全 文 :·1216· 中草药ChineseTraditionalandHerbalDrugs第36卷第8期2005年8月
药材与资源
Crystallography,morphology,andthermapropertiesofstarch
inFritillariathunbergiiandF.ussurensisaswellas
comparisonwithpotatostarch
WANGShu—junl,GAOWen—yuan¨,JIAWei2,XIAOPei—gen3
(1.TheCollegeofPharmaceuticsandB otechnology,TianiinUniversity,Tianjin300072,China;2.School
ofPharmacy,ShanghaiJi oTongUn versity,Shanghai200030,China;3.InstituteofMedicinalPlant,
ChineseAcademyofMedicalSciencesandPekingUnionMedicalCo lege,Beijing100094,China)
Abstract:ObjectiveTofullyunderstandtheme icinalpl ntsofFritillariaL.,thephysicochemical
propertiesofstarchintwospeciesofFritillariaL.,F.thunbergiiandF.ussurensis.werenvestigatedby
meansofvariousanalyticalmethods.MethodsThepropertiesofstarchinthetwodifferentspeciesof
FritillariaL.werecomparedbyX—raydiffraction,scanningelectrom croscope(SEM)andthe—
mogravimetricanalysis(TGA).ResultsThecrystalypeofstarchinthetWOspeciesofFritillariaL.
wasthecharacteristicB—typewhichwasinconsistentwiththatofpotatostarch.Thedegreesofcrystallini—
tyofF.thunbergiistarchandF.ussurensisstarchwereabout29.9%and20.1%,respectively.However,
thedegreeofcrystallinityofthepotatostarchwas44.9%.Fromthecrystallinitydegreeofthestarchin
tWOspeciesofFritillariaL., tcouldbeconcludedthathecontentofamyloseinF.ussurensisstarchwas
higherthanthatinF.thunbergiistarch.ThegranulesizeofthestarchintwospeciesofFritillariaL.
rangedfrom5to40扯m,whichwereallsmallerthanthatofthepotato.Thestarchgranuleintwospecies
ofFritillariaL.w sincycloidalorelliptic—shape.Itcouldbeconcludedthathethermalstabilityof he
starchintWOspeciesofFritillariaL.w sdifferentduetothedifferentstructuresofdifferentstarchinvar—
iousplantsbyTGA.ConclusionThephysicochemicalpropertiesofstarchintwodifferentspeciesofFrit—
illariaL.differalotduetotheirgeographicalor gin.
Keywords:FritillariaL.;starch;crystaUography;morphology;thermalstability
浙贝母和平贝母中淀粉的结晶学、形态学和热性质研究及与马铃薯淀粉的比较
王书军1,高文远”,贾 伟2,肖培根3
(1.天津大学药物科学与技术学院,天津300072;2.上海交通大学药学院,上海200030;
3.中国医学科学院中国协和医科大学药用植物研究所,北京 100094)
摘 要:目的 为了能够更加充分了解贝母属药用植物,通过各种分析方法对两种贝母——浙贝母和平贝母中所
包含的淀粉的物理化学性质进行了研究。方法 采用X射线衍射,扫描电子显微镜(SEM)以及热分析(TGA)的方
法对两种贝母中淀粉的性质进行了比较。结果通过研究发现,两种贝母淀粉的晶体类型都为典型的B型,这与马
铃薯淀粉的晶体类型是一致的。浙贝母和平贝母淀粉的结晶度分别为29.9%和20.1%,而马铃薯淀粉的结晶度为
44.9%。从两种贝母淀粉的结晶度可以看出,平贝母淀粉中直链淀粉的量要高于浙贝母淀粉中直链淀粉的量。两种
贝母淀粉的颗粒尺寸为5~40/tm,而且他们都小于马铃薯淀粉的颗粒尺寸。两种贝母淀粉颗粒的形状是圆形的和
椭圆形的。热稳定性表明由于植物来源的不同导致淀粉颗粒结构不同,从而热稳定性存在明显的差异。结论两种
贝母淀粉由于来源不同,物理化学性质存在明显的差异。
关键词:贝母属;淀粉;结晶学;形态学;热稳定性
中图分类号:R282 文献标识码:A 文章编号:0253—2670(2005)08—1216—05
收稿日期:2004—12-06
*通讯作者高文远Tel:(022)87401895E—mail:edwinll@eyou.com
万方数据
中草药ChineseTraditionalandHerbalDrugs第36卷第8期2005年8月·1217·
1 IntrOductiOn
ThebulbsofspeciesofFritillariaL.,Beimu,
havebeenusedasoneofthemostimportantanti—
tussive,expectorant,a dantihypertensivedrugs
intraditionalChinesemedicine(TCM)forthou—
sandsofyears.Variouschemicalandpharmacolo—
gicalstudiesonBeimuhavedemonstratedth the
majorbioactiveingredientstorelievecoughare
alkaloidsinthebulbswiththeirtypesandcontents
varyingindifferentspeciesofFritillariaL.Upto
now。tensofalkaloidsinbulbsofFritillariaL.
havebeeninvestigatedand ightisosteroidal
alkaloidsincludingepeiedine,beiedinone,
isovertivine,vertivine,verticinone,hupehenine,
ebeienine,andimperialinerestablisheda bioac—
tivecomponents[卜⋯.Inaddition.somenon—alka—
loidconstituentsco ainingsaponin,terpenoids,
steroids,succinicacid,thymidine,andadenisinei
differentspeciesofFritillariaL.h vealsobeen
identifiedc引.
However,littleresearchhasbeencarriedout
onthestarchinthebulbsofF—tillariaL.Asre—
portedearlier,themaincomponentinthebulbsof
speciesofFritillariaL. sstarchoccupyingap—
proximately80%contentintheotalbiomass[9|.
Thismedicinalpl nts arch,however,hasalways
beenignoredan isposedofresultinginthewaste
ofbiomassinresourcesofFritillariaL.
Starchisanimportantpolysaccharidereserved
inhigherplants.Itconsistsof womaincompo—
nents,amyloseandamylopectin.Nativestarch
playsanimportantroleinthefoodandplasticin—
dustryasaninexpensive,renewable,andbiode—
gradablenaturalesource[1。~12I.Differenttypesof
starchderivedfromdifferentplantshavedifferent
properties.Inordertomakefulluseofthemedi—
cinalp antresourcesofFritillariaL.,thephysico—
chemicalpropertiesofstarchinthetwospeciesof
FritillariaL.werestudiedcomprehensively.
2 Materialsandmethods
2.1 PlantresourcesofFritillariaL.andpre—
treatment:F.thunbergiiMiq.andF.ussurensis
Maxim.wereprovidedbyMeiweiTCMCompany
(Anguo,HebeiProv nce,China)andwereidenti—
fledbyProfessorGaoWen—yuan,TianjinUniver—
sity,China.Thenativpotatostarch(16%mois—
ture)containing30%amyloseand70%amy—
lopectin。wasobtainedfromXuanweiRunkai
StarchCompany(Xuanwei,YunnanProvince,
China).
Thetwospeciesof FritillariaL. were
cleaned,comminutedtopowder,andthendriedin
anovena dkeptinadesiccator.Thed iedpowder
wasextractedwith85%ethanolt45℃for48h.
Thesedimentwaswashedwith85%alcoholfor
severaltimes,andthenesiccatedatambienttem—
peratureforfurtheruse.
2.2 Fouriertransforminfrared(FT—IR)spec—
troscopy:IRspectrawereobtainedwithBIO—
RADFTS3000IRSpectrumScanner(BIo—RAD。
USA).ThestarcandthepowdersofFritillaria
L.(includingthoseextractedwith85%alcoholfor
48h)werebl ndedwithKBrpowder,respective—
ly,andpressedintotabletsbeforemeasurement.
2.3 X—raypowderdiffractionmeasurements:
MonochromaticCu—K。radiation(wavelength一
0.1542nm)wasproducedbyaBDX3300X-ray
PowderDiffractometer(BeijingUniversityEquip—
mentManufacturer,China).ThespeciesofFritil-
lariaL.andstarchpowderwe epackedtightlyin
arectangularaluminumcell.Thesamplesw reex—
posedtotheX—raybeamfromanX—raygenerator
runningat36kVand20mA.Thescanningre—
gionsofthediffractionangle2 0were10。一30。.
whichoveredmostofthesignificantdiffraction
peaksofthestarchrystallites.Duplicatedmea—
surementsweremadeatambienttemperature.Ra—
diationwasdetectedwithaproportionaldetector.
2.4 Determinationofthecrystallinitydegree:
Thecrystallinitydegreeofsampleswaquantita—
tivelyestimatedfollowingthemethodofNaraand
Komiya(1983)[13].Asmoothcurvewhichonnect—
edpeakbaselineswacomputer—plottedonthe
diffractograms(Fig.1).Theareabovethe
smoothcurvewastakenasthecrystallineportion
andthe10wera eabetweensmoothcurveandlin—
earbaselinewhichonnectedthtwopointsofin—
tensity20of30。and10。inthesampleswataken
astheamorphoussection.Theupperdiffraction
peakareandthetotaldiffractionareaverthe
iffractionangle10。一30。20wereintegratedusing
SmadchromSoftware(MorganandKennedyRe—
search,Australia).Theratioofupperareatototal
diffractionwastakenasthecrystallinitydegree.
万方数据
.1218. 中草药ChineseTraditionalandHerbalDrugs第36卷第8期2005年8月
Ditfractionangle/20
Fig.1Calculationofrelativecrystallinitydegree
Theequationofcrystallinitydegreeis as
follows:x,一A。/(A,+A。)
Where:X。referstocrystallinitydegree;A,referstocrys—
tallizedareaonX—raydiffractogram;A。referstoamorphous
areaonX—-raydiffractogram
2.5 Scanningelectronmicroscope(SEM):Ana—
lysisofscanningelectronmicrographsw sper—
formedwithanenvironmentalscanningelectron
microscope(ESEM.PhilipsXL一3).Starchsam-
piesweresuspendedinacetonetoobtainasuspen—
sion.Onedropofthestarch—acetonesusp nsion
wasdroppedonaglasslide.Thestarchwascoat—
edwithgoldpowdertoavoidelectronicchargeun—
derthelectronbeamaftertheacetonevolatilized.
Anacceleratingpo e tialof30kVwasusedduring
micrography.
2.6 Themogravimetricanalysis(TGA):The
thermalpropertiesofthesamplesw remeasured
withaZTY—ZPtypeThermalAnalyzer(Beijing
UniversityEquipmentMa ufacture,China).The
weightofsamplesvariedfrom4—6mg.Thesam—
Dleswereheatedfromroomtemperatureto500℃
ata rateof15。C/min.ThederivativesofTGA
thermogramswereobtainedusingorigin6.0analy—
sis oftware.
3 Resultsandiscussions
3.1 FT—IRspectroscopy:AsshowninFig.2,the
FT—IRspectraofthetwopowdersofFritillaria
L.
aresimilarwitheachotherandthatofpotato
starch.ThenoticeabledifferencesbetweentheFT—
IRspectraofthetwopowdersofFritillariaL.and
thepotatostarchwerepeaksat2362cm~,2337
cm一1and1528cm~.whichdidnotappearonthe
FT—IRspectrumofpotatostarch.Thepeaksat
2362cm~,2337cm一1mrghtbeduetothenoise
peaksofC02inthetest.However,thepeaka
1528cm一1mightberesultedfromthesmall
moleculeconstituentsinthewospeciesofFritil—
lar施L.Therew threecharacteristicpeaks
o{starchbetween1019cm一1and1156cm~,
attributedtoC—Obondstretching[1“.Thepeak
near1.019cm一1wasascribedtotheC—Ostretchof
C—O—Cinstarch,andthepeaksnear1081and
1 156cm一1weremainlyattributedtoC—Ostretch
ofC—O—Hinstarch.Therewerealsothreestrong
peaksat1162,1081,and1019cm-1inthespec—
traofthetwopowdersofFritillariaL.indicating
thathemajorcomponentsofthetwopowderso{
FritillarinL.werestarch.
4
wavenumbers/cm-1
a—potatos archb-F.thunbergiipowderc—F.ussurensispowder
Fig.2FT—IRspectraoftwopowdersofFritillaria
L·
andpotatostarch
Thespectraofpotatostarchandthetwopow—
dersofF一£iz如一日L.extractedwith85%ethanol
at45,Cfor48hwerepresentedinFig.3·
d0卜一00—31_500—3100—0—25T_0 2100—0115—00—1r000—15004
Wavenumbers/cm一1
a—potatostarchb-F.ussurensisstarchc—F.thunbergiistarch
Fig.3FT—IRspectraofpotatostarchandtwopowders
ofFritill口riaL.extractedwith85%ethanol
at45℃for48h
AsillustratedbyFig.3,thewopowdersof
FritillarinL.extractedwith85%ethanolresulted
inthesameFT—IRspectraasthepotatostarch·
Thepeakat1528cmlinFT—IRspectra(Fig.2)
ofthetwopowdersofFritillariaL.disappeared,
indicatingthatsomeofthesmall—molecularchemi—
calsinthepowdersofFritillariaL.weremoved
万方数据
中草药ChineseTraditionalandHerbalDrugs第36卷第8期2005年8月·1219·
bythethanolextraction.Intherwords。the
residuesofthepowdersofFritillariaL.afterex—
tractionwerebasicallystarch.
3.2 X—Raydiffractionanalysis:Muchofthein—
formationab uts archcrystallinepropertieswas
acquiredfromX—raypowderdiffractionstudies.
StarchcanbeclassifiedtoA,B,andCforms.In
thenativegranularfo ms,thestarchformAwas
associatedmainlywithcerealstarch,suchasmaize
starchandwheats arch.TheX—raypatternsof
thesekindsofstarchgavethestrongerdiffraction
peaksataround15。,17。,18。,and23。:Thestarch
formBwasusuallyobtainedfromtuberstarch,
suchaspotatostarchandcannastarch.The
strongestdiffractionpeakftheX—raydiffraction
patternappearedat17。20.Therewerealsoafew
smallpeaksat2臼valuesof20。,22。,and24。.The
starchformCwasa mixtureofbothAandB
types,suchassmooth—seededpeastarchandvari—
OUSbeanstarchEl4].
TheX—raypowderdiffractogramsforthetwo
starchesofFritillariaL.andpotatostarchwere
showninFig.4.
1696
1r——1F——■犷———i—10
Diffractionangle/20
a—potatos archb-F.ussurensisstarchc—F,thunbergiistarch
Fig.4X-Raydiffractionspectraoftwostarches
ofFritillariaL.andpotatostarch
ThetwostarchesofFritiUariaL.showedthe
highlysimilarX—raydiffractionspectrawiththatof
potatostarch.Aswellknown,potatos rch
showedthecharacteristicB—typeattern.Thetwo
starchesofFritillariaL.gavethestrongest
diffractionpeakataround17。2护andafewsmall
peaksataround20valuesof15。,20。,22。。and
24。.Thisresultdemonstratedth thtwostarch—
esofFritillariaL.werealsocharacteristicB—type
starch.
Thecrystallinitydegreeofthreekindsof
starchcalculatedfromtheabovefigureswashown
inTable1.Forthisevaluation.starchwi hthe
samemoisturecontentsatapproximately10%was
usedinordertominimizetherrorbetweendiffer—
entsamples.Thecrystallinitydegreeofthepotato
starchwasabout44.9%,andF.thunbergiistarch
andF.ussurensisstarchwereabout29.9%and
20·l%,respectively.Generally,thehigherthe
contentoftheamylose,thelowerthecrystallinity
degreeofthestarch.Hence,theontentofthe
amyloseintheF.ussurensisstarchwashigherthan
thatintheF.thunbergiistarch,andthecontentof
amyloseinthepotatostarchwasthelowestin he
threestarches.
Table1 X—Raydiffractiondataftwostarches
ofFritillariaL.andpotatostarch
Samples Crystallinitydegree/%Crystalpattern
3.3 SEMAnalysis:Morphologyofstarchesfrom
differentplantsourcesvariedwiththegenotype
andculturalpractices,dependingonthebiochem—
istryofthechloroplastor myloplast,aswellas
physiologyoftheplant[15|.Thegranularstructures
ofpotato,F.thunbergii,andF.ussure sisstarch
showedsignificantvariationsn sizeandshape
whenviewedbySEM.Scanningelectronmicro..
graphsofthestarchgranulesfromtwospeciesof
FritillariaL.andpotatowereillustratedinFig.5.
a—F.thunbergiistarchb-F.ussurensisstarchc—potatos arch
Fig.5SEMofF.thunbergii,F.ussurensis,
andpotatostarch
抛九
~Ⅵ龇n飞爻撇~父Ⅲ^∥∥;拶
万方数据
·1220· 中草药ChineseTraditionalandHerbalDrugs第36卷第8期2005年8月
AsshowninFig.5,thegranulesizeoftheF.
thunbergiistarchrangedfrom5to40tim.Theav—
erageparticlesizerangedfrom5to20timforsmall
and20to40肛mforlargeF.thunbergiistarch
granules.TheaverageparticlesizofindividualF.
ussurensisstarchgranuleswasimilartothatofthe
F.thunbergii.Theaveragesizeofpotatostarch
granules,however,wassignific ntlygreaterhan
theformertwostarchgranulesofFritillariaL.,
rangingfrom25to40timforsmalland40to100
umforlargeranules.Potatostarchgranulesap—
pearedtobeovalandirregularorcuboidalin
shape.However,thestarchgranulesw reincy—
cloidalorelliptic—shapefortwospeciesofFritillar-
施L.AccordingtotheX-raydiffractionanalysis。
thecrystalp tternofthestarchinthetwospecies
ofFritillariaL.w scharacteristicB—type.B—Type
starchgranulesw reroughlysphericalorpolygo—
nalinshape.Physicochemicalproperties,suchas
lightransmittability,amylosecontent,water—
absorptioncapacityandswellingpowerofthe
starchgranulesvaried,depending0nthegranule
sizeandstarchoriginofFritillariaL.
3.4 Thermalproperties:Thethermogramsofthe
twospeciesofFritillariaL.andpotatostarch
werepresentedinFig.6.
1.1
l0
09
08
07
0.6
O.5
0.4
0.3
Temperature/C
a—potatos archb-F.ussurensisstarchc—F.thunbergiistarch
Fig.6TGAthermogramsoftwospeciesstarch
ofFritillariaL.andpotato
Twowell—definedshiftswereobservedinthe
TGAcurves.Thefirsthift,ataround100℃,
wasproducedbywatervaporationinthethree
kindsofstarch;thesecondshifts artedat200‘C,
resultingfromthethermaldegradationofstarch
occurred.Theproc sscontinuedgra uallyupto
400‘C.
Thethermalstabilityofthetwospeciesstarch
ofFritillariaL.andpotatowasdifferentfrom
eachother,duetothedifferentstructuresofstarch
fromvariousplants.Comparatively,thethermal
stabilityoftheF.ussurensisstarchwasthebesta—
mongthethreekindsofstarch.Furtherresea ch
ontheinnerstructureofstarchofFritillariaL.
willbecarriedoutinthenearfuture.
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摹/s∞o:嘎一菪
万方数据
浙贝母和平贝母中淀粉的结晶学、形态学和热性质研究及与
马铃薯淀粉的比较
作者: 王书军, 高文远, 贾伟, 肖培根, WANG Shu-jun, GAO Wen-yuan, JIA Wei, XIAO
Pei-gen
作者单位: 王书军,高文远,WANG Shu-jun,GAO Wen-yuan(天津大学药物科学与技术学院,天津,300072)
, 贾伟,JIA Wei(上海交通大学药学院,上海,200030), 肖培根,XIAO Pei-gen(中国医学科
学院,中国协和医科大学药用植物研究所,北京,100094)
刊名: 中草药
英文刊名: CHINESE TRADITIONAL AND HERBAL DRUGS
年,卷(期): 2005,36(8)
被引用次数: 2次
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modified potato starches[外文期刊] 2002
15.Narpinder S;Jaspreet S;Lovedeep K Morphological,thermal,and rheological properties of starches
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