CN114907840A - 监测细胞内gsh浓度的荧光金纳米团簇及其制备方法 - Google Patents

监测细胞内gsh浓度的荧光金纳米团簇及其制备方法 Download PDF

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CN114907840A
CN114907840A CN202210231753.8A CN202210231753A CN114907840A CN 114907840 A CN114907840 A CN 114907840A CN 202210231753 A CN202210231753 A CN 202210231753A CN 114907840 A CN114907840 A CN 114907840A
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张忠洁
刘璐
李宗祥
冯燕
朱满洲
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Abstract

本发明公开了监测细胞内GSH浓度的荧光金纳米团簇及其制备方法，该荧光金纳米团簇制备的方法步骤如下：将小分子硫醇配体和氯金酸在甲醇水溶液中混合反应，反应后经超滤制得监测细胞内GSH浓度的荧光金纳米团簇。本发明首次合成可用于细胞内GSH的定性检测原子精确的水溶性纳米团簇，提供了一种新的检测GSH的纳米材料；荧光金纳米团簇可以选择性的与GSH反应，不受生物体内其他物质的干扰，且对GSH具有13μM的极低检出限。

Description

监测细胞内GSH浓度的荧光金纳米团簇及其制备方法
技术领域
本发明涉及纳米团簇技术领域，尤其涉及监测细胞内GSH浓度的荧光金纳米团簇及其制备方法。
背景技术
目前金纳米团簇检测GSH主要是通过向团簇的***配体上连接一些基团，实现对团簇表面的功能化。但是这种方法会导致水溶性团簇的尺寸增加，从而不易被人体代谢掉。除此之外，根据文献报道，功能化的团簇尺寸通常在10nm以上，较大尺寸的团簇也会导致团簇在细胞内聚集，从而影响检测结果。
发明内容
基于背景技术存在的技术问题，本发明提出了监测细胞内GSH浓度的荧光金纳米团簇及其制备方法，具有细胞内检测、检出限低等优点。
本发明提出的监测细胞内GSH浓度的荧光金纳米团簇的制备方法，方法步骤如下：将小分子硫醇配体和氯金酸在甲醇水溶液中混合反应，反应后经超滤制得监测细胞内GSH浓度的荧光金纳米团簇。
优选地，所述小分子硫醇为嘌呤类硫醇、叶酸类硫醇或嘧啶类硫醇。
优选地，所述小分子硫醇为6-硫鸟嘌呤。
优选地，所述6-硫鸟嘌呤与所述氯金酸的摩尔比为1:20-40。
优选地，所述甲醇水溶液中水和甲醇的体积比为1:2-6。
优选地，反应的温度为20-50℃，时间为5-48h。
本发明提出的上述方法制备的监测细胞内GSH浓度的荧光金纳米团簇。
优选地，所述荧光金纳米团簇分子式为Aum(SR)n，式中SR为配体。
优选地，所述荧光金纳米团簇分子式中m＝21，n＝16。
本发明提出的上述荧光金纳米团簇在检测细胞内GSH浓度中的应用。
本发明的有益技术效果：
(1)本发明首次合成可用于细胞内GSH的定性检测原子精确的水溶性纳米团簇，提供了一种新的检测GSH的纳米材料。
(2)本发明合成的荧光金纳米团簇可以选择性的与GSH反应，不受生物体内其他物质的干扰。
(3)本发明合成的荧光金纳米团簇的尺寸仅为1nm左右，从而有效的避免了团簇在细胞中的聚集，更容易被人体代谢掉。
(4)本发明合成的荧光性水溶性纳米团簇对GSH具有13μM的极低检出限。
附图说明
图1为本发明提出的荧光金纳米团簇的质谱图；
图2为本发明提出的荧光金纳米团簇的DLS检测结果图；
图3为本发明提出的荧光金纳米团簇的特异性检测GSH效果图；
图4为本发明提出的荧光金纳米团簇的GSH滴定图；
图5为本发明提出的荧光金纳米团簇的监测细胞内GSH的示意图。
具体实施方式
实施例1
一种监测细胞内GSH浓度的荧光金纳米团簇的制备方法，方法步骤如下：将氯金酸、6-硫鸟嘌呤室温下在水和甲醇的混合溶剂中混合均匀，反应后用3KDa 超滤管超滤，最终得到纯化的荧光金纳米团簇。
其中：氯金酸与6-硫鸟嘌呤的摩尔比1:40，水和甲醇的体积比为1:6；反应的温度为35℃，时间为24h。
实施例2
一种监测细胞内GSH浓度的荧光金纳米团簇的制备方法，方法步骤如下：将氯金酸、6-硫鸟嘌呤室温下在水和甲醇的混合溶剂中混合均匀，反应后用3KDa 超滤管超滤，最终得到纯化的荧光金纳米团簇。
其中：氯金酸与6-硫鸟嘌呤的摩尔比1:20，水和甲醇的体积比为1:2；反应的温度为20℃，时间为5h。
实施例3
一种监测细胞内GSH浓度的荧光金纳米团簇的制备方法，方法步骤如下：将氯金酸、6-硫鸟嘌呤室温下在水和甲醇的混合溶剂中混合均匀，反应后用3KDa 超滤管超滤，最终得到纯化的荧光金纳米团簇。
其中：氯金酸与6-硫鸟嘌呤的摩尔比1:30，水和甲醇的体积比为1:4；反应的温度为50℃，时间为48h。
以实施例1制备的一种监测细胞内GSH浓度的荧光金纳米团簇及其应用为例进行相关的性能测试，其中：
为了检测荧光金纳米团簇的选择性，并探索其在细胞传感中的潜在应用，我们研究了外来离子的影响。选择生物分子，如L-组氨酸(L-His)、半胱氨酸(Cys)、甘氨酸(Gly)、亮氨酸(Leu)、谷氨酸(Glu)、赖氨酸(Lys)、组氨酸(His) 和精氨酸(Arg)，阳离子Zn2+，K+，Na+，Cu2+，Mg2+，Fe2+，Fe3+，Cu+浓度为 2μmol/L(与GSH等量)作为对照实验，比较荧光金纳米团簇对GSH的选择性，结果表明该荧光纳米团簇能实现对GSH的高选择性检测。
为了研究荧光纳米团簇对GSH的敏感性，我们将其与不同浓度的GSH混合。随着GSH浓度从0增加到12μmol/L，纳米团簇的荧光强度逐渐降低。随着GSH 含量的增加，猝灭效果逐渐增强。此外，结果如图4所示，在0-5μM下，根据检出限＝3σ/s，GSH的检测限(LOD)为13μmol/L。
图1为荧光金纳米团簇的质谱图，用3KDa超滤管纯化2mL，1.5mmol/L抗癌性纳米团簇，用处于负离子模式下的高分辨率质谱仪(Waters Q-TOF premier，购自美国沃特世公司进行质谱测试)，并对其分子式进行模拟，由图1可知荧光纳米团簇团簇在1381Da和1726Da处有两组峰，用Isopro软件进行模拟，图1 中的小插图证明理论峰与实验峰十分吻合，则该纳米团簇的分子式为Au21(SR)16 (SR＝配体)，价电子数N*＝m-n-q＝21-16+1＝6。因此，ESI-MS也证明了制备的荧光金团簇具有6e结构。
图2为荧光金纳米团簇的尺寸图，取2mL纯化后的溶液，用DLS(激光粒度仪，型号为ZS90，生产商为马尔文)测量其尺寸，由图2可知，本发明制备的荧光金纳米团簇的尺寸仅为1nm左右，远小于现有的功能化的荧光金纳米团簇的尺寸(10nm以上)，从而有效的避免了团簇在细胞中的聚集，更容易被人体代谢掉。
图3为荧光金纳米团簇特异性检测GSH的效果图，具体的测试方法为：配制浓度为2μmol/L的L-组氨酸(L-His)、半胱氨酸(Cys)、甘氨酸(Gly)、亮氨酸(Leu)、谷氨酸(Glu)、赖氨酸(Lys)、组氨酸(His)和精氨酸(Arg)，阳离子Zn2+，K+，Na+，Cu2+，Mg2+，Fe2+，Fe3+，Cu+溶液，分别取2μL加入100μL 金纳米团簇中，在荧光检测仪中测试发射强度。
图4为荧光金纳米团簇检测GSH的滴定图，具体的测试方法为：配制浓度为1μmol/L的GSH，以加入100μL金纳米团簇中，在荧光检测仪中测试发射强度。
图5为荧光金纳米团簇细胞内检测GSH的效果图，具体的测试方法为：将癌细胞Hela细胞在96孔板中孵育过夜。弃掉旧培养基，加入浓度为20μg/mL 的金纳米团簇，2h后，加入浓度为1μmol/L的GSH 0μL，4μL，8μL，12μL，用激光共聚焦显微镜拍摄荧光照片。
以上仅为本发明的较佳实施例而已，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、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.监测细胞内GSH浓度的荧光金纳米团簇的制备方法，其特征在于，方法步骤如下：将小分子硫醇配体和氯金酸在甲醇水溶液中混合反应，反应后经超滤制得监测细胞内GSH浓度的荧光金纳米团簇。
2.根据权利要求1所述的监测细胞内GSH浓度的荧光金纳米团簇的制备方法，其特征在于，所述小分子硫醇为嘌呤类硫醇、叶酸类硫醇或嘧啶类硫醇。
3.根据权利要求2所述的监测细胞内GSH浓度的荧光金纳米团簇的制备方法，其特征在于，所述小分子硫醇为6-硫鸟嘌呤。
4.根据权利要求1所述的监测细胞内GSH浓度的荧光金纳米团簇的制备方法，其特征在于，所述小分子硫醇配体与所述氯金酸的摩尔比为1:20-40。
5.根据权利要求1所述的监测细胞内GSH浓度的荧光金纳米团簇的制备方法，其特征在于，所述甲醇水溶液中水和甲醇的体积比为1:2-6。
6.根据权利要求1所述的监测细胞内GSH浓度的荧光金纳米团簇的制备方法，其特征在于，反应的温度为20-50℃，时间为5-48h。
7.如权利要求1-6任一项所述方法制备的监测细胞内GSH浓度的荧光金纳米团簇。
8.根据权利要求7所述的监测细胞内GSH浓度的荧光金纳米团簇，其特征在于，所述荧光金纳米团簇分子式为Aum(SR)n，式中SR为配体。
9.根据权利要求8所述的监测细胞内GSH浓度的荧光金纳米团簇，其特征在于，所述荧光金纳米团簇分子式中m＝21，n＝16。
10.如权利要求7-8任一项所述的荧光金纳米团簇在检测细胞内GSH浓度中的应用。
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