CN112521565A - 一种聚异丙烯酰胺球修饰的荧光硅点的制备方法及其制备的荧光硅点和应用 - Google Patents
一种聚异丙烯酰胺球修饰的荧光硅点的制备方法及其制备的荧光硅点和应用 Download PDFInfo
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Abstract
本发明公开了一种聚异丙烯酰胺球修饰的荧光硅点的制备方法及其制备的荧光硅点和应用，该制备方法包括：将柠檬酸钠、3‑氨丙基三乙氧基硅烷在甘油中反应制成硅纳米晶量子点；将硅纳米晶量子点、1‑(3‑二甲氨基丙基)‑3‑乙基碳二亚胺盐酸盐、N‑羟基琥珀酰亚胺、叶酸在纯水中反应得到叶酸修饰的硅纳米晶量子点；将N‑异丙基烯酰胺、N，N’‑亚甲基二丙烯酰胺、叶酸修饰硅纳米晶量子点、过硫酸钾在纯水中反应得到聚异丙烯酰胺球修饰的荧光硅点。本发明制备的聚异丙烯酰胺球修饰的荧光硅点荧光硅点细胞毒性小，有响应温度变化的功能，其可用于癌细胞原位成像和温度检测，同时制备工艺简单易行，易于规模化生产。
Description
技术领域
本发明属于荧光硅点技术领域，具体涉及一种聚异丙烯酰胺球修饰的荧光硅点的制备方法及其制备的荧光硅点和应用。
背景技术
细胞内温度是细胞活动的基本特性，复杂神经递质的释放会引起细胞内温度的变化。此外，高温导致的癌细胞死亡可能会激活免疫系统对抗肿瘤。因此，细胞内温度的检测在生物医学中有重要应用。聚(N-异丙基丙烯酰胺)(PNIPAM)作为一种高分子聚合物，最低临界溶解温度(LCST)约为33℃，当环境温度低于LCST时，PNIPAM会发生体积相转变，是水溶性良好的材料，而当环境温度高于LCST时，PNIPAM是憎水的，就会蜷缩成更小的体积。由于其随环境温度的变化，可以表现出良好的体积相变行为，因此它已广泛的应用于各种领域，如：药物传输、可控释放、传感器设计等。量子点具有尺寸可调以及半峰宽窄等优良的荧光性能然而常用的碲化镉量子点等因含有镉元素而具有较大的细胞毒性。硅纳米晶量子点不含重金属元素且具有可调谐的荧光发射性能而收到广泛关注然而硅量子点在需高压条件下制备。对设备要求不高，具有温度敏感特性的硅点也未有报道。设计制备特定的荧光硅点用于检测癌细胞内温度变化指导肿瘤的光热治疗以及其他医学监测具有重要意义。
发明内容
发明目的：针对现有技术存在的问题，本发明提供了一种聚异丙烯酰胺球修饰的荧光硅点的制备方法，可以制备出温度敏感荧光硅点，温敏荧光硅点具有良好的温度依赖性荧光“开-关”特性，可以作为特异性识别肿瘤细胞的温度指示剂，并且其制备过程简单，且表面叶酸修饰使其能够特异性靶向癌细胞并在癌细胞表面成像。
本发明还提供该温敏荧光硅点的制备方法以及该温敏荧光硅点在癌细胞原位成像和温度检测中的应用。
技术方案：为了实现上述目的，本发明所述一种聚异丙烯酰胺球修饰的荧光硅点的制备方法，包括如下步骤：
(1)将柠檬酸钠、3-氨丙基三乙氧基硅烷在甘油中反应制成硅纳米晶量子点；
(2)将硅纳米晶量子点、1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐、N-羟基琥珀酰亚胺、叶酸在超纯水中反应得到叶酸修饰的硅纳米晶量子点；
(3)将N-异丙基烯酰胺、N，N’-亚甲基二丙烯酰胺、叶酸修饰硅纳米晶量子点、过硫酸钾在纯水中反应得到聚异丙烯酰胺球修饰的荧光硅点。
其中，步骤(1)中将柠檬酸钠加入到甘油中，通入惰性气体保护，搅拌后加入3-氨丙基三乙氧基硅烷(APTES)继续搅拌后高温反应后冷却至室温得到硅点粗品溶液。
进一步地，将冷却至室温的硅点粗品溶液转移至截留分子量为3500Da(MWCO:3500Da)的透析袋中，以超纯水作为透析液进行透析，收集透析袋内的溶液，得到硅纳米晶量子点溶液，保存。
其中，步骤(2)中将硅纳米晶量子点溶液中加入羧基活化剂EDC和氨基活化剂NHS，加入超纯水，超声完全溶解于纯水中，通入惰性气体，搅拌后向其中加入叶酸水溶液，继续反应得到的叶酸修饰的硅纳米晶量子点粗品溶液。
进一步地，将得到的叶酸修饰的硅纳米晶量子点粗品溶液转移至截留分子量为8～14kDa(MWCO:8000-14000Da)的透析袋中，以超纯水作为透析液进行透析收集透析袋内的溶液，得到叶酸修饰的硅纳米晶量子点溶液避光保存。
其中，步骤(3)中将N-异丙基丙烯酰胺(NIPAM)和交联剂N,N'-亚甲基二丙烯酰胺(MBA)，溶于超纯水中，超声完全溶解，通入惰性气体，搅拌后加入叶酸修饰的硅纳米晶量子点溶液和过硫酸钾(KPS)，继续搅拌后，加热反应，结束后冷却至室温得到聚异丙烯酰胺球修饰的荧光硅点粗品溶液。
进一步地，将得到聚异丙烯酰胺球修饰的荧光硅点粗品溶液转移至截留分子量为8～14kDa的透析袋中透析，以超纯水作为透析液进行透析，收集透析袋内的溶液，冻干得到固体粉末聚异丙烯酰胺球修饰的荧光硅点避光保存。
作为优选，第三步反应条件为：室温通惰性气体搅拌30min使氧气完全除尽后，加入叶酸修饰的硅纳米晶量子点和过硫酸钾。控制温度低于低临界温度(室温)搅拌反应30min后，封口，控制温度高于低临界温度(70℃)搅拌反应4h。更具体地，聚丙烯酰胺球修饰的荧光硅点需要经历两个聚合阶段，第一阶段控制温度低于低临界温度使荧光硅点在聚丙烯酰胺网络上均匀铺展，低临界温度为32℃，控制温度低于低临界温度即在室温下反应；第二阶段控制温度高于低临界温度，使聚丙烯酰胺网络内陷将荧光硅点包裹在内部得到聚丙烯酰胺球修饰的荧光硅点，控制温度高于低临界温度即在在70℃下反应。
本发明所述的聚异丙烯酰胺球修饰的荧光硅点的制备方法所制备的聚异丙烯酰胺球修饰的荧光硅点。
本发明所述的聚异丙烯酰胺球修饰的荧光硅点的制备方法所制备的聚异丙烯酰胺球修饰的荧光硅点在制备肿瘤细胞的温度指示剂和原位成像试剂中的应用。
具体地，本发明制备的聚异丙烯酰胺球修饰的荧光硅点可用于癌症细胞中如乳腺癌细胞、宫颈癌细胞等细胞表面原位成像和温度检测。
作为优选，本发明的上述聚异丙烯酰胺球修饰的荧光硅点的制备方法，第一步的具体过程为：将柠檬酸钠加入到甘油中，通入氩气保护，搅拌20min后加入3-氨丙基三乙氧基硅烷(APTES)(作为硅源)，继续搅拌10min后转移到油浴锅中，温度升高至185℃继续反应1.5h。反应结束后，将冷却至室温的硅点粗品转移至截留分子量为3500Da(MWCO:3500Da)的透析袋中，以超纯水作为透析液，透析24h，收集透析袋内的溶液。第二步的具体过程为：将硅纳米晶量子点溶液加入圆底烧瓶中，随后加入羧基活化剂1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)和氨基活化剂N-羟基琥珀酰亚胺(NHS)，加入超纯水，超声完全溶解于纯水中，通入氩气保护，搅拌30min后向其中加入0.5mg/mL的叶酸水溶液，继续反应3h，得到的叶酸修饰的硅纳米晶量子点粗品溶液转移至截留分子量为8～14kDa(MWCO:8000～14000Da)的透析袋中，以超纯水作为透析液，透析24h,收集透析袋内的溶液，将叶酸修饰的硅纳米晶量子点溶液避光保存。第三步的具体过程为：在圆底烧瓶中加入N-异丙基丙烯酰胺(NIPAM)和交联剂N,N'-亚甲基二丙烯酰胺(MBA)，溶于2mL的超纯水中，超声完全溶解，通入氩气保护，搅拌30min，当氧气完全去除后加入叶酸修饰的硅纳米晶量子点溶液(SiNPs-FA)3mL和200μL的过硫酸钾(KPS)，继续室温搅拌30min后，封口，温度升高至70℃油浴反应4h，反应结束后，冷却至室温，粗品转移至截留分子量为8～14kDa(MWCO:8000～14000Da)的透析袋中，以超纯水作为透析液，透析24h，收集透析袋内的溶液，冻干得到聚异丙烯酰胺球修饰的荧光硅点避光保存。
本发明以甘油为溶剂，在常压下制备了具有良好水溶性的硅纳米晶量子点。硅纳米晶量子点粒径较小，能在血液中自由运动并通过血液运输运送到机体的各个器官，硅纳米晶量子点本身具有荧光属性可以用于细胞的荧光成像，在其表面接上叶酸，使其能与癌细胞上过表达的叶酸受体特异性结合从而实现靶向癌细胞。在叶酸修饰的硅纳米晶单体聚合过程中，控制不同聚合阶段的温度(低于低临界温度和高于低临界温度)可以实现一锅法合成温敏荧光硅点。本发明首次制备了一种聚异丙烯酰胺球修饰的荧光硅点并用于温敏癌细胞成像和温度检测，从而解决了现有荧光材料生物相容性差以及温敏检测癌细胞选择性差等等技术问题。
本发明制备的一种聚异丙烯酰胺球修饰的荧光硅点，其可用于癌细胞原位成像和温度检测。该聚异丙烯酰胺球修饰的荧光硅点制备工艺简单易行，易于规模化生产。本发明的聚异丙烯酰胺球修饰的荧光硅点制备方法为：在常压下制备了具有良好水溶性的硅纳米晶量子点，叶酸通过氨基和羧基反应与纳米硅键合，从而用于癌细胞特异性识别。叶酸修饰的硅纳米晶量子点在单体聚合过程中，只需控制温度在较低临界溶液温度(LCST)以下和高于LCST时，就可以一锅法制备聚异丙烯酰胺修饰的温敏荧光硅点。
有益效果：与现有技术相比，本发明具有如下优点：
1、本发明制备的聚异丙烯酰胺球修饰的荧光硅点表面包裹着温敏材料聚异丙烯酰胺，有响应温度变化的功能，能实现在细胞中对温度的检测。
2、本发明制备的聚异丙烯酰胺球修饰的荧光硅点是光学性能稳定的纳米荧光材料，其表面修饰有叶酸，能进入到细胞，吸附在叶酸受体过表达的癌细胞表面，能实现对癌细胞的原位成像。
3、本发明制备的聚异丙烯酰胺球修饰的荧光硅点细胞毒性小，不影响细胞的正常生长。
4、本发明制备的聚异丙烯酰胺球修饰的荧光硅点在纯水中呈蓝色荧光，随着癌细胞表面叶酸过表达，聚异丙烯酰胺球修饰的荧光硅点在癌细胞表面大量聚集，在荧光共聚焦成像中显强蓝色荧光。随着温度的升高，聚异丙烯酰胺球修饰的荧光硅点的荧光逐渐猝灭，从而实现对细胞内温度的检测。
5、本发明的聚异丙烯酰胺球修饰的荧光硅点制备工艺简单易行，易于规模化生产。
6、本发明的聚异丙烯酰胺球修饰的荧光硅点的荧光发射可涵盖从紫外区至近红外区的范围，且硅点的荧光性质随粒径大小可调谐，与传统的量子点和有机荧光染料相比，硅点无毒无害、生物相容性好且光稳定性较强，在细胞内可以实现荧光成像。硅量子点可以在体内代谢分解排出体外，没有潜在的长期毒副作用。
附图说明
图1为本发明制备的聚异丙烯酰胺球修饰的荧光硅点的光学性能表征。
图2为本发明制备的聚异丙烯酰胺球修饰的荧光硅点的温度响应性能图。
图3为本发明制备的硅纳米晶量子点的温度响应性能图。
图4为本发明制备的叶酸修饰的硅纳米晶量子点的温度响应性能图。
图5为本发明制备的聚异丙烯酰胺球修饰的荧光硅点的细胞成活率的关系图。
图6为本发明制备的聚异丙烯酰胺球修饰的荧光硅点与宫颈癌以及乳腺癌细胞在荧光共聚焦显微镜下的成像图。
具体实施方式
下面结合具体实施例和附图对本发明进一步进行说明。
实施例中所述实验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1
制备聚异丙烯酰胺球修饰的荧光硅点
1、硅纳米晶量子点的制备
将0.3180g柠檬酸钠加入到8mL甘油中，通入氩气保护，搅拌20min后加入2mL 3-氨丙基三乙氧基硅烷(APTES)(作为硅源)，继续搅拌10min后转移到油浴锅中，温度升高至185℃继续反应1.5h。反应结束后，将冷却至室温得到硅点粗品溶液转移至截留分子量为3500Da(MWCO:3500Da)的透析袋中，以超纯水作为透析液，透析24h，收集透析袋内的溶液，得到硅纳米晶量子点溶液，避光保存。
2、叶酸修饰的硅纳米晶量子点的制备
将2mL硅纳米晶量子点加入圆底烧瓶中，随后加入32mg羧基活化剂1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)和20mg氨基活化剂N-羟基琥珀酰亚胺(NHS)，再加入4mL的超纯水，超声完全溶解于纯水中，通入氩气保护，搅拌30min后向其中加入0.5mg/mL的叶酸水溶液4mL，继续搅拌反应3h，得到的表面被叶酸修饰的硅纳米晶量子点粗品溶液转移至截留分子量为8～14kDa(MWCO:8000～14000Da)的透析袋中，以超纯水作为透析液，透析24h,收集透析袋内的溶液，得到叶酸修饰的硅纳米晶量子点溶液(SiNPs-FA)，避光保存。
3、聚异丙烯酰胺球修饰的荧光硅点的制备
在圆底烧瓶中加入N-异丙基丙烯酰胺(NIPAM)310mg和交联剂N,N'-亚甲基二丙烯酰胺(MBA)3.4mg，加入2mL的超纯水，超声完全溶解，通入氩气保护，搅拌30min，当氧气完全去除后加入叶酸修饰的硅纳米晶量子点溶液(SiNPs-FA)3mL和200μL的过硫酸钾(KPS)，继续室温搅拌30min后，封口，温度升高至70℃油浴反应4h，反应结束后，冷却至室温，得到的粗品溶液转移至截留分子量为8～14kDa(MWCO:8000～14000Da)的透析袋中，以超纯水作为透析液，透析24h,收集透析袋内的溶液，冻干得到聚异丙烯酰胺球修饰的荧光硅点避光保存。
实施例2
实施例1制得聚异丙烯酰胺球修饰的荧光硅点的光学性能表征。
称取10mg实施例1中制得的聚异丙烯酰胺球修饰的荧光硅点，配成浓度为10mg/mL的PBS缓冲溶液(0.1mM)。
荧光光谱测试：测试上述溶液的荧光发射光谱图。荧光发射光谱测定以404nm激发，激发与发射的狭缝宽度为5nm/5nm。所得荧光发射光谱图见图1，说明成功合成具有强烈蓝色荧光的硅点。该实验结果表明，聚异丙烯酰胺球修饰的荧光硅点仍然具有强烈荧光。
实施例3
实施例1制得的聚异丙烯酰胺球修饰的荧光硅点的温度响应性能表征。
称取10mg实施例1中制得的聚异丙烯酰胺球修饰的荧光硅点，配成浓度为10mg/mL的PBS缓冲溶液(0.1mM)。
荧光光谱测试：取上述溶液在17℃和47℃先后测荧光发射光谱图，重复5次。荧光发射光谱测定以404nm激发，激发与发射的狭缝宽度为5nm/5nm。所得温度响应性能图见图2，图2显示随着温度的升高，聚异丙烯酰胺球修饰的荧光硅点的荧光强度逐渐降低，荧光硅点具有预期的温度响应性能。该实验结果表明，反复的热冷循环不会影响聚异丙烯酰胺球修饰的荧光硅点的荧光强度且聚异丙烯酰胺球修饰的荧光硅点的荧光强度与温度呈负相关。说明本发明制备的聚异丙烯酰胺球修饰的荧光硅点具有稳定的温度响应性能。
此外，在低温下本发明的荧光硅点具有较高的荧光强度即温度依赖性荧光“开”的特性，在高温下本发明的荧光硅点的荧光强度逐渐猝灭即荧光“关”的特性。在五次反复的热冷循环中，荧光硅点的荧光强度都表现出随温度升高荧光强度降低，随温度降低荧光强度升高的规律。本发明将这样的规律称为温度依赖特性。
本实施例中，以实施例1中的步骤(1)溶液冻干得到的硅纳米晶量子点和步骤(2)溶液冻干得到的叶酸修饰的硅点，按上述相同试验条件，测试单独的硅点和叶酸修饰的硅点在不同温度下(17-47℃)的荧光发射光谱图，如图3和图4，结果表明单独的硅点和叶酸修饰的硅点的荧光强度都不随温度变化，证明聚异丙烯酰胺球的修饰是使荧光硅点具备温度响应特性的重要步骤。
实施例4
实施例1中制得聚异丙烯酰胺球修饰的荧光硅点对细胞生长的影响
称取0.1mg实施例1中制备的聚异丙烯酰胺球修饰的荧光硅点，配成浓度为0.1mg/mL的PBS缓冲液(0.1mM)，作为母液。
取上述母液20μL加入到一定量的PBS缓冲液(0.1mM，pH7.4)，使聚异丙烯酰胺球修饰的荧光硅点的终浓度分别为0μg/mL、20μg/mL、40μg/mL、60μg/mL、80μg/mL、100μg/mL、200μg/mL。用上述不同浓度聚异丙烯酰胺球修饰的荧光硅点200uL分别与96孔中贴壁生长的乳腺癌细胞(MCF-7细胞)、宫颈癌细胞(HeLa细胞)37℃孵化24h，测试这两种细胞的存活率，得到聚异丙烯酰胺球修饰的荧光硅点对细胞存活率的影响见图5，图5显示浓度为200ug/mL的聚异丙烯酰胺球修饰的荧光硅点孵化细胞24h后细胞的存活率仍然为原来的85％，证明该荧光硅点具有良好的生物相容性。以上结果表明聚异丙烯酰胺球修饰的荧光硅点几乎没有细胞毒性，不影响细胞的正常生长。
实施例5
实施例1中制得聚异丙烯酰胺球修饰的荧光硅点用于癌细胞原位成像和温度检测。
称取1mg实施例1中制备的聚异丙烯酰胺球修饰的荧光硅点，配成浓度为200μg/mL的PBS缓冲液(0.1mM)，用上述200μL缓冲液在不同的温度(17-42℃)孵化96孔中贴壁生长的乳腺癌细胞(MCF-7细胞)、宫颈癌细胞(HeLa细胞)1h，拍荧光共聚焦图像，成像结果见图6，标尺为20μm，图6说明不同温度下的荧光硅点的荧光强度不一样，随着温度升高荧光硅点的荧光逐渐猝灭。
以上结果表明，聚异丙烯酰胺球修饰的荧光硅点会吸附在叶酸受体过表达的癌细胞表面显明亮的蓝色荧光且随着温度的升高癌细胞表面的聚异丙烯酰胺球修饰的荧光硅点的荧光会逐渐减弱，证明该聚异丙烯酰胺球修饰的荧光硅点可以用于癌细胞的原位成像和温度检测，可以作为特异性识别肿瘤细胞的温度指示剂和原位成像试剂。
Claims (9)
1.一种聚异丙烯酰胺球修饰的荧光硅点的制备方法，其特征在于，包括如下步骤：
(1)将柠檬酸钠、3-氨丙基三乙氧基硅烷在甘油中反应制成硅纳米晶量子点；
(2)将硅纳米晶量子点、1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐、N-羟基琥珀酰亚胺、叶酸在超纯水中反应得到叶酸修饰的硅纳米晶量子点；
(3)将N-异丙基烯酰胺、N，N’-亚甲基二丙烯酰胺、叶酸修饰硅纳米晶量子点、过硫酸钾在纯水中反应得到聚异丙烯酰胺球修饰的荧光硅点。
2.根据权利要求1所述的制备方法，其特征在于，步骤(1)中将柠檬酸钠加入到甘油中，通入惰性气体保护，搅拌后加入3-氨丙基三乙氧基硅烷(APTES)继续搅拌后高温反应后冷却至室温得到硅点粗品溶液。
3.根据权利要求2所述的制备方法，其特征在于，将冷却至室温的硅点粗品溶液优选转移至截留分子量为3500Da的透析袋中，以超纯水作为透析液进行透析，收集透析袋内的溶液，得到硅纳米晶量子点溶液，避光保存。
4.根据权利要求1所述的制备方法，其特征在于，步骤(2)中将硅纳米晶量子点溶液中加入羧基活化剂1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)和氨基活化剂N-羟基琥珀酰亚胺(NHS)，加入超纯水，超声完全溶解于超纯水中，通入惰性气体，搅拌后向其中加入叶酸水溶液，继续反应得到的叶酸修饰的硅纳米晶量子点粗品溶液。
5.根据权利要求4所述的制备方法，其特征在于，将得到的叶酸修饰的硅纳米晶量子点粗品溶液转移至截留分子量为8～14kDa的透析袋中，以超纯水作为透析液进行透析收集透析袋内的溶液，避光保存。
6.根据权利要求1所述的制备方法，其特征在于，步骤(3)中将N-异丙基丙烯酰胺(NIPAM)和交联剂N,N'-亚甲基二丙烯酰胺(MBA)，溶于超纯水中，超声完全溶解，通入惰性气体，搅拌后加入叶酸修饰的硅纳米晶量子点溶液(SiNPs-FA)和过硫酸钾(KPS)，继续搅拌后，加热反应，结束后冷却至室温得到聚异丙烯酰胺球修饰的荧光硅点粗品溶液。
7.根据权利要求6所述的制备方法，其特征在于，将得到聚异丙烯酰胺球修饰的荧光硅点粗品溶液转移至截留分子量为8～14kDa的透析袋中透析，以超纯水作为透析液进行透析，收集透析袋内的溶液，冻干得到聚异丙烯酰胺球修饰的荧光硅点避光保存。
8.一种权利要求1所述的聚异丙烯酰胺球修饰的荧光硅点的制备方法所制备的聚异丙烯酰胺球修饰的荧光硅点。
9.一种权利要求1所述的聚异丙烯酰胺球修饰的荧光硅点的制备方法所制备的聚异丙烯酰胺球修饰的荧光硅点在制备肿瘤细胞的温度指示剂和原位成像试剂中的应用。
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| CN113237855A (zh) * | 2021-04-30 | 2021-08-10 | 安徽大学 | 基于量子点的生物传感器制备及癌细胞摄取监测方法 |
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| CN115093848A (zh) * | 2022-08-11 | 2022-09-23 | 郑州中科生物医学工程技术研究院 | 一种黄色荧光硅量子点及制备方法与应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113237855A (zh) * | 2021-04-30 | 2021-08-10 | 安徽大学 | 基于量子点的生物传感器制备及癌细胞摄取监测方法 |
| CN113237855B (zh) * | 2021-04-30 | 2023-09-26 | 安徽大学 | 基于量子点的生物传感器的癌细胞摄取监测方法 |
| CN113432753A (zh) * | 2021-08-30 | 2021-09-24 | 中国工程物理研究院流体物理研究所 | 一种利用荧光单峰宽度温度响应特性的测温方法 |
| CN115093848A (zh) * | 2022-08-11 | 2022-09-23 | 郑州中科生物医学工程技术研究院 | 一种黄色荧光硅量子点及制备方法与应用 |
| CN115093848B (zh) * | 2022-08-11 | 2023-10-20 | 郑州中科生物医学工程技术研究院 | 一种黄色荧光硅量子点及制备方法与应用 |
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