Fabrication of Novel Polymer Nanoparticle-Based Fluorescence Resonance Energy Transfer Systems and their Tunable Fluorescence Properties

In this study, two hydrophobic fluorescent dyes, nitrobenzoxadiazolyl (NBD) and 9-(diethylamino)benzo[a]phenoxazin-5-one (NR) with different doping ratios were incorporated into polymer nanoparticles to constitute novel polymer nanoparticle-based fluorescence resonance energy transfer (FRET) systems via a facile one-step mini-emulsion polymerization. Spectroscopic characteristics demonstrate that the two fluorophores have been successfully embedded into the nanoparticles, and the fluorescence emission intensity of the two hydrophobic dyes can be greatly enhanced in aqueous media. The as-prepared fluorescent nanoparticles also display a uniform small size (ca. 55 nm), high dye load, intense fluorescence, as well as controllable amount and ratio of the two dyes. The observed FRET efficiencies (16.0–75.2%), as well as the distance (r) between NBD (donor) and NR (acceptor), is closely correlated to the doping ratio of two dyes. Moreover, by varying the doping ratio of two dyes, the fluorescent nanoparticles would exhibit multicolor through FRET upon a single wavelength excitation, and the fluorescence emission signals of the dye-doped nanoparticles could be accurately tuned. These results indicate that the as-prepared uniform FRET-mediated nanoparticles are of high interest in multiplexed bioanalysis.     

用高分子保护的纳米MgO的合成

本文利用高分子表面保护的化学沉淀方法成功地制备了粒径分布均匀的类球型纳米MgO。并对所制得的纳米粒子采用红外光谱（IR）、透射电镜（TEM）、差热及热重分析（TG－DTA）和X射线衍射（XRD）等现代分析测试手段进行了表面形貌、结构、晶形和组成等的表征。结果表明利用高分子的表面保护作用能够控制纳米微粒的形状和大小;由于聚乙烯醇分子中多羟基与金属离子间强的相互作用,因此获得的纳米微粒径更小,分散性更好。     

多功能水溶性聚合物配体制备纳米颗粒*

以多功能水溶性聚合物配体制备的纳米颗粒具有小尺寸、单分散、生物相容性良好的特点,同时还具备近红外荧光、超顺磁性等特殊物理性质,弥补了传统方法制备纳米颗粒的缺陷。本文综述了近年来多功能水溶性聚合物配体制备贵金属纳米颗粒、磁性纳米颗粒、纳米量子点以及复合结构纳米颗粒的进展;阐述了多功能水溶性聚合物配体在制备纳米颗粒方面的优势;分析了多功能水溶性聚合物的结构、分子量、浓度等因素对制备纳米颗粒的影响。最后,探讨了小尺寸、单分散、水溶性的纳米颗粒在配体交换、药物靶向传输体系、疾病检测、生物标签、核磁共振成像以及光电学等领域的应用,并展望了多功能水溶性聚合物配体制备纳米颗粒的研究方向。     

聚合物燃烧方法制备Co_3O_4纳米粒子

纳米粒子因其独特的物理化学特性成为近年来材料科学领域的研究热点 .制备方法是获得性能优越材料的关键 .Co3 O4 具有正常的尖晶石结构 ,Co2 占据八面体位置 ,在空气中低于 80 0℃时十分稳定 ,是优良的催化剂材料 [1,2 ] ,采用燃烧方法可通过控制反应条件在不发生沉淀的情况下获得化学组成均匀的复合氧化物粉体[4～ 7] .本文利用聚合物燃烧方法探索制备粒径均匀、分散性好的立方 Co3 O4 纳米粒子 .选择聚乙烯醇 ( PVA)的原因是其分子内包含大量的羟基极性基团 ,能与金属离子尤其是过渡金属离子形成良好的化学键 ,促使金属离子在 PVA…     

超细荧光聚合物纳米微球的制备

合成了具有较高荧光量子产率(0.69)和良好光稳定性的可聚合荧光染料单体,该荧光染料的光稳定性高于商品化的染料罗丹明B。 通过氧化还原引发剂引发乳液聚合制备了超细荧光聚合物纳米微球,将染料分子共价连接在聚合物链上。 使用非离子表面活性剂Triton X-100作为乳化剂、甲基丙烯酸甲酯(MMA)作为单体和助乳化剂,制备的超细纳米微球平均粒径为22 nm,而不加MMA时制备出的纳米微球平均粒径在150 nm左右。 由于微球表面带有苄氯基团,为进一步的微球功能化提供了途径。     

新型pH敏感相分离高分子的制备及其在免疫分析中的应用

聚Ｎ 异丙基丙烯酰胺 (ＰＮＩＰ)温度敏感高分子以其独特的温度敏感性质已成功地应用于免疫分析[1～ 6] .但这类温度敏感相分离免疫分析的反应温度必须控制在ＰＮＩＰ的相转变温度 ( 31℃ )以下 ,这不可避免地会影响免疫反应速率 .ｐＨ敏感高分子是另一类对环境敏感的智能型高分子 ,在其相转变ｐＨ值附近发生沉淀与溶解的可逆性变化 .目前 ,ｐＨ敏感高分子在免疫分析中的应用并没有受到重视 ,研究得较少[7] .这主要是由于 ｐＨ敏感高分子的相转变 ｐＨ值大都在 3左右 ,在此ｐＨ条件下 ,免疫反应生成的抗原 抗体免疫复合物会受到不同程度的…     

基于ZnS纳米粒子的有机凝胶荧光薄膜的制备及其传感性能

本文首先采用油水界面法制备发光纳米ZnS粒子,再通过物理混合法,将其分散在溶有小分子胶凝剂的有机溶液中,流延于玻璃基质表面,得到ZnS荧光薄膜。实验结果表明,ZnS纳米粒子的平均粒径大小约为200 nm,具有立方晶型结构,并且在杂化薄膜中具有良好的分散性;胶凝剂形成的网络结构对ZnS纳米粒子具有良好的限域效应,表现为稳定的发光性能;气敏实验表明,该杂化膜对挥发性有机单胺和二胺具有灵敏的选择性传感作用;且其灵敏度随着杂化薄膜中ZnS担载量的增大逐渐提高;可逆性实验表明该薄膜对乙二胺蒸汽具有良好的可逆响应性。     

Preparation of Epoxy-Functionalized Magnetic Polymer Nanospheres for Magnetically Targeted Radiotherapy

Magnetic poly(styrene?methyl methacrylate-glycidyl methacrylate)/Fe₃O₄ nanospheres with epoxy groups were prepared by modified one-step mini-emulsion polymerization in the presence of Fe₃O₄ ferrofluids. The products were characterized by fourier-transform infrared spectrum, transmission electron microscopy, thermogravimetric analysis and vibrating sample magnetometer. After surface modification with diaminopropane, histidine was covalently linked to the amine group of magentic nanospheres using glutaraldehyde as crosslinker. Finally, the preliminary labeling study based on non-radioactive rhenium was carried out and the labeling efficiency reached 80.4%. Such magnetic nanospheres had promising potential in magnetically targeted radiotherapy of cancer.     

智能聚合物包覆的金纳米粒子*

本文综述了智能聚合物包覆的金纳米粒子的研究进展,重点介绍了智能聚合物包覆金纳米粒子的制备方法,包括原位合成法、配体置换法、表面引发聚合法和表面接枝聚合法等,以及智能聚合物包覆的金纳米粒子的智能响应类型,如温度敏感型、pH敏感型、pH/电解质双重敏感型、pH/温度双重敏感型、溶剂敏感型等。     

J-Aggregate-Based FRET Monitoring of Drug Release from Polymer Nanoparticles with High Drug Loading

Understanding drug-release kinetics is critical for the development of drug-loaded nanoparticles. We developed a J-aggregate-based Förster-resonance energy-transfer (FRET) method to investigate the release of novel high-drug-loading (50 wt %) nanoparticles in comparison with low-drug-loading (0.5 wt %) nanoparticles. Single-dye-loaded nanoparticles form J-aggregates because of the high dye-loading (50 wt %), resulting in a large red-shift (≈110 nm) in the fluorescence spectrum. Dual-dye-loaded nanoparticles with high dye-loading using FRET pairs exhibited not only FRET but also a J-aggregate red-shift (116 nm). Using this J-aggregate-based FRET method, dye-core–polymer-shell nanoparticles showed two release processes intracellularly: the dissolution of the dye aggregates into dye molecules and the release of the dye molecules from the polymer shell. Also, the high-dye-loading nanoparticles (50 wt %) exhibited a slow release kinetics in serum and relatively quick release in cells, demonstrating their great potential in drug delivery.     

Stable Polymer Nanoparticles with Exceptionally High Drug Loading by Sequential Nanoprecipitation

Poor solubility often leads to low drug efficacy. Encapsulation of water‐insoluble drugs in polymeric nanoparticles offers a solution. However, low drug loading remains a critical challenge. Now, a simple and robust sequential nanoprecipitation technology is used to produce stable drug‐core polymer‐shell nanoparticles with high drug loading (up to 58.5 %) from a wide range of polymers and drugs. This technology is based on tuning the precipitation time of drugs and polymers using a solvent system comprising multiple organic solvents, which allows the formation of drug nanoparticles first followed by immediate precipitation of one or two polymers. This technology offers a new strategy to manufacture polymeric nanoparticles with high drug loading having good long‐term stability and programmed release and opens a unique opportunity for drug delivery applications.     

半导体纳米粒子与金纳米粒子间荧光共振能量转移研究

采用水相法合成的CdTe半导体纳米粒子作为能量给体, 通过Schiff碱反应将单链DNA连接到表面. 采用柠檬酸钠还原氯金酸法制取的Au纳米粒子作为能量受体, 通过Au—S键将单链DNA连接到表面. 通过DNA链间的杂交, 构建了荧光共振能量转移体系(FRET). 测定了CdTe-DNA、 探针体系和探针体系+目标DNA的荧光强度. 结果表明, 探针体系的荧光强度最弱, 加入目标DNA后, 体系荧光增强, 表明该体系的构建是成功的.     

Photoswitchable Fluorescent Nanoparticles: Preparation,Properties and Applications

This minireview highlights recent advances of research dedicated to photoswitchable fluorescent nanoparticles and their applications. Recently, several strategies have been developed to synthesize nanoparticles with optically switchable emission properties: either fluorescence on/off or dual‐alternating‐color fluorescence photoswitching. The underlying mechanisms of fluorescence photoswitching enable many different types of photoswitchable fluorescent nanoparticles to change fluorescence colors, thus validating the basis of the initial photoswitching design. Among all possible applications, the usage of photoswitchable fluorescent nanoparticles to empower super‐resolution fluorescence imaging and to label biological targets was subsequently reviewed. Finally, we summarize the important areas regarding future research and development on photoswitchable fluorescent nanoparticles.     

壳层厚度可调控的Ag@Pd@Pt纳米粒子的合成和甲酸电催化研究

在本课题组研究55 nm Au@Pd@Pt对甲酸电催化效果基础上,我们采用Ag取代Au制备55 nm Ag@Pd@Pt纳米粒子以降低催化剂的成本,并对甲酸的电催化行为进行研究. 研究表明：少量Pt的存在可大幅度提高催化剂的活性,当Pt的覆盖度为0.5 单原子层（ML）时,起始氧化电位最为靠前,氧化峰电流最大,这与Au@Pd@Pt纳米粒子对甲酸电催化行为类似. 与Au@Pd@Pt纳米粒子相比,其最佳起始氧化电位偏正0.05 V,但电催化活性并没有明显的降低. 通过改变催化剂比表面积研究甲酸的电催化行为,发现将9 nm Ag纳米粒子作为内核的9 nm Ag@Pd@Pt负载在活性炭中,在保持催化活性不变的情况下,碳载的催化剂价格可比55 nm Au@Pd@Pt纳米粒子降低220倍左右.     

Development of Semiconducting Polymer Nanoparticles for Photoacoustic Imaging

Semiconducting polymer nanoparticles (SPNs) have evolved into a new class of photonic materials with great potential for biomedical applications. Depending on the polymer structures, SPNs can be developed into optical agents for fluorescence and chemiluminescence imaging, photosensitizers for photodynamic therapy, and heat converters for photothermal therapy. In this feature article, recent work is summarized on the development of SPNs for in vivo photoacoustic (PA) imaging, a state‐of‐the‐art imaging modality that converts light energy into mechanical acoustic waves to provide deep tissue penetration. The structure–property relationship and doping approaches are discussed to reveal the importance of promoting nonradiative decay in amplifying the PA brightness of SPNs. Moreover, their imaging applications, including lymph node mapping, tumor imaging, and monitoring of pathological indexes, are highlighted. These studies demonstrate that SPNs can serve as versatile PA agents for advanced molecular imaging applications.

     

刺激响应聚合物在金纳米粒子催化体系中的应用

刺激响应聚合物是近几年来研究的热点之一,这类聚合物能够感受外界刺激而发生响应,产生物理或化学性质的变化。金纳米粒子由于量子效应,具有良好的催化性质,因此有广阔的应用前景。但是在实际的应用中却常常面临易于团聚的问题,因此时常需要将其负载于载体之上。将刺激响应聚合物引入金纳米粒子催化体系之中,一方面可以发挥普通载体所能起到的分散作用,防止金纳米粒子团聚,另一方面也可实现可控催化,可以通过外界条件的改变来调控金纳米粒子的催化性能。本文综述了该体系近期的研究进展,从体系的构建方式、刺激响应类型等方面进行了论述,并对该体系的研究与应用进行了总结与展望。     

A Novel Fluorescence Immunoassay Based on Two-time Amplified Fluorescence Signal by Hemin and Magnetic Nanoparticles for the Detection of Antigen

Abstract

A novel, selective, and sensitive magnetic-mimetic enzyme fluorescence immunoassay method for antigen detection has been developed by taking advantage of a magnetic separation process and the amplification feature of the hemin label. This method is based on a twice amplified fluorescence signal. The signal is first amplified due to the ultrasmall size and the high surface-to-volume ratio of the silica-coated magnetite nanoparticles, which enable the nanoparticles to carry much more antibodies. Second, the mimetic enzyme (hemin) as a labeling reagent catalyzes the reaction of p-hydroxyphenyl acetic acid and H₂O₂ can further amplify the fluorescence signal. This protocol was also evaluated for a sandwich-type immunoassay of human IgG, and the calibration graph for human IgG was linear over the range of 0–100 ng mL^?1 with a detection limit of 9.8 ng mL^?1. This method can easily separate magnetic nanoparticles from the solution, which simplified the process and played a promising role for various applications in immunoassay.     

基于水溶性共轭聚合物荧光增强测定精氨酸

在水溶液中,精氨酸(Arg)能使水溶性共轭聚合物P1的荧光高灵敏、特异性地增强,从而建立了一种免标记的荧光增强型Arg检测新方法.该方法Arg检测的线性范围为6.0×10-8～3.06×10-6 mol/L和3.06×10-6～7.11×10-5 mol/L;检出限为2.0×10-8 mol/L.方法简单、快捷、选择性好、灵敏度高,可用于盐酸精氨酸注射液样品的检测.     

Photoinduced Fluorescence Activation and Nitric Oxide Release with Biocompatible Polymer Nanoparticles

A viable strategy to encapsulate a fluorophore/photochrome dyad and a nitric oxide photodonor within supramolecular assemblies of a cyclodextrin‐based polymer in water was developed. The two photoresponsive guests do not interact with each other within their supramolecular container and can be operated in parallel under optical control. Specifically, the dyad permits the reversible switching of fluorescence on a microsecond timescale for hundreds of cycles, and the photodonor enables the irreversible release of nitric oxide. Furthermore, these supramolecular assemblies cross the membrane of human melanoma cancer cells and transport their cargo in the cytosol. The fluorescence of one component allows the visualization of the labeled cells, and its switchable character could, in principle, be used to acquire super‐resolution images, while the release of nitric oxide from the other induces significant cell mortality. Thus, our design logic for the construction of biocompatible nanoparticles with dual functionality might evolve into the realization of valuable photoresponsive probes for imaging and therapeutic applications.     

含联苯PPV类共轭聚合物的合成及荧光性能研究

在催化剂聚氯乙烯-四乙烯五胺负载钯配合物(PVC-TEPA-Pd)的作用下,利用Heck反应,二碘联苯与苯乙烯反应可以得到4,4′-二苯乙烯基联苯。进一步用二碘联苯和二乙烯基苯反应可以成功地将联苯基元引入聚合物主链,得到一种新型的含联苯结构的PPV类共轭聚合物,通过红外光谱对聚合物结构进行了表征,并对聚合物的荧光性能进行了研究,发现其荧光发射光谱峰位于500nm,与4,4′-二苯乙烯基联苯荧光发射光谱峰相比,发生了明显的红移。由于分子结构中存在较大共轭体系,两种物质在多种溶剂中的溶解性均较差。