一鍋法製備高螢光氮摻雜石墨烯量子點感測與篩選蜂蜜中的四環素

One-Pot Synthesis of Highly Fluorescent N-doped Graphene Quantum Dots for Sensing and Screening of Tetracycline in Honey

甘松融(Kan, Song Rong)

指導教授 ： 凌永健

國立清華大學/理學院/化學系/碩士(2015年)

摘要

石墨烯量子點具有量子限制侷限（quantum confinement）和邊緣效應（edge effect），其特殊性質近年來受到高度重視，因此得以在螢光應用上蓬勃發展。石墨烯量子點具有低毒性、溶解度高、化學惰性和穩定的發光性質，主要用於感測器和生物成像。
　　本研究分兩部分，第一部分研發由下向上法合成石墨烯量子點，利用檸檬酸與兩個不同的胺基酸(甘胺酸、半胱胺酸)在一鍋脫水反應後，合成出兩種摻雜氮原子的石墨烯量子點(N-doped Graphene Quantum Dots, N-GQDs)，胺基酸在此反應中同時扮演碳源和氮源的雙重角色，以甘胺酸合成的量子產率約為14%，半胱胺酸合成的量子產率約為58%，相較於其他一鍋法合成的GQD，具有較高螢光產率之優點。合成出的產物，利用FTIR、PL、TEM、UV、AFM與XPS等儀器進行表徵分析，結果顯示我們成功的以快速、簡易的一鍋法方式合成摻雜氮原子的石墨烯量子點。
第二部分利用N-GQDs的優點，運用在蜂蜜中四環素（tetracycline）的感測，發展快速篩選方法，達到零有機溶劑、簡便、快速的目的。感測機制基於操控N-GQDs螢光的開閉、N-GQDs和四環素間的π-π堆疊作用力、和猝滅N-GQD的螢光。利用標準添加法測定蜂蜜中的四環素，偵測極限為4 ppb，回收率為77-112%，相對標準偏差為14.5%。應用於21件市售蜂蜜樣品的快篩，篩選結果顯示4件有四環素殘留量。

關鍵字

含氮石墨烯量子點 ； 螢光 ； 四環素 ； 蜂蜜

並列摘要

Graphene quantum dots (GQDs) are nano-sized materials having unique properties like the quantum confinement effect and edge effect which has led to its emergence in fluorescence-based applications. The low toxicity, high solubility, chemically inertness, and stable luminescent properties of GQDs must be explored further for its application in sensors and bio imaging studies.
A one-pot synthesis of GQDs based on the bottom-up approach has been developed in this study with citric acid and amino acids（glycine、cysteine） precursors to successfully achieve two N-doped Graphene Quantum Dots (N-GQD). In this reaction, amino acid plays dual role of donating both carbon and nitrogen atom. These as-prepared N-GQDs have a high quantum yield of 14（glycine） and 58%（cysteine） as compared to previously reported GQDs. The final product has been characterized using FT-IR, PL, TEM, UV-Vis, XPS, and AFM, which shows successful nitrogen doping as GQDs.
These highly fluorescent N-GQDs have been used for faster sensing of tetracycline in honey, making this, a green method as it does not involve the use of any toxic reagent. The detection is based on the on-off mechanism and fluorescent control of N-GQDs. The sensing is primarily based on a π-π stacking interaction between N-GQD and tetracycline by quenching the fluorescence of N-GQDs. Detection of honey has been carried out using a standard addition method. A detection limit of 4 μg·L−1, recovery of 77-112%, and a relative standard deviation of 14.5% is a proof to a highly sensitive detection. Further, rapid detection of 21 commercial honey samples has been carried out, of which, four samples have been found with the presence of tetracyclin.

並列關鍵字

N-doped Graphene Quantum Dots ； fluorescent ； tetracycline ； honey

參考文獻

1. 盧柏樑, 高醫醫訊,2003.

14. 行政院衛生署, 署授食字第1011902056號, 2012

2. Fleming, A. G. Can. Med. Assoc. J. 20, 11–13 (1929).

9. Snyder, L. m, R. J. J. Kirkland, J. W. Dolan, Introduction to Modern Liquid Chromatography

11. Lequin, R. (2005). "Enzyme immunoassay (EIA)/enzyme-linked immunosorbent assay (ELISA)". Clin. Chem. 2005, 51 (12): 2415–8.