以珈瑪環丁內酯為基底及具推拉電子官能基團的螢光化學感測器

Abstract

本論文利用多組成反應合成出以珈瑪環丁內酯為基底，透過接上一個具螯合金屬離子的離子接受器如三唑環類、二-（2-吡啶甲基）胺、苯並噻唑及苯並噁唑，而製備出螢光化學感測分子，並在乙腈溶液中對銀、鈉、鈣、鈷、銅、鎂、錳、鎳、鋅、汞離子做篩選。 螢光感測的行為與珈瑪環丁內酯上官能基的有關，有些會使螢光放射增強，有些則會使螢光淬熄。這些螢光化學感測器對特定離子的選擇性、偵測極限、結合比例、結合常數及加入特定離子後，所造成量子產率的變化情形如下: 化合物6c對銅及鈷離子的偵測極限分別為2.88±0.13×10-7 M及3.01±0.19×10-7 M，且會以1:1的方式與銅及鈷離子螯合，結合常數分別為6.38±0.30×104 M-1及2.64±0.09×104 M-1。加入1.0當量的銅及鈷離子後，量子產率也由原本的0.00532降至0.00121及0.00030。 化合物6h對銅及鈷離子的偵測極限分別為8.27±0.90×10-8 M及7.29±1.18×10-8 M，也會以1:1的方式與銅及鈷離子螯合，結合常數分別為2.26±0.34×104 M-1及1.02±0.23×104 M-1。加入1.0當量的銅及鈷離子後，量子產率也由原本的0.0158降至0.00098及0.00093。 化合物10b除了對銅及鈷離子有較好的感測效果外，對鎳離子的螢光淬熄效果也相當不錯。10b對銅、鈷離子及鎳離子偵測極限分別為1.26±0.14×10-6 M、1.22±0.06×10-6 M及1.45±0.14×10-6 M，也會以1:1的方式與銅、鈷及鎳離子螯合，結合常數分別為1.22±0.14×105 M-1、1.02±0.04×104 M-1及7.32±0.41×103 M-1。加入1.0當量的銅、鈷及鎳離子後，量子產率也由原本的0.154降至0.004、0.002及0.003。 另外，也可以得到螯合銀離子後，使螢光放射增強的螢光化學感測分子，雖然對銀離子的選擇性不佳，但其感測到銀離子後，螢光放射增強的行為，還是極具發展潛力，如化合物10a、10c及10g。 化合物10a對銀離子的偵測極限為1.35±0.02×10-7 M，且會以1:1的方式與銀離子螯合，結合常數為2.77±0.08×104 M-1。加入1.0當量的銀離子後，量子產率也由原本的0.0031提升至0.0145。 化合物10c對銀離子的偵測極限為1.31±0.23×10-7 M，以1:1的方式與銀離子螯合，結合常數為3.26±1.21×104 M-1。加入1.0當量的銀離子後，量子產率也由原本的0.004提升至0.018。 化合物10g對銀離子的偵測極限為1.60±0.07×10-7 M，以1:1的方式與銀離子螯合，結合常數為2.04±0.02×104 M-1。加入1.0當量的銀離子後，量子產率也由原本的0.0013提升至0.010。 最後也得到了對鋅離子有良好的金屬離子選擇性，且會使螢光放射增強的感測器，如化合物10e、10f、10h及10j。 化合物10e對鋅離子的偵測極限為5.40±0.66×10-7 M，且會以1:1的方式與鋅離子螯合，結合常數為1.68±0.34×104 M-1。加入1.0當量的鋅離子後，量子產率也由原本的0.0033提升至0.0097，加入3.0當量的鋅離子後，量子產率更提升至0.028。 化合物10f對鋅離子的偵測極限為8.10±0.64×10-7 M，以1:1的方式與鋅離子螯合，結合常數為3.60±0.18×104 M-1。加入1.0當量的鋅離子後，量子產率也由原本的0.0026提升至0.0040，加入10.0當量的鋅離子後，量子產率更提升至0.043。 化合物10h對鋅離子的偵測極限為2.97±0.09×10-8 M，以1:1的方式與鋅離子螯合，結合常數為8.39±0.20×103 M-1。加入1.0當量的鋅離子後，量子產率也由原本的0.0026提升至0.0165，加入10.0當量的鋅離子後，量子產率更提升至0.181。 化合物10j對鋅離子的偵測極限為3.25±0.63×10-8 M，以1:1的方式與鋅離子螯合，結合常數為1.33±0.13×104 M-1。加入1.0當量的鋅離子後，量子產率也由原本的0.0013提升至0.0117，加入10.0當量的鋅離子後，量子產率更提升至0.135。

In this thesis, we used -lactone derivatives featuring triazole, N,N-Bis(2-picolyl)(2-azidoethyl)amine, benzothiazole, 6-methoxy benzothiazole and benzoxazole binding motif as fluorescent chemosensors for detecting metal ions. We investigated fluorescence changes upon addition of nitrate salts of a wide range of metal ions including Ag+, Na+, Ca2+, Co2+, Cu2+, Mg2+, Mn2+, Ni2+, Zn2+, Hg2+ in acetonitrile. The fluorescent responsive behavior was highly dependent on the attached functionalities on the -lactone core structure―some of the chemosensors behave as turn-off sensors while some as turn-on ones. The properties of the studied chemosensors, including ion selectivity, detection limit, binding ratio, binding constant and quantum yield change are summarized below: The detection limit of 6c in the presence of Cu2+ and Co2+ were 2.88±0.13×10-7 M and 3.01±0.19×10-7 M, and the binding ratio of 6c with Cu2+ and Co2+ were determined as 1:1 with binding constants found to be 6.38±0.30×104 M-1 and 2.64±0.09×104, respectively. The quantum yield of 6c decreased from 0.00532 to 0.00121 and 0.00030 respectively after addition of 1.0 equivalent of Cu2+ and Co2+. The detection limit of 6h in the presence of Cu2+ and Co2+ were 8.27±0.90×10-8 M and 7.29±1.18×10-8 M, and the binding ratio of 6h with Cu2+ and Co2+ were also determined as 1:1 with binding constants found to be 2.26±0.34×104 M-1 and 1.02±0.23×104, respectively. The quantum yield of 6h decreased from 0.0158 to 0.00098 and 0.00093 respectively after addition of 1.0 equivalent of Cu2+ and Co2+. Significant fluorescence quenching of 10b was not only observed in the presence of Cu2+ and Co2+ but also Ni2+. The detection limit of 10b in the presence of Cu2+、Co2+ and Ni2+ were 1.26±0.14×10-6 M、1.22±0.06×10-6 M and 1.45±0.14×10-6 M, and the binding ratio of 10b with Cu2+、Co2+ and Ni2+ were also determined as 1:1 with binding constant found to be 1.22±0.14×105 M-1、1.02±0.04×104 M-1 and 7.32±0.41×103 M-1, respectively. The quantum yield of 10b decreased from 0.154 to 0.004、0.002 and 0.003 respectively after addition of 1.0 equivalent of Cu2+、Co2+ and Ni2+. We also synthesized a Ag+-selective turn-on fluorescent sensor. Although it exhibits poor ion selectivity, such as 10a、10c and 10g, the fluorescent enhancement behavior still shows highly development potential in the future. The detection limit of 10a in the presence of Ag+ was 1.35±0.02×10-7 M and the binding ratio of 10a with Ag+ was determined as 1:1 with binding constant found to be 2.77±0.08×104 M-1, respectively. The quantum yield of 10a enhanced from 0.0031 to 0.0145 respectively after addition of 1.0 equivalent of Ag+. The detection limit of 10c in the presence of Ag+ was 1.31±0.23×10-7 M and the binding ratio of 10c with Ag+ was determined as 1:1 with binding constant found to be 3.26±1.21×104 M-1, respectively. The quantum yield of 10c enhanced from 0.004 to 0.018 respectively after added 1.0 equivalent addition of Ag+. The detection limit of 10g in the presence of Ag+ was 1.60±0.07×10-7 M and the binding ratio of 10g with Ag+ was determined as 1:1 with binding constant found to be 2.04±0.02×104 M-1, respectively. The quantum yield of 10g enhanced from 0.0013 to 0.010 respectively after addition of 1.0 equivalent of Ag+. A turn-on fluorescent sensor 10e、10f、10h and 10j were prepard by the similar method, which showed highly selectivity toward Zn2+. The detection limit of 10e in the presence of Zn2+ was 5.40±0.66×10-7 M and the binding ratio of 10e with Zn2+ were determined as 1:1 with binding constant found to be 1.68±0.34×104M-1, respectively. The quantum yield of 10e enhanced from 0.0031 to 0.0145 and 0.028 respectively after addition of 1.0 and 3.0 equivalent of Zn2+. The detection limit of 10f in the presence of Zn2+ was 8.10±0.64×10-7 M and the binding ratio of 10f with Zn2+ were determined as 1:1 with binding constant was found to be 3.60±0.18×104 M-1, respectively. The quantum yield of 10f enhanced from 0.0026 to 0.0040 and 0.043 respectively after addition of 1.0 and 10.0 equivalent of Zn2+. The detection limit of 10h in the presence of Zn2+ was 2.97±0.09×10-8 M and the binding ratio of 10h with Zn2+ were determined as 1:1 with binding constant found to be 8.39±0.20×103 M-1, respectively. The quantum yield of 10h enhanced from 0.0026 to 0.0165 and 0.181 respectively after addition of 1.0 and 10.0 equivalent of Zn2+. The detection limit of 10j in the presence of Zn2+ was 3.25±0.63×10-8 M and the binding ratio of 10j with Zn2+ were determined as 1:1 with binding constant found to be 1.33±0.13×104 M-1, respectively. The quantum yield of 10j enhanced from 0.0013 to 0.0117 and 0.135 respectively after addition of 1.0 and 10.0 equivalent of Zn2+.