高分子-无机复合纳米微球的制备和诊疗应用

目前,高分子-无机复合纳米微球因兼有高分子微球和无机纳米材料两者的性能优势而备受关注。其中,由可塑生物相容性的高分子与拥有特殊光、磁及电学性质的无机物组成的纳米微球,在疾病诊疗中应用前景广阔。功能高分子同多种无机粒子、活性分子可以复合形成多功能纳米微球,用于实现多模态成像诊断和可视化跟踪治疗。本文基于复合纳米微球的各种合成方法介绍,阐述了它们在靶向药物传输、生物成像、细胞分离、生物传感及热疗等诊疗领域的应用。同时,对纳米医疗领域前景和挑战进行了评述,为构建新型诊疗复合纳米微球提供有用信息。     

油酸/PSt/TiO_2复合纳米微球的制备

纳米复合材料是近年来化学、物理及材料科学研究最活跃的领域之一 .有机 -无机复合纳米微球的制备和性能研究是这一研究领域的一个重要分支 .有机 -无机复合纳米微球兼有有机材料、无机材料和纳米材料的特性 ,特别是“球形”结构使其具有微观的“滚动”特性而倍受摩擦学工作者的青睐 .目前聚合物纳米微球的摩擦学性能研究已取得了重要进展 [1～ 4 ] .段标等 [3,5]认为聚合物微球的润滑机理是在摩擦过程中 ,微球进入摩擦表面 ,因其弹性和球形 ,而起到一定的滚动作用 ;高载荷下 ,微球变形并在摩擦表面形成聚合物润滑膜 .然而有关聚合物 /无机…     

新型室温酯化法接枝聚合物改性SiO_2纳米微粒

提出了一种在室温、大气环境等温和条件下通过酯化反应将端羧基聚合物链接枝到纳米SiO2微球表面从而制备有机/无机复合纳米微粒的新方法.该方法通过以下两个步骤得以实现,即第一,用3-环氧丙基三甲氧基硅烷对纳米SiO2微球表面进行改性处理,接着将引入到纳米SiO2表面的环氧基团转化为烷羟基基团;第二,通过引入到纳米SiO2微球表面的烷羟基与聚合物中的端羧基在室温下发生酯化反应,从而将聚合物接枝到纳米SiO2表面制得复合微球.利用XPS、FTIR、TEM和TGA等测试手段对纳米SiO2的改性过程以及聚合物接枝后得到的复合微球进行了表征.研究结果表明,该室温酯化接枝方法具有较高的接枝率,接枝到无机纳米微粒表面的聚合物占复合微球质量的55wt%～70wt%;接枝聚合物后,纳米SiO2微球的粒径从40nm增加到64～75nm,从而得到了以SiO2为核、以聚合物为壳的有机-无机复合微球.     

SiO_2/PVAc无机-有机复合微球的合成及其膜性能研究

以纳米二氧化硅粒子(SiO2)为稳定剂,在少量反应型阴离子乳化剂——烯丙氧基羟丙磺酸钠(HAPS)作助稳定剂的情况下,制备了具有草莓型结构的二氧化硅/聚醋酸乙烯酯(SiO2/PVAc)无机-有机纳米复合微球.研究表明,纳米SiO2与PVAc的氢键作用是形成这种单分散草莓型SiO2/PVAc无机-有机纳米复合微球的关键.透射电镜(TEM)观察显示,纳米SiO2吸附在PVAc表面,形成草莓型结构.讨论了纳米二氧化硅溶胶的种类和用量、乳化剂种类对复合微球形态及其膜性能的影响,并讨论了复合微球的形成机理.     

有机-无机纳米复合微球研究进展北大核心CSCD

有机-无机纳米复合微球是指两种或两种以上的粒子经表面包覆或复合处理后形成的纳米尺度颗粒。近年来,有机-无机纳米复合微球在各领域具有广泛应用前景而备受关注。本文归纳了目前比较成熟的合成技术和先进工艺,将制备有机-无机纳米复合微球的方法分为溶胶-凝胶法、原位聚合法及其他实验方法,详细介绍了原位聚合法,分别从各类方法的特点和应用等方面进行详尽地分析和阐述,并对有机-无机纳米复合微球的实际应用做了比较系统的总结。最后,展望了有机-无机纳米复合微球的发展和前景。     

荧光团杂化纳米SiO2微球作为生物标记探针的应用研究

近年来 ,无机发光量子点[1,2 ] 、荧光纳米乳液微球[3 ,4 ] 及发光团掺杂 Si O2 纳米粒子[5] 等纳米荧光探针的出现 ,为生物标记提供了新的发展领域 .将有机染料以共价方式包埋在 Si O2 中所得的复合材料具有独特的光学性质 ,然而其在生物标记方面的应用并未得到重视[6 ,7] .本实验通过控制荧光团修饰的硅烷前体在反相胶束体系中的水解缩合 ,合成了用于生物染色和诊断的高灵敏度、高稳定性的新型荧光团杂化纳米 Si O2 微球 ( NFHS微球 ) .在 NFHS微球中 ,荧光团以共价方式地均匀分散在 Si O2 网络结构中 ,避免了与外界体系中溶解氧的…     

pH值响应的壳聚糖纳米微球的合成及吸附镍离子研究

本工作于水中简单地合成了生物相容且可生物降解的壳聚糖/聚丙烯酸纳米微球,产物具有优异的水稳定性和单分散性。通过傅里叶变换红外光谱、动态光散射、透射电子显微镜、扫描电子显微镜和zeta电位对所得纳米微球的理化性质进行表征,结果显示壳聚糖纳米微球的表面结构和zeta电位对pH值改变具有响应性。携带丰富官能团的产物微球为装填其它活性材料提供了功能位点,因此,可将该纳米微球用作水中去除镍离子的吸附剂。本文从吸附时间、pH值、温度及起始离子浓度等方面研究了纳米微球的吸附行为,发现壳聚糖微球对镍离子的吸附量可以高达44.41mg/g。此外,吸附等温线遵循Freundlich等式,而其动力学符合拟二级模型。     

纳米TiO_2微球对聚氨酯的改性

采用十六胺作为表面修饰剂,通过一种简单易行的方法成功制备了纳米TiO_2微球.分别利用傅立叶红外光谱仪(FTIR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等表征手段对纳米TiO_2微球进行了结构和形貌表征.将制备的纳米TiO_2微球添加到水性聚氨酯基体(WPU)中,测试了其性能.结果表明,纳米TiO_2微球的添加显著提高了WPU的抗紫外线性能、耐水性和热稳定性等.     

无皂乳液聚合法制备聚甲基丙烯酸甲酯包覆厚度可控的纳米核-壳二氧化硅微球

用改进的Stöber法和无皂乳液聚合法制备窄分布的二氧化硅/PMMA核-壳纳米微球. 用改进的Stöber法将3-乙氧基甲基丙烯酸丙基硅烷(MPS)修饰在纳米的二氧化硅表面后, 用无皂乳液聚合法制备核-壳纳米微球. 该法简单有效且得到厚度均匀的聚合物包覆层. 随着单体MMA用量的增加, 用动态光散射法测量, PMMA壳层的厚度从6.4 nm增加到96.3 nm. 热重分析表明, PMMA的含量从22.25%增加到93.41%. 扫描电子显微镜和透射电子显微镜结果表明, 得到的是包覆良好、表面光滑的核-壳无机/聚合物纳米微球.     

中空SiO_2纳米微球的制备与表征

在乙醇/氨水介质中,将SiO2包覆在聚乙烯吡咯烷酮(PVP)功能化的聚苯乙烯(PS)微粒表面,利用一步法得到了中空纳米二氧化硅微球;研究了影响中空纳米二氧化硅微球形成的主要因素,并探讨了中空纳米SiO2微球的可能形成机理.结果表明,在一定的反应时间下,当氨水用量为0.6 mL、温度为70℃时,可以获得空心结构的SiO2纳米微球;通过控制四乙基原硅酸盐(TEOS)的量可以调节微球的包覆层厚度.     

纳米二氧化钛粉体及薄膜制备的研究进展

本文对近几年有关纳米二氧化钛粉体及薄膜的制备研究进行综述。重点介绍及评述了以无机钛盐和有机钛盐为前驱体制备纳米二氧化钛粉体及利用自组装方法制备二氧钛薄膜的最新研究成果。对今后研究工作的趋势进行了探讨。     

Complex Inorganic/Organic Core-Shell Particles by an Inverse Emulsion Technique

Two synthetic approaches to modify the surface of inorganic particles are presented. In the first approach the inorganic particles are prepared in-situ in a confined space in inverse emulsions. The used amphiphilic statistical copolymers act not only as emulsifiers, but they also hydrophobize the remaining inorganic particles after the precipitation. This approach represents a versatile method to obtain various inorganic nanoparticles as well as more complex inorganic materials like core-multiple shell and perovskite-based nanoparticles. The second procedure uses preformed inorganic particles, as an aqueous dispersion, to modify them with surface active amphiphilic copolymers in a multicomponent solvent system. This method turns out to be a simple but highly efficient method to modify preformed inorganic nanoparticles. The particles are characterized by SEM, TEM and dynamic light scattering. The modified inorganic nanoparticles are suitable to be homogenously incorporated into a polymer matrix to form transparent nanocomposite materials.     

Recent progress in the synthesis of inorganic nanoparticles

Nanoparticles probably constitute the largest class of nanomaterials. Nanoparticles of several inorganic materials have been prepared by employing a variety of synthetic strategies. Besides synthesizing nanoparticles, there has been considerable effort to selectively prepare nanoparticles of different shapes. In view of the great interest in inorganic nanoparticles evinced in the last few years, we have prepared this perspective on the present status of the synthesis of inorganic nanoparticles. This article includes a brief discussion of methods followed by reports on the synthesis of nanoparticles of various classes of inorganic materials such as metals, alloys, oxides chalcogenides and pnictides. A brief section on core-shell nanoparticles is also included.     

四种无机纳米颗粒对塑料抗紫外性能的研究进展

无机纳米颗粒在塑料抗紫外的研究中一直备受关注,主要介绍了四种(TiO₂、ZnO、SiO₂、CeO₂)典型的无机纳米颗粒在该领域的应用。首先归纳了其既能吸收又能反射或散射紫外线的抗紫外机理;其次,分别论述了不同无机纳米颗粒适用的紫外光波长范围,以在塑料中的添加方法和应用特点为主线,重点介绍了国内外四种无机纳米颗粒在塑料抗紫外性能中的研究现状和进展;最后,将四种无机纳米颗粒在塑料抗紫外性能中的应用特点进行了对比,提出了应用过程中存在的分散和相容性差等问题,以期为无机纳米颗粒的深入应用和发展提供一定的参考。     

From Precision Synthesis of Block Copolymers to Properties and Applications of Nanoparticles

Inorganic nanoparticles have become a research focus in numerous fields because of their unique properties that distinguish them from their bulk counterparts. Controlling the size and shape of nanoparticles is an essential aspect of nanoparticle synthesis. Preparing inorganic nanoparticles by using block copolymer templates is one of the most reliable routes for tuning the size and shape of nanoparticles with a high degree of precision. In this Review, we discuss recent progress in the design of block copolymer templates for crafting spherical inorganic nanoparticles including compact, hollow, and core–shell varieties. The templates are divided into two categories: micelles self‐assembled from linear block copolymers and unimolecular star‐shaped block copolymers. The precise control over the size and morphology of nanoparticles is highlighted as well as the useful properties and applications of such inorganic nanoparticles.     

Recent advances in the preparation of hybrid nanoparticles in miniemulsions

In this review, we summarize recent advances in the synthesis of hybrid nanoparticles in miniemulsions since 2009. These hybrid nanoparticles include organic–inorganic, polymeric, and natural macromolecule/synthetic polymer hybrid nanoparticles. They may be prepared through encapsulation of inorganic components or natural macromolecules by miniemulsion (co)polymerization, simultaneous polymerization of vinyl monomers and vinyl-containing inorganic precursors, precipitation of preformed polymers in the presence of inorganic constituents through solvent displacement techniques, and grafting polymerization onto, from or through natural macromolecules. Characterization, properties, and applications of hybrid nanoparticles are also discussed.     

Phthalhydrazide nanoparticles as new highly reusable organic photocatalyst in the photodegradation of organic and inorganic contaminants

Phthalhydrazide nanoparticles are introduced as a new, efficient, stable and reusable organic photocatalyst for the photodegradation of a range of azo dyes, including methyl orange, methyl red, congo red and yellow titan, 4‐nitrophenol and permanganate as important organic and inorganic contaminants. Various experimental parameters including pH, photocatalyst dose, dye concentration and illumination time were investigated for methyl orange as a model substrate. The results revealed high degradation efficacy, up to 93.6%, for methyl orange in 20 min. Moreover, a preliminary kinetic study along with a proposed photodegradation mechanism is included in this study. Mechanistic investigations showed that phthalhydrazide behaved as a photoreduction catalyst. With the addition of Cl^? ion, as a hole scavenger, photodegradation efficacy for methyl orange was improved. Results showed that phthalhydrazide nanoparticles behaved better than commercial bulk phthalhydrazide and both performed as successful photocatalysts for photoreduction of the mentioned organic and inorganic compounds.     

有机大分子导向无机纳米粒子的分级有序自组装

本文主要综述了基于特定分子设计的有机大分子导向下的无机纳米粒子的分级有序自组装.可以有效导向无机纳米粒子组织的有机大分子主要包括合成大分子和生物大分子,前者如具有氢键识别功能的大分子、聚电解质、嵌段大分子、树枝状大分子;后者如DNA、糖类以及蛋白质.所涉及的无机纳米粒子通常需要通过单层修饰使之与特定的大分子具有识别功能,或者设计表面带有正或负电荷使之与带有负或正电荷的大分子相互识别.该领域的研究在先进功能材料及仿生材料方面具有重要意义.     

Interfacially formed organized planar inorganic, polymeric and composite nanostructures

This paper discusses synthetic strategies for fabrication of new organized planar inorganic, polymeric, composite and bio-inorganic nanostructures by methods based on chemical reactions and physical interactions at the gas-liquid interface, Langmuir monolayer technique, interfacial ligand exchange and substitution reactions, self-assembling and self-organization processes, DNA templating and scaffolding. Stable reproducible planar assemblies of ligand-stabilized molecular nanoclusters containing definite number of atoms have been formed on solid substrate surfaces via preparation and deposition of mixed Langmuir monolayers composed by nanocluster and surfactant molecules. A novel approach to synthesis of inorganic nanoparticles and to formation of self-organized planar inorganic nanostructures has been introduced. In that approach, nanoparticles and nanostructures are fabricated via decomposition of insoluble metal-organic precursor compounds in a layer at the gas-liquid interface. The ultimately thin and anisotropic dynamic monomolecular reaction system was realized in that approach with quasi-two-dimensional growth and organization of nanoparticles and nanostructures in the plain of Langmuir monolayer. Photochemical and redox reactions were used to initiate processes of interfacial nucleation and growth of inorganic phase. It has been demonstrated that morphology of resulting inorganic nanostructures can be controlled efficiently by variations of growth conditions via changes in state and composition of interfacial planar reaction media, and by variations of composition of adjacent bulk phases. Planar arrays and chains of iron oxide and ultrasmall noble metal (Au and Pd) nanoparticles, nanowires and new organized planar disk, ring, net-like, labyrinth and very high-surface area nanostructures were obtained by methods based on that approach. Highly organized monomolecular polymeric films on solid substrates were obtained via deposition of Langmuir monolayer formed by water-insoluble amphiphilic polycation molecules. Corresponding nanoscale-ordered planar polymeric nanocomposite films with incorporated ligand-stabilized molecular metallic nanoclusters and interfacially grown nanoparticles were fabricated successfully. Novel planar DNA complexes with amphiphilic polycation monolayer were formed at the gas-aqueous phase interface and then deposited on solid substrates. Toroidal and new net-like conformations were discovered in those complexes. Nanoscale supramolecular organization of the complexes was dependent on cationic amphiphile monolayer state during the DNA binding. These monolayer and multilayer DNA/amphiphilic polycation complex Langmuir-Blodgett films were used as templates and nanoreactors for generation of inorganic nanostructures via metal cation binding with DNA and following inorganic phase growth reactions. As a result, ultrathin polymeric nanocomposite films with integrated DNA building blocks and organized inorganic semiconductor (CdS) and iron oxide quasi-linear nanostructures were formed. It has been demonstrated that interaction of deposited planar DNA/amphiphilic polycation complexes with bulk phase colloid inorganic cationic ligands (CdSe nano-rods) can result in formation of new highly organized hybrid bio-inorganic nanostructures via interfacial ligand exchange and self-organization processes. The methods developed can be useful for investigation of fundamental mechanisms of nanoscale structural organization and transformation processes in various inorganic and molecular systems including bio-molecular and bio-inorganic nanostructures. Also, those methods are relatively simple, environmentally safe and thus could prove to be efficient practical instruments of molecular nanotechnology with potential of design and cost-effective fabrication of new controlled-morphology organized planar inorganic and composite nanostructured materials. Possible applications of obtained nanostructures and future developments are also discussed.     

纳米材料的自组装研究进展

本文主要评述了近年来纳米材料自组装的研究进展，即对以纳米材料(包括零维的纳米粒子和一维的纳米管/线)为单元而开展的自组装方面的工作进行了介绍。将纳米材料自组装为各种尺度的有序结构会产生更优异的整体的协同性质，这对于以纳米材料为基础而构筑的微纳米器件有着重要的意义。由于目前纳米材料的研究主要集中在零维和一维体系，因此，本文分别就此两种体系的自组装行为进行了评述。具体内容包括：单分子层薄膜修饰的无机纳米粒子的自组装、大分子修饰的无机纳米粒子的自组装、未被修饰的无机纳米粒子的自组装；表面张力及毛细管力诱导的一维纳米材料的自组装、模板诱导的一维纳米材料的自组装、静电力诱导的一维纳米材料的自组装。