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研究生:林繼勇
研究生(外文):Chi-yun Lin
論文名稱:一、偵測陰、陽離子之新雙官能基化學偵測劑的理論研究。二、二羧酸鹽陰離子之顏色感測器的理論研究。
論文名稱(外文):Part1: Theoretical Study of Novel Chemosensors with Difunctional Receptor for Complexation with Anions and Cations.Part2: Theoretical Study of Colorimetric Receptors for Dicarboxylate Anions.
指導教授:顏耀平
指導教授(外文):Yao-pin Yen
學位類別:碩士
校院名稱:靜宜大學
系所名稱:應用化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2007/07/
畢業學年度:95
語文別:中文
論文頁數:103
中文關鍵詞:偵測劑
外文關鍵詞:receptor
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Part 1
摘要
N-Benzo-15-crown-5- N''-(4-nitronaphthyl)thiourea (12) 是具有能同時偵測陰、陽離子的新化學偵測劑。為了探討 receptor 12 分別與 F–、 Cl–、 Br–、 CH3CO2- 和 C6H5CO2- 等陰離子結合時之鍵結能力以及與 Na+、 K+ 等陽離子,或在 Na+ 離子存在下與 F– 陰離子之鍵結能力之大小,以 RHF/6-31G(d) 層次做理論計算,找出最佳幾何優選及最穩定能量時的鍵結能力;發現 F–、 Cl–、 Br– 和 CH3CO2- 、 C6H5CO2- 中的 O 會和 receptor 12 中之 thiourea 的 H 形成鍵結。尤其在偵測 F– 陰離子時,發現會產生 deprotonation 的現象。此現象與由 1H NMR 滴定法中所得之證據相符合,而在偵測 Na+、 K+ 陽離子時,由鍵結能力可知 Na+ 的鍵結能力大於 K+ ,因為 Na+ 的離子大小 (ionic diameter 1.90) 與 15-crown-5 (cavity diameter 1.7-2.2 ) 之環穴結構較為適合,使其能夠進行 intermolecular actions。其次探討F–、 Cl–、 Br–、 CH3CO2- 、C6H5CO2- 等陰離子分別與 receptor 12 中 thiourea形成鍵結時,N 原子電荷密度的改變,得知與 F– 鍵結時,N 原子電荷密度有增加的現象,以及計算 K+、 Na+ 陽離子與 receptor 12 中 15-crown-5 上之 O 形成鍵結時,O 原子電荷密度的改變,得知在 15-crown-5 上之 O 原子電荷密度沒有改變,計算 receptor 12 在 Na+ 陽離子存在時偵測 F– 離子的鍵結情形,此時並沒有發生 deprotonation 的現象。另外探討 receptor 12 (LH) 與 F– 結合形成 complex 後會發生 deprotonation (L-) 現象且在 UV-vis 吸收峰有紅移現象,以半經驗

性計算方法 (PM3) 做理論計算,發現 LH 在 HOMO 時的電子密度是集中在 thiourea 的 S 原子上,而在 LUMO 時則集中在 nitronaphthyl ring,反之形成 L- 時其電子很明顯會 delocalization 在 nitro group 上造成紅移現象。
Part 2
摘要
6個新的 chromogenic receptors,
1,4-bis(p-nitrophenylthiourelyene-ethene-amino)anthraquinone (15)、
1,4-bis(p-nitronaphthylthiourelyene-ethene-amino)anthraquinone (16)、
1-(4-nitronaphthylthiourelyene-ethene-amino)-4-
(4-phenyl-thiourelyene-ethene-amino)anthraquinone (17)、
1-(4-nitronaphthylthiourelyene-ethene-amino)-4-
(4-nitrophenyl-thiourelyene-ethene-amino)anthraquinone (18)、
1-(4-nitronaphthylthiourelyene-ethene-amino)-4-
(4-cyanophenyl-thiourelyene-ethene-amino)anthraquinone (19) 和
1-(4-nitronaphthylthiourelyene-ethene-amino)-4-
(4-trifluoromethylphenyl-thiourelyene-ethene-amino)anthraquinone (20) 是具有能用肉眼辨識二羧酸鹽陰離子之感測器,為了探討 receptors 分別與 malonate、 succinate、 glutarate、 adipate、 maleate、 fumarate、 phthalate、 isophthalate 和 terephthalate 等二羧酸鹽陰離子結合時的鍵結能力,以 RHF/6-31G(d) 層次做理論計算,找出最佳幾何優選及最穩定能量時的鍵結能力,發現 malonate、 succinate、 glutarate、 adipate、 maleate、 fumarate、 phthalate、 isophthalate 和 terephthalate 等二羧酸鹽陰離子中的 O 會和 receptors 中之 thiourea 的 H 形成鍵結。尤其在偵測 malonate、 maleate 和 phthalate 等二羧酸鹽陰離子時,發現會產生 deprotonation 的現象,導致顏色的變化。

此現象與由 1H NMR 滴定法中所得之證據相符合。另外探討 malonate、 succinate、 glutarate、 adipate、 maleate、 fumarate、 phthalate、 isophthalate 和 terephthalate 等二羧酸鹽陰離子分別與 receptors 中之 thiourea 的 H 形成鍵結時,N 原子電荷密度的改變,得知與 malonate、 maleate 和 phthalate 形成鍵結時,N 原子電荷密度有增加的現象。
Abstract
Receptor 12 is a novel chemosensor with difunctional receptor for complexation with anions and cations. In order to probe into the binding between receptor 12 and F-, Cl-, Br-, CH3CO2-, C6H5CO2-, Na+ and K+. The binding between receptor 12 and F- when Na+ exists Na+, that Na+ ion have, we do the theoretical study with RHF/6-31G(d ) level, to find out the best geometry optimum seeking and the binding energy under the stablest energy situation. To discover F -, Cl -, Br- and oxygen atom witch exists in CH3CO2- and C6H5CO2- would binding to hydrogen atom of thiourea of receptor 12. To detect will produce the deprotonation while we detect F- anion. The phenomenon tallies with the evidence from 1H NMR titration. Besides, we know that the binding of Na+ is greater than K+ while we are detecting Na+, K+ ions. Because of the size of Na+ ion (ionic diameter 1.90) is fitter for the ring cave structure with 15-crown-5 (cavity diameter 1.7-2.2 ), thus the intermolecular actions can be advanced. Secondly, we probe into the change of the electron density of N atom when F-, Cl-, Br-, CH3CO2- and C6H5CO2- bind respectively with thioure in receptor 12. We figure out that thiourea bind with F-, the electron density of nitrogen atom has increased. It doesn’t change that the electron density of oxygen atom on 15-crown-5. To calculate the binding between receptor 12 and F- when Na+ exists, we don’t see any deprotonation. To probe receptor 12 (LH ) binds with F- ion would produce the complex, thus deprotonation (L- ) would appear, deprotonation and at the absorption band of UV-vis would have redshift or not, To do the theoretical study by semiempirical calculations (PM3) method, It can be observed both for LH and for L- that the electron density in the HOMO is essentially centered on the thiourea sulfur atom, whereas in the LUMO it is mainly located on the but nitro-naphthyl ring. However, delocalization towards the NO2 group is distinctly more pronounced in the L- form, which accounts for
the marked redshift of the absorption band.

Abstract
Six new chromogenic receptors (15, 16, 17, 18, 19 and 20) are the ones
which can distinguish dicarboxylate anion with the naked eye. In order to probe into the binding which receptors respectively bind with malonate, succinate, glutarate, adipate, maleate, fumarate, phthalate, isophthalate and terephthalate, we do the theoretical study with RHF/6-31G (d ) level to find out the optimized geometries and the stablest binding. We find hydrogen atom of the thiourea in receptors would bind with the oxygen atom of dicarboxylate anions such as malonate, succinate, glutarate, adipate, maleate, fumarate, phthalate, isophthalate and terephthalate. Especially when detecting dicarboxylate anions, such as malonate, maleate and phthalate, we find that will have deprotonation, and then the color is changed. This phenomenon corresponds with the evidence from 1H NMR titration. Furthermore, we explore the change of the electron density of nitrogen atom, when hydrogen atom of thiourea in receptors binds respectively with malonate, succinate, glutarate, adipate, maleate, fumarate, phthalate isophthalate and terephthalate.We find that the hydrogen atom binds with malonate, maleate
and phthalate, the electron density of nitrogen atom is increasing.
目錄
PART 1
壹、緒論------------------------------------------------------------------------------1
貳、計算方法-----------------------------------------------------------------------15
參、結果與討論--------------------------------------------------------------------18
(一)、幾何優選的計算------------------------------------------------------18
(二)、電荷密度的計算------------------------------------------------------27
(三)、半經驗性計算方法---------------------------------------------------29
(四)、Binding energy 的計算----------------------------------------------30
肆、結論-----------------------------------------------------------------------------32
伍、文獻資料-----------------------------------------------------------------------34

PART 2
壹、緒論-----------------------------------------------------------------------------35
貳、計算方法-----------------------------------------------------------------------55
參、結果與討論--------------------------------------------------------------------57
(一)、幾何優選的計算------------------------------------------------------57
(二)、電荷密度的計算------------------------------------------------------94
肆、結論----------------------------------------------------------------------------101
伍、文獻資料----------------------------------------------------------------------102
陸、附錄
文獻資料
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伍、文獻資料
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