荧光纳米材料的合成制备、性质表征和应用研究
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摘要
在生物医药等领域中，荧光标记技术已经成为人们在研究生物大分子的构型、生物分子之间的相互作用和纳米载药系统中纳米载体进入细胞的机制过程中必不可少的研究工具。它已经成为人们观察生物领域的第三只“眼”。合成性能卓越的荧光标记材料是促进荧光标记技术发展和进步的关键。荧光标记材料通常包括有机染料、半导体量子点、复合荧光纳米粒子和贵金属纳米簇。后三者由于其尺寸在纳米的级别上，被称为荧光纳米标记材料。荧光纳米标记材料具有优良的光学性质，被研究者所青睐，成为新一代的荧光标记材料。由于复合荧光纳米粒子和贵金属纳米簇具有良好的生物相容性和抗光漂白的能力，因此成为人们广泛研究的荧光纳米材料之一。对于复合荧光纳米粒子来说，纳米基质和染料分子复合的方式、复合的浓度、复合的机制以及复合后形成荧光纳米粒子的结构都能影响其发光性质。弄清这些因素是如何影响复合荧光纳米粒子的发光性质，对于指导人们合成性能优良的荧光标记材料具有非常重要的意义。贵金属纳米簇由于具有优良的光稳定性、较大的斯托克位移和良好的生物相容性等优点，使其在生物领域中有很大的应用前景。在水溶液中，银纳米簇显示出比金纳米簇更强的荧光发射效率。但是，由于银纳米簇化学活性高，比表面大和表面活化能高，在水溶液中容易发生聚集，所以选择合适的模板剂或保护剂是成功合成银纳米簇的关键。利用新型的，功能化的模板剂或保护剂合成银纳米簇，对银纳米簇的性能和潜在的应用领域都有很大的影响。本论文主要讨论染料复合的荧光粒子和贵金属纳米簇的合成制备以及应用的研究，主要研究内容总结如下：
1，染料掺杂的PMMA聚合物纳米粒子的制备合成,发光性质和其应用研究
利用包埋和粘附两种复合方式，实现了染料分子Ru(bpy)_3Cl_2和PMMA(聚甲基丙烯酸甲酯)纳米粒子的复合，合成了复合型荧光纳米粒子。利用荧光寿命法探究了粘附和包埋方式形成的复合型荧光纳米粒子的结构，结果显示它们都具有核壳结构。核壳结构的具体的成分比例如下：对于包埋型复合荧光纳米粒子，40%的染料分子位于纳米球的表面，60%的染料分子位于纳米球核内部；对于粘附型复合荧光纳米粒子，16%的染料分子位于纳米球的核内，84%的染料分子位于纳米球的表面。和PMMA纳米基质复合后，染料的发光效率有所提高；在复合了同等浓度的染料分子后，包埋型的荧光纳米粒子的发光效率高于粘附型的；而且包埋型的纳米粒子抗外界不良环境的能力强于粘附型的。选用不同的引发剂可以合成带不同电性的PMMA纳米球。我们发现带正电的Ru(bpy)3Cl2只能和带负电的PMMA纳米球复合，而不能和带正电的纳米球复合，这说明染料和纳米基质之间的相互作用力主要为静电吸引力。
对于这种电性可调的纳米基质来说，可选择的与其复合的染料分子的范围大大拓展。我们选用具有绿光发射性质的带负电的荧光素钠和带正电的R6G，黄光发射性质的带正电的RB分别和带不同电性的PMMA纳米球复合。同样，这些带电荷的染料和纳米基质复合主要的驱动力为静电吸引作用力。我们对染料和纳米基质复合的方式和复合的浓度进行了优化，合成出了多色的高发光亮度的复合型荧光纳米粒子。这种PMMA荧光纳米粒子不经过任何的生物修饰即可进入到小白鼠的血癌细胞中，点亮细胞。
2，采用羧酸化的具有核壳结构的聚合物纳米粒子为模板剂，采用原位生长的方法制备银纳米簇
采用无皂种子聚合的方法合成了具有核壳结构的聚合物纳米粒子。这些纳米粒子的核分别由PMMA(聚甲基丙烯酸甲酯)，PS(聚苯乙烯)和SiO_2（二氧化硅）构成，壳的成分都由PMAA（聚甲基丙烯酸）组成。用这些羧酸化的聚合物纳米粒子为模板剂，在AgNO_3存在的情况下，采用光化学还原的方法合成了具有荧光发射性质的银纳米簇。反应液的pH，羧酸根和AgNO_3的比例在银纳米簇合成过程中起了重要作用。获得的银纳米簇的发光效率在6-12%之间，银纳米簇的组成较为宽泛，包括Ag_2和Ag3，还有少量Ag_4, Ag_5和Ag_6。用上述模板剂采用原位生成的方法合成银纳米簇，通过一步反应就实现了银纳米簇和聚合物纳米粒子的复合。这种复合，有利于提升银纳米簇的稳定性，，银纳米簇在存放了一年后仍能很好的保持原来的荧光发射性质；还有利于扩展银纳米簇的应用范围。我们把合成的银纳米簇复合纳米粒子应用到细胞成像领域中，它可以很好的点亮细胞。
3，采用羧酸化的环糊精为模板剂合成了银纳米簇
合成了不同羧酸根取代的—环糊精，并以它们为模板剂合成银纳米簇。实验证明：羧酸根取代度越大，越有利于银纳米簇的形成。当取代度小于4时，合成的银纳米簇很快发生聚集，所以只有银纳米粒子生成；反应液的pH和反应物质之间的比例对银纳米簇的合成和性质影响也很大。我们对这些反应条件进行了优化。
利用小分子模板剂合成的银纳米簇虽然量子产率较低，只有2%，但是由于模板剂体积较小，不影响银纳米簇本身的性质。我们用环糊精合成的银纳米簇做抑菌试剂，发现银纳米簇的抑菌效果比银离子和经典银溶胶的效果都好，这可能是由于其比表面较大，表面活化能高所造成的。
4，采用修饰的蚕丝为模板剂原位生长银纳米簇
合成了PAA（聚甲基丙烯酸）修饰的蚕丝，并以此为模板剂，成功地合成了银纳米簇。我们发展了一种新型的合成银纳米簇的模板剂。它不仅实现了原位生长银纳米簇的目的，而且通过一步反应就实现了银纳米簇和蚕丝的结合，使蚕丝具有了荧光发射的性质，是合成荧光蚕丝的一种新方法。在中国，近3000年来，蚕丝由于其优良的性质，比如良好的吸潮性，透气，保温和优异的机械性能，一直被作为高档纺织品原料。此外，在生物医药等领域，如细胞培养支架，人造骨基质和药物控释，蚕丝也有广泛的应用。但是它一种蛋白纤维，容易滋生细菌和其他微生物，导致纤维损坏和皮肤敏感。人们对蚕丝纤维的抗菌能力比较关注。利用聚丙烯酸（PAA）改性的蚕丝，原位生长银纳米簇，我们获得了一种即具有荧光发射性质又具有抗菌活性的新型蚕丝纤维。这种方法也适用于修饰大多数天然纤维和人造纤维。与绿色荧光蛋白掺杂的蚕丝相比，这是一种容易处理，成本低，耗时少荧光丝纤维的制备方法。而且制备的荧光蚕丝有较好的抗菌活性。
In the fields of biology and medicine, the fluorescence labeling technique hasbeen the essential tool for studying on the configuration of biological macromolecules,the interaction between biological molecules and the action mechanism of nanocarrierinto the cell in the systems of nano-drug delivery. It has been the third “eyes” forresearcher to observe biological phenomena. The synthesis of fluorescent materialspossessing excellent properties is crucial for promoting the development and progressof fluorescence labeling. Generally, the luminescent materials for biological labelinginclude organic dyes, semiconductor quantum dots, composite fluorescentnanoparticles and noble metal nanoclusters. The latter three, owing to their size innano-level, are well known as the novel luminescent nanomaterials. Owing to theexcellent photostability, the luminescent nanomaterials attract many researchers andbecome the next generation of luminescent makers. Here, we mainly discuss thepreparation and application of the dye doped polymer nanoparticles and noble metalnanoclusters. Composite strategies, concentration and mechanism among nano-matrices, dye molecules and the structure of prepared luminescent nanoparticles havegreat impact on the luminescent properties of composite luminescent nanoparticles. Itis significant for us to figure out how the above factors affect the luminescentproperties of composite luminescent nanoparticles. And it will helpful for people toprepare composite luminescent nanoparticles for more excellent properties. Noblemetal nanoclusters have great applicable prospect in the biological fields owing totheir predominant photostability, larger Stoke shift and good biocompatibility. Silvernanoclusters present stronger fluorescence than Au nanoclusters in aqueous solution.Due to the chemical instability and the high surface energy of silver nanoclusters, theytended to interact with each other and had a natural tendency to aggregate, forminglarger nanoparticles. Therefore, a proper stabilizing scaffold or template is thusindispensable. The choices of novel, functional template or stabilizing scaffold havegreat impact on the properties and the optional application areas of silvernanoclusters. According to the excellent luminescent properties and application prospects of the Ag nanoclusters embedded composite luminescent nanoparticles, themain research contents are summarized as follows:
1, The studies on the preparation of dye doped PMMA nanoparticles and theirluminescent properties and applications.
A dye, Ru(bpy)3Cl2, was combined with nano-matrices PMMA (polymethylmethacrylate) by two strategies as the embedding (Em-PMMA nanopartcles) and theadsorbing (Ad-PMMA nanoparticles) approaches to obtain the novel compositeluminescent nanoparticles. The fluorescence lifetime of two kinds of compositeparticles can tell us that both them have a core-shell structure. For the Em-PMMAnanopartcles,40%of dye molecules lied in the surface of nanoparticle and60%ofdye molecules located in the inner of nanoparticles; For Ad-PMMA nanoparticles,16%of dye molecules lied in the inner of nanoparticles and84%of dye molecules onthe surface of nanoparticles. The quantum yields of dye molecules increased after theycombining with PMMA nanoparticles. The luminescent intensity of the Em-PMMAnanopartcles was higher than that of Ad-PMMA nanoparticles when containing thesame amount of dye molecules. The resisting ability for outside adverse environmentshowed the Em-PMMA nanopartcles was much stronger than the Ad-PMMAnanoparticles. The surface potentials of PMMA nanoparticles can be adjusted bychoosing different initiators. We found that the positively charged Ru(bpy)3Cl2can beintegrated with the negatively charged PMMA nanoparticles while they can not becombined with the positively charged, which suggested that it was the electrostaticattraction that drove the combination of dye molecules and nano-matrices. For thenano-matrices of adjustable surface potentials, the options of dye molecules which canbe combined with nano-matrices have been expanded. The negatively chargedfluorescein sodium and negatively charged rhodamine6G were combined withPMMA nanoparticles with different surface potentials. Similarly, the mechanism fordye molecules encapsulating in the PMMA nano-matricesm was the electrostaticattraction. The composite strategies and the concentration of dye molecules wereoptimized. Finallymulticolored and high brightness dye@PMMA nanocompositeswere prepared. And these multicolored polymer nanoparticles can easily stain bloodcancer cells without further surface modification.
2, In situ synthesis of silver nanoclusters templated by the carboxylated polymernanoparticles with the core-shell structure.
The method of soapless seeded emulsion polymerization was applied for synthesizing the core-shell polymer nanoparticles. The core of these polymernanoparticles were PMMA (polymethyl methacrylate), PS (polystyrene) and SiO2(silicon dioxide) respectively and all of the composition of shell was made of PMAA(polymethacrylic acid). The water-soluble fluorescent Ag nanoclusters were preparedby the method of photochemical reduction using the template of these carboxylatedpolymer nanoparticles. The pH values of reaction solution and the ratios of carboxylgroups and AgNO3were proved to be important for the synthesis process of silvernanoclusters that. The quantum yield of Ag nanoclusters was6-12%. There was awide distribution of the number of Ag atoms consisting of Ag2-6. When using thecore-shell carboxylated polymer nanoparticles as the templates for in situ synthesis ofAg nanoclusters, the composition of Ag nanoclusters and polymer nanoparticles canbe realized in one-step reaction, which is helpful to extend the application ranges ofAg nanoclusters. And the stability of Ag nanoclusters was enhanced when combiningwith polymer nanoparticles. The Ag nanoclusters can maintain the originalfluorescence intensity even experiencing one year storage. Owing to the protecting ofpolymer nanoparticles, the ability of resisting outside adverse environment wasimproved. The prepared Ag nanoclusters@polymer nanoparticles had successfullybeen applied for bioimaging.
3, Synthesis and characterization of Ag nanoclusters templated bycarboxymethyl-β-cyclodextrin (CM-β-CD)
The CM-β-CD molecules with different degree of substitution of carboxylicgroups were synthesized and they were applied as the template for preparing Agnanoclusters. The experiment showed that the more degree of substitution ofcarboxylic groups, the better for formation of Ag nanoclusters. When the degree ofsubstitution of carboxylic groups on per β-cyclodextrin molecule was smaller than4,the prepared Ag nanoclusters was very instability, tending to aggregate and led to theformation of Ag nanoparticles. It played an important role during the synthesisprocess of silver nanoclusters that the pH of reaction solution and the ratio of carboxylgroups and AgNO3and these reaction conditions were optimized for obtaining higherbrightness. Although the quantum yield of Ag nanoclusters templated by smallmolecules was low, just2%, the natural properties of Ag nanoclusters were notaffected by CM-β-CD. The Ag nanoclusters templated by CM-β-CD was used as anew antibacterial reagent and found that the antibacterial ability of Ag nanoclusters was stronger than Ag ions and typical Ag nanoparticles owing to the high surfaceenergy of Ag nanoclusters.
4, In situ synthesis of silver nanoclusters on modified silk via ultravioletlight-induced reduction
The silk modified by PAA was used as a template to prepare Ag nanoclusterssuccessfully. We developed a novel template for synthesizing Ag nanoclusters. It notonly realized the in situ synthesis of Ag nanoclusters but also finished the combinationof Ag nanoclusters and silk fibres and the completion of function of silk. This is a newsynthesis way for fluorescent silk. Since in China, silk has been used as a luxurytextile material over3000years owing to their excellent properties such as moistureabsorption, oxygen permeability, heat retention and outstanding mechanical properties.In addition, in many biomedical fields such as cell culture scaffolds, artificial bonematrices and controlled drug release, the silkworm silk has been proved to be asuitable candidate. However, this protein fiber has the potential to be a hospitable hostfor the generation and propagation of microorganisms, resulting in fiber damages andskin irritations. So the antimicrobial ability of silk fibers has been concerned. By thein situ growth of Ag nanoclusters on silk fibers modified by the polymer polyacrylicacid (PAA), we obtained a novel silk fibre with luminescence and antibacterialactivity. This method is also applicable for most natural and artificial fibres.Comparing with green fluorescent protein doped silk fibre, this is a easily handled,low-cost and less time-consuming method for preparing fluorescent silk fiber. Theproduced Ag nanoclusters@silk fibres were expected to exhibit good antibacterialproperty.
1，染料掺杂的PMMA聚合物纳米粒子的制备合成,发光性质和其应用研究
利用包埋和粘附两种复合方式，实现了染料分子Ru(bpy)_3Cl_2和PMMA(聚甲基丙烯酸甲酯)纳米粒子的复合，合成了复合型荧光纳米粒子。利用荧光寿命法探究了粘附和包埋方式形成的复合型荧光纳米粒子的结构，结果显示它们都具有核壳结构。核壳结构的具体的成分比例如下：对于包埋型复合荧光纳米粒子，40%的染料分子位于纳米球的表面，60%的染料分子位于纳米球核内部；对于粘附型复合荧光纳米粒子，16%的染料分子位于纳米球的核内，84%的染料分子位于纳米球的表面。和PMMA纳米基质复合后，染料的发光效率有所提高；在复合了同等浓度的染料分子后，包埋型的荧光纳米粒子的发光效率高于粘附型的；而且包埋型的纳米粒子抗外界不良环境的能力强于粘附型的。选用不同的引发剂可以合成带不同电性的PMMA纳米球。我们发现带正电的Ru(bpy)3Cl2只能和带负电的PMMA纳米球复合，而不能和带正电的纳米球复合，这说明染料和纳米基质之间的相互作用力主要为静电吸引力。
对于这种电性可调的纳米基质来说，可选择的与其复合的染料分子的范围大大拓展。我们选用具有绿光发射性质的带负电的荧光素钠和带正电的R6G，黄光发射性质的带正电的RB分别和带不同电性的PMMA纳米球复合。同样，这些带电荷的染料和纳米基质复合主要的驱动力为静电吸引作用力。我们对染料和纳米基质复合的方式和复合的浓度进行了优化，合成出了多色的高发光亮度的复合型荧光纳米粒子。这种PMMA荧光纳米粒子不经过任何的生物修饰即可进入到小白鼠的血癌细胞中，点亮细胞。
2，采用羧酸化的具有核壳结构的聚合物纳米粒子为模板剂，采用原位生长的方法制备银纳米簇
采用无皂种子聚合的方法合成了具有核壳结构的聚合物纳米粒子。这些纳米粒子的核分别由PMMA(聚甲基丙烯酸甲酯)，PS(聚苯乙烯)和SiO_2（二氧化硅）构成，壳的成分都由PMAA（聚甲基丙烯酸）组成。用这些羧酸化的聚合物纳米粒子为模板剂，在AgNO_3存在的情况下，采用光化学还原的方法合成了具有荧光发射性质的银纳米簇。反应液的pH，羧酸根和AgNO_3的比例在银纳米簇合成过程中起了重要作用。获得的银纳米簇的发光效率在6-12%之间，银纳米簇的组成较为宽泛，包括Ag_2和Ag3，还有少量Ag_4, Ag_5和Ag_6。用上述模板剂采用原位生成的方法合成银纳米簇，通过一步反应就实现了银纳米簇和聚合物纳米粒子的复合。这种复合，有利于提升银纳米簇的稳定性，，银纳米簇在存放了一年后仍能很好的保持原来的荧光发射性质；还有利于扩展银纳米簇的应用范围。我们把合成的银纳米簇复合纳米粒子应用到细胞成像领域中，它可以很好的点亮细胞。
3，采用羧酸化的环糊精为模板剂合成了银纳米簇
合成了不同羧酸根取代的—环糊精，并以它们为模板剂合成银纳米簇。实验证明：羧酸根取代度越大，越有利于银纳米簇的形成。当取代度小于4时，合成的银纳米簇很快发生聚集，所以只有银纳米粒子生成；反应液的pH和反应物质之间的比例对银纳米簇的合成和性质影响也很大。我们对这些反应条件进行了优化。
利用小分子模板剂合成的银纳米簇虽然量子产率较低，只有2%，但是由于模板剂体积较小，不影响银纳米簇本身的性质。我们用环糊精合成的银纳米簇做抑菌试剂，发现银纳米簇的抑菌效果比银离子和经典银溶胶的效果都好，这可能是由于其比表面较大，表面活化能高所造成的。
4，采用修饰的蚕丝为模板剂原位生长银纳米簇
合成了PAA（聚甲基丙烯酸）修饰的蚕丝，并以此为模板剂，成功地合成了银纳米簇。我们发展了一种新型的合成银纳米簇的模板剂。它不仅实现了原位生长银纳米簇的目的，而且通过一步反应就实现了银纳米簇和蚕丝的结合，使蚕丝具有了荧光发射的性质，是合成荧光蚕丝的一种新方法。在中国，近3000年来，蚕丝由于其优良的性质，比如良好的吸潮性，透气，保温和优异的机械性能，一直被作为高档纺织品原料。此外，在生物医药等领域，如细胞培养支架，人造骨基质和药物控释，蚕丝也有广泛的应用。但是它一种蛋白纤维，容易滋生细菌和其他微生物，导致纤维损坏和皮肤敏感。人们对蚕丝纤维的抗菌能力比较关注。利用聚丙烯酸（PAA）改性的蚕丝，原位生长银纳米簇，我们获得了一种即具有荧光发射性质又具有抗菌活性的新型蚕丝纤维。这种方法也适用于修饰大多数天然纤维和人造纤维。与绿色荧光蛋白掺杂的蚕丝相比，这是一种容易处理，成本低，耗时少荧光丝纤维的制备方法。而且制备的荧光蚕丝有较好的抗菌活性。
In the fields of biology and medicine, the fluorescence labeling technique hasbeen the essential tool for studying on the configuration of biological macromolecules,the interaction between biological molecules and the action mechanism of nanocarrierinto the cell in the systems of nano-drug delivery. It has been the third “eyes” forresearcher to observe biological phenomena. The synthesis of fluorescent materialspossessing excellent properties is crucial for promoting the development and progressof fluorescence labeling. Generally, the luminescent materials for biological labelinginclude organic dyes, semiconductor quantum dots, composite fluorescentnanoparticles and noble metal nanoclusters. The latter three, owing to their size innano-level, are well known as the novel luminescent nanomaterials. Owing to theexcellent photostability, the luminescent nanomaterials attract many researchers andbecome the next generation of luminescent makers. Here, we mainly discuss thepreparation and application of the dye doped polymer nanoparticles and noble metalnanoclusters. Composite strategies, concentration and mechanism among nano-matrices, dye molecules and the structure of prepared luminescent nanoparticles havegreat impact on the luminescent properties of composite luminescent nanoparticles. Itis significant for us to figure out how the above factors affect the luminescentproperties of composite luminescent nanoparticles. And it will helpful for people toprepare composite luminescent nanoparticles for more excellent properties. Noblemetal nanoclusters have great applicable prospect in the biological fields owing totheir predominant photostability, larger Stoke shift and good biocompatibility. Silvernanoclusters present stronger fluorescence than Au nanoclusters in aqueous solution.Due to the chemical instability and the high surface energy of silver nanoclusters, theytended to interact with each other and had a natural tendency to aggregate, forminglarger nanoparticles. Therefore, a proper stabilizing scaffold or template is thusindispensable. The choices of novel, functional template or stabilizing scaffold havegreat impact on the properties and the optional application areas of silvernanoclusters. According to the excellent luminescent properties and application prospects of the Ag nanoclusters embedded composite luminescent nanoparticles, themain research contents are summarized as follows:
1, The studies on the preparation of dye doped PMMA nanoparticles and theirluminescent properties and applications.
A dye, Ru(bpy)3Cl2, was combined with nano-matrices PMMA (polymethylmethacrylate) by two strategies as the embedding (Em-PMMA nanopartcles) and theadsorbing (Ad-PMMA nanoparticles) approaches to obtain the novel compositeluminescent nanoparticles. The fluorescence lifetime of two kinds of compositeparticles can tell us that both them have a core-shell structure. For the Em-PMMAnanopartcles,40%of dye molecules lied in the surface of nanoparticle and60%ofdye molecules located in the inner of nanoparticles; For Ad-PMMA nanoparticles,16%of dye molecules lied in the inner of nanoparticles and84%of dye molecules onthe surface of nanoparticles. The quantum yields of dye molecules increased after theycombining with PMMA nanoparticles. The luminescent intensity of the Em-PMMAnanopartcles was higher than that of Ad-PMMA nanoparticles when containing thesame amount of dye molecules. The resisting ability for outside adverse environmentshowed the Em-PMMA nanopartcles was much stronger than the Ad-PMMAnanoparticles. The surface potentials of PMMA nanoparticles can be adjusted bychoosing different initiators. We found that the positively charged Ru(bpy)3Cl2can beintegrated with the negatively charged PMMA nanoparticles while they can not becombined with the positively charged, which suggested that it was the electrostaticattraction that drove the combination of dye molecules and nano-matrices. For thenano-matrices of adjustable surface potentials, the options of dye molecules which canbe combined with nano-matrices have been expanded. The negatively chargedfluorescein sodium and negatively charged rhodamine6G were combined withPMMA nanoparticles with different surface potentials. Similarly, the mechanism fordye molecules encapsulating in the PMMA nano-matricesm was the electrostaticattraction. The composite strategies and the concentration of dye molecules wereoptimized. Finallymulticolored and high brightness dye@PMMA nanocompositeswere prepared. And these multicolored polymer nanoparticles can easily stain bloodcancer cells without further surface modification.
2, In situ synthesis of silver nanoclusters templated by the carboxylated polymernanoparticles with the core-shell structure.
The method of soapless seeded emulsion polymerization was applied for synthesizing the core-shell polymer nanoparticles. The core of these polymernanoparticles were PMMA (polymethyl methacrylate), PS (polystyrene) and SiO2(silicon dioxide) respectively and all of the composition of shell was made of PMAA(polymethacrylic acid). The water-soluble fluorescent Ag nanoclusters were preparedby the method of photochemical reduction using the template of these carboxylatedpolymer nanoparticles. The pH values of reaction solution and the ratios of carboxylgroups and AgNO3were proved to be important for the synthesis process of silvernanoclusters that. The quantum yield of Ag nanoclusters was6-12%. There was awide distribution of the number of Ag atoms consisting of Ag2-6. When using thecore-shell carboxylated polymer nanoparticles as the templates for in situ synthesis ofAg nanoclusters, the composition of Ag nanoclusters and polymer nanoparticles canbe realized in one-step reaction, which is helpful to extend the application ranges ofAg nanoclusters. And the stability of Ag nanoclusters was enhanced when combiningwith polymer nanoparticles. The Ag nanoclusters can maintain the originalfluorescence intensity even experiencing one year storage. Owing to the protecting ofpolymer nanoparticles, the ability of resisting outside adverse environment wasimproved. The prepared Ag nanoclusters@polymer nanoparticles had successfullybeen applied for bioimaging.
3, Synthesis and characterization of Ag nanoclusters templated bycarboxymethyl-β-cyclodextrin (CM-β-CD)
The CM-β-CD molecules with different degree of substitution of carboxylicgroups were synthesized and they were applied as the template for preparing Agnanoclusters. The experiment showed that the more degree of substitution ofcarboxylic groups, the better for formation of Ag nanoclusters. When the degree ofsubstitution of carboxylic groups on per β-cyclodextrin molecule was smaller than4,the prepared Ag nanoclusters was very instability, tending to aggregate and led to theformation of Ag nanoparticles. It played an important role during the synthesisprocess of silver nanoclusters that the pH of reaction solution and the ratio of carboxylgroups and AgNO3and these reaction conditions were optimized for obtaining higherbrightness. Although the quantum yield of Ag nanoclusters templated by smallmolecules was low, just2%, the natural properties of Ag nanoclusters were notaffected by CM-β-CD. The Ag nanoclusters templated by CM-β-CD was used as anew antibacterial reagent and found that the antibacterial ability of Ag nanoclusters was stronger than Ag ions and typical Ag nanoparticles owing to the high surfaceenergy of Ag nanoclusters.
4, In situ synthesis of silver nanoclusters on modified silk via ultravioletlight-induced reduction
The silk modified by PAA was used as a template to prepare Ag nanoclusterssuccessfully. We developed a novel template for synthesizing Ag nanoclusters. It notonly realized the in situ synthesis of Ag nanoclusters but also finished the combinationof Ag nanoclusters and silk fibres and the completion of function of silk. This is a newsynthesis way for fluorescent silk. Since in China, silk has been used as a luxurytextile material over3000years owing to their excellent properties such as moistureabsorption, oxygen permeability, heat retention and outstanding mechanical properties.In addition, in many biomedical fields such as cell culture scaffolds, artificial bonematrices and controlled drug release, the silkworm silk has been proved to be asuitable candidate. However, this protein fiber has the potential to be a hospitable hostfor the generation and propagation of microorganisms, resulting in fiber damages andskin irritations. So the antimicrobial ability of silk fibers has been concerned. By thein situ growth of Ag nanoclusters on silk fibers modified by the polymer polyacrylicacid (PAA), we obtained a novel silk fibre with luminescence and antibacterialactivity. This method is also applicable for most natural and artificial fibres.Comparing with green fluorescent protein doped silk fibre, this is a easily handled,low-cost and less time-consuming method for preparing fluorescent silk fiber. Theproduced Ag nanoclusters@silk fibres were expected to exhibit good antibacterialproperty.
引文
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