钆基稀土纳米颗粒的制备及应用研究进展
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摘要
稀土元素因具有特殊的4f电子结构、相对大的原子序数和独特的光电磁性质,吸引了研究者的广泛关注,被应用于稀土基纳米颗粒的制备上,特别是钆基纳米粒子的制备及理化性能研究方面。研究表明,稀土基纳米材料易掺杂其他稀土及金属离子,稳定性好,声子能量低,具有较大的中子吸收截面的特性,因而在发光、生物及医药等领域得到了广泛的应用。研究者们通过采用不同的制备方法得到了不同形貌和结构的稀土纳米材料,以改善其发光性能、弛豫性能、药物携带性能、靶向性等,以便更好地将其应用于发光、成像、医学治疗等不同领域中。制备氧化钆纳米粒子的方法多为液相法,该法具有操作简单、粒度可控、分散性好的特点。稀土发光材料能吸收或发射从紫外光区到红外光区的各种波长的电磁波辐射,因此近年来,除了研究不同稀土离子掺杂氧化钆对其发光性能的影响外,研究者们还利用多种稀土离子的共掺杂、稀土离子与金属离子的共掺杂,以达到调节发光、提高色彩饱和度以及发光强度的目的。钆离子因拥有七个未配对电子而被用作磁共振造影剂。目前,临床上应用最多的是以纳米氧化铁为主的阴性造影剂和以二乙三胺五醋酸钆(Gd-DTPA)为主的阳性造影剂。但纳米氧化铁成像存在信号强度较低、图像较暗、易产生伪影等问题,所以目前对于阴性造影剂的研究较少。而Gd-DTPA与氧化钆相比,后者磁性粒子密度高于前者,因此,近来的研究热点集中于通过优化制备工艺来提高氧化钆纳米材料的弛豫性能,以及通过结合氧化钆纳米材料的荧光特性,来实现其光学-磁共振成像(MRI)双模态探测功能。另外,高原子序数的钆还能作为放射增敏剂,可增加肿瘤细胞放射治疗的敏感性,相比于金、铪、铋等同样具有放射增敏潜力的增敏剂,钆基放射增敏剂能结合MRI实现图像引导放射治疗。同时,相比于铅元素,钆具有更高的射线吸收性能,因此其在屏蔽材料的应用上受到重视。本文比较了氧化钆纳米颗粒的几种主要制备方法及它们的优缺点,简述氧化钆纳米颗粒在发光材料、医学治疗、屏蔽材料方面的应用,并指出其研究尚存在的问题及发展方向。
In recent years,rare earth elements have attracted extensive attention due to their special 4 f electronic structure,relatively large atomic number and unique optical and magnetic properties. Thus,they have been widely adopted in the preparation of rare earth based nanoparticles,especially,the preparation and physicochemical properties of gadolinium-based nanoparticles. The studies demonstrated that the rare earth-based nanomaterials are easily doped with other rare earth as well as metal ions,with good stability,low phonon energy,and a large neutron absorption cross-section,which have been extensively applied in the fields of luminescence,biological and medicine.Researchers have obtained rare earth nanomaterials with various morphologies and microstructures via different preparation methods,for improving their luminescence properties,relaxation properties,drug carrying properties and targeting. so the nanoparticles can be better applied in different fields,such as luminescence,imaging,medical treatment and so on. The gadolinium oxide nanoparticles is mostly prepared by liquid phase method since the operation has the characteristics of simple operation,particle size is controllable and the dispersibility of nanoparticles is good.The rare earth luminescent materials can absorb or emit electromagnetic wave radiation of various wavelengths from ultraviolet to infrared regions. Therefore,to study the influence of different rare earth ions doped gadolinium oxide on their luminescence performance,researchers have also utilized the co-doping of various rare earth ions,rare earth ions and metal ions to achieve the goal of regulating the luminescence,ameliorating the color saturation and the luminescence intensity by adjusting the doping ratio.Gadolinium ion is used as a magnetic resonance contrast agent on account of its seven unpaired electrons. Currently,the most commonly used negative contrast agent in clinic is mainly based on nano-iron oxide,and the positive contrast agent is mainly based on gadolinium-diethylenetriamine pentaacetic(Gd-DTPA). There are few investigations on negative contrast agents since the nano-iron oxide imaging exists a series of problems,such as low signal intensity,dark image and artifacts Gadolinium oxide has higher density of magnetic particles than that of the Gd-DTPA,therefore,the recent research hotspots have been revolved round improving the relaxation properties of gadolinium oxide nanomaterials through optimizing the preparation process,and combining the fluorescence and magnetism of gadoliniumoxide nanomaterials to realize the dual mode detection function of optical magnetic resonance imaging(MRI). Besides,high atomic number of gadolinium can act as a radiosensitizer as well,which may enhance the sensitivity of tumor cells to radiotherapy. Hafnium and bismuth are both sensitizers with radiosensitizating potential as well as the gold,furthermore,the Gd-based sensitizers combining MRI can realize image-guided radiation therapy. Moreover,gadolinium has attached importance to the application of shielding materials due to its higher ray absorption properties than that of the lead.This paper compares several main preparation methods ofgadolinium oxide nanoparticles and their characteristics. The applications of gadoli-nium oxide nanoparticles in luminescent materials,medical treatment and shielding materials are briefly described and finally the existing problems and development directions of gadolinium oxide nanoparticles are pointed out.
In recent years,rare earth elements have attracted extensive attention due to their special 4 f electronic structure,relatively large atomic number and unique optical and magnetic properties. Thus,they have been widely adopted in the preparation of rare earth based nanoparticles,especially,the preparation and physicochemical properties of gadolinium-based nanoparticles. The studies demonstrated that the rare earth-based nanomaterials are easily doped with other rare earth as well as metal ions,with good stability,low phonon energy,and a large neutron absorption cross-section,which have been extensively applied in the fields of luminescence,biological and medicine.Researchers have obtained rare earth nanomaterials with various morphologies and microstructures via different preparation methods,for improving their luminescence properties,relaxation properties,drug carrying properties and targeting. so the nanoparticles can be better applied in different fields,such as luminescence,imaging,medical treatment and so on. The gadolinium oxide nanoparticles is mostly prepared by liquid phase method since the operation has the characteristics of simple operation,particle size is controllable and the dispersibility of nanoparticles is good.The rare earth luminescent materials can absorb or emit electromagnetic wave radiation of various wavelengths from ultraviolet to infrared regions. Therefore,to study the influence of different rare earth ions doped gadolinium oxide on their luminescence performance,researchers have also utilized the co-doping of various rare earth ions,rare earth ions and metal ions to achieve the goal of regulating the luminescence,ameliorating the color saturation and the luminescence intensity by adjusting the doping ratio.Gadolinium ion is used as a magnetic resonance contrast agent on account of its seven unpaired electrons. Currently,the most commonly used negative contrast agent in clinic is mainly based on nano-iron oxide,and the positive contrast agent is mainly based on gadolinium-diethylenetriamine pentaacetic(Gd-DTPA). There are few investigations on negative contrast agents since the nano-iron oxide imaging exists a series of problems,such as low signal intensity,dark image and artifacts Gadolinium oxide has higher density of magnetic particles than that of the Gd-DTPA,therefore,the recent research hotspots have been revolved round improving the relaxation properties of gadolinium oxide nanomaterials through optimizing the preparation process,and combining the fluorescence and magnetism of gadoliniumoxide nanomaterials to realize the dual mode detection function of optical magnetic resonance imaging(MRI). Besides,high atomic number of gadolinium can act as a radiosensitizer as well,which may enhance the sensitivity of tumor cells to radiotherapy. Hafnium and bismuth are both sensitizers with radiosensitizating potential as well as the gold,furthermore,the Gd-based sensitizers combining MRI can realize image-guided radiation therapy. Moreover,gadolinium has attached importance to the application of shielding materials due to its higher ray absorption properties than that of the lead.This paper compares several main preparation methods ofgadolinium oxide nanoparticles and their characteristics. The applications of gadoli-nium oxide nanoparticles in luminescent materials,medical treatment and shielding materials are briefly described and finally the existing problems and development directions of gadolinium oxide nanoparticles are pointed out.
引文
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