幾種稀土摻雜發(fā)光材料的制備及其應(yīng)用研究
發(fā)布時(shí)間：2018-10-17 20:32
【摘要】：稀土元素由于其獨(dú)特的電子層結(jié)構(gòu)，具有一般元素?zé)o法比擬的化學(xué)和物理性質(zhì)，因而在生物成像、環(huán)境催化、照明與顯示、光電轉(zhuǎn)換等諸多領(lǐng)域得到了廣泛的應(yīng)用，被譽(yù)為新材料的寶庫(kù)。首先在生物醫(yī)學(xué)領(lǐng)域，癌癥是當(dāng)今人類亟需攻克的醫(yī)學(xué)難題，而稀土納米材料作為藥物載體實(shí)現(xiàn)癌癥的早期診斷和治療已經(jīng)引起了研究人員的廣泛重視。特別是稀土摻雜上轉(zhuǎn)換納米材料，可以通過(guò)多光子過(guò)程將近紅外光轉(zhuǎn)換成可見(jiàn)光和紫外光。上轉(zhuǎn)換過(guò)程有其獨(dú)特的優(yōu)勢(shì)，包括對(duì)生物組織穿透深度較深，無(wú)背景熒光干擾，信噪比較高。此外，氟化物由于具有聲子能量較低、電離度高、電阻系數(shù)較高等特點(diǎn)而被認(rèn)為是最有效的上轉(zhuǎn)換發(fā)光基質(zhì)材料。其次，上轉(zhuǎn)換發(fā)光由于可產(chǎn)生發(fā)光共振能量傳遞(LRET)，在環(huán)境領(lǐng)域也有一些應(yīng)用。不僅如此，在現(xiàn)代照明、顯示等領(lǐng)域，稀土離子摻雜的發(fā)光材料也有著重要的應(yīng)用。通過(guò)稀土離子的共激發(fā)，基質(zhì)材料向稀土離子的能量傳遞以及稀土離子之間的敏化作用，實(shí)現(xiàn)了發(fā)光顏色可調(diào)控的發(fā)射，從而用于FED紅、綠、藍(lán)全色顯示領(lǐng)域�；谙⊥岭x子摻雜的發(fā)光材料廣泛的應(yīng)用，本論文主要研究了以下幾方面內(nèi)容： 采用溶劑熱法合成了聚乙烯亞胺(PEI)包覆的NaGdF4:Yb/Er上轉(zhuǎn)換發(fā)光納米粒子。在制備過(guò)程中添加表面活性劑PEI后，得到的NaGdF4:Yb/Er納米粒子具有均勻的形貌，良好的水溶性，同時(shí)納米粒子的存在又降低了PEI原本的毒性。對(duì)材料進(jìn)行了相關(guān)的細(xì)胞毒性和體外細(xì)胞成像實(shí)驗(yàn)，材料可用于上轉(zhuǎn)換發(fā)光(UCL)和核磁共振(MRI)雙模式細(xì)胞成像，表面的PEI為其應(yīng)用于基因傳遞癌癥治療提供了可能性。 采用靜電紡絲法制備具有磁性的上轉(zhuǎn)換發(fā)光二氧化硅納米管。首先通過(guò)溶劑熱法合成具有上轉(zhuǎn)換發(fā)光性質(zhì)的磁性納米粒子NaYF4:Yb/Er/Gd(MUCNPs)。隨后利用靜電紡絲法制備MUCNPs摻雜的二氧化硅前驅(qū)體纖維。將前驅(qū)體纖在600oC高溫煅燒，得到最終產(chǎn)物。合成的材料具有規(guī)則的管狀形貌，良好的生物相容性，以及磁性的同時(shí)還具有上轉(zhuǎn)換發(fā)光性質(zhì)。采用阿霉素(DOX)作為抗癌藥物模型研究材料的藥物負(fù)載和緩釋效果，材料表現(xiàn)出明顯的藥物釋放pH響應(yīng)性。材料還可用于上轉(zhuǎn)換發(fā)光(UCL)和核磁共振(MRI)雙模式細(xì)胞成像。 采用溫和的溶劑熱法合成具有良好結(jié)晶性的、單分散的梭形油相HAp:Yb/Er納米晶，并通過(guò)表面活性劑F127將油相納米晶轉(zhuǎn)換成了水溶性納米晶。利用TEM觀察樣品被Hela癌細(xì)胞吞噬的全過(guò)程。HAp與人體骨成分相似，MTT實(shí)驗(yàn)表明制備得到的樣品具有出色的生物相容性，在980nm近紅外光照射下發(fā)出強(qiáng)烈的紅色和綠色上轉(zhuǎn)換發(fā)光，并研究了材料的體外細(xì)胞成像性質(zhì)。 采用靜電紡絲法制備具有不同上轉(zhuǎn)換發(fā)光顏色的NaYF4@SiO2納米管，用于有色廢水處理。靜電紡絲法的成本低，方法簡(jiǎn)單，易于工業(yè)化批量生產(chǎn)。合成的管狀材料具有較大的比表面積和孔徑，可通過(guò)物理和化學(xué)鍵合來(lái)吸附廢水中的有色染料，采用亞甲基藍(lán)和羅丹明6G作為廢水模型來(lái)研究材料的吸附行為和再生循環(huán)利用能力。同時(shí)，通過(guò)向二氧化硅納米管中摻雜不同種類的上轉(zhuǎn)換發(fā)光納米粒子，產(chǎn)生多種上轉(zhuǎn)換發(fā)光顏色的同時(shí)會(huì)發(fā)生熒光共振能量傳遞(LRET)效應(yīng)，可用來(lái)檢測(cè)吸附或交聯(lián)到材料表面的有色染料，，也是判斷吸附過(guò)程進(jìn)度的重要參數(shù)。 采用高溫固相法制備CaGdAlO4: Tb3+/Eu3+發(fā)光材料。在紫外光和低壓陰極射線激發(fā)下，分別研究了Tb3+和Eu3+分別單摻和共摻于CaGdAlO4中的光致發(fā)光性能和陰極射線發(fā)光性能。通過(guò)改變Tb3+和Eu3+的摻雜比例，將最終實(shí)現(xiàn)單一白光發(fā)射。具體研究了體系中激活離子之間的能量傳遞作用、能量傳遞機(jī)理和發(fā)光顏色的調(diào)控，探討了其在全彩色FED中的應(yīng)用前景。
[Abstract]:Because of its unique electron layer structure, the rare earth element has the chemical and physical properties of general elemental oxygen, and has been widely used in many fields such as biological imaging, environmental catalysis, illumination and display, photoelectric conversion and so on. It is known as a treasure house of new materials. First of all, in the field of biomedicine, cancer is the medical problem which the human needs to overcome today, and the early diagnosis and treatment of the rare-earth nanometer material as the drug carrier has attracted much attention of researchers. in particular, that rare-earth-doped transition nano material can convert the near-infrared light into visible light and ultraviolet light through the multi-photon process. The up-conversion process has its unique advantages, including deep penetration depth of biological tissue, no background fluorescence interference and high signal-to-noise ratio. In addition, fluoride is considered to be the most effective upconversion luminescent matrix material due to the characteristics of low phonon energy, high ionization degree, high resistance coefficient and the like. Secondly, the upconversion luminescence has some applications in the field of environment due to the generation of luminescence resonance energy transfer (LRSET). Furthermore, in modern illumination, display and other fields, rare-earth ion-doped luminescent materials also have important applications. Through co-excitation of rare earth ions, the energy transfer of the matrix material to the rare earth ions and the sensitization between the rare earth ions, the emission of the light-emitting color can be regulated and controlled, thus being used in the field of FED red, green and blue full color display. Based on the wide application of rare earth ion-doped luminescent materials, the paper mainly studies the following aspects: Synthesis of NaGdF4: Yb/ Er coated NaGdF4: Yb/ Er by solvent thermal method When the surface active agent PEI is added in the preparation process, the obtained NaGdF4: Yb/ Er nanometer particles have uniform morphology and good water solubility, Toxicity. Related cytotoxicity and in vitro cell imaging experiments are performed on materials that can be used for both upconversion luminescence (UCL) and nuclear magnetic resonance (MRI) dual mode cell imaging, and PEI for the surface provides for its application to gene transfer cancer therapy. can be prepared by electrostatic spinning method, Preparation of Magnetic Nanoparticles NaYF4: Yb/ Er/ Gd (MU) with Upconversion Luminescence Properties by Solvent Thermal Method CNPs), followed by the use of an electrostatic spinning process for the preparation of a MUCNPs-doped silica The precursor fiber is prepared from precursor fiber at 600oC high temperature, the resultant material has regular tubular morphology, good biocompatibility, In addition, adriamycin (DOX) was used as the drug loading and slow release effect of anticancer drug model study material, and the material showed obvious drug release. pH responsiveness. Materials can also be used for up-conversion luminescence (UCL) and nuclear magnetic resonance (MRI) dual-mode Using a mild solvent thermal method to synthesize a monodisperse shuttle-shaped oil phase HAp: Yb/ Er nanocrystals, the oil phase nanocrystals were converted by surfactant F127. The water-soluble nano-crystals were formed. The samples were observed by TEM. HAp is similar to human bone composition, and MTT assay shows that the prepared sample has excellent biocompatibility, emits strong red and green conversion luminescence under the irradiation of 980nm near infrared light, In vitro cell imaging properties: NaYF4@SiO2 with different upconversion luminescence colors is prepared by electrostatic spinning The invention relates to an electrostatic spinning method, which is low in cost and simple in method. The synthetic tubular material has larger specific surface area and pore diameter, can adsorb the colored dye in the waste water through physical and chemical bonding, At the same time, by doping different kinds of up-conversion luminescent nanoparticles into the silicon dioxide nanotube, a fluorescence resonance energy transfer (LRSET) effect can occur while producing a plurality of upconversion luminescence colors, The colored dye attached to the surface of the material is also a judgment Preparation of CaGdAlO4 by High Temperature Solid Phase Method Tb3 +/ Eu3 + luminescent materials were used to study the luminescence of Tb3 + and Eu3 + in CaGdAlO4, respectively. Light-emitting and cathode-ray emission properties, by changing the doping of Tb3 + and Eu3 + In this paper, the energy transfer function, energy transfer mechanism and emission color of activated ions in the system are studied.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB34
[Abstract]:Because of its unique electron layer structure, the rare earth element has the chemical and physical properties of general elemental oxygen, and has been widely used in many fields such as biological imaging, environmental catalysis, illumination and display, photoelectric conversion and so on. It is known as a treasure house of new materials. First of all, in the field of biomedicine, cancer is the medical problem which the human needs to overcome today, and the early diagnosis and treatment of the rare-earth nanometer material as the drug carrier has attracted much attention of researchers. in particular, that rare-earth-doped transition nano material can convert the near-infrared light into visible light and ultraviolet light through the multi-photon process. The up-conversion process has its unique advantages, including deep penetration depth of biological tissue, no background fluorescence interference and high signal-to-noise ratio. In addition, fluoride is considered to be the most effective upconversion luminescent matrix material due to the characteristics of low phonon energy, high ionization degree, high resistance coefficient and the like. Secondly, the upconversion luminescence has some applications in the field of environment due to the generation of luminescence resonance energy transfer (LRSET). Furthermore, in modern illumination, display and other fields, rare-earth ion-doped luminescent materials also have important applications. Through co-excitation of rare earth ions, the energy transfer of the matrix material to the rare earth ions and the sensitization between the rare earth ions, the emission of the light-emitting color can be regulated and controlled, thus being used in the field of FED red, green and blue full color display. Based on the wide application of rare earth ion-doped luminescent materials, the paper mainly studies the following aspects: Synthesis of NaGdF4: Yb/ Er coated NaGdF4: Yb/ Er by solvent thermal method When the surface active agent PEI is added in the preparation process, the obtained NaGdF4: Yb/ Er nanometer particles have uniform morphology and good water solubility, Toxicity. Related cytotoxicity and in vitro cell imaging experiments are performed on materials that can be used for both upconversion luminescence (UCL) and nuclear magnetic resonance (MRI) dual mode cell imaging, and PEI for the surface provides for its application to gene transfer cancer therapy. can be prepared by electrostatic spinning method, Preparation of Magnetic Nanoparticles NaYF4: Yb/ Er/ Gd (MU) with Upconversion Luminescence Properties by Solvent Thermal Method CNPs), followed by the use of an electrostatic spinning process for the preparation of a MUCNPs-doped silica The precursor fiber is prepared from precursor fiber at 600oC high temperature, the resultant material has regular tubular morphology, good biocompatibility, In addition, adriamycin (DOX) was used as the drug loading and slow release effect of anticancer drug model study material, and the material showed obvious drug release. pH responsiveness. Materials can also be used for up-conversion luminescence (UCL) and nuclear magnetic resonance (MRI) dual-mode Using a mild solvent thermal method to synthesize a monodisperse shuttle-shaped oil phase HAp: Yb/ Er nanocrystals, the oil phase nanocrystals were converted by surfactant F127. The water-soluble nano-crystals were formed. The samples were observed by TEM. HAp is similar to human bone composition, and MTT assay shows that the prepared sample has excellent biocompatibility, emits strong red and green conversion luminescence under the irradiation of 980nm near infrared light, In vitro cell imaging properties: NaYF4@SiO2 with different upconversion luminescence colors is prepared by electrostatic spinning The invention relates to an electrostatic spinning method, which is low in cost and simple in method. The synthetic tubular material has larger specific surface area and pore diameter, can adsorb the colored dye in the waste water through physical and chemical bonding, At the same time, by doping different kinds of up-conversion luminescent nanoparticles into the silicon dioxide nanotube, a fluorescence resonance energy transfer (LRSET) effect can occur while producing a plurality of upconversion luminescence colors, The colored dye attached to the surface of the material is also a judgment Preparation of CaGdAlO4 by High Temperature Solid Phase Method Tb3 +/ Eu3 + luminescent materials were used to study the luminescence of Tb3 + and Eu3 + in CaGdAlO4, respectively. Light-emitting and cathode-ray emission properties, by changing the doping of Tb3 + and Eu3 + In this paper, the energy transfer function, energy transfer mechanism and emission color of activated ions in the system are studied.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB34
【共引文獻(xiàn)】
相關(guān)期刊論文 前10條
1 胡偉漢,張國(guó)義,劉立志,吳湖炳,李立,高遠(yuǎn)紅,潘q
本文編號(hào)：2277878
本文鏈接：http://sikaile.net/kejilunwen/cailiaohuaxuelunwen/2277878.html
最近更新
教材專著
