CN113604212A - 一种高荧光强度的上、下转换稀土掺杂纳米材料及其制备方法 - Google Patents
一种高荧光强度的上、下转换稀土掺杂纳米材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及纳米荧光材料的技术领域,具体涉及一种高荧光强度的上、下转换稀土掺杂纳米材料及其制备方法,该纳米材料包含具有声子能量低的NaYF4主体结构、稳定晶相的Gd3+、发射激子Tm3+、调节荧光强度的锂离子Li+和惰性壳层NaGdF4。本发明的纳米材料粒子通过在稀土掺杂的NaYF4纳米材料中引入不同浓度的小尺寸Li+,诱导纳米材料晶格皱缩或膨胀,直接影响稀土金属的配位环境和晶体场裂分,从而提升纳米材料的荧光强度,在波长808nm激光激发下表现出1473nm下转换荧光;同时,在波长1064nm激光激发下表现出800nm上转换荧光。
Description
技术领域
本发明涉及纳米荧光材料的技术领域,具体涉及一种高荧光强度的上、下转换稀土掺杂纳米材料及其制备方法。
背景技术
荧光成像技术从分子角度出发,利用光学探针的荧光强度作为检测、分析信号,直观、精确反映生物体内的组织结构和功能信息,为病理机制研究和医学临床诊断等相关领域提供了便利。近红外荧光成像技术因其具有快速和实时显示,高分辨率和高灵敏度,成本相对较低和使用方便等优点正在医学分子成像方面飞速发展。相较于近红外一区(NIR-I,700-1000nm),光在近红外二区(NIR-II,1000-1700nm)生物组织自身吸收、散射弱,可极大地提高光穿透能力和成像质量,使得NIRII荧光成像逐渐成为热点研究。
迄今为止,可用于进行NIRII荧光成像的材料主要为给体-受体-给体型有机小分子荧光染料、有机共轭聚合物和稀土掺杂纳米粒子。小分子荧光染料和有机共轭聚合物因其碳-碳键形成独特的π共轭结构而具有良好的荧光、光热、光动力性能,但也正因这种庞大的共轭结构,导致合成步骤繁琐,水溶性差。稀土掺杂纳米粒子的发光来源于稀土离子的4f电子在不同能级上的跃迁,其发射带窄、光稳定性好,可通过精准筛选掺杂稀土离子调控荧光波长,但量子产率较低亟待提升。因此,设计合成具有强荧光量子产率的稀土掺杂纳米粒子具有重要意义。
发明内容
本发明的目的之一在于提供一种高荧光强度的上、下转换稀土掺杂纳米材料,通过引入不同摩尔浓度的Li+,诱导晶格皱缩或膨胀,改变纳米粒子的上、下转换荧光强度。
本发明的目的之二在于提供一种高荧光强度的上、下转换稀土掺杂纳米材料的制备方法,制备工艺简便,易于调节。
本发明实现目的之一所采用的方案是:一种高荧光强度的上、下转换稀土掺杂纳米材料,其特征在于:该纳米材料包含具有声子能量低的NaYF4主体结构、稳定晶相的Gd3+、发射激子Tm3+、调节荧光强度的锂离子Li+和惰性壳层NaGdF4。
优选地,该纳米材料的通式为Na(1-x)YF4:LixGd0.2Tm0.005@NaGdF4,其中x为0.01-0.10。
优选地,该纳米材料在波长808nm激光激发下表现出1473nm下转换荧光;在波长1064nm激光激发下表现出800nm上转换荧光。
优选地,该纳米材料的粒径为20-200nm。
本发明实现目的之二所采用的方案是:一种所述的高荧光强度的上、下转换稀土掺杂纳米材料的制备方法,包括以下步骤:
(1)将一定量的Y(CF3COO)3、Gd(CF3COO)3、Tm(CF3COO)3、CF3COONa和CF3COOLi、油胺、油酸和十八烯混合后,在惰性气氛下、330-350℃下保温一定时间后冷却至室温,得到稀土、Li+掺杂NaYF4纳米核,即Na(1-x)YF4:LixGd0.2Tm0.005纳米核;
(2)通过溶剂热法,在制备好的Na(1-x)YF4:LixGd0.2Tm0.005纳米核表面包覆NaGdF4壳层,即得到稀土、Li+掺杂NaYF4纳米核壳结构,即为Na(1-x)YF4:LixGd0.2Tm0.005@NaGdF4。
优选地,所述步骤(1)中,CF3COONa、Y(CF3COO)3、Gd(CF3COO)3、Tm(CF3COO)3、和CF3COOLi的摩尔比为(1-x):0.795:0.2:0.005:x。
首先利用溶剂挥发法合成三氟乙酸化物前体:Y(CF3COO)3、Gd(CF3COO)3、Tm(CF3COO)3、CF3COONa和CF3COOLi;其次将三氟乙酸前体通过一定比例混合于油酸、油胺和十八烯中,通过溶剂热法,在惰性气体保护下制备纳米核Na(1-x)YF4:LixGd0.2Tm0.005NPs;最终滴加壳层种子溶液至上述制备的纳米核溶液中,从而在其表面包覆NaGdF4壳层。形成沉淀经离心后,用乙醇和正己烷洗涤产物,干燥获得Na(1-x)YF4:LixGd0.2Tm0.005@NaGdF4 NPs。
进一步地,三氟乙酸化物前体为Y(CF3COO)3、Gd(CF3COO)3、Tm(CF3COO)3。合成路线如下:
具体制备过程:90℃下将稀土氧化物(Y2O3、Gd2O3、Tm2O3)溶解于CF3COOH中并干燥,加以OM至完全溶解以获得三氟乙酸化物前体;CF3COOLi 90℃下直接溶解在OM中;CF3COONa90℃下直接溶解在OA中。
进一步地,纳米核NaYF4:xLi0.2Gd0.005Tm NPs合成路线如图7所示:
具体制备过程:在110℃下将一定比例的三氟乙酸化物前体混合在OA、OM和ODE中抽真空,并进一步地在氮气气氛下快速升温至340℃,搅拌1小时,获得NaYF4:xLi0.2Gd0.005Tm NPs。
进一步地,核壳结构纳米材料Na(1-x)YF4:LixGd0.2Tm0.005@NaGdF4NPs合成路线如图8所示:
具体制备过程:在纳米粒子溶液中匀速滴加溶解在OA和OM混合物中的CF3COONa和Gd(CF3COO)3前体,在340℃下继续搅拌30分钟,从而在纳米粒子表面包覆上未掺杂的NaGdF4壳层。产物冷却至室温后,用乙醇作为沉降剂加入到反应液中得到沉淀,并用正己烷和乙醇的混合溶液反复离心、洗涤,获得目标产物纳米材料粉末。
具体的,一种所述的高荧光强度的上、下转换稀土掺杂纳米材料的制备方法,包括以下步骤:
S1.制备稀土、Li+掺杂NaYF4纳米核:
第一步:合成三氟乙酸化物前体的油酸或油胺溶液:
2.5mmol氧化钇(以下简称Y2O3)、15mmol三氟乙酸(以下简称CF3COOH)和1mL超纯水在90℃下混合直至Y2O3完全溶解,溶液澄清。进一步将溶剂挥发获得5mmol三氟乙酸钇(以下简称Y(CF3COO)3)白色固体粉末。加以10mL油胺(以下简称OM)在90℃至完全溶解得到0.5M Y(CF3COO)3OM溶液。
2.5mmol氧化钆(以下简称Gd2O3)、15mmol CF3COOH和1mL超纯水在90℃下混合直至Gd2O3完全溶解,溶液澄清。进一步将溶剂挥发获得5mmol三氟乙酸钆(以下简称Gd(CF3COO)3)白色固体粉末。加以10mL OM在90℃下搅拌至完全溶解得到0.5MGd(CF3COO)3OM溶液。
1mmol氧化铥(以下简称Tm2O3)、6mmol CF3COOH和0.5mL超纯水在90℃下混合直至Tm2O3完全溶解,溶液澄清。进一步将溶剂挥发获得2mmol三氟乙酸铥(以下简称Tm(CF3COO)3)白色固体粉末。加以10mL OM在90℃下搅拌至完全溶解得到0.2MTm(CF3COO)3OM溶液。
7.5mmol三氟乙酸钠(以下简称CF3COONa)溶解在10mL油酸(以下简称OA)溶液中得到0.75M CF3COONa OA溶液。
5mmol三氟乙酸锂(以下简称CF3COOLi)溶解在10mL OM溶液中得到0.5M CF3COOLiOM溶液。
第二步:通过溶剂热法制备稀土、Li+掺杂的NaYF4纳米核:
(1-x)mmol CF3COONa OA溶液、0.795mmol Y(CF3COO)3OM溶液、0.2mmol Gd(CF3COO)3OM溶液、0.005mmol Tm(CF3COO)3OM溶液、x mmol CF3COOLi OM溶液、0.5mL OA、3.2mL十八烯(以下简称ODE)加入到三口瓶中搅拌混合,升温至110℃,抽真空10分钟除去低沸点溶剂。待低沸点溶剂除尽,将上述溶液通入氮气,以15℃/min的速度升温至340℃,反应1小时,获得稀土、Li+掺杂NaYF4纳米核(以下简称Na(1-x)YF4:LixGd0.2Tm0.005 NPs,x=0,0.01,0.03,0.05,0.07,0.10)。
第三步:通过溶剂热法,在制备好的稀土、Li+掺杂NaYF4纳米核表面包覆NaGdF4壳层:
将1mmol CF3COONa OA溶液、1mmol Gd(CF3COO)3OM溶液、1mL OA、1mL OM在90℃下混合搅拌30分钟获得NaGdF4壳层种子溶液。在上述纳米核溶液中以1滴/s的速度滴加壳层种子溶液,在340℃下继续搅拌30分钟,从而在纳米核表面包覆上未掺杂的NaGdF4壳层。待反应结束将溶液降至室温,沉淀用乙醇和正己烷(v:v=1:1)在10000rpm下离心洗涤三次并干燥,获得稀土、Li+掺杂NaYF4纳米核壳结构(以下简称Na(1-x)YF4:LixGd0.2Tm0.005@NaGdF4NPs,x=0,0.01,0.03,0.05,0.07,0.10)。
本发明中,Na(1-x)YF4:LixGd0.2Tm0.005@NaGdF4,的具体含义为所述的纳米核引入Gd3+摩尔浓度为20%,Tm3+摩尔浓度为0.5%,Li+摩尔浓度为x。其中Li+的引入为替换NaYF4中的Na+。
本发明具有以下优点和有益效果:
1.本发明的纳米材料粒子是以NaYF4掺杂Gd3+、Tm3+以及不同浓度的Li+为纳米核,表面包覆惰性壳层形成的核壳结构纳米粒子,通过在稀土掺杂的NaYF4纳米材料中引入不同浓度的小尺寸Li+,诱导纳米材料晶格皱缩或膨胀,直接影响稀土金属的配位环境和晶体场裂分,从而提升纳米材料的荧光强度。
2.本发明的高荧光强度的上、下转换稀土掺杂纳米材料粒子尺寸均一,分散性良好,上、下转换荧光强度明显提升,在波长808nm激光激发下表现出1473nm下转换荧光;同时,在波长1064nm激光激发下表现出800nm上转换荧光,可作为NIRII荧光成像造影剂,用于疾病诊断。此外,还可与光热试剂、光动力试剂、化学药物等相结合,制备纳米诊疗药物,应用于生物医学诊疗领域,具有广阔前景。
3.本发明的制备方法成本低,工艺操作简单,原料易得廉价,生产设备简单,易于制备。
附图说明
图1为实施例4中掺杂不同浓度的Li+的纳米材料X射线衍射图谱;
图2为实施例5中掺杂不同浓度的Li+的纳米材料扫描电镜图片;
图3为实施例6中掺杂不同浓度的Li+的纳米材料上转换荧光光谱;
图4为实施例6中掺杂不同浓度的Li+的纳米材料上转换荧光800nm处峰值;
图5为实施例7中掺杂不同浓度的Li+的纳米材料下转换荧光光谱;
图6为实施例6中掺杂不同浓度的Li+的纳米材料下转换荧光1473nm处峰值;
图7为纳米核Na(1-x)YF4:LixGd0.2Tm0.005NPs合成路线图;
图8为核壳结构纳米材料Na(1-x)YF4:LixGd0.2Tm0.005@NaGdF4 NPs合成路线图。
具体实施方式
为更好的理解本发明,下面的实施例是对本发明的进一步说明,但本发明的内容不仅仅局限于下面的实施例。
下列实施例中所述的有关试剂均是市售Y2O3、Gd2O3、Tm2O3、CF3COOH、CF3COONa、CF3COOLi、OA、OM、ODE未经任何处理。
实施例1:合成三氟乙酸化物前体的OA或OM溶液
2.5mmol Y2O3、15mmol CF3COOH和1mL超纯水在90℃下混合直至Y2O3完全溶解,溶液澄清。进一步将溶剂挥发获得5mmol Y(CF3COO)3白色固体粉末。加以10mL OM在90℃至完全溶解得到0.5M Y(CF3COO)3OM溶液。
2.5mmol Gd2O3、15mmol CF3COOH和1mL超纯水在90℃下混合直至Gd2O3完全溶解,溶液澄清。进一步将溶剂挥发获得5mmol Gd(CF3COO)3白色固体粉末。加以10mL OM在90℃下搅拌至完全溶解得到0.5M Gd(CF3COO)3OM溶液。
1mmol Tm2O3、6mmol CF3COOH和0.5mL超纯水在90℃下混合直至Tm2O3完全溶解,溶液澄清。进一步将溶剂挥发获得2mmol Tm(CF3COO)3白色固体粉末。加以10mL OM在90℃下搅拌至完全溶解得到0.2M Tm(CF3COO)3OM溶液。
7.5mmol CF3COONa溶解在10mL OA溶液中得到0.75M CF3COONa OA溶液。
5mmol CF3COOLi溶解在10mL OM溶液中得到0.5M CF3COOLi OM溶液。
实施例2:通过溶剂热法制备Na(1-x)YF4:LixGd0.2Tm0.005NPs
(1-x)mmol CF3COONa OA溶液、0.795mmol Y(CF3COO)3OM溶液、0.2mmol Gd(CF3COO)3OM溶液、0.005mmol Tm(CF3COO)3OM溶液、x mmol CF3COOLi OM溶液、0.5mL OA、3.2mL ODE加入到三口瓶中搅拌混合,升温至110℃,抽真空10分钟除去低沸点溶剂。待低沸点溶剂除尽,将上述溶液通入氮气,以15℃/min的速度升温至340℃,反应1小时,获得Na(1-x)YF4:LixGd0.2Tm0.005NPs,其中x=0,0.01,0.03,0.05,0.07,0.10。
实施例3:通过溶剂热法,制备Na(1-x)YF4:LixGd0.2Tm0.005@NaGdF4 NPs
将1mmol CF3COONa OA溶液、1mmol Gd(CF3COO)3OM溶液、1mL OA、1mL OM在90℃下混合搅拌30分钟获得NaGdF4壳层种子溶液。在实施例2制备的纳米核溶液中以1滴/s的速度滴加壳层种子溶液,在340℃下继续搅拌30分钟,从而在纳米核表面包覆上未掺杂的NaGdF4壳层。待反应结束将溶液降至室温,沉淀用乙醇和正己烷(v:v=1:1)在10000rpm下离心洗涤三次并干燥,获得Na(1-x)YF4:LixGd0.2Tm0.005@NaGdF4 NPs,其中x=0,0.01,0.03,0.05,0.07,0.10。
实施例4:晶型表征
将实施例3所合成的干燥粉末样品进行X射线衍射仪表征,如图1a所示,可证明所合成的纳米材料均与六角相的NaYF4主体一致;如图1b所示,调整Li+掺杂的摩尔浓度,可观察到谱图的移动,为晶格皱缩或膨胀的表现。
实施例5:形貌表征
将实施例3所合成的0.1mg/mL样品分散在正己烷中,滴在硅片上,待干燥后进行形貌测试,如图2所示,可以发现所制备的样品尺寸在47~50nm,且分散性良好。
实施例6:上转换光谱测试
将实施例3所合成的干燥粉末样品夹在两个石英片中,选择外置1064nm激光器作为光源(功率密度为382mW/cm2)进行荧光发射光谱测试。如图3所示,样品在800nm处表现出上转换荧光发射。且当Li+掺杂的摩尔浓度为5%时,上转换荧光发射强度最大(图4),说明该掺杂浓度为优选浓度。
实施例7:下转换光谱测试
将实施例3所合成的干燥粉末样品夹在两个石英片中,选择外置800nm激光器作为光源(功率密度为178mW/cm2)进行荧光发射光谱测试。如图5所示,样品在1473nm处表现出下转换荧光发射。且当Li+掺杂的摩尔浓度为5%时,上转换荧光发射强度最大(图6),说明该掺杂浓度为优选浓度。
以上所述是本发明的优选实施方式而已,当然不能以此来限定本发明之权利范围,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和变动,这些改进和变动也视为本发明的保护范围。
Claims (6)
1.一种高荧光强度的上、下转换稀土掺杂纳米材料,其特征在于:该纳米材料包含具有声子能量低的NaYF4主体结构、稳定晶相的Gd3+、发射激子Tm3+、调节荧光强度的锂离子Li+和惰性壳层NaGdF4。
2.根据权利要求1所述的高荧光强度的上、下转换稀土掺杂纳米材料,其特征在于:该纳米材料的通式为Na(1-x)YF4:LixGd0.2Tm0.005@NaGdF4,其中x为0.01-0.10。
3.根据权利要求1所述的高荧光强度的上、下转换稀土掺杂纳米材料,其特征在于:该纳米材料在波长808nm激光激发下表现出1473nm下转换荧光;在波长1064nm激光激发下表现出800nm上转换荧光。
4.根据权利要求1所述的高荧光强度的上、下转换稀土掺杂纳米材料,其特征在于:该纳米材料的粒径为20-200nm。
5.一种如权利要求1-4中任一项所述的高荧光强度的上、下转换稀土掺杂纳米材料的制备方法,其特征在于,包括以下步骤:
(1)将一定量的Y(CF3COO)3、Gd(CF3COO)3、Tm(CF3COO)3、CF3COONa和CF3COOLi、油胺、油酸和十八烯混合后,在惰性气氛下、330-350℃下保温一定时间后冷却至室温,得到稀土、Li+掺杂NaYF4纳米核,即Na(1-x)YF4:LixGd0.2Tm0.005纳米核;
(2)通过溶剂热法,在制备好的Na(1-x)YF4:LixGd0.2Tm0.005纳米核表面包覆NaGdF4壳层,即得到稀土、Li+掺杂NaYF4纳米核壳结构,即为Na(1-x)YF4:LixGd0.2Tm0.005@NaGdF4。
6.根据权利要求4所述的高荧光强度的上、下转换稀土掺杂纳米材料的制备方法,其特征在于:所述步骤(1)中,CF3COONa、Y(CF3COO)3、Gd(CF3COO)3、Tm(CF3COO)3、和CF3COOLi的摩尔比为(1-x):0.795:0.2:0.005:x。
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