1、褶合光譜法原理

 

褶合光譜法(ConvolutionSpectrometry)是以Glenn’S正(zheng)交(jiao)函(han)數(shu)法(fa)為(wei)基(ji)礎(chu)，並(bing)包(bao)容(rong)了(le)導(dao)數(shu)光(guang)譜(pu)法(fa)的(de)一(yi)種(zhong)新(xin)的(de)數(shu)學(xue)變(bian)換(huan)方(fang)法(fa)。其(qi)基(ji)本(ben)原(yuan)理(li)是(shi)利(li)用(yong)褶(zhe)合(he)變(bian)換(huan)技(ji)術(shu)將(jiang)化(hua)合(he)物(wu)的(de)原(yuan)始(shi)吸(xi)收(shou)光(guang)譜(pu)轉(zhuan)變(bian)為(wei)褶(zhe)合(he)光(guang)譜(pu)，顯(xian)示(shi)出(chu)原(yuan)始(shi)吸(xi)收(shou)光(guang)譜(pu)在(zai)構(gou)成(cheng)上(shang)的(de)局(ju)部(bu)細(xi)節(jie)特(te)征(zheng)，其(qi)本(ben)質(zhi)是(shi)與(yu)一(yi)種(zhong)稱(cheng)為(wei)“數學顯微鏡”的離散小波變換(wavelertransform
，WT)xiangyizhideshuxuebianhuanjishu
，shiduiyishiyuhanshuxingshideyuanshixishouguangpushishipinyuhanshudejuyubianhuan，yinernengyouxiaodicongxinhaozhongtiquxinxi，tongguoshensuohepingyidengyunsuangongnengduixinhaojinxingduochiduxihuafenxi。zheheguangpushangdemeiyigezhi
，douyuyiduanbochangqujianneiwuzhidexiguangtexingxiangduiying
，yinerzheheguangputongyangjuyoudingxingdingliangdetezheng。jiziwaifenguangguangdufazhongxishouduyunongdudexianxingguanxizhuanbianchengshuxuefenliangyunongdudexianxingguanxi，liyongzhehequxianzhijiandechayixingshilailianghua，congerweiwuzhidedingxingdingliangtigonglelilunjichu。

 

2、褶合光譜法在藥物分析領域中的應用

 

褶合光譜法在藥學方麵的應用，主要是藥物的定性鑒別(包括雜質的限量檢查)和定量測定及檢測藥物的穩定性等幾方麵。

 

2.1 藥物的定性鑒別及雜質的限量檢查

 

經典的分光光度法對物質進行定性
，主要是根據吸收光譜的峰、穀(gu)或(huo)者(zhe)它(ta)們(men)比(bi)值(zhi)的(de)差(cha)異(yi)判(pan)斷(duan)是(shi)否(fou)為(wei)同(tong)一(yi)物(wu)質(zhi)，由(you)於(yu)它(ta)不(bu)能(neng)對(dui)吸(xi)收(shou)光(guang)譜(pu)的(de)全(quan)波(bo)長(chang)範(fan)圍(wei)進(jin)行(xing)反(fan)映(ying)，因(yin)而(er)不(bu)能(neng)完(wan)全(quan)反(fan)映(ying)物(wu)質(zhi)結(jie)構(gou)的(de)本(ben)質(zhi)特(te)征(zheng)。另(ling)外(wai)，由(you)於(yu)紫(zi)外(wai)可(ke)見(jian)光(guang)譜(pu)為(wei)寬(kuan)帶(dai)吸(xi)收(shou)，曲(qu)線(xian)形(xing)狀(zhuang)一(yi)般(ban)變(bian)化(hua)不(bu)大(da)，不(bu)同(tong)化(hua)合(he)物(wu)的(de)吸(xi)收(shou)光(guang)譜(pu)的(de)細(xi)微(wei)差(cha)異(yi)常(chang)被(bei)其(qi)相(xiang)同(tong)部(bu)分(fen)所(suo)掩(yan)蓋(gai)
，因(yin)而(er)經(jing)典(dian)的(de)分(fen)光(guang)光(guang)度(du)法(fa)很(hen)難(nan)將(jiang)結(jie)構(gou)相(xiang)似(si)的(de)化(hua)合(he)物(wu)區(qu)分(fen)開(kai)來(lai)。而(er)褶(zhe)合(he)光(guang)譜(pu)的(de)定(ding)性(xing)技(ji)術(shu)充(chong)分(fen)利(li)用(yong)了(le)整(zheng)條(tiao)光(guang)譜(pu)所(suo)含(han)的(de)結(jie)構(gou)信(xin)息(xi)對(dui)物(wu)質(zhi)定(ding)性(xing)，首(shou)先(xian)通(tong)過(guo)褶(zhe)合(he)變(bian)換(huan)對(dui)原(yuan)始(shi)吸(xi)收(shou)光(guang)譜(pu)進(jin)行(xing)以(yi)正(zheng)交(jiao)多(duo)項(xiang)式(shi)為(wei)基(ji)的(de)正(zheng)交(jiao)變(bian)換(huan)和(he)正(zheng)交(jiao)分(fen)解(jie)
，將(jiang)紫(zi)外(wai)可(ke)見(jian)吸(xi)收(shou)光(guang)譜(pu)分(fen)解(jie)為(wei)成(cheng)百(bai)上(shang)千(qian)條(tiao)褶(zhe)合(he)光(guang)譜(pu)，然(ran)後(hou)將(jiang)逐(zhu)條(tiao)褶(zhe)合(he)光(guang)譜(pu)進(jin)行(xing)配(pei)對(dui)比(bi)較(jiao)
，具(ju)體(ti)而(er)言(yan)
，就(jiu)是(shi)比(bi)較(jiao)m維(m為測試點波長數)空間中兩個矢量是否重合。如果是同一物質，則兩矢量的夾角為零，相關係數為1
，fouzeweibutongwuzhi。zheheguangpufadedingxingxitongshijieshiwuzhiduiguangxishoutexingdexiweibianhua，shiduiyaowuneizaitediandefanying。youwenxianbaodao，zheheguangpufadedingxingxitongshixianledui10種結構相似的類固醇激素類藥物的鑒別

，以及5種(zhong)二(er)氫(qing)卟(bu)吩(fen)金(jin)屬(shu)絡(luo)合(he)物(wu)類(lei)物(wu)質(zhi)的(de)鑒(jian)別(bie)。實(shi)驗(yan)結(jie)果(guo)表(biao)明(ming)
，此(ci)方(fang)法(fa)對(dui)於(yu)紫(zi)外(wai)可(ke)見(jian)光(guang)吸(xi)收(shou)光(guang)譜(pu)非(fei)常(chang)相(xiang)似(si)的(de)化(hua)合(he)物(wu)的(de)鑒(jian)別(bie)極(ji)其(qi)有(you)效(xiao)，對(dui)於(yu)結(jie)構(gou)相(xiang)似(si)且(qie)能(neng)滿(man)足(zu)測(ce)定(ding)要(yao)求(qiu)的(de)有(you)機(ji)物(wu)或(huo)無(wu)機(ji)離(li)子(zi)
，均(jun)能(neng)達(da)到(dao)鑒(jian)別(bie)的(de)目(mu)的(de)。褶(zhe)合(he)光(guang)譜(pu)法(fa)的(de)定(ding)性(xing)功(gong)能(neng)也(ye)可(ke)擴(kuo)展(zhan)到(dao)雜(za)質(zhi)的(de)限(xian)量(liang)檢(jian)查(zha)。利(li)用(yong)褶(zhe)合(he)光(guang)譜(pu)法(fa)可(ke)揭(jie)示(shi)純(chun)品(pin)與(yu)含(han)限(xian)量(liang)雜(za)質(zhi)的(de)非(fei)純(chun)品(pin)對(dui)光(guang)吸(xi)收(shou)的(de)細(xi)微(wei)差(cha)異(yi)

，並(bing)以(yi)差(cha)譜(pu)點(dian)的(de)形(xing)式(shi)加(jia)以(yi)定(ding)量(liang)表(biao)達(da)。茅(mao)誌(zhi)安(an)等(deng)應(ying)用(yong)該(gai)方(fang)法(fa)對(dui)阿(e)司(si)匹(pi)林(lin)腸(chang)溶(rong)片(pian)中(zhong)水(shui)楊(yang)酸(suan)的(de)限(xian)量(liang)進(jin)行(xing)了(le)檢(jian)測(ce)
，通(tong)過(guo)對(dui)純(chun)品(pin)進(jin)行(xing)自(zi)我(wo)訓(xun)練(lian)處(chu)理(li)，得(de)出(chu)具(ju)有(you)一(yi)定(ding)置(zhi)信(xin)度(du)、由(you)上(shang)下(xia)限(xian)圈(quan)定(ding)的(de)褶(zhe)合(he)光(guang)譜(pu)標(biao)準(zhun)
，與(yu)人(ren)工(gong)製(zhi)備(bei)的(de)含(han)限(xian)量(liang)雜(za)質(zhi)的(de)非(fei)純(chun)品(pin)測(ce)得(de)的(de)褶(zhe)合(he)光(guang)譜(pu)比(bi)較(jiao)，確(que)定(ding)限(xian)量(liang)雜(za)質(zhi)差(cha)譜(pu)點(dian)值(zhi)域(yu)，以(yi)此(ci)為(wei)判(pan)別(bie)依(yi)據(ju)，對(dui)樣(yang)品(pin)進(jin)行(xing)測(ce)定(ding)
，並(bing)與(yu)藥(yao)典(dian)法(fa)比(bi)較(jiao)
，結(jie)果(guo)一(yi)致(zhi)。另(ling)有(you)文(wen)獻(xian)報(bao)道(dao)，鄭(zheng)紅(hong)等(deng)用(yong)此(ci)係(xi)統(tong)對(dui)DNA樣品中苯酚
、anjisuanheneidusujinxinglexianliangjiance，keyongyushenghuayangpinfenxi。shiyanjieguozhengming
，gaifaduixianliangjidihuozhexishouquxianyuzhuyaojiqixiangsideyizhizazhidexianliangjianzhakuaisuyouxiao。

 

2.2 藥物的定量

 

2.2.1 單dan組zu分fen定ding量liang根gen據ju褶zhe合he光guang譜pu原yuan理li可ke知zhi

，當dang背bei景jing幹gan擾rao褶zhe合he光guang譜pu的de某mou個ge數shu學xue分fen量liang沒mei有you貢gong獻xian而er待dai測ce組zu分fen有you貢gong獻xian時shi，即ji可ke認ren為wei背bei景jing幹gan擾rao已yi被bei消xiao除chu。由you於yu渾hun濁zhuo背bei景jing(如片劑輔料的影響)tongchangzhiyouchangshuxianggongxian，yinci，yingyongzheheguangpufakeyibuduiyangpinjinxingyuxianfenli，jikeshixianduiyaowudezhunquedingliang。youyuzheheguangpuxinxiliangda，qienengzidongxuanzezuijiabochanghezuiyouhuiguifangchengjisuanyaowunongdu，yincijiaoyibanfangfazidonghuachengdugao，caozuojiandan。gaojinbodengyingyongzheheguangpufazaiganraozufengongcundeqingkuangxiaduixueqingzhongaoshapuqindenongdujinxingleceding；劉世軍等應用該方法測定胃康膠囊中鹽酸小檗堿的含量；李堅等采用褶合光譜分析法，樣品不經分離
，直接測定複方鹽酸異丙嗪糖漿中鹽酸異丙嗪的含量。

 

2.2.2 shuangzufendingliangyingyongzheheguangpufakeshixianduizhongdieguangpudeshuangzufenhunhewudedingliangfenxi。jiyuzheheguangpujuyounenggouweiraoshuxuefenliangzhiweilingdepingjunbochangzhoushangxiaqifudetexing，shuangzufenhunhewuzhongmeiyizhongzufendezhehequxianjunyougudingdeguolingdian，yinci，keyiqizhongyizufendeguolingbochangdianduilingyizufenjinxingdingliang，fanzhiyitong。yuchangguifenxifabijiao，jieguowuxianzhuxingchayi。tongshi
，bujingfenlizhijiedingliangyebimianlegezhonghuaxuefenliguochengdefansuo、費時
，以及由此產生的誤差。有文獻報道，應用該方法測定了雙組分複方製劑的含量。

 

2.2.3 多duo組zu分fen定ding量liang由you於yu多duo組zu分fen藥yao物wu中zhong各ge物wu質zhi的de過guo零ling點dian都dou可ke能neng不bu同tong
，所suo以yi不bu能neng用yong共gong同tong的de過guo零ling點dian來lai定ding量liang，因yin而er對dui多duo組zu分fen混hun合he物wu

，根gen據ju褶zhe合he光guang譜pu法fa與yu吸xi收shou光guang譜pu同tong樣yang具ju有you線xian性xing和he加jia合he性xing的de特te點dian
，以yi褶zhe合he光guang譜pu為wei基ji礎chu，結jie合he偏pian最zui小xiao二er乘cheng法fa可ke解jie決jue多duo組zu分fen定ding量liang。研yan究jiu結jie果guo表biao明ming
，不bu同tong數shu值zhi計ji算suan方fang法fa的de舍she人ren誤wu差cha對dui結jie果guo影ying響xiang甚shen小xiao，對dui結jie果guo誤wu差cha影ying響xiang最zui大da的de是shi待dai測ce組zu分fen的de分fen析xi信xin號hao與yu其qi分fen析xi信xin號hao的de重zhong疊die程cheng度du。當dang它ta們men相xiang關guan性xing越yue大da
，分fen析xi結jie果guo越yue不bu理li想xiang。考kao慮lv到dao褶zhe合he光guang譜pu能neng放fang大da化hua合he物wu吸xi收shou光guang譜pu所suo存cun在zai的de細xi微wei差cha異yi，減jian少shao數shu學xue相xiang關guan性xing，加jia上shang褶zhe合he光guang譜pu信xin息xi量liang大da，在zai褶zhe合he光guang譜pu基ji礎chu上shang應ying用yong偏pian最zui小xiao二er乘cheng法fa對dui其qi進jin行xing定ding量liang分fen析xi，即ji可ke從cong中zhong篩shai選xuan出chu最zui佳jia結jie果guo。據ju文wen獻xian報bao道dao，應ying用yong褶zhe合he光guang譜pu法fa可ke實shi現xian對dui多duo組zu分fen藥yao物wu的de定ding量liang。

 

2.3 yaowudewendingxingshiyantongguocedingpeiwuzhonggezufendehanliangbianhua，keyiduipeiwuwendingxingjinxingkaocha。zheheguangpufayingyongyuyaowuwendingxingceding，congzhenggexishoufanweikaochaxishouquxiandebianhua，tongguozheheguangpufa“放大”chayigongneng，buzhuojiqixiweidebianhua，bingyisanweizheheguangpuchapudiandexingshijiayidingliangbiaoda，jiketongshifanyingwuzhizaiguidingshijianyunei，yidingbochangchuxishouduzhidebianhua(量的指標)和在規定時間域內由光譜形狀變化表現出來的物種同一性變化(質的指標)
，彌(mi)補(bu)了(le)常(chang)規(gui)分(fen)光(guang)光(guang)度(du)法(fa)和(he)傳(chuan)統(tong)動(dong)力(li)學(xue)分(fen)析(xi)在(zai)穩(wen)定(ding)性(xing)考(kao)察(cha)時(shi)隻(zhi)能(neng)反(fan)映(ying)量(liang)指(zhi)標(biao)的(de)不(bu)足(zu)，克(ke)服(fu)了(le)單(dan)一(yi)紫(zi)外(wai)吸(xi)收(shou)峰(feng)值(zhi)定(ding)量(liang)在(zai)藥(yao)物(wu)穩(wen)定(ding)性(xing)測(ce)定(ding)中(zhong)以(yi)偏(pian)蓋(gai)全(quan)的(de)缺(que)陷(xian)，並(bing)實(shi)現(xian)了(le)定(ding)性(xing)結(jie)果(guo)的(de)定(ding)量(liang)表(biao)達(da)。鄭(zheng)紅(hong)等(deng)應(ying)用(yong)該(gai)方(fang)法(fa)對(dui)頭(tou)孢(bao)呱(pai)酮(tong)和(he)舒(shu)巴(ba)坦(tan)溶(rong)液(ye)的(de)穩(wen)定(ding)性(xing)進(jin)行(xing)測(ce)定(ding)
；劉荔荔等考察了5種臨床靜滴液的化學穩定性；陸lu峰feng等deng考kao察cha了le褶zhe合he光guang譜pu法fa與yu高gao效xiao液ye相xiang色se譜pu法fa分fen析xi氟fu康kang唑zuo及ji其qi常chang用yong配pei伍wu的de穩wen定ding性xing。結jie果guo表biao明ming兩liang方fang法fa間jian無wu顯xian著zhu性xing差cha異yi，驗yan證zheng了le褶zhe合he光guang譜pu法fa替ti代dai高gao效xiao液ye相xiang色se譜pu法fa用yong於yu藥yao物wu配pei伍wu穩wen定ding性xing考kao察cha的de可ke行xing性xing。

 

2.4 其它褶合光譜分析法的實質是一種信號處理技術，具有線性和加合性特點的任何信號均可用褶合變換技術處理。因此．褶合光譜分析法不僅適用於紫外-可見吸收光譜，也同樣適用於紅外、熒光、核磁共振及色譜分析儀等分析信號的處理
，已被廣泛應用於許多學科領域。陸峰等采用褶合光譜法考察紫外線致脫氧核糖核酸(DNA)突變，以褶合光譜差譜值的形式量化地表達DNA細微突變的程度

，其靈敏度遠高於二階導數光譜法。DNA中(zhong)添(tian)加(jia)二(er)甲(jia)亞(ya)碸(feng)後(hou)表(biao)現(xian)的(de)褶(zhe)合(he)光(guang)譜(pu)差(cha)譜(pu)變(bian)化(hua)與(yu)高(gao)效(xiao)毛(mao)細(xi)管(guan)電(dian)泳(yong)指(zhi)紋(wen)圖(tu)譜(pu)的(de)結(jie)果(guo)一(yi)致(zhi)。褶(zhe)合(he)光(guang)譜(pu)法(fa)分(fen)析(xi)過(guo)程(cheng)簡(jian)單(dan)快(kuai)速(su)，可(ke)用(yong)於(yu)抗(kang)紫(zi)外(wai)線(xian)損(sun)傷(shang)、抗突變藥物的初步篩選。鄭紅等應用褶合光譜法對β-半乳糖苷酶的活性進行了測定，證實與吸光度值分析法相比

，本法不僅更加簡便
、快速，而且靈敏度和精確性也很高。

 

3、結語

 

應ying用yong褶zhe合he光guang譜pu法fa能neng夠gou對dui複fu雜za體ti係xi不bu經jing分fen離li即ji可ke實shi現xian測ce定ding。操cao作zuo更geng為wei簡jian便bian。而er褶zhe合he光guang譜pu法fa也ye有you其qi不bu足zu之zhi處chu。如ru目mu前qian還hai不bu能neng用yong於yu含han未wei知zhi成cheng分fen的de複fu雜za體ti係xi的de測ce定ding等deng
，但dan是shi隨sui著zhe光guang譜pu采cai集ji器qi和he計ji算suan機ji技ji術shu的de迅xun猛meng發fa展zhan，相xiang信xin褶zhe合he光guang譜pu法fa將jiang會hui有you更geng廣guang泛fan的de應ying用yong。