三氮雜茂修飾金奈米粒子應用於偵測金屬離子

Abstract

在第一章中，以檸檬酸還原金奈米，以4-(prop-2-ynyloxy)pyridine (PP)修飾，再進行click reaction，使疊氮化合物1-(azidomethyl)-4-nitrobenzene和4-(prop-2-ynyloxy)pyridine碳碳三鍵端形成一五員環triazole。利用金奈米粒子聚集後表面電漿共振改變的特性，對各種金屬離子進行選擇性實驗，合成針對鉻三價離子具有選擇性的NTP@AuNPs。利用表面具有triazole五員環修飾的NTP@AuNPs波長639nm的吸收值，可以定量5 μM ~ 65 μM的Cr3+濃度，偵測極限為3.3 μM。NTP@AuNPs還能運用於細胞實驗中，偵測鉻離子的存在。 延續上章，在第二章中，第一步使用的PP修飾分子，但改用NaBH4 還原金奈米粒子。再加入一端為N3取代醚醇化合物2-(2-(2-azidoethoxy)ethoxy)ethanol進行第二步click reaction，使疊氮化合物和4-(prop-2-ynyloxy)pyridine碳碳三鍵端形成一五員環triazole。利用金奈米粒子聚集後表面電漿共振改變的特性，對各種金屬離子進行選擇性實驗，合成針對鉻三價離子具有選擇性的PTE@AuNPs。利用表面具有triazole五員環修飾的PTE@AuNPs波長665 nm的吸收值，可以定量0.5 μM ~ 6 μM的Cr3+濃度，偵測極限為0.0107 μM。 最後一章，使用NaBH4還原金奈米粒子，在溶液中同時添入5-(1,2-dithiolan-3-yl)-N-(prop-2-yn-1-yl)pentanamide，雙硫閉環化合物受到NaBH4影響而開環，和金奈米粒子表面形成Au-S鍵，穩定地修飾金奈米粒子。再加入疊氮化合物2-(2-(2-azidoethoxy)ethoxy)ethanol進行第二步click reaction，使疊氮化合物和4-(prop-2-ynyloxy)pyridine碳碳三鍵端形成一五員環triazole。利用金奈米粒子聚集後表面電漿共振改變的特性，對各種金屬離子進行選擇性實驗，合成針對鋁離子具有選擇性的TTP@AuNPs。利用表面具有triazole五員環修飾的TTP@AuNPs波長700 nm的吸收值，可以定量0.5 μM ~ 5 μM的Al3+濃度，偵測極限為0.0205 μM。

A sensitive, selective colorimetric Cr3+ detection method has been developed by using click-synthesized gold nanoparticles (NTP@AuNPs). Gold nanoparticles were prepared by reducing HAuCl4 with trisodium citrate, and then make 4-(prop-2-ynyloxy)pyridine (PP) as the first capping agent. Finally, by adding Cu(I), the azide part of 1-(azidomethyl)-4-nitrobenzene and the acetylene part of PP were combined to form a triazole structure. Since, we have synthesized 4-((1-(4-nitrobenzyl)-1H-1,2,3-triazol-4-yl)oxy)pyridine@AuNPs (NTP@AuNPs). IR spectra suggested that PP and NTP were capped on the surface of the gold nanoparticles. Aggregation of NTP@AuNPs was induced immediately in the presence of Cr3+ ions, yielding a color change from red to purple. This Cr3+-induced aggregation of NTP@AuNPs was monitored using naked eyes first and then UV-vis spectroscopy with a detection limit of 3.3 μM. The NTP@AuNPs bound by Cr3+ showed excellent selectivity compared to other metal ions (Ag+, Al3+, Ca2+, Cd2+, Co2+, Cr6+, Cu2+, Fe2+, Fe3+, Hg2+, Mg2+, Mn2+, Ni2+, Pb2+, and Zn2+). In addition, the NTP@AuNPs were also used to detect Cr3+ in lake water samples, with low interference.

PTE@AuNPs were prepared by reducing HAuCl4 with sodium borohydride, in the presence of 4-(prop-2-ynyloxy)pyridine (PP). Then, by adding Cu(I), the azide part of 2-(2-(2-azidoethoxy)ethoxy)ethanol and the acetylene part of PP were combined to form a triazole structure. We have synthesized 2-(2-(2-(4-(pyridin-4-yloxy)-1H-1,2,3-triazol-1-yl)ethoxy)ethoxy)ethanol@AuNPs @AuNPs (PTE@AuNPs). IR spectra suggested that PP and PTE were capped on the surface of the gold nanoparticles. Aggregation of PTE@AuNPs was induced immediately in the presence of Cr3+ ions, yielding a color change from red to blue. This Cr3+-induced aggregation of PTE@AuNPs was monitored using first the naked eye and then UV-vis spectroscopy with a detection limit of 0.0225 μM. The PTE@AuNPs bound by Cr3+ showed excellent selectivity compared to other metal ions (Ag+, Al3+, Ca2+, Cd2+, Co2+, Cr6+, Cu2+, Fe2+, Fe3+, Hg2+, Mg2+, Mn2+, Ni2+, Pb2+, and Zn2+). The TTP@AuNPs were used to detect Cr3+ in lake water samples, with low interference. A sensitive, selective colorimetric Al3+ detection method has been developed by using click-synthesized gold nanoparticles (TTP@AuNPs). Gold nanoparticles were prepared by reducing HAuCl4 with sodium borohydride, in the presence of 5-(1,2-dithiolan-3-yl)-N-(prop-2-yn-1-yl)pentanamide (TP). Then, by adding Cu(I), the azide part of 2-(2-(2-azidoethoxy)ethoxy)ethanol and the acetylene part of TP were combined to form a triazole structure. We have synthesized 5-(1,2-dithiolan-3-yl)-N-((1-(2-(2-(2-hydroxyethoxy)ethoxy)ethyl)-1H-1,2,3-triazol-4-yl)methyl)pentanamide@AuNPs (TTP@AuNPs). IR spectra suggested that TP and TTP were capped on the surface of the gold nanoparticles. Aggregation of TTP@AuNPs was induced immediately in the presence of Al3+ ions, yielding a color change from red to blue. This Al3+-induced aggregation of TTP@AuNPs was monitored using first the naked eye and then UV-vis spectroscopy with a detection limit of 0.415 μM. The TTP@AuNPs bound by Al3+ showed excellent selectivity compared to other metal ions (Ag+, Ca2+, Cd2+, Co2+, Cr3+, Cr6+, Cu2+, Fe2+, Fe3+, Hg2+, Mg2+, Mn2+, Ni2+, Pb2+, and Zn2+). The TTP@AuNPs were used to detect Al3+ in lake water samples, with low interference.