新型高效稀土光子能量转换材料研究与生物应用探索

发布时间：2018-04-28 15:47

本文选题：能量转换 + 量子剪裁效率　；参考：《吉林大学》2015年博士论文

【摘要】：纳米材料具有的特殊的光学，电学，磁学等方面优越的物理性质，使其在生物与能源领域的应用快速发展。其中稀土掺杂的纳米发光材料有着传统发光材料无法比拟的优势，近年来，稀土发光材料在生物荧光检测与太阳能谱的光转换研究方面展示了诱人的前景，已成为光谱物理与纳米材料领域研究的热点之一。尽管稀土发光材料在这些领域的研究已经取得了一定的进展，但是在实际应用中仍然存在着不足。因此，本论文研究了稀土纳米发光材料光子能量转换的基本性质，设计了新型高效纳米发光材料结构并对其在生物荧光检测等方面的应用进行了探索，取得的成果如下： [1]采用高温热解法合成了NaYF4:Yb3+/Er3+纳米粒子，研究了其在多波长激发下的近红外量子剪裁，确定了其剪裁通道和Er3+向Yb3+的能量传递效率，最高达68.2%。理论估算了其量子剪裁效率，为186-193%。 [2]采用水热法合成了YVO4: Bi3+/Nd3+, Yb3+，通过发射光谱与动力学测量研究了Bi3+/Nd3+向Yb3+的能量传递过程，理论推导出实际量子剪裁效率计算公式，并以此确定YVO4: Bi3+, Yb3+和YVO4: Nd3+, Yb3+分别在355nm和467nm激发下的实际剪裁效率，其结果远远小于理论估算值。 [3]研究了980nm激光激发下稀土氧化物高强度的全波段超宽带发射，并把这种现象归结为有效的交叉弛豫过程和光子雪崩过程的影响。同时，这种氧化物红外波段的超宽带发射的性能也为其在集成光波导器件应用上提供了可能。 [4]利用水热法合成了PEI-NaYF4:Yb3+/Tm3+及巯基乙酸(TGA)修饰的CdTe量子点，，通过静电吸附作用使二者相连从而发生能量传递。利用这种复合结构检测血清中的铅离子并得了很好的线性度(R=0.996)和较低的检测限(80nM)，同时克服了可见光激发所造成的血清的自发荧光。 [5]采用自组装法合成了NaYF4:Yb3+, Tm3/TiO2反蛋白石复合薄膜，并利用TiO2光子晶体调制，增强了NaYF4:Yb3+, Tm3+的上转换发光，最优增强为43倍。基于该复合薄膜，生物素与亲和素之间的特异性连接以及Tm与FITC之间的共振能量传递，实现对亲和素的高灵敏度检测，确定其线性度为0.996,检测限为48pmol,灵敏度为34pmol-1。 [6]利用纳米打印技术和上转换荧光共振能量传递原理制作CEA检测试纸，实现了对CEA抗原高灵敏度和便携化的检测。
[Abstract]:Nanomaterials have special optical, electrical, magnetic and other excellent physical properties, which make their applications in the field of biology and energy rapid development. The rare earth doped nano-luminescent materials have unparalleled advantages compared with the traditional luminescent materials. In recent years, rare earth luminescent materials have shown attractive prospects in the research of bioluminescence detection and photoconversion of solar energy spectrum. It has become one of the hotspots in the field of spectral physics and nanomaterials. Although some progress has been made in the research of rare earth luminescent materials in these fields, there are still some shortcomings in practical applications. Therefore, the basic properties of photonic energy conversion of rare earth nano-luminescent materials are studied in this paper. The structure of novel high-efficient nano-luminescent materials is designed and its applications in biological fluorescence detection are explored. The results obtained are as follows. [1] NaYF4:Yb3 / er _ 3 nanoparticles were synthesized by high-temperature pyrolysis. The near infrared quantum tailoring under multi-wavelength excitation was studied, and the energy transfer efficiency of its clipping channel and Er3 to Yb3 was determined, with a maximum energy transfer efficiency of 68.2. The quantum tailoring efficiency is estimated to be 186-1931. [2] YVO4: Bi3 / Nd3, Yb3 was synthesized by hydrothermal method. The energy transfer process from Bi3 / ND 3 to Yb3 was studied by means of emission spectra and kinetic measurements. The actual tailoring efficiency of YVO4: Bi3, Yb3 and YVO4: Nd3, Yb3 under the excitation of 355nm and 467nm is determined, and the result is far less than the theoretical estimate. [3] the high intensity full-band ultra-wideband emission of rare earth oxides excited by 980nm laser is studied, and this phenomenon is reduced to the effect of effective cross-relaxation process and photon avalanche process. At the same time, the performance of this oxide infrared band UWB emission also provides a possibility for its application in integrated optical waveguide devices. [4] CdTe quantum dots modified by PEI-NaYF4:Yb3 / TM 3 and thioglycolic acid (TGA) were synthesized by hydrothermal method. The two QDs were connected by electrostatic adsorption and energy transfer occurred. The complex structure was used to detect the lead ions in the serum and the linearity was good. The low detection limit was 80 nm M ~ (-1), and the autofluorescence caused by the excitation of the visible light was overcome at the same time. [5] NaYF4:Yb3 and Tm3/TiO2 inverse opal composite films were synthesized by self-assembly method. The up-conversion luminescence of NaYF4:Yb3 and Tm3 was enhanced by using TiO2 photonic crystal modulation, and the optimal enhancement was 43 times. Based on the specific connection between biotin and avidin and the resonant energy transfer between TM and FITC, the high sensitivity detection of avidin was achieved. The linearity, detection limit and sensitivity were 0.996, 48pmol-1 and 34pmol-1, respectively. [6] the high sensitivity and portability of CEA antigen detection was realized by using nanometer printing technology and upconversion fluorescence resonance energy transfer principle.
【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB383.1

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