吸附層析法通常用於預濃縮樣品與製備型分離樣品，然而，一般 研究所注重的卻僅限於管外濃縮與分離的結果，至於管內樣品的吸附 機制與濃度分布則無深入研究。因此本研究以全管柱偵測系統配合衝 破實驗來觀察吸附型管柱內的樣品吸附機制與濃度分佈，並和 Pai 所 提出的郵包模型理論互相比較。
在亞甲基藍水溶液之衝破實驗研究中發現，亞甲基藍如同肉眼所 見的由管柱前端緩慢地往管柱後端載入；但若把管柱全長分為 n 段，
隨著低濃度亞甲基藍水溶液持續注入管柱，樣品雖是如肉眼所見的由 第一段開始載入至第 n 段，但在載入時並不會先載滿第一段後才開始 載入第二段。
若將此衝破實驗所得的 k 值與 R0值代入郵包模型中，則由郵包模 型中所計算出的理論圖形會和實驗圖形之誤差和 n 值有關。研究發現，
實驗空圖和較低 n 值所模擬出來的理論空圖較為相近，因為實驗中所 使用的管柱為手動填充，內部並不緊密，可視為效能較差、板數較低 之玻璃管柱；而郵包模型中之 n 值概念和理論板數概念相近，故 n 值 越小，越符合理論板數較低的實驗管柱。當所 n 值設定為 10 時，經 由郵包模型所模擬出的理論圖形會與實驗圖形有約 23.01%誤差，當 n 值為 20 時，則理論圖形與實驗圖形將有 42.58%之誤差，若 n 值提高
66
到 100，理論圖形與實驗圖形甚至完全不相符；由此可見，若郵包模 型中的 n 值越大，則模擬出的理論圖形會越偏離實驗結果。
本研究也釐清了各項實驗條件對樣品於吸附型管柱內的吸附機 制與濃度分布的影響。首先，研究發現，當樣品的動態吸附平衡常數 較小時，吸附能力較差，造成管內空圖的波形較為平緩，這是因為樣 品吸附於 C18吸附劑的相對時間較短，因此其在管內的移動速度便會 較快。
若改變樣品的濃度，則樣品濃度越高，會因有效管柱容量增加及 聚合體的形成使得單位樣品的載入速度較慢，但卻不會影響管內空圖 的波形，因為此兩因素皆不影響樣品本身吸附能力的強度。
而流速快慢也會影響樣品於吸附型管柱內的吸附情形，較快的流 速將使樣品較快抵達後方的吸附劑並吸附於其上，使得單位體積樣品 載入速度較快；因此，流速太快也是造成理論空圖和實驗空圖之誤差 的來源。
改變樣品溶劑比例成分則會明顯地影響樣品於吸附型管柱內的 吸附機制與濃度分布。這是因為低極性的亞甲基藍較易溶於極性低的 乙醇中，當溶劑為 100%的去離子水時，亞甲基藍偏向吸附於非極性 的 C18上，並花費較長的時間吸附於其上，造成移動速度緩慢。相對 於水，乙醇則因極性較小而使得亞甲基藍較易溶於其中，使得亞甲基
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藍吸附於 C18上的時間較短，造成移動速度較快。因此，改變溶劑成 分比例將影響樣品的吸附能力，進而改變波形的平緩程度。
本研究利用全管柱偵測系統，全面性地觀察樣品於吸附型管柱內 的吸附機制與濃度分布，彌補一般層析系統所使用的單通道偵測器之 缺點，從而得知許多以往不為人知的吸附現象。
藉由全管柱偵測系統，未來將可繼續進行「混合物樣品於吸附型 管柱內的吸附與分離情形」，從而了解混合物樣品於吸附型管柱內的 競爭情形與分離機制，對吸附層析法有更深入的認識。
68
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