CN110016043A - 一种具有发射白光性质的金纳米团簇及其制备方法 - Google Patents
一种具有发射白光性质的金纳米团簇及其制备方法 Download PDFInfo
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- 229910052737 gold Inorganic materials 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 45
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
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- GWOLZNVIRIHJHB-UHFFFAOYSA-N 11-mercaptoundecanoic acid Chemical compound OC(=O)CCCCCCCCCCS GWOLZNVIRIHJHB-UHFFFAOYSA-N 0.000 claims description 14
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Abstract
本发明属于发光材料制备技术领域，公开了一种具有发射白光性质的金纳米团簇及其制备方法。该具有发射白光性质的金纳米团簇包括均为核壳结构的金纳米团簇A和金纳米团簇B，金纳米团簇A和金纳米团簇B的核均为粒径为1nm～3nm的金粒子；金纳米团簇A的壳为含硫配体；金纳米团簇B的壳为含氮配体。制备方法包括：将组氨酸与蛋氨酸混合均匀后，再溶解于强碱溶液中，加热至45℃～55℃后，加入HAuCl4，反应3.5h～4.5h，冷冻干燥，得到具有发射白光性质的金纳米团簇；本发明采用一步法成功制备出具有发射白光性质的金纳米团簇，制备方法简单，所需时间短。
Description
技术领域
本发明属于发光材料制备技术领域，特别涉及一种具有发射白光性质的金纳米团簇及其制备方法。
背景技术
实现制备双荧光峰或多荧光峰金属纳米团簇并使其荧光发射谱产生叠加从而表现出白光发射，目前所采用的方法多为分别制备单一组分、单一波长的金属纳米团簇，再通过溶液或固体粉末混合手段形成光谱叠加形成能够白光发射的金属纳米团簇。但是在实际合成上述能够白光发射的金属纳米团簇时，由于所选多种配体之间的性质差异，导致最终合成产物多个峰值间存在较大差异而无法产生发光颜色叠加形成宏观的白光发射现象。
此外，虽然，有理论上能够通过两步法合成上述能够白光发射的金属纳米团簇，但是在实际合成过程中，具有不同发射波长的金属纳米团簇，由于不同波长的金属纳米团簇合成条件如温度、时间、配体浓度、配体性质和反应溶液酸碱性等差异，无法在同样条件下一步法合成具备白光发射性质的金属纳米团簇，而目前使用的二步法在合成方法和合成时间相较一步法而言较为繁琐、漫长。
发明内容
本发明的目的在于，针对现有白光发射的金属纳米团簇在合成过程中存在的上述问题，提供一种具有发射白光性质的金纳米团簇及其制备方法。本发明的这种制备方法是通过选取合适的配体组合，通过一步法成功合成出具有发射白光性质的金纳米团簇；这种合成方法较传统的二步法，合成所需时间段，操作简单。此外，本发明合成的具有发射白光性质的金纳米团簇还能够应用于细胞标记、细胞荧光成像方面。
本申请采用的技术方案为：
一种具有发射白光性质的金纳米团簇，包括均为核壳结构的金纳米团簇A和金纳米团簇B，所述金纳米团簇A和所述金纳米团簇B的核均为粒径为1nm～3nm的金粒子，所述金纳米团簇A的壳为含硫配体，所述金纳米团簇B的壳为含氮配体；且所述金纳米团簇A的荧光发射光谱范围为550nm～850nm；所述金纳米团簇B的荧光发射光谱范围为380nm～750nm。
进一步的，所述含硫配体为11-巯基十一烷酸或蛋氨酸；所述含氮配体为组氨酸。
本发明还提供了上述具有发射白光性质的金纳米团簇的制备方法，包括如下步骤
将含氮配体与含硫配体混合均匀后溶解于强碱溶液中，得到pH为10～12的混合溶液；然后将混合溶液加热至45℃～55℃后，再加入HAuCl4，并于45℃～55℃下搅拌反应3.5h～4.5h，反应完毕后冷冻干燥，得到粉末，所述粉末即为具有发射白光性质的金纳米团簇；
其中，当含硫配体为蛋氨酸时，所述含氮配体、含硫配体以及HAuCl4的物质的量之比为：6.5～8.5：2.1～2.3：0.25；
当含硫配体为11-巯基十一烷酸时，所述含氮配体、含硫配体以及HAuCl4的物质的量之比为：8.25～10.25：0.15～0.35：0.25。
进一步的，所述强碱溶液中0.4mol/L～0.6mol/L的NaOH溶液。
进一步的，当含硫配体为蛋氨酸时，所述含氮配体、含硫配体以及HAuCl4的物质的量之比为：7.5：2.2：0.25；
当含硫配体为11-巯基十一烷酸时，所述含氮配体、含硫配体以及HAuCl4的物质的量之比为：9.25：0.24：0.25。
与现有技术相比，本发明的有益效果是：
本发明的金纳米团簇具有发射白光的性质。
其制备方法中采用两种配体-含氮配体与含硫配体，在同等条件下，采用一步法就能够成功制备得到具有两种金纳米团簇，两种金纳米团簇具有不同的荧光发射光谱，两种金纳米团簇之间的荧光发射光谱发生重叠，表现出白光荧光发生性质；本发明的制备方法简单，所需时间短。
附图说明
图1是本发明实施例3的金纳米团簇的荧光光谱图；
图2是本发明实施例3的金纳米团簇的色度坐标图；
图3是本发明实施例6的金纳米团簇的荧光光谱图；
图4是本发明实施例6的金纳米团簇的色度坐标图；
图5是本发明实施例3的金纳米团簇的TEM图。
具体实施方式
为了使本发明的技术手段、创作特征、达到目的与功效易于明白了解，下面将结合本发明的具体实施例和附图，对本发明的技术方案进行清楚、完整地描述。
当实施例给出数值范围时，应理解，除非本发明另有说明，每个数值范围的两个端点以及两个端点之间任何一个数值均可选用。除非另外定义，本发明中使用的所有技术和科学术语与本技术领域技术人员通常理解的意义相同。除实施例中使用的具体方法、设备、材料外，根据本技术领域的技术人员对现有技术的掌握及本发明的记载，还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。
实施例1
一种具有发射白光性质的金纳米团簇，包括均为核壳结构的金纳米团簇A和金纳米团簇B，金纳米团簇A和所述金纳米团簇B的核均为粒径为1nm～3nm的金粒子；金纳米团簇A的壳为蛋氨酸，金纳米团簇B的壳为组氨酸；金纳米团A的荧光发射光谱范为550nm～850nm；金纳米团簇B的荧光发射光谱范为380nm～750nm。
上述具有发射白光性质的金纳米团簇的制备方法，包括如下步骤：
将组氨酸与蛋氨酸混合均匀后，再溶解于强碱溶液中，得到pH为10～12的混合溶液；然后将混合溶液加热至45℃后，搅拌加入HAuCl4，并于45℃下搅拌反应3.5h，冷冻干燥，得到粉末，所述粉末即为具有发射白光性质的金纳米团簇；
其中组氨酸、蛋氨酸以及HAuCl4的物质的量之比为：6.5：2.1：0.25。
强碱溶液为0.4mol/L的NaOH溶液。
实施例2
与实施例1的不同是制备方法，具体为：
将组氨酸与蛋氨酸混合均匀后，再溶解于强碱溶液中，得到pH为10～12的混合溶液；然后将混合溶液加热至55℃后，搅拌加入HAuCl4，并于55℃下搅拌反应4.5h，冷冻干燥，得到粉末，所述粉末即为具有发射白光性质的金纳米团簇；
其中组氨酸、蛋氨酸以及HAuCl4的物质的量之比为：8.5：2.3：0.25。
强碱溶液为0.6mol/L的NaOH溶液。
实施例3
与实施例1的不同是制备方法，具体为：
将750uL 0.1M组氨酸与200uL 0.11M蛋氨酸混合均匀后，再溶解于55uL 0.5M强碱溶液中，得到pH为10～12的混合溶液；然后将混合溶液加热至50℃后，搅拌加入250uL10mMHAuCl4，并于50℃下搅拌反应4h，冷冻干燥，得到粉末，所述粉末即为具有发射白光性质的金纳米团簇；
其中组氨酸、蛋氨酸以及HAuCl4的物质的量之比为：7.5：2.2：0.25。
强碱溶液为0.5mol/L的NaOH溶液。
实施例4
一种具有发射白光性质的金纳米团簇，包括均为核壳结构的金纳米团簇A和金纳米团簇B，金纳米团簇A和所述金纳米团簇B的核均为粒径为1nm～3nm的金粒子，金纳米团簇A的壳为11-巯基十一烷酸或蛋氨酸(11-MUA)，金纳米团簇B的壳为组氨酸；金纳米团A的荧光发射光谱范为550nm～850nm；金纳米团簇B的荧光发射光谱范为380nm～750nm。
上述具有发射白光性质的金纳米团簇的制备方法，包括如下步骤：
将11-巯基十一烷酸溶解于强碱溶液，完全溶解后，再加入组氨酸，得到pH为10～12的混合溶液；然后将混合溶液加热至45℃后，搅拌加入HAuCl4，并于45℃下搅拌反应3.5h，冷冻干燥，得到粉末，所述粉末即为具有发射白光性质的金纳米团簇；
其中组氨酸、11-巯基十一烷酸以及HAuCl4的物质的量之比为：8.25：0.15：0.25。
强碱溶液为0.4mol/L的NaOH溶液。
实施例5
与实施例4的不同是制备方法，具体为：
将11-巯基十一烷酸溶解于强碱溶液，完全溶解后，再加入组氨酸，得到pH为10～12的混合溶液；然后将混合溶液加热至55℃后，搅拌加入HAuCl4，并于55℃下搅拌反应4.5h，冷冻干燥，得到粉末，所述粉末即为具有发射白光性质的金纳米团簇；
其中组氨酸、11-巯基十一烷酸以及HAuCl4的物质的量之比为：10.25：0.35：0.25。
强碱溶液为0.6mol/L的NaOH溶液。
实施例6
与实施例4的不同是制备方法，具体为：
将13mg 11-巯基十一烷酸溶解于10mL 0.2M强碱溶液，完全溶解后，取3.2mL溶解的再加入11-巯基十一烷酸与3.7mL 0.2M组氨酸混合并搅拌，得到pH为10～12的混合溶液；然后将混合溶液加热至50℃后，搅拌情况下缓慢加入1mL 20Mm HAuCl4，并于50℃下搅拌反应4h，冷冻干燥，得到粉末，所述粉末即为具有发射白光性质的金纳米团簇；
其中组氨酸、11-巯基十一烷酸以及HAuCl4的物质的量之比为：9.25：0.24：0.25。
强碱溶液为0.5mol/L的NaOH溶液。
为了验证发明的具有发射白光性质的金纳米团簇的性质，我们做了如下实验，以实施例3和实施例6制备得到具有发射白光性质的金纳米团簇为例。
首先，我们对实施例3制备得到的粉末进行TEM扫描测试，结果如图5所示，从图5中能够看出具有发射白光性质的金纳米团簇的粒径为1nm～3nm。
我们还将实施例3制备得到粉末(具有发射白光性质的金纳米团簇——L-His-MetAu NCs)溶解在去离子水中，得到第一样品溶液；然后将第一样品溶液置于比色皿中，并用爱丁堡FLS980荧光光谱仪进行光谱测试，进行分峰拟合后得到结果如图1所示，因为文献记载有壳为组氨酸的金纳米团簇的荧光发射光谱范围为400nm～750nm，所以从图1中能够得到荧光光谱峰值在380nm～750nm范围的金纳米团簇为壳为组氨酸的金纳米团簇的荧光发射光谱，而另外峰值范在550nm～850nm范围内的金纳米团簇为壳为蛋氨酸的金纳木团簇的荧光发射光谱。此外，同时使用ColorCalculator软件将图1的荧光光谱数据转换为色度坐标，结果如图2所示。
从图1中能够看出第一样品溶液呈现两个荧光峰值，发射范围为380nm～850nm，且荧光发射光谱覆盖整个可见光区。从图2能够看出，根据样品溶液的所测光谱计算得到的色度坐标为(0.31,0.31)，说明本发明实施例3的金纳米团簇具有发射白光的性质。
首先，我们将实施例6制备得到粉末(具有发射白光性质的金纳米团簇——L-His-11-MUA Au NCs)溶解在去离子水中，得到第二样品溶液；然后将第二样品溶液置于比色皿中，并用爱丁堡FLS980荧光光谱仪进行光谱测试，进行分峰拟合后得到结果如图3所示，因为文献记载有壳为组氨酸的金纳米团簇的荧光发射光谱范围为400nm～750nm，所以从图3中能够得到荧光光谱峰值在380nm～750nm范围的金纳米团簇为壳为组氨酸的金纳米团簇的荧光发射光谱，而另外峰值范在550nm～850nm范围内的金纳米团簇为壳为11-巯基十一烷酸的金纳木团簇的荧光发射光谱。此外，同时使用ColorCalculator软件将图3的荧光光谱数据转换为色度坐标，结果如图4所示。
从图3中能够看出第一样品溶液呈现两个荧光峰值，发射范围为380nm～850nm，且荧光发射光谱覆盖整个可见光区。从图2能够看出，根据样品溶液的所测光谱计算得到的色度坐标为(0.329,0.332)，说明本发明实施例6的金纳米团簇具有发射白光的性质。
此外，因为本发明的具有发射白光性质的金纳米团簇具有发射白光的性质，所以本发明的具有发射白光性质的金纳米团簇有望应用于细胞标记和细胞荧光成像方面。
综上所述，本发明采用一步法成功制备出具有发射白光性质的金纳米团簇，制备方法简单，所需时间短。
以上公开的仅为本发明的较佳实施例，但是，本发明实施例并非局限于此，任何本领域的技术人员能思之的变化都应落入本发明的保护范围。
Claims (5)
1.一种具有发射白光性质的金纳米团簇，其特征在于，包括均为核壳结构的金纳米团簇A和金纳米团簇B，所述金纳米团簇A和所述金纳米团簇B的核均为粒径为1nm～3nm的金粒子，所述金纳米团簇A的壳为含硫配体，所述金纳米团簇B的壳为含氮配体；且所述金纳米团簇A的荧光发射光谱范围为550nm～850nm；所述金纳米团簇B的荧光发射光谱范围为380nm～750nm。
2.如权利要求1所述具有发射白光性质的金纳米团簇，其特征在于，所述含硫配体为11-巯基十一烷酸或蛋氨酸；所述含氮配体为组氨酸。
3.如权利要求1或2所述具有发射白光性质的金纳米团簇的制备方法，其特征在于，包括如下步骤：
将含氮配体与含硫配体混合均匀后溶解于强碱溶液中，得到pH为10～12的混合溶液；然后将混合溶液加热至45℃～55℃后，再加入HAuCl4，搅拌反应3.5h～4.5h，反应完毕后冷冻干燥，得到粉末，所述粉末即为具有发射白光性质的金纳米团簇；
其中，当含硫配体为蛋氨酸时，所述含氮配体、含硫配体以及HAuCl4的物质的量之比为：6.5～8.5：2.1～2.3：0.25；
当含硫配体为11-巯基十一烷酸时，所述含氮配体、含硫配体以及HAuCl4的物质的量之比为：8.25～10.25：0.15～0.35：0.25。
4.如权利要求3所述的具有发射白光性质的金纳米团簇的制备方法，其特征在于，所述强碱溶液为浓度0.4mol/L～0.6mol/L的NaOH溶液。
5.如权利要求3所述的具有发射白光性质的金纳米团簇的制备方法，其特征在于，当含硫配体为蛋氨酸时，所述含氮配体、含硫配体以及HAuCl4的物质的量之比为：7.5：2.2：0.25；
当含硫配体为11-巯基十一烷酸时，所述含氮配体、含硫配体以及HAuCl4的物质的量之比为：9.25：0.24：0.25。
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