以氟標記 C4-對稱釩酸鹽中心之四聚簇狀體進行增效式金屬離子之篩選並透過氟化高效液相層析技術放大轉譯

Amplified Transcription from Subnano to Real Time Domain by Ion-specific Encapsulation and Recognition of Perfluorinated, C4-symmetric Vanadate Clusters

温叔枝(Wen, Shu Chih)

指導教授 ： 陳建添

國立清華大學/理學院/化學系/碩士(2016年)

摘要

以本實驗室過去所開發之氧釩四聚簇狀體應用於離子篩選為基礎，結合氟標記分離策略，將單體氧釩錯合物亞柳胺基模板的 C(5) 位置引入含氟碳鏈，並利用此單體與偏釩酸鹽增效式自組裝得到鉗合鈉、鉀及銫離子的四聚簇狀體 (1-Na, 1-K, 1-Cs)，再進一步將鈉離子置換為銣、銀、汞及鉛離子 (1-Rb, 1-Ag, 1-Hg, 1-Pb)。將前述四聚簇狀體注射入氟化高效液相層析管柱中，由於離子半徑差異會影響四聚簇狀體底盤緊密度，因而改變氟標記與管柱作用力，導致滯留時間之差異。
實驗結果發現滯留時間由短到長依序為 1-Na → 1-K → 1-Rb → 1-Cs，推測原因為鉗合離子半徑增加，使四聚簇狀體底盤更加緊密，尾端的氟標記碳鏈彼此夾角更小，與塗敷矽膠管柱上的氟化碳鏈 (Si(CH2)2C8F17) 擺動方向更接近平行，作用力增加，最終導致滯留時間增長。而鈉離子鉗合之四聚簇狀體在鋅、鎘、汞離子並存環境下對於汞離子具有篩選專一性，且 1-Na 及 1-Hg 兩者滯留時間差 3.6 分鐘。綜合以上結果，本研究不僅成功藉由氟標記之應用辨識出不同離子鉗合之四聚簇狀體以及簡化離子篩選結果之判讀，也是將氟標記分離策略應用於離子篩選辨識的首例。

關鍵字

金屬離子篩選辨識 ； 氟標記 ； C4-對稱四聚簇狀體 ； 氟化高效液相層析

並列摘要

A fluorous-tailor-designed vanadyl methoxide complex bearing p-(3′-perfluorobutyl)propoxyphenyl group at the C5 position of the salicylidene template was synthesized and then subjected to MVO3-induced (M = Na, K, Cs) self assembly to form M+-encapsulated quadruplexes 1-Na, 1-K and 1-Cs. The sodium ion of quadruplex 1-Na can be replaced by Rb+, Ag+, Hg2+ and Pb2+ to form quadruplexes 1-Rb, 1-Ag, 1-Hg and 1-Pb, and 1-Na has specific selectivity to Hg2+ with co-existence of Zn2+, Cd2+ and Hg2+. These cluster complexes were then injected into fluorous HPLC column. A systematic survey regarding the effect of the encapsulated metal ions within the alkali family and Hg2+ on the changes of interaction between fluorous-tail vanadyl complexes and fluorous column was performed by retention time on chromatography data. It was found that the retention time became longer as the size of alkali metal increased, and it’s due to the increasing of the encapsulated metal ion size from Na+ to Cs+ in the quadruplex caused its four lower rim regions of the resulting cluster (i.e, the four p-(3′-perfluorobutyl)propoxyphenyl groups) get closer and more parallel to fluorous-tail on the silica gel, thus inducing larger interaction tccess of amplified transcription of recognition o stationary phase. Notably, retention times between 1-Na and 1-Hg was deviated about 3.6 minutes, they can be distinguished clearly. This research revealed that the success of amplified transcription of recognition results from subnano to real time domain by combining fluorous-tag separation strategy with ion-specific encapsulated quadruplexes.

並列關鍵字

metal-ion specific recognition ； fluorous-tag ； C4-symmetric cluster ； fluorous high performance liquid chromatography

參考文獻

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