CN112067587B - 一种高量子产率硫量子点的制备及其用于抗坏血酸的测定方法 - Google Patents
一种高量子产率硫量子点的制备及其用于抗坏血酸的测定方法 Download PDFInfo
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Abstract
本发明公开一种高量子产率硫量子点的制备及其用于抗坏血酸的测定方法。本发明所述高量子产率硫量子点是以聚乙二醇‑400为助溶剂和钝化剂,在碱性条件下,采用超声微波辅助法制备得到的。该方法制备的硫量子点其荧光量子产率为58.65%。以上述高量子产率硫量子点为荧光探针,基于Ce(IV)对其荧光的猝灭作用,以及Ce(IV)与抗坏血酸的氧化还原反应,在Ce(IV)、抗坏血酸及硫量子点共存时,硫量子点的荧光猝灭被抑制,因而实现对抗坏血酸的定量检测。该方法成本低廉、灵敏度高、线性关系好、操作简便易行、选择性好,可用于实际样品中抗坏血酸的测定,因而具有较好的临床应用前景。
Description
技术领域
本发明涉及一种高量子产率硫量子点的制备及其用于抗坏血酸的测定方法,属于分析化学及纳米技术领域。
背景技术
硫量子点(Sulfur Quantum Dots) 是一种新型单一元素荧光量子点材料,因其具有可以调谐的荧光发射、良好的光稳定性、较大的斯托克斯位移及较好的生物相容性等优异的荧光性能,并且还具有制备成本低廉,独特的抗菌特性等优势,有望逐渐取代重金属量子点和有机染料,广泛应用于催化、分析、生物 、医药等领域。迄今为止,研究者对硫量子点的研究仍处于初级阶段,因其制备工艺复杂、功能单一、量子产率低的缺陷极大限制了应用。
L-抗坏血酸 (Ascorbic Acid),通常又叫维生素C (Vitamin C),是重要的水溶性维生素之一,是人体必需的重要成分。作为一种具有g-内酯结构的己糖酸,抗坏血酸的高还原性使其成为有效的抗氧化剂。它在维持新陈代谢和机体各项功能方面起着重要作用。同时它能与自由基反应,也是一种治疗普通感冒,癌症和精神疾病的辅助药物。抗坏血酸缺乏会引发坏血病和免疫力低下,而抗坏血酸滥用则直接导致腹泻,肾结石和胃痉挛。由于抗坏血酸与人体健康水平息息相关,所以开发一种能在实际应用中检测血清抗坏血酸的方法可以评估人体生理情况,及时纠正抗坏血酸缺乏症,具有重要的临床意义。
目前,抗坏血酸的测定方法很多,大量文献上已有报道,主要集中于以下几种方法:电化学法、滴定法、高效液相色谱法、光度法、酶法、荧光光谱法、伏安法等。其中,某些方法要求的实验条件较为苛刻和操作技术较高,而有些方法步骤复杂繁琐,不利于快速分析的要求。
本发明采用超声微波辅助法方法制备得到高量子产率硫量子点。该方法制备的硫量子点其荧光量子产率为58.65%。以上述高量子产率硫量子点为荧光探针, Ce(IV)可有效猝灭其荧光;基于Ce(IV)与抗坏血酸的氧化还原反应,在Ce(IV)、抗坏血酸及硫量子点共存时,硫量子点的荧光猝灭被抑制,从而实现对抗坏血酸的定量检测,建立了一种高灵敏、高选择、快速的抗坏血酸测定新方法。
发明内容
本发明的目的是提供一种高量子产率硫量子点的制备及其应用于抗坏血酸的测定方法。利用硫量子点和Ce(IV)构建符合荧光探针,利用荧光分析法构建线性关系曲线,进而实现对抗坏血酸的定量检测,该方法成本低廉、灵敏度高、线性关系好、操作简便易行、选择性好,可用于实际样品中抗坏血酸的测定,因而具有较好的临床应用前景。
本发明采取的技术方案为:
以聚乙二醇-400为助溶剂和钝化剂,在碱性条件下,采用超声微波法对升华硫粉进行前处理得到硫纳米颗粒,继而通过加入过氧化氢对其表面进行刻蚀,同时使用微波辅助刻蚀过程,经离心、上清液过滤、滤液透析后得到高量子产率水溶性硫量子点溶液。
所述超声微波法对升华硫粉进行前处理时间为0.5-2 h,过氧化氢浓度为7~15wt%,微波辅助刻蚀时间1~2 h,反应温度为50~90 ℃。
所述离心条件为:离心机转速6000~8000 rpm/min,离心时间为10 min。
所述滤液透析指的是经截留分子量为100-500Da的透析袋中进行透析12~36 h。
本发明所述的一种高量子产率硫量子点用于抗坏血酸的测定方法,其特征是将上述的制备方法制备得到的硫量子点溶液和Ce(IV)溶液混合,并加入缓冲液,得到硫量子点/Ce(IV)荧光探针混合溶液,荧光猝灭,测试364 nm激发波长下的荧光强度,然后同时将抗坏血酸样品加入硫量子点/Ce(IV)荧光探针混合溶液中,测试364 nm激发波长下的荧光强度。
所述硫量子点/Ce(IV)荧光探针混合溶液中,缓冲液的pH值为3,Ce(IV)溶液的终浓度为20 μM。
其荧光强度变化值与抗坏血酸浓度在1~10 µM范围内呈良好的线性关系,检测限为0.289 µM。
具体地说,本发明所述的一种氧化钨量子点的制备方法,其特征是方法步骤为:
步骤1:采用升华硫粉为原料,称取硫粉,加入聚乙二醇-400、片状氢氧化钠、超纯水,于超声微波协同萃取仪中50~90 ℃反应。
步骤2:向步骤1所得的产物中加入7~15wt%的过氧化氢,并继续放入超声微波协同萃取仪中反应。
步骤3:将步骤2所得的产物放入离心机中进行离心,离心机转速6000~8000 rpm/min,离心时间为10 min。
步骤4:使用100-500Da的透析袋将步骤3所得的离心上清液进行透析12~36 h,即可得到硫量子点溶液
本发明以廉价的硫粉为硫源,所得硫量子点具有良好的荧光性能和光稳定性,其在激发波长为364 nm时,在440 nm波长处具有最强的荧光强度,且荧光发射峰的峰形良好。且制备过程操作简单,是一种绿色无污染的制备方法。制备得到的硫量子点量子产率高,为58.7%,粒径分布均匀,为2.22 ± 0.6 nm。
本发明还提供了根据所述的制备方法制备得到的硫量子点在检测抗坏血酸中的应用。四价铈离子可以在酸性条件下猝灭硫量子点的荧光;而抗坏血酸的强还原性能将氧化态的铈离子还原,硫量子点荧光不被猝灭,从而实现对抗坏血酸的测定。硫量子点溶液和Ce(IV)溶液混合(缓冲液:pH=3的无水柠檬酸-柠檬酸钠溶液),得到硫量子点/Ce(IV)复合荧光探针溶液,荧光猝灭,测试364 nm激发波长下的荧光强度,然后将不同终浓度的抗坏血酸溶液同时加入硫量子点/Ce(IV)复合荧光探针溶液中,测试各体系在364 nm激发波长下的荧光强度;以1~10 µM范围内的抗坏血酸浓度为横坐标,453 nm处的荧光强度差值为纵坐标,构建标准曲线,进而计算得到待测液中抗坏血酸的浓度。
随着Ce(IV)离子浓度的增加,在pH=3的柠檬酸钠体系中硫量子点的荧光逐渐被猝灭,当Ce(IV)浓度达到20 μM时,硫量子点的荧光猝灭达到60%;随着Ce(IV)浓度的继续增加,硫量子点的荧光进一步猝灭,但猝灭效率显著降低。因此,本专利选择Ce(IV)浓度达到20 μM用于抗坏血酸检测。在1~10 µM的浓度范围内抗坏血酸浓度与荧光强度变化值呈线性关系,检测限为0.289 µM。
本发明的有益效果:与现有技术相比,本发明公开的微波辅助合成硫量子点的制备方法环保简单,步骤简单易行、合成时间大大缩短,产物荧光量子产率高、荧光性能稳定。同时,可直接利用硫量子点与Ce(IV)离子构建的复合荧光探针实现对抗坏血酸的定量检测,该检测方法灵敏度高、线性关系好、操作简便易行、选择性好、抗干扰能力强。
附图说明
图1为实施例1中硫量子点的透射电镜图。
图2为在不同激发波长之下的实施例1中的硫量子点的荧光发射光谱图。
图3为不同浓度的Ce(IV)加入硫量子点溶液中的荧光发射光谱图。
图4为不同浓度抗坏血酸溶液加入硫量子点/Ce(IV)荧光探针复合溶液中的荧光发射光谱图;插图:以抗坏血酸浓度对检测体系在453 nm处的荧光强度值构建的标准曲线。
图5为硫量子点/Ce(IV)体系检测抗坏血酸的抗干扰实验图。1为空白样品,2为抗坏血酸,3为铜离子,4为亚铁离子,5为钙离子,6为铁离子,7为钠离子,8为钾离子,9为葡萄糖,10为尿素, 11为半胱氨酸, 12为谷胱甘肽,13为多巴胺。
具体实施方式
下面结合附图和具体实施例对本发明作进一步阐述,本发明并不限于此。
实施例1
一种高量子产率硫量子点的制备方法,包括以下步骤:
准确称取0.175 g升华硫粉,加入1.2 mL聚乙二醇-400,并加入0.8 g NaOH,混合均匀后,70 ℃超声微波法1 h,加入5 mL 12 wt%的H2O2并继续微波1 h,将得到的产物硫量子点,采用7000 rpm离心10 min,取上清液用100-500 D的透析袋透析12 h纯化后密封保存即得到硫量子点溶液。
利用透射电镜对硫量子点的形貌进行分析,如图1所示,可以看出所制备的硫量子点为球形,粒径分布均匀,直径平均在2.22 ± 0.6 nm。
如图2所示,本发明所制备的硫量子点在较宽激发范围内,其最大发射波长保持不变,不具有激发依赖性,证明该方法制备的硫量子点的尺寸分布范围较窄且表面状态相对均匀。通过绝对量子产率的表征,本制备方法得到的硫量子点量子产率为56.65%。当激发波长为364 nm时,硫量子点的荧光光谱在波长440 nm处具有最强的荧光发射峰,峰形良好。
实施例2
硫量子点/Ce(IV)荧光探针复合溶液中Ce(IV)浓度的选择:将柠檬酸钠缓冲(10mM,1325 μL, pH= 3), 实施例1制得的硫量子点 (75 μL)和不同浓度的的硫酸铈溶液 (50μL)先后加入2毫升EP管中,37 °C反应10分钟,测定上述体系的453 nm处的荧光强度。如图3所示,向该溶液中加入不同浓度Ce(IV)之后,硫量子点的荧光便会急剧猝灭,且随着Ce(IV)离子浓度的增加,在pH=3的柠檬酸钠体系中硫量子点的荧光逐渐被猝灭,当Ce(IV)浓度达到20 μM时,硫量子点的荧光猝灭达到60 %,随着Ce(IV)浓度的继续增加,硫量子点的荧光进一步猝灭,但猝灭效率显著降低。因此,本专利选择Ce(IV)浓度达到20 μM用于抗坏血酸检测。
实施例3
实施例1得到的硫量子点溶液在检测抗坏血酸中的应用。
所述检测的方法为:将柠檬酸钠缓冲(10 mM,1325 μL, pH= 3), 实施例1制得的硫量子点 (75 μL),不同浓度的抗坏血酸溶液(50 μL)和0.6 mM的硫酸铈溶液 (50 μL)先后加入2毫升EP管中,37°C反应10分钟。硫量子点溶液和Ce(IV)溶液混合(缓冲液:pH=3的无水柠檬酸-柠檬酸钠溶液),得到硫量子点/ Ce(IV)荧光探针复合溶液,荧光猝灭,测试364nm激发波长下的荧光强度,然后将不同终浓度的抗坏血酸溶液同时加入硫量子点/Ce(IV)荧光探针复合溶液中,测试各体系在364 nm激发波长下的荧光强度;以1~10 µM范围内的抗坏血酸浓度为横坐标,453 nm处的荧光强度差值为纵坐标,构建标准曲线,进而计算得到待测液中抗坏血酸的浓度。如图4所示,在1~10 µM的浓度范围内抗坏血酸浓度与荧光强度变化值呈线性关系,线性相关系数为R=0.990,检测限为0.289 µM。
实施例4
选择性实验:为了探究硫量子点荧光探针检测抗坏血酸的选择性,本发明选择了一些血清中常见的干扰物质铜离子(Cu2+),亚铁离子(Fe2+),钙离子(Ca2+),铁离子(Fe3+),钠离子(Na+),钾离子(K+),葡萄糖(Glu), 尿素(Urea), 半胱氨酸(Cys), 谷胱甘肽(GSH)及多巴胺(DA)来做选择性实验。从图5中可以看出,干扰物质对检测抗坏血酸的干扰作用基本可以忽略不计,表明该荧光传感器对抗坏血酸检测具有良好的选择性。
以上所述仅为本发明的典型实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改,等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (3)
1.一种高量子产率硫量子点用于抗坏血酸的测定方法,其特征在于,所述硫量子点的制备方法是以聚乙二醇-400为助溶剂和钝化剂,在碱性条件下,采用超声微波法对升华硫粉进行前处理得到硫纳米颗粒,继而通过加入过氧化氢对其表面进行刻蚀,同时使用微波辅助刻蚀过程,经离心、上清液过滤、滤液透析后得到高荧光量子产率水溶性硫量子点溶液;所述超声微波法对升华硫粉进行前处理时间为1 h,过氧化氢浓度为12%,微波辅助刻蚀时间1 h,反应温度为70 ℃;所述硫量子点是球形的水溶性硫量子点,其平均直径为2.22±0.6 nm;将上述制备方法制备得到的硫量子点溶液和Ce(IV)溶液混合,并加入缓冲液,得到硫量子点/Ce(IV)荧光探针混合溶液,荧光猝灭,测试364 nm激发波长下的荧光强度,然后同时将抗坏血酸样品加入硫量子点/Ce(IV)荧光探针混合溶液中,测试364 nm激发波长下的荧光强度。
2.根据权利要求1所述的测定方法,其特征在于,所述硫量子点/Ce(IV)荧光探针混合溶液中,缓冲液的pH值为3,Ce(IV)溶液的终浓度为20 μM。
3.根据权利要求1所述的测定方法,其特征在于,荧光强度变化值与抗坏血酸浓度在1~10 µM范围内呈良好的线性关系,检测限为0.289 µM。
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