CN115404075A - 一种磁性石墨烯量子点及其制备方法与应用 - Google Patents
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Abstract
本发明公开了一种磁性石墨烯量子点及其制备方法与应用。制备方法包括以下步骤:将抗坏血酸亚铁水溶液进行水热反应,得到磁性石墨烯量子点。通过本发明提供的磁性石墨烯量子点制备方法能够便捷、快速获得磁性石墨烯量子点,所得磁性石墨烯量子点尺寸为3~10nm,碳和铁的质量比为3~6:1~2,可用于制备增强成像造影剂,缩短成像时间、提高成像对比度、提高影像学诊断的准确度,或者体外制备诊断探针,提高体外诊断技术的准确度。
Description
技术领域
本发明涉及石墨烯制备技术领域,尤其涉及一种磁性石墨烯量子点及其制备方法与应用。
背景技术
石墨烯量子点作为一种新型的石墨烯纳米材料,其尺寸为纳米级,具有带隙可调、分散性优良、生物相容性佳、高荧光量子产率等优点,可用作荧光成像造影剂与荧光体外诊断技术的检测探针。石墨烯量子点因其优异的荧光性能而被用作荧光成像的造影剂或探针,而磁性石墨烯量子点可以在实现荧光增强成像的基础上,实现核磁共振增强成像,提高组织间对比度,即磁性石墨烯量子点可结合荧光成像与核磁共振成像,为临床影像学诊断等提供更为准确的参考。除此之外,磁性石墨烯量子点还可用于双模式体外诊断领域,用于同时检测待测标志物对磁信号与荧光信号的影响,提高检测准确率。
目前磁性石墨烯量子点的获取主要依赖于至少两步反应:第一步为石墨烯量子点的获取,包括“自下而上”法与“自上而下”法两类,即分别聚合碳化小分子前驱体与使用氧化切割石墨烯获得石墨烯量子点;第二步为磁性修饰,在石墨烯量子点的界面中,其边缘原子常被含氧(–COOH、–OH、–CHO等)与含氮(–NH2、–NH–等)官能团所饱和,可与磁性基团通过形成酯键、醚键、酰胺键或产生配位结构等实现磁性修饰。上述磁性石墨烯量子点的获取方法需使用多种原料与多步反应实现,步骤繁琐,反应产物可控性低。
因此,如何设计一种更便捷、快速的磁性石墨烯量子点制备方法是本领域技术人员需要解决的问题。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种便捷、快速的磁性石墨烯量子点制备方法。
本发明另一目的在于提供通过上述制备方法制备得到的磁性石墨烯量子点。
本发明再一目的在于提供上述磁性石墨烯量子点的应用。
为了解决上述技术问题,本发明采取的技术方案为:一种磁性石墨烯量子点的制备方法,包括以下步骤:将抗坏血酸亚铁水溶液进行水热反应,得到磁性石墨烯量子点。
作为优选方案,所述抗坏血酸亚铁水溶液浓度为1~10mg/mL。
作为优选方案,水热反应温度为120~180℃,水热反应时间为3~24h。
一种磁性石墨烯量子点,通过上述制备方法制备得到,其尺寸为3~10nm,碳和铁的质量比为3~6:1~2。上述磁性石墨烯量子点的弛豫率为200~500L/(mmol·s),荧光发射波长为300~600nm,不仅具有铁氧化物的磁性,还具有石墨烯量子点的荧光特性。
本发明还提供了上述磁性石墨烯量子点在制备增强成像造影剂中的应用。
作为优选方案,所述增强成像造影剂为核磁共振-荧光双模式增强成像造影剂。
本发明还提供了上述磁性石墨烯量子点在制备体外诊断探针中的应用。
作为优选方案,所述体外诊断探针为核磁共振弛豫-荧光双模式体外诊断探针。
作为优选方案,上述磁性石墨烯量子点在应用于增强成像或体外诊断之前,先将磁性石墨烯量子点洗涤,分散成磁性石墨烯量子点分散液。相比于现有技术,本发明实施例具有如下有益效果:
1、本发明提供了一种便捷、快速的磁性石墨烯量子点制备方法,制备过程仅需一步,原料(即前驱体)仅需一种,反应条件简易可控,产物提纯简易。前驱体抗坏血酸亚铁中既包含了合成石墨烯量子点所需的碳源,也包含了合成磁性铁氧化物的铁源。
2、本发明获得的磁性石墨烯量子点的弛豫率为200~500L/(mmol·s),荧光发射波长为300~600nm,不仅具有铁氧化物的磁性,还具有石墨烯量子点的荧光特性,不仅可作为核磁共振-荧光双模式增强成像造影剂使用,以提高成像对比度、提高影像学诊断的准确度;还可作为核磁共振弛豫-荧光双模式体外诊断技术的探针使用,以提高体外诊断技术的准确度和灵敏度。
附图说明
图1为是实施例1获取的磁性石墨烯量子点分散液的透射电子显微镜照片。
图2为实施例1获取的磁性石墨烯量子点分散液在极低场磁共振***中测得的弛豫率拟合曲线,T2表示为核磁共振横向弛豫时间。
图3为实施例1获取的磁性石墨烯量子点分散液的荧光发射谱。
图4为实施例1获取的磁性石墨烯量子点分散液用于荷瘤小鼠核磁共振增强成像的核磁共振图像。
图5为实施例1获取的磁性石墨烯量子点分散液用于荷瘤小鼠荧光增强成像的荧光照片。
图6为实施例2获取的磁性石墨烯量子点分散液用作核磁共振弛豫传感技术探针时弛豫时间的变化曲线,T2表示为核磁共振横向弛豫时间。
图7为实施例2获取的磁性石墨烯量子点分散液用作荧光探针时荧光强度比值的变化曲线,F值为荧光探针与链球菌蛋白G不同混合时间的荧光强度,F0为空白样的荧光强度。
图8为实施例3获取的磁性石墨烯量子点分散液用作核磁共振弛豫传感技术探针时检测不同浓度标志物的弛豫时间对比,T2表示为核磁共振横向弛豫时间。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
实施例1提供了一种磁性石墨烯量子点分散液,制备方法包括以下步骤:
S1、将5mg/mL的抗坏血酸亚铁水溶液进行180℃水热反应3h,得到磁性石墨烯量子点。
S2、将磁性石墨烯量子点离心洗涤,离心条件为转速8000rpm/min时间10min,重悬于水中,得到磁性石墨烯量子点分散液。
使用X射线光电子能谱能谱分析对上述制备方法所得磁性石墨烯量子点分散液中的磁性石墨烯量子点进行表征,得知其中碳含量为30%,铁含量为20%。
实施例2
实施例2提供了一种磁性石墨烯量子点分散液,与实施例1的制备方法基本相同,不同之处有:
抗坏血酸亚铁水溶液浓度为1mg/mL;
水热反应温度为120℃,时间为24h;
离心条件为10000rpm/min,时间为2min。
根据上述方法所得磁性石墨烯量子点分散液中的磁性石墨烯量子点碳含量为60%,铁含量为10%。
实施例3
实施例3提供了一种磁性石墨烯量子点分散液,与实施例1的制备方法基本相同,不同之处有:
抗坏血酸亚铁水溶液浓度为10mg/mL;
水热反应温度为150℃,时间为12h;
离心条件为3000rpm/min,时间为4min。
根据上述方法所得磁性石墨烯量子点分散液中的磁性石墨烯量子点碳含量为40%,铁含量为15%。
实施例4磁性石墨烯量子点的性能测试
将实施例1~3获得的磁性石墨烯量子点分散液通过透射电子显微镜观察其中磁性石墨烯量子点尺寸,通过极低场磁共振***测定弛豫率,并测定其荧光发射波长。
如图1所示,在透射电子显微镜下测得实施例1获得的磁性石墨烯量子点的尺寸为5nm;如图2所示,在极低场磁共振***中测得的弛豫率拟合曲线测得实施例1获得的磁性石墨烯量子点分散液中磁性石墨烯量子点横向弛豫率为230L/(mmol·s);如图3所示,通过荧光发射谱证明实施例1获得的磁性石墨烯量子点分散液的最大荧光发射波长为427nm。
实施例2获得的磁性石墨烯量子点分散液中磁性石墨烯量子点的尺寸为3nm,横向弛豫率为200L/(mmol·s),最大荧光发射波长为600nm。
实施例3获得的磁性石墨烯量子点分散液中磁性石墨烯量子点的尺寸为10nm,横向弛豫率为500L/(mmol·s),最大荧光发射波长为300nm。
实施例5磁性石墨烯量子点在核磁共振-荧光双模式增强成像领域的应用
将实施例1获得的磁性石墨烯量子点作为核磁共振-荧光双模式增强成像造影剂。通过观察荷瘤小鼠核磁共振图像(图4)以及荷瘤小鼠荧光图像(图5)可得:采用实施例1所得的磁性石墨烯量子点作为增强成像造影剂显著提高了荷瘤小鼠肿瘤组织与正常组织间的对比度。
实施例6磁性石墨烯量子点在核磁共振弛豫-荧光双模体外诊断领域的应用
利用EDC/NHS点击化学反应,将实施例2获得的磁性石墨烯量子点与免疫球蛋白G通过酰胺键偶联(偶联方法参见Sens.Actuators B Chem.:2021,337:129786.),获得特异性磁性石墨烯量子点,记为磁性探针或荧光探针,可与链球菌蛋白G特异性结合。
如图6所示,在极低场磁共振***(测试方法可参见Biosens.Bioelectron.:2016,80:661–665.)中,随着实施例2中磁性石墨烯量子点所得的磁性探针与链球菌蛋白G间混合时间增加,T2值逐渐增大,并在混合30min时稳定在470ms左右,表明当混合时间为30min时磁性探针与链球菌蛋白G已充分结合。与空白样的T2相比,实施例2所得的磁性探针与链球菌蛋白G结合后T2变化值为371ms。因此,可根据空白样与待测样品之间的T2差异来判断待测样品中是否含有链球菌蛋白G。如图7所示,通过实施例2的磁性石墨烯量子点所得的荧光探针与链球菌蛋白G随着混合时间增加,F/F0值逐渐减小,当混合时间达到30min时,F/F0值趋于稳定,表明当混合时间为30min时荧光探针与链球菌蛋白G已充分结合,与前述特异性磁性石墨烯量子点作为磁性探针时与链球菌蛋白G的结合时间一致。
如图8所示,将实施例3的磁性石墨烯量子点所得的磁性探针与不同浓度的链球菌蛋白G混合,并在二者充分结合后测试其T2值,通过评估T2值与空白样之间的差异,可知特异性磁性石墨烯量子点检测免疫球蛋白G的检测灵敏度为0.1ng/mL,具有较高的检测灵敏度。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步的详细说明,应当理解,以上所述仅为本发明的具体实施例而已,并不用于限定本发明的保护范围。特别指出,对于本领域技术人员来说,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种磁性石墨烯量子点的制备方法,其特征在于,包括以下步骤:将抗坏血酸亚铁水溶液进行水热反应,得到磁性石墨烯量子点。
2.如权利要求1所述的磁性石墨烯量子点的制备方法,其特征在于,包含以下各项中至少一项:
所述抗坏血酸亚铁浓度为1~10mg/mL;
所述水热反应温度为120~180℃,水热反应时间为3~24h。
3.一种磁性石墨烯量子点,其特征在于,通过权利要求1或2所述制备方法制备得到,磁性石墨烯量子点尺寸为3~10nm,碳和铁的质量比为3~6:1~2。
4.如权利要求4所述磁性石墨烯量子点在制备增强成像造影剂中的应用。
5.如权利要求1所述磁性石墨烯量子点在制备体外诊断探针中的应用。
6.如权利要求4所述的应用,其特征在于,所述增强成像造影剂为核磁共振-荧光双模式增强成像造影剂。
7.如权利要求5所述的应用,其特征在于,所述体外诊断探针为核磁共振弛豫-荧光双模式体外诊断探针。
8.如权利要求4或5所述的应用,其特征在于,应用前,将所述磁性石墨烯量子点洗涤,分散成磁性石墨烯量子点分散液。
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