.2
1.56 80.0 82.8 56.3 54.8 58.8 50.8
3.12 60.7 66.5 66.7 62.7 67.2 60.8
6.25 41.2 38.5 83.2 80.3 86.8 78.3
12.5 18.0 20.8 95.3 98.3 93.3 91.3
M.sativa
0.78 78.3 84.2 42.3 40.3 46.3 35.2
1.56 71.4 76.7 61.2 61.2 65.3 60.3
3.12 56.7 61.7 75.8 73.3 69.8 64.8
6.25 38.5 37.1 88.3 86.7 90.2 84.2
12.5 10.0 21.4 100 100 100 90.2
BoththealcoholextractandtheethylacetatepartofalcoholextractfromgreenpeelofJ.mandshurica
exhibitalelopathy(inhibitingseedgerminationandseedlinggrowth)onB.chinesis, R.sativusandM.
sativa.Theirefectswereextract-concentrationdependent, increasingwiththeincreaseofextractconcentra-
tion.Therateofseedgerminationwaslessthan 50% whentheconcentrationofbothextractswasabove
6.25g/Lforfivedaysonthreeplantspecies.Theinhibitingrateofseedlinggrowth(alsoinhibitingrateof
growthofyoungroots)wasmorethan50%whentheconcentrationofbothextractwasabove1.56g/Lforfive
daysonthreeplantspecies.Thealelopathyofalcoholextractandethylacetatepartofalcoholextractfrom
greenpeelofJ.mandshuricadecreasedintheorderofB.chinesis, M.sativaandR.sativus.
Alkindsofalelochemicalscanafectseedgerminationthroughafectingseedcelmembrane
permeability, celdivisionanddiferentiation, respiration, proteinsynthesis, geneexpression, andhormone
synthesisandequilibrium.Thealelopathicefectsonseedgerminationarerelatedtothetypesand
48　 林　产　化　学　与　工　业 第 28卷
concentrationsofalelochemicals, speciesofrecipientplants, andenvironmentalconditions[ 8] .
2.2　Analysisofchemicalcomponentsoftheethylacetatepartofalcoholextract
ThetotalioncurrentchromatogramoftheethylacetatepartofalcoholextractfromgreenpeelofJ.
mandshuricabyGC-MSwasasshowninFig.1.
Fig.1　Totalioncurrentchromatogram
ofthe ethylacetate partof
alcoholextract
Thechemicalcomponentsandrelativecontentsintheethyl
acetatepartofalcoholextractfromgreenpeelofJ.mandshuricaby
GC-MSwereanalyzedasshowninTable2.
Thechemicalcomponentsintheethylacetatepartofalcohol
extractfromgreenpeelofJ.mandshuricawithrelativecontentwere:
5-hydroxy-1, 4-naphthalenedione(juglone)ofGCcontent31.20%,
n-hexadecanoicacidofGCcontent9.99%, 7-methoxy-1-tetraloneof
GCcontent7.99%, 1 , 5-naphthalenediolofGCcontent7.15%,
2, 6-dimethoxy-phenolofrelativeconten4.36%, 4-butoxy-benzalde-
hydeofGCcontent3.23%, 5-(hydroxymethyl)-2-furancarboxalde-
hydeofGCcontent2.96%, 1, 3-dihydroxyacetonedimmerofGC
content2.94%, glycerinofGCcontent2.77%, 1(3H)-isobenzo-
furanoneoftheGCcontent2.57% byGC-MS.Twenty-fourcom-
poundsintheethylacetatepartofalcoholextracthavebeenidentifiedwithtotalGCcontentof94.55%.
Table2　AnalysisoftheethylacetatepartofalcoholextractbyGC-MS
No. retentiontime/min compounds Mr formula　
relative
content/%
similarity
/%
1 3.65 glycerin 92 C3H8O3 2.77 78
2 4.33 1, 3-dihydroxyacetonedimer 180 C6H12O6 2.94 53
3 4.75 benzofuran, 2, 3-dihydro- 120 C8H8O 1.05 80
4 5.34 4H-pyran-4-one, 2, 3-dihydro-3, 5-dihydroxy-6-methyl- 144 C6H8O4 1.55 90
5 5.83 2-furancarboxaldehyde, 5-(hydroxymethyl)- 126 C6H6O3 2.96 90
6 6.58 1(3H)-isobenzofuranone 134 C8H6O2 2.57 80
7 6.76 2-methoxy-4-vinylphenol 150 C9H10O2 1.02 95
8 7.96 [ 1, 3] diazepan-2, 4-dione 128 C5H8N2O2 1.05 64
9 8.60 pentanedioicacid, dibutylester 244 C13H24O4 1.04 78
10 9.95 phenol, 2, 6-dimethoxy- 154 C8H10O3 4.36 94
11 10.44 1, 2, 3-benzenetriol 126 C6H6O3 1.75 92
12 12.15 1, 4-naphthalenedione, 5-hydroxy- 174 C10H6O3 31.20 96
13 12.55 1(2H)-naphthalenone, 3, 4-dihydro-6, 7-dihydroxy- 178 C10H10O3 1.86 90
14 13.38 benzaldehyde, 4-butoxy- 178 C11H14O2 3.23 70
15 13.69 n-hexadecanoicacid 256 C16H32O2 9.99 97
16 14.21 4-((1E)-3-hydroxy-1-propenyl)-2-methoxyphenol 180 C10H12O3 2.13 97
17 16.03 hexadecanoicacid, methylester 270 C17H34O2 1.39 92
18 16.20 4-hydroxy-2-methoxycinnamaldehyde 178 C10H10O3 1.01 90
19 16.90 7-methoxy-1-tetralone 176 C11H12O2 7.99 82
20 17.16 hexadecanoicacid, ethylester 284 C18H36O2 1.86 96
21 17.34 1, 5-naphthalenediol 160 C10H8O2 7.15 96
22 17.81 linoleicacidethylester 308 C20H36O2 1.32 99
23 18.13 9, 12-octadecadienoicacid(Z, Z)- 280 C18H32O2 1.03 99
24 20.43 9, 12, 15-octadecatrien-1-ol, (Z, Z, Z)- 264 C18H32O 1.33 91
3　Conclusions
3.1　BoththealcoholextractandtheethylacetatepartofalcoholextractfromgreenpeelofJ.mandshurica
exhibitalelopathy(inhibitingseedgerminationandseedlinggrowth)onB.chinesis, R.sativusandM.sativa.
Theirefectswereextract-concentrationdependent, increasingwiththeincreaseofextractconcentration.The
rateofseedgerminationwaslessthan50% whentheconcentrationofbothextractswasabove6.25g/Lfor
第 3期 孙墨珑 ,等:核桃楸外果皮提取物的化感作用及成分分析 49　
fivedaysonthreeplantspecies.Theinhibitingrateofseedlinggrowth(alsoinhibitingrateofgrowthofyoung
roots)wasmorethan50%whentheconcentrationofbothextractwasabove1.56g/Lforfivedaysonthree
plantspecies.ThealelopathyofalcoholextractandethylacetatepartofalcoholextractfromgreenpeelofJ.
mandshuricadecreasedintheorderofB.chinesis, M.sativaandR.sativus.
3.2　ThechemicalcomponentsintheethylacetatepartofalcoholextractfromgreenpeelofJ.mandshurica
withhighGCcontentwere:5-hydroxy-1, 4-naphthalenedione(juglone)ofGCcontent31.20%, n-hexade-
canoicacidofGCcontent9.99%, 7-methoxy-1-tetraloneofGCcontent7.99%, 1, 5-naphthalenediolof
GCcontent7.15%, 2, 6-dimethoxy-phenolofGCcontent4.36%, 4-butoxy-benzaldehydeofGCcontent
3.23%, 5-(hydroxymethyl)-2-furancarboxaldehydeofGCcontent2.96%, 1, 3-dihydroxyacetonedimmerof
GCcontent2.94%, glycerinofGCcontent2.77%, 1(3H)-isobenzofuranoneofGCcontent2.57% by
GC-MS.Twenty-fourcompoundsintheethylacetatepartofalcoholextracthavebeenidentifiedwithtotalGC
contentof94.55%.
References:
[ 1]任宪威.树木学(北方本)[ M] .北京:中国林业出版社 , 1997.
[ 2]朴仁哲 ,赵洪颜 ,朴京一 ,等.核桃楸青果皮提取液对植物生长的影响 [ J] .天然产物研究与开发 , 2006(18):11-14.
[ 3]孙墨珑 ,宋湛谦 ,方桂珍.核桃楸总黄酮及胡桃醌含量测定 [ J] .林产化学与工业 , 2006, 26(2):93-95.
[ 4] SUNMo-long, WANGYan-mei, SONGZhan-qian, etal.Insecticidalactivitiesandactivecomponentsofthealcoholextractfromgreenpeelof
Juglansmandshurica[ J] .ForestResearch, 2007, 18(1):62-64.
[ 5]许绍惠 ,许泓.胡桃属植物毒性成分及其应用[ J] .沈阳农业大学学报 , 1990, 21(2):167-170.
[ 6]李浩然 ,泽桑梓 ,刘宏屏 ,等.植物的化感作用及其在林业经营中的运用 [ J] .西部林业科学 , 2006, 35(1):121-124.
[ 7]李合生.现代植物生理学 [ M] .北京:高等教育出版社 , 2002.
[ 8] PENGShao-lin, WENJun, GUOQi-feng.Mechanismandactivevarietyofalelochemicals[J] .ActaBotanicaSinica, 2004, 46(7):757-766.
《生物质化学工程 》 2006年增刊目录
　　《生物质化学工程》 2006年增刊是配合 “中国林业生物质能源发展研讨会”出版的论文集, 共刊出主题报告 、考察报告 、
特邀报告和研究报告 74篇 , 384页 ,定价 100元(含邮资)。需要者请直接汇款至 《生物质化学工程》编辑部订购。地址:
210042南京市锁金五村 16号林化所内;联系电话:(025)85482492;http://www.bce.ac.cn;E-mail:lchg@chinajoural.net.cn。
增刊目次如下:
文章 题目 文 章 题目
发挥资源优势 、强化科技创新、大力促进林业生物质能源加快发展
德国瑞典林业生物质能源利用技术考察报告
生态能源林———未来生物质燃料油原料基地
生物质能源与能源林业若干问题研究
植物纤维制备燃料乙醇的关键技术
生物质能源开发与应用现状和前景
生物质基高分子新材料———能源替代的重要方向
林业生物质热化学转化利用研究现状
林间剩余物热电联产综合开发关键装备与技术研究
能源柳研究现状与国内引种栽培
发展中国林木生物质成型燃料
四种木本植物油制取生物柴油的研究
中国薪炭林培育技术
我国生物柴油产业化制备技术及其发展趋势
木质纤维生物转化乙醇技术
生物质热裂解和化学液化制燃料油技术现状及展望
我国亚热带能源林研究展望
建立灌木能源林概念并构筑林业可再生能源新产业链
木本生物质能源的发展现状和对策
典型户用农村生物质能源工程能量流动研究
生物质能源发展问题与对策
木质生物质的能源化及功能性环境材料制备
桉树生物质能源的优势 、现状和潜力
对云南木本生物能源资源培育的初浅设想
木质能源麻疯树产业发展对策研究
黄连木优树选择与良种繁育技术的研究
黄鼠树引种及栽培试验
香胶树组织培养繁殖技术
橡树资源———优质林木生物质能源发展战略研究
云南小桐子资源及其生物柴油原料林发展策略
西北沙区 4种能源树种评价研究
油楠作为能源植物开发利用的思考
蒸汽爆破处理胡枝子的同步糖化发酵制备乙醇研究
固定化酶及全细胞生物催化合成生物柴油的研究进展
酵母工程菌降解纤维素的研究进展
木本油料植物山核桃新品种的选育
木质纤维素原料生产燃料酒精开发技术研究进展
湖南省林木生物质能科研和产业化现状与展望
(下转 60页)