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研究生: 洪煥毅
Hung, Hiroki
論文名稱: 具側臂之冠醚與金屬離子錯合之質譜及電導法研究
Using Mass Spectrometry and Transport Method to Study the
指導教授: 劉高家秀
Liu Gao, Jia-Xiu
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
畢業學年度: 84
語文別: 中文
論文頁數: 100
中文關鍵詞: 索套冠醚電灑法
英文關鍵詞: Lariat Crown Ether, ESI
論文種類: 學術論文
相關次數: 點閱:109下載:0
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  • 摘要: 以快速原子撞擊法 (FAB) 和電灑法 (ESI) 研究不同側臂索套型
    冠醚2a ~ 2h與金屬離子在溶液中的錯合情形。在利用快速原子撞擊法中
    ,可以發現2d和Ag+有極佳的錯合能力。另外,對於Cu2+和Pb2+,此一系
    列索套型冠醚也有不錯的錯合能力。 在此,我們也使用電灑法來探討會
    對此一系列索套型冠醚和金屬離子錯合能力產生影響的因素,包括了溶液
    的組成,負離子的種類與加入陽離子 (Rb+, Cs+) 的影響。因此,可以利
    用這些因素來控制此一系列索套型冠醚和金屬離子錯合 (Li+, Na+) 的選
    擇性。一般而言,2a ~ 2h對Li+有著較佳的選擇性,但若改變一些條件,
    如提高水於甲醇中的比例,或添加Rb+, Cs+,則可增加其對Na+選擇性。
    另外,我們也利用電灑法發展出兩種新的應用。其一為利用電灑法求出冠
    醚和金屬離子錯合之穩定常數,我們也成功地求出2a ~ 2h對Li+, Na+,
    K+的穩定常數。其二則是利用電灑法和冠醚與金屬離子錯合之性質,求出
    溶液中的微量金屬離子含量。由此方法求出於HPLC等級的甲醇中
    (Mallinckrodt) 約含有3.6 x 10-6M 的K+。

    Abstract : Fast atom bombardment mass spectrometry (FAB-MS)
    and electrospray mass spectrometry(ES-MS) were used to study the
    complexation of various lariat crown ethers(2a ~ 2h) with metal
    ions in solution.In FAB-MS, 2d has the best selectivity toward
    Ag+ among others metal ions, and the simalar results was
    observed in ES-MS.In addition, these lariat crown ethers have
    good complexation abilities with some transition metal ions
    (Cu2+ and Pb2+) as shown in FAB-MS directly. In ES-MS, factors
    that influence the complexation behaviour were studied. These
    factors include the solvent condition, counteranions and added
    cations (Cs+, Rb+). All of these effect the experimental results
    respectively. So they can be used to control ion-selectivity of
    these lariat crown ethers toward Li+ or Na+.In methanol, all
    these lariat crown ethers prefer to complex with Li+ as compared
    with Na+and K+ ions. These sequence of selectivity is Li+>Na+>
    K+. As the precentage of water increases, selectivity toward Na+
    also increases. Calibration method has been developed and has
    been shown to be essential in these studies. Two new
    applications are developed in ES-MS. First, we used the ES-MS to
    estimate the stability constants (Ks) of these lariat crown
    ethers with IA metal ions (Li+, Na+ and K+). The Ks values of
    these lariat crown ethers are about 105 with Li+, 104 with Na+,
    and 103 with K+ in methanol. Second, we used ES-MS to detect the
    trace metal ions (Na+, K+) contaminated in solutions. Even with
    HPLC grade methanol ( Mallinckrodt ), 3.6 x 10-6 M of K+ were
    detected.
    Abstract : Fast atom bombardment mass spectrometry (FAB-MS)

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