本研究利用全管柱偵測系統觀察液相層析之波峰壓縮效應,在第 四章中,觀察樣品在等位沖提條件中之流動訊號,結果得知,樣品在 k 值越大之條件下,其空間波峰寬度(s)較窄,並且在不同 k 值條件下,
樣品在注入至管柱入口端時,其空間波峰寬度(s)與 成 正 比 之關係,然而當樣品受移動相沖提往管柱後端位移時,受滯留效應等 因素在 k 值越大之條件下其空間波峰寬度越寬,而當樣品在流析出管 柱之際,會受到樣品之移速不同而影響其在管柱外偵測器之波峰寬度。
在第五章中,觀察樣品在非線性層析下之波峰壓縮效應現象,並提出 在梯度沖提模式下,較正確以及簡便之方法計算理論板數與樣品移速,
相較於一般以時間單位計算出之理論板數 Nt,所提出理論板數 Nt*計 算結果,更接近於正確空間單位理論板數 N 之結果。和傳統方式計 算理論板數相比,其結果顯示有大幅的改善,在某些實驗中有高達四 倍的改進。
影響層析波峰寬度變化的原因是相當廣泛的,舉凡所有發生在移 動相與固定相兩相間的物理作用力、化學作用力等都會對樣品之層析 行為產生變化,諸如此類的研究發展至今,已相當完備,雖然本研究 中探討的方法與以往不同,然而,以全管柱偵測系統之方法,可全面 性地觀測樣品在管柱中之流動訊號,可以彌補一般層析系統之偵測器
1 1 k
所不足,有助於釐清層析空間和時間訊號之差異,對於層析分離現象 可以提供更入微的觀察。
未來研究將利用全管柱偵測系統進一步觀察樣品在梯度沖提模 式中,使用溶劑強度不同之移動相時,其交界處會產生波峰壓縮效應,
以及溶劑交界處會產生不穩定之情形,進而使得其時圖產生不規則波 形,由於液相層析常以梯度沖提模式來提高分離效率以及減少所需分 析時間,然而甚少研究針對在時圖中產生不規則波形之成因作解釋,
因此,未來將以全管柱偵測系統搭配管柱外偵測器來觀察此現象,並 且更進一步解釋此一現象成因。
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附錄
附錄 A-2 梯度沖提實驗,管內空圖之波峰位置所對應取點時間
附錄 A-3 三管柱在等位沖提實驗中,以空間波峰寬度(s)
2,對於管柱 位置作圖所得線性斜率與 R2值
管柱 1
k 值
0.84 1.23 2.05 3.29 5.34 8.44 13.1 斜率 0.0381 0.0462 0.0507 0.0514 0.0522 0.0564 0.0674
R2 0.9956 0.9932 0.9916 0.9888 0.9894 0.9826 0.9989 管柱 2
k 值
0.84 1.16 2.34 3.42 5.28 7.19 9.45 斜率 0.0399 0.0512 0.0506 0.0587 0.0678 0.0839 0.118
R2 0.9935 0.9200 0.9655 0.9812 0.9647 0.9829 0.9761 管柱 3
k 值
2.03 2.80 3.70 4.35 5.52 6.47 7.61 10.0 斜率 0.0145 0.0164 0.0227 0.0307 0.0339 0.0455 0.0552 0.0679
R2 0.9697 0.9850 0.9774 0.9792 0.9824 0.9892 0.9865 0.9863 註:詳細線性圖形見圖 4-13。詳細實驗條件列於表 3-2 中
附錄 A-4 三管柱在等位沖提實驗中,以時間波峰寬度(t)
2,對於管柱 位置作圖所得線性斜率與 R2值
管柱 1
k 值
0.84 1.23 2.05 3.29 5.34 8.44 13.1 斜率 0.0006 0.0014 0.0026 0.0055 0.0132 0.0305 0.0901
R2 0.9537 0.9827 0.9797 0.9910 0.9925 0.9902 0.9985 管柱 2
k 值
0.84 1.16 2.34 3.42 5.28 7.19 9.45 斜率 0.0011 0.0013 0.0022 0.0046 0.0131 0.0319 0.0776
R2 0.9573 0.9677 0.8888 0.9758 0.9696 0.0867 0.9701 管柱 3
k 值
2.03 2.80 3.70 4.35 5.52 6.47 7.61 10.0 斜率 0.0103 0.0148 0.0273 0.0517 0.0829 0.150 0.263 0.576
R2 0.9859 0.9592 0.9657 0.9881 0.9869 0.9896 0.9812 0.9682 註:詳細線性圖形見圖 4-14。詳細實驗條件列於表 3-2 中