彩搜网

技术文章
当前位置:彩搜网 > 技术文章 >
干货丨且看如何利用梯度洗脱方法一招破解出峰问题--原理篇
发布时间:2020-11-13   点击次数:111次

WOMENXIANLAIKANYIZHANGTU

TONGGUOYIZHANGZHIGUANDETULAITANTAOJINTIANDEHUATI

ZHEISANZHANGSEPUTUDETIAOJIANRUXIA:

CESHIWUZHIWEIC1-C10DEWANJIANTONGXILIEYANSHENGDEYANSHENGDEYANAIJIBENBINGMIZUOANHUANGXIAN

这三张色谱图给您的直观感觉是什么?

●ATUDENGDUXITUO,95:5DEJIACHUNSHUI,10GEFENGZAI10minCHUFENG,FENGHENJIANRUI(ZHAI),KESHIJIXIANBUFENLI。

●BTUDENGDUXITUO,80:20DEJIACHUNSHUI,10GEFENGZAI50minCHUFENG,HOUMIANDEFENGMINGXIANZHANKUAN,FENGAIPANG。

●CTUTIDUXITUO,SUOYOUWUZHIZAI20minCHUFENG,FENLIDUHEXIANGYINGDOULIANGHAO。

 

这三张图看完后,您是否有如下疑问?

●DENGDUXITUO,YAOMEJIGEFENGFENBUKAI,YAOMEFENKAILE,SHIJIANZHANG,CHUXIANAIPANGFENG,DENGDUXITUOBUSHIHEDUOZUFENFENLIMA,TONGXINGGAOSUWODUOZUFENYIBANYAOSHIYONGTIDUXITUO,ZHEISHIWEISHENME?

●TIDUXITUOSHIZENMESHIXIANHUAHEWUZAIHAODEFENLIDUXIA,YOUBAOCHISEPUFENGBUZHANKUAN,CHUXIANJIANRUIDESEPUFENGDE?

●ZENMESHEZHITIDU,ZENMEQUEDINGYIGEHAODETIDUXITUOFANGFA?

WEILEJIEJUEDAJIADEKUNHUO,

WOMENJINTIANJIUSHIYAOLAITANTAO,

WEISHENMEDUOZUFENYAOSHIYONGTIDUFA,

TIDUXITUOZENMEYOUHUA。

对于多组分的检测,我们希望什么?

1、LIANGHAODEFENLIDU

2、HAODEXIANGYING,FENGGAOHEFENGMIANJI,SEPUBUZHANKUAN,DEDAOZHAIDESEPUFENG。

SHOUXIAN,WOMENLAIKANKANYINGXIANGSEPUFENLIDUDEYINSUSHISHENME?

ZHEILIJIDAJIAFANGSHANGYIGEFENLIDUDEGUANXISHI:

image.png

SHIZIZHONGDERWEIFENLIDU,kWEIRONGLIANGYINZI,aWEIFENLIYINZI。

WOMENLAIHUIGUYIXIAJIBENZHISHI:

image.png

tM 为不被固定相保留的死时间,

tR为化合物的保留时间(从进样到出现浓度最大值的时间),

tR为化合物的调整保留时间。

RONGLIANGYINZI:SHIHUAHEWUZAIYE-GULIANGXIANGDADAOFENPEIPINGHENGSHI,ZUFENZAIGUDINGXIANGYULIUDONGXIANGZHONGDEZHILIANGBIZHI,YINCIYOUBEICHENGWEIZHILIANGFENPEIXISHU。

image.png

FENLIYINZI:FENLIYINZISHIZAITONGYISEPUXITONGTIAOJIANXIABAOLIUDECHAYIDELIANGDU

DANGα=1SHI,LIANGGESEPUFENGJUYOUXIANGTONGDEBAOLIUSHIJIANBINGGONGLIUCHU。

DUIYUDUOZUFEN,WOMENXUDESHI,ZAIYIDINGDESHIJIANNEIJIANGZUFENFENLI,BINGQIEDEDAOYIDINGDESEPUKUANDUDEFENG(JIANFENG);NEIMEXIANGYAOLIANGHAODEFENLIDU,XUYAODESHIXIANGLINDELIANGGEHUAHEWUNENGDADAOJIXIANFENLI,SHOUXIANKANYIXIAFENLIDUGONGSHI,KANKANSHENMEYINGXIANGFENLIDU:

image.png

其中:image.png;我们可以看到,在同一色谱系统,两个化合物的分离因子,与此色谱系统下,化合物自身特性相关,当α越大,分离度也将越大。

而其中:image.png

KEJIAN,K’ZENGDA,KEYITIGAOFENLIDU。

WOMENZHIDAO,TIDUXITUOCHENGXUZAIGAIBIANLIUDONGXIANGDEBILI,YIDADAOFENLIDEMUDE,NEIMETIDUXITUOJIUJINGSHIZENMELAIYINGXIANGFENLIDUDENI?

WOMENYIFANXIANGSEPUXITONGWEILI,LAIKANYIXIA,DANGWOMENGAIBIANLELIUDONGXIANGBILISHI,k’DEBIANHUAQINGKUANG。

image.png

ZHEISHIYIZHANGFANXIANGSEPUTUZHONG,HUAHEWUDElgk’YULIUDONGXIANGZHONGYOUJIXIANGBILIDEGUANXITU,JINSIWEIXIANXINGDEGUANXITU。CONGZHEIZHANGTU,KEYIKANCHU,ZAIFANXIANGSEPUZHONG,lgk’SUIZHEψBILIZENGDA,ZHUJIANJIANGDI,k’YEZHUJIANJIANXIAO。

JI:  lgk’ =Aψ+B (AWEIQUXIANDEXIELV,BWEIJIEJU)。

TONGGUOZHEIZHANGTU,WOMENLAISHUOMINGWEISHENMEXUYAOTIDUXITUO,

DUIYUHUAHEWU1,2

Ψ=0.45SHI,lgk1’ =0.97,k1’=9.33;

lgk2’=1.27,   k2’=18.6;

RUGUOWOMENSHIYONGDENGDUXITUO,YOUJIXIANGDEBILVWEI45%,WOMENHUIFAXIAN,YOUYUCISHIDEk1’=9.33, k2’=18.6,k’DOUDAYU10,ZHEIGESHIHOU,HUAHEWUYUGUDINGXIANGZUOYONGDESHIJIANJIAOZHANG,YINCIKEYIXIANGXIANG,ZAIZHEIGESHIHOUHUAHEWU1,HEHUAHEWU2 CHUFENGSHIJIANDOUBIJIAOKAOHOU,ERQIEYOUYUQIANGDEZUOYONGLI,DAOZHILIUDONGXIANGWUFAZAIYIGEDUANDESHIJIANNEIJIANGHUAHEWUXITUOCHULAI,YINCIFENGDOUBIANDEBIJIAOAIPANG,YEJIUSHIKUANFENG,RUTU:

image.png

DUIYUHUAHEWU1,2

Ψ=0.65SHI,lgk1’ =-0.21,k1’=0.61;

lgk2’=-0.35,   k2’=0.44;

如果我们使用等度洗脱,有机相的比率为65%,我们会发现,由于此时的k1’=0.61, k2’=0.44,k’都接近于0,此时化合物会被流动相快速带出,形成尖峰,但由于两个化合物得K'都很小,而且接近,会形成共流出物,而且,第yi个峰出峰时间最hao大于2tM(K’=0)值,反映得图如下:

image.png

NEIMERUGUOSHITIDUXITUO,HUIZENMEYANGNI:

 

ZAITIDUXITUOGUOCHENGZHONG,K’DEZHIHUISUILIUDONGXIANGDEBIANHUAERGAIBIAN,HUAHEWUBEILIUDONGXIANGXITUODAICHUSEPUZHUDAODAJIANCEQIDEBAOLIUSHIJIAN,YUHUAHEWUCONGJINYANGKAISHI,DAOLIUCHUSEPUZHUDEZHEIYIDUANSHIJIANNEIPINGJUNDEK’DEDAXIAO,YIJISEPUZHUZHANG,LIUDONGXIANGDELIUSUDENGYOUGUAN,ERHUAHEWUSHIFOUNENGCHANSHENGZHAIDESEPUFENG,ZEQUJUEYUWUZHIZAIJIANGYAOTUOLISEPUZHUDESHIHOU,K’NENGFOUBIJIAOXIAO(JIYUGUDINGXIANGDEZUOYONGLIZUGOUXIAO,NENGBEIKUAISUCHONGXICHUQU)。

DAYIGEBIFANG:

一辆汽车和一辆摩托车,通过一个长度为Lkm的隧道,汽车初始速度为20Km/h,摩托车的初始速度为35km/h,汽车的加速度为1.5m/s2,摩托车的加速度为0.8m/s2,那么谁将先通过隧道,汽车能否实现超车?

image.png

QISHIRUGUOSUIDAOZUGOUDUAN,YOUYUCHUSHIYOUYUMOTUOCHESUDUKUAI,SUIRANJIASUDUXIAO,DANSHIQICHEZHENGTIDEYIDONGSUDURENGRANXIAOYUMOTUOCHE,QICHEDEPINGJUNSUDUJIUXIAOYUMOTUOCHEDESUDU,ZAIZHEIGEZHENGTISHUIPINGSHANG,QICHEJIUHUIBIMOTUOCHEMANDAODA,LIRU:DANGL=100mSHI,QICHETONGGUODESHIJIANWEI8.42S,MOTUOCHETONGGUODESHIJIANWEI7.78S。

image.png

XIANGFAN,RUGUOSUIDAOZUGOUZHANG,NEIMEQICHEZAIZHEIDUANJULISHANGDEPINGJUNCHESUJIUBIMOTUOCHEKUAI,NEIMEQICHEJIUNENGSHIXIANWANDAOCHAOCHE,LIRUDANGL=1000mSHI,TONGGUOSUIDAODESHIJIAN,MOTUOCHEWEI39.3S;ERQICHEWEI33S。

ZHEIGEBIFANGLIMIANDEZHANGWEILDESUIDAO(BUTONGDESUIDAOZHANGDUFANYINGLECHEZITONGGUOSUIDAODEJIASUSHIJIANDEZHANGDUAN,DAOZHIZUIZHONGTONGGUOSUIDAODEPINGJUNSUDUBUYIYANG),ZHEIGEJIUXIANGDANGYUSEPUZHUZHANG,CHUSHISUDUJIUXIANGDANGYUCHUSHILIUDONGXIANGBILIXIADEHUAHEWUDEK’,JIASUDUJIUXIANGDANGYUlgK’YUψXIANXINGQUXIANDEQUXIANXIELV,WOMENTONGCHANGSHUOSEPUZHUZHUZIZHANGDUSHIYIDINGDE,LIUDONGXIANGZAITIDUBIANHUADEGUOCHENGZHONG,ZAIZHEIGESHIJIANDUANNEI,NEIMEXIANGTONGDEZHUZIZHANGDU,K’BIANHUADESULVBUTONG(JIURUTONGCHEZIDEJIASUDUYIYANG),ZAIZHENGGESEPUXINGWEISHANGDEPINGJUNZHIK’(RUTONGCHEZIZAITONGGUOSUIDAODEPINGJUNSUDUV’),JIUBUYIYANG,RUGUOZAITIDUBIANHUADESHIJIANFANWEINEI,TONGGUOXIANGTONGDESEPUZHU,K’DEPINGJUNZHIYUEXIAO,JIUYUERONGYIXIANBEIXITUOCHUSEPUZHU,YINCIWOMENBUNENGGUANGGUANZHUHUAHEWUDECHUSHIK’,HAIXUYAOGUANZHUHUAHEWUDEK’DEBIANHUASULV,ZHEIJIUHENHAODEJIESHILE,WEISHENMEYOUDEWUZHIZAITONGYIGENSEPUZHUSHANG,ZAIATIDUSHI,HUAHEWUXBIHUAHEWUGXIANCHUFENG,ERZAILINGWAIYIGETIDUSHI,QUESHIGXIANCHUFENG(XINGSHIFASHENGLENIZHUAN)。ZUIZHONGSHEIXIANCHUFENG,YUZHEIXIEYINSUYOUGUAN,LINGWAIDANGJIEJINSUIDAOCHUKOUSHI,RUOQICHESUDUJIADAOYUEKUAI(XIANGDUIYUHUAHEWUDEK’YUEXIAO),NEIMEQICHEHUOZHEMOTUOCHEZHENGTITONGGUOSUIDAODESHIJIANJIUYUEDUAN(t=CHESHENZHANGDU/CHESU),DUIYINGYUCISHIHUAHEWUCHUFENGDESEPUFENGKUANDUJIUYUEZHAI。

image.png

例如,车身长为2.5m,如果最终通过隧道时车速为23m/s,则汽车完全通过隧道的时间为:0.10S,如果这时候车速为15m/s,则汽车完全通过隧道的时间为:0.16S,我们看到,出隧道时,车速越快,车子通过隧道的时间越短,反映在色谱上,就是峰的宽窄了。色谱峰流出的峰宽度反映在色谱图上的宽度即t1-t0

image.png

总结

1、DUIYURONGLIANGYINZIK’FANWEIHENDADEHUAHEWUZU,FENLIKEYIYOUXIANKAOLVTIDUXITUO。

2、DUOZUFENDEFENLICELVE,KAOLVHESHIDEFENXISHIJIANNEI,DEDAOZHAIFENGHEHAODEFENLIDU

3、TIDUXITUOSHILIYONGBIANHUADEYOUJIXIANGBILI,JIQIANGDUBUTONG,DADAOGAIBIANHUAHEWUZAILIANGXIANGZHONGDEZUOYONGLIDAXIAO。

4、lg K’YUψJINSIXIANXINGGUANXI

5、K’SUIψDEBIANHUAQUSHIDEBUTONG,SHIDETIDUXITUOJIANGBUTONGHUAHEWUZAISEPUSHANGDEBAOLIUSHIJIANCHAYILADA,SHENZHICHUXIANCHAOCHE。

6、K’≈0SHI,HUAHEWUJIHUYUGUDINGXIANGWUZUOYONGLI,NENGKUAISUTONGGUOSEPUZHU,CHANSHENGJIANFENG。

 

 

上海安谱实验科技股份有限公司版权所有   |   传真:86-021-54248311
中国驰名品牌 本公司(www.anpel.com.cn)主营产品:o2si标准品,CNW固相萃取小柱,薄层色谱TLC,Anpel超声波清洗器,CNW样品瓶,WITEG玻璃产品
联系人:Anpel
电话:

手机:
15618125765
  • 点击这里给我发消息