本論文主要是利用電灑質譜法研究索套冠醚的錯合與生藥的定性、定量兩方面。利用電灑質譜法探討索套型對稱雙苯-16-冠-5醚 (sym-dibenzo-16-crown-5)對IA族陽離子選擇性之研究，已經證明此類索套型冠醚對金屬離子鋰在甲醇中有極佳的選擇性，但在逐漸提高溶劑系統中水的比例後，其親水性官能機側臂的冠醚，對金屬離子鈉之選擇性將會逐漸提高；具疏水性官能機側臂之冠醚則無此現象。
此外陰離子的種類亦會影響此類冠醚與鹼金屬離子在甲醇中的錯合行為，影響程度與所使用鹽類生成熱的大小有關。其結果為 RNO3>Rcl>RBr (R=ICrownNa+/ICrownLi+)。我們亦發現此類索套型冠醚對金屬離子鋰及鈉的選擇性，會受到額外添加銣離子與銫離子的影響，其原因已經證實為金屬離子銣（或銫）與此類索套型冠醚側臂之作用所造成，且索套型冠醚側臂約立體障礙對額外添加金屬離子的影響性遠大於實驗時所使用溶劑系統的影響。
我們已經成功地發展出一簡單的方法可求得相對被離子化修正值 s'，利用此相對被離子化修正值 s'，我們可以直接由各質譜峰線的高度來計算各化合物實際存在於溶劑中的濃度比，亦即 [C-M1+]/[C-M2+]=S'x(ICM1/ICM2+)。利用相對被離子化修正值 S'修正後的質譜峰線高度所代表的濃度，我們可求得此類索套型冠醚與鋁、鈉及鉀金屬離子於甲醇中錯合之穩定常數值 (Ks, stabilityconstant)。並利用特定冠醚對金屬離子具有特別選擇性、極佳錯合力的特點，發展出利用質譜圖峰線高度求得溶液中金屬離子含量之新方法。
在應用串聯式質譜技術對生藥定性與定量的研究，我們已獲知黃連中各主要成份的斷裂途徑，並經由所歸納出來的結果，不但可用以區分同分子量的異構物，還能鑑定出黃柏粗萃物中的主成份為 berberine 及palmatine，再經由質譜圖的峰線高度。可求出其含量分別為 6.4x10-3M 及3.2x10-3M。在樟芝中則利用有效藥理化合物的特徵性斷裂離子，以選擇離子掃描 (SIM) 或子代離子掃描的技術，我們可以鑑定璋芝乙醇粗萃物中確實含有此化合物。

Lariat crown ethers and Chinese herb medicines are the two areas investigated in this thesis. Selectivity of the lariat crown ethers toward metal ions can be estimated easily with ESI-MS. All sym-dibenzo-16-crown-5 ethers 2a ~ 2g have been shown to be most selective toward Li+ among alkali metal ions in pure methanoi. When water is introduced, the influences on selectivity will be controlled by the nature of theirrespective side arms. The selectivity toward Na+ will increase when its side arm is hydrophilic and the steric hindrance is small; and the selectivity is favor to Li+ still when its side arm is hydrophobic and the steric hindrance is large.
Selectivity of lariat crown ethers towarrd Li+, Na- and K+ also changes with different counter anions. Nitrates give the best Na+ selectivity; and the ratio R, IcNa+/IcLi+, is RNo3 > RCl > RBr. It appears that heats of formation of the used salts are the important parameter in controlling the selectivies of these lariat crown ethers toward alkali cations.
Externally added cation such as Rb- or Cs- will affect the selectivity of lariat crown ethers toward Na+ and Li+ due to the ligating interaction with donor atoms of the side arm. The influence of Cs+ is larger than that of Rb+, and the steric hindrance of the side arm is a more important parameter in controlling selectivity than the percentage of water in the solvent system.
Calibration for relative cationization efficiencies of the meltallated crowns [Crown+M]+ have been shown to be essential for comparison of selectivity in ligand metal interactions. By using the peak intensities which have been corrected by the relative cationization efficiencies S, an easy and fast method for determination of the stability constants of different metal ion complexes with crown and lariat crown ethers using ESI-MS has been developed. With this kind of calibration, concentration of the metal ion can also be calculated directly by measuring their respective peak intensities.
Combination of ESI/MS and ESI/MS/MS is useful for structural elucidation of some protoberberine alkaloids from Coptidis Rhizoma. Important fragmentation pathways have been proven by tandem mass techniques. Using the diagnostic fragments, the major contents in the Phellidendri Cortex (rutaceous plant) have been identified as berberine and palmatine; and their concentrations have been estimated as 6.4 x 10-3 M and 3.2 x 10-3 M, respectively in the crude extract.
4α-Methylergosta-8,24(28)-dien-3,7,11-trion-26-oic acid and 4α-methylergosta-8,24(28)-dien-3,11-dion-7β-ol-26-oic acid are two clinically active components found in Antrodia cinnamomea. Using the specific fragmentation in their mass spectra together with the ratio of these diagnostic ions in their respective SIM mass spectra, and/or their MS/MS spectra, a fast, simple, and efficient mass spectral method has been developed for identification of these compounds in Antrodia cinnamomea preparations without prior isolation of the individual compound.