旋光度2.2.7.OPTICALROTATION旋光是手性物质的特性,即能使偏振光的平面旋转。Opticalrotationisthepropertydisplayedbychiralsubstancesofrotatingtheplaneofpolarisationofpolarisedlight.右旋物质的旋光度为正的(+),即右旋物质可以使偏振光平面顺时针方向旋转;左旋物质的旋光度为负的(-)。Opticalrotationisconsideredtobepositive(+)fordextrorotatorysubstances(i.e.thosethatrotatetheplaneofpolarisationinaclockwisedirection)andnegative(−)forlaevorotatorysubstances.精确的旋光度αmλt是指,在温度下,波长为λ的光透过长1m或含1kg/m3旋光活性物质的液体,所发生的旋转,用弧度(rad)
表
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示。实际操作中,旋光度常用mrad﹒m2﹒kg-1表示。Thespecificopticalrotationαmλtistherotation,expressedinradians(rad),measuredatthetemperaturetandatthewavelengthλgivenbya1mthicknessofliquidorasolutioncontaining1kg/m3ofopticallyactivesubstance.Forpracticalreasonsthespecificopticalrotationαmλtisnormallyexpressedinmilliradiansmetresquaredperkilogram(mrad·m2·kg−1).本药典采用以下常规定义ThePharmacopoeiaadoptsthefollowingconventionaldefinitions.纯液体旋光度α:旋光度α以角度(°)表示,即20℃下,1dm长测定管的纯液体使钠光谱D线(λ=589.3nm)的偏振光平面所旋转的角度;对于溶液,按专论规定
方法
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制备。Theangleofopticalrotationofaneatliquidistheangleofrotationα,expressedindegrees(°),oftheplaneofpolarisationatthewavelengthoftheD-lineofsodium(λ=589.3nm)measuredat20°Cusingalayerof1dm;forasolution,themethodofpreparationisprescribedinthemonograph.液体旋光度αD20:测定即20℃下,1dm长的测定管的含待测液体的溶液使钠光谱D线(λ=589.3nm)的偏振光平面所旋转的角度(°),即溶液旋光度α。溶液中液体旋光度,由溶液旋光度α除以溶液中被
检测
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液体的密度(g/cm3)计算得出。ThespecificopticalrotationαD20ofaliquidistheangleofrotationα,expressedindegrees(°),oftheplaneofpolarisationatthewavelengthoftheD-lineofsodium(λ=589.3nm)measuredat20°Cintheliquidsubstancetobeexamined,calculatedwithreferencetoalayerof1dmanddividedbythedensityexpressedingramspercubiccentimetre.固体物质的旋光度αD20:测定20℃下,1dm长测定管的含被测物质1g/ml的溶液使钠光谱D线(λ=589.3nm)的偏振光平面所旋转的角度,即溶液旋光度α。溶液中固体物质的旋光度由溶液的旋光度α计算得出。溶液中某物质的旋光度与溶剂和浓度有关。ThespecificopticalrotationαD20ofasubstanceinsolutionistheangleofrotationα,expressedindegrees(°),oftheplaneofpolarisationatthewavelengthoftheD-lineofsodium(λ=589.3nm)measuredat20°Cinasolutionofthesubstancetobeexaminedandcalculatedwithreferencetoalayerof1dmcontaining1g/mLofthesubstance.Thespecificopticalrotationofasubstanceinsolutionisalwaysexpressedwithreferencetoagivensolventandconcentration.按本药典采用的惯例,旋光度不标注单位;它的实际单位为(°)﹒ml﹒dm-1﹒g-1。IntheconventionalsystemadoptedbythePharmacopoeiathespecificopticalrotationisexpressedbyitsvaluewithoutunits;theactualunits,degreemillilitresperdecimetregram[(°)·ml·dm−1·g−1]areunderstood.本药典的旋光度同国际标准单位旋光度的换算关系如下:TheconversionfactorfromtheInternationalSystemtothePharmacopoeiasystemisthefollowing:αmλt=αλt×0.1745如果专论有特别要求,按要求选择温度(可能不是20℃)和波长。Incertaincasesspecifiedinthemonographtheangleofrotationmaybemeasuredattemperaturesotherthan20°Candatotherwavelengths.旋光计的读数必须精确到0.01°。测量范围通常由鉴定用石英片检查;测量范围内线性由蔗糖溶液检查。Thepolarimetermustbecapableofgivingreadingstothenearest0.01°.Thescaleisusuallycheckedbymeansofcertifiedquartzplates.Thelinearityofthescalemaybecheckedbymeansofsucrosesolutions.方法Method.20±0.5℃下,旋光计调零,用钠光谱的D线(λ=589.3nm)测定,或者按专论要求的温度测定旋光度。测定液体的旋光度,测定前放入封闭的空测定管,调零;测定固体的旋光度,测定前放入盛有所用溶剂测定管,调零。DeterminethezeroofthepolarimeterandtheangleofrotationofpolarisedlightatthewavelengthofTheD-lineofsodium(λ=589.3nm)at20±0.5°C,unlessotherwiseprescribed.Measurementsmaybecarriedoutatothertemperaturesonlywherethemonographindicatesthetemperaturecorrectiontobemadetothemeasuredopticalrotation.Determinethezerooftheapparatuswiththetubeclosed;forliquidsthezeroisdeterminedwiththetubeemptyandforsolidsfilledwiththeprescribedsolvent按下式计算旋光度:Calculatethespecificopticalrotationusingthefollowingformulae.纯液体旋光度:Forneatliquids:αD20=αl∙ρ20溶液中物质的旋光度:c为浓度,单位g/l。Forsubstancesinsolution:wherecistheconcentrationofthesolutioningramsperlitre.αD20=1000αl∙c按下式计算以g/l为单位的溶解物质的浓度c,或以m/m百分比为单位的浓度c′:Calculatethecontentcingramsperlitreorthecontentc′inpercentm/mofadissolvedsubstanceusingthefollowingformulae:c=1000αl∙αD20c‘=1000αl∙αD20∙ρ20α=20±0.5°C下,旋光度读数,单位度(°)l=测定管长度,单位dm。ρ20=20°C下溶液密度,单位g/cm3,本药典在2.2.5节中以相对密度代替密度。c=溶解物质的浓度,单位g/l。c′=溶解物质的浓度,单位g/l。α=angleofrotationindegreesreadat20±0.5°C;l=lengthindecimetresofthepolarimetertube;ρ20=densityat20°Cingramspercubiccentimetre.ForthepurposesofthePharmacopoeia,densityisreplacedbyrelativedensity(2.2.5).