摘要
相比传统的有机荧光染料,胶体半导体纳米晶,通常称为量子点,具有许多独特的性质,如荧光质量高,激发光谱宽,发射光谱尺寸可调,量子产率高,光化学稳定等,这些优越的性质,使其在化学、医学、材料学、细胞生物学、分子生物学等领域展现出巨大的应用前景。近年来,基于量子点的荧光传感器引起了人们广泛的研究兴趣,因为它可以产生出截然不同的靶向信号,用于各种物质的定性和定量分析。本论文瞄准这一前沿研究方向,在对量子点的发展历程进行简要综述的基础上,拟定了一条基本的研究思路,即从量子点的合成出发,研究其特殊的光学行为、设计基于量子点的高质量荧光传感器用于化学分析中,主要从以下几方面展开工作：
一、“关-开”型量子点荧光传感器的合成及其在Cd2=测定中的应用。以巯基丙酸为包覆剂,在水溶液中合成出近红外荧光发射CdTe/CdS核／壳量子点(QDs),并进行系统表征。采用吡咯烷二硫代甲酸铵盐对QDs进行修饰,引起荧光淬灭现象。Cd2+加入后,荧光又逐渐增强,并且荧光强度与Cd2=浓度呈现出线性关系。因此,可发展为一种基于荧光‘关-开’模型的QDs传感器。实验结果表明,相比于其它金属离子,此类传感器具有较高的灵敏性和选择性,在真实样品探测中表现出优越的分析能力。在0-2pM的浓度内,可替代ICP-AES技术用于Cd2=的高效测定。与传统的荧光淬灭型传感器相比,此类“关-开”型QDs传感器的可信度更高,且具有更低的检测限(6nm)。
二、量子点-罗丹明(R6G)复合物传感器的合成及其用于谷胱甘肽的探测。水相合成巯基丙酸包覆的CdTe QDs,通过静电吸附形成R6G-QDs复合物,并对其进行系统表征。加入谷胱甘肽(GSH,0～80μM),引起此复合物荧光光谱发生改变,其中的R6G与QDs荧光强度比率(FR6C/FQDs)与GSH浓度几乎呈线性关系,进而获得了一种基于R6G-QDs的比率荧光GSH传感器。其它干扰因素如硫醇、氨基酸的共存及pH的改变,均不会对FR6G/FQDs造成明显干扰,表现出良好的敏感性和选择性。相比单荧光强度传感器和传统仪器分析技术,本方法具有更简易、快捷和廉价的优点,检测限可低至15nM。本方法有望发展成为其它分子或离子的比率荧光传感器,有助于在生物样品和生物医学体系中对GSH水平进行深入研究。
三、多功能量子点比率传感器的合成及其应用于pH和Cd2=的分析。在水溶液中,通过氢键作用将巯基乙酸包覆的CdTe QDs与有机染料(异硫氰酸荧光素,FITC)结合,形成FITC-QDs复合物。随溶液pH的升高,复合物中F1TC(520nm)和QDs(595nm)的荧光光谱均呈现有规律的增强,荧光强度比率(I520/I595)与pH(5.3-8.7)呈线性关系,进而可发展为一种比率荧光pH传感器。向复合物中加入S2-可引起QDs的荧光淬灭,继续加入Cd2=,使S2-修饰QDs的荧光增强。因此,可建立了一种基于“关-开”模型的比率荧光Cd2=传感器。实验结果证实,I520/I595与Cd2=浓度(0.1-15μM)呈比例关系,且S2-与Cd2=的加入均未明显影响FITC的荧光。此传感器可对复杂和真实样品进行探测,具有较高的灵敏性和选择性,在同等条件下可取代ICP-AES技术的应用。本方法可用于发展其它类型的QDs离子或分子探针,有助于对复杂体系进行分析。
四、量子点-凝胶复合物的合成、荧光性质及应用。选择巯基丙酸包覆的CdTe QDs为荧光剂,聚(N-异丙基丙烯酰胺-甲基丙烯酸)为凝胶,通过静电吸附将QDs包埋入凝胶中形成了复合凝胶,并对其形貌、荧光性质及应用进行了研究。结果表明,此复合凝胶的荧光在25-45℃之间具有热敏性和可逆性,荧光强度随温度升高而减弱,随温度降低而增强。在共聚焦显微镜下,呈现出明亮的荧光成像。此外,还考察Cu2+(0～2μM)对复合物的荧光淬灭现象,实验数据证实：该荧光反应对Cu2=是高选择性的,荧光强度与Cu2=浓度具有线性关系,可发展成一种基于复合凝胶的荧光传感器,用于Cu2=的定性和定量探测。
Compared to traditional organic fluorescent dyes, colloidal semiconductor nanocrystals (also referred to as quantum dots, QDs) possess many unique properties, such as high-quality luminescence, the broad excitation, size-tunable photoluminescence (PL) spectra, relatively high quantum yield and photochemical stability, which make QDs an attractive alternative to organic dyes in applications. These excellent properties exhibit great foreground in potential fields, including chemistry, medicine, materials, cell biology, molecule biology, and so forth. In the past few years, QDs-based PL sensors have generated an increasing interest because they can give birth to a distinct target signal for qualitative and quantificational analysis of various substances. The dissertation aimed to this advanced research direction, summarized a refined development of QDs and established a basic research method, that is, the following works have mainly been performed by taking QDs synthesis, characterization, particular PL behavior and PL sensors applied in chemical analysis as the line of this dissertation:
One:A near-infrared-emitting CdTe/CdS core/shell quantum dots-based OFF-ON photo-luminescence sensor for highly selective and sensitive detection of Cd2+. Herein, near-infrared-emitting CdTe/CdS QDs were synthesized and regularly characterized in aqueous media with3-mercaptopropionic acid as a stabilizer. PL of the as-prepared QDs was quenched due to the addition of ammonium pyrrolidine dithiocarbamate, and became enhanced after adding Cd2+Furthermore, the relationship between PL intensity and the concentration of Cd2+was almost linear. Therefore, a novel QDs sensor based on a PL "OFF-ON" mode could be designed. Experimental results confirmed that this sensor of Cd2+was of high selectivity and sensitivity over other metal ions, and exhibited perfect analysis performance in real and complicate samples. This proposed method could even substitute the ICP-AES for the determination of Cd2+in the concentration range from0.1to2μM. Compared to conventional sensors based on a PL quenching mode, the "OFF-ON" PL sensor in our case presented a superior reliability and a lower detection limit, which was only6nm.
Two:Rhodamine6G (R6G) conjugated-CdTe quantum dots used for a highly sensitive and selective ratiometric fluorescent sensor of glutathione (GSH). By electrostatic interactions in aqueous solution,3-mercaptopropionic acid capped-CdTe QDs and R6G were conjugated to form R6G-QDs conjugates, together with a systemic characterization. The addition of GSH (0～80μM) induced regular PL response of conjugates, and PL intensity of R6G (lR6G) to that of QDs (IQDS) in conjugates was near linear toward the concentration of GSH, which could be developed as a ratiometric PL sensor of GSH. Related experiments testified that the sensor was of high selectivity and sensitivity over other thiols and amino acids. In comparison with other single-intensity-based PL sensors and traditional analytical techniques, this ratiometric PL sensor was more facile, rapid, low-cost, and exhibited a lower limit detection of15nM. The proposed method could be applied to develop other types of QDs-based molecular or ionic probes for ratiometric PL sensing, and was beneficial to the in-depth research of GSH levels in biological samples and biomedical systems.
Three:Fluorescein isothiocyanate (FITC) conjugated-CdTe quantum dots as novel dual-functionally ratiometric fluorescence sensors of pH and cadmium ions. In aqueous solution, FITC and2-mercaptoacetic acid capped-CdTe QDs were conjugated by hydrogen bonding, and formed FITC-QDs conjugates. With the pH increasing, both PL intensity of FITC (520nm) and QDs (595nm) in these conjugates showed regular enhancement. The ratiometric PL intensity (lFITC/IQDS) was near linear toward the pH from5.3to8.7. In addition, S2-induced PL quenching of QDs and the addition of Cd2+resulted in PL enhancement of S2--modified QDs. Thus, based on this PL "OFF-ON" mode, a ratiometric PL sensor of Cd2+could be achieved. Experimental results suggested that/lFITC/IQDS was almost linear toward the concentration of Cd2+in the range from0.1to15μM. Meanwhile, the addition of S2-and Cd2+hardly affect PL intensities of FITC. This proposed method for detecting pH and Cd2+was highly sensitive and selective in real and complicated samples, and could replace ICP-AES at the same condition. This proposed sensor can help to develop other related QDs-based ratiometric PL sensors of ions or molecules for the in-depth analysis of complex systems.
Four:Preparation, luminescence properties and applications of quantum dots-micro gels conjugates. In this chapter,3-mcrcaptopropionic acid capped-CdTe QDs and polymers of N-isopropylmethacylamide and2-methylacrylic acid (that is, P(NIPAM-MAA)) were utilized as PL reagent and microgels, respectively. Due to electrostatic interactions, QDs were entrapped into microgels network to form QDs-P(NIPAM-MAA) hybrid microgels, whose configuration, particular PL properties and applications in PL imaging and sensors were seriously studied in following experiments. According to experimental results, hybrid microgels displayed fully reversible PL behavior between25℃and45℃. The PL intensity was reduced with the each increment of temperature, and then PL was recovered because of temperature dropping. In addition, there was bright PL imaging detected by the confbcal fluorescence microscope. The PL response of hybrid microgeis to Cu2+(0～2μM) was highly selective, and the relationship between PL intensity and the concentration of Cu2+was linear proportion, which could be used as a hybrid micro gels-based sensor for qualitative and quantitative detection of Cu2+
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