液相二氧化钛纳米微粒的荧光和共振散射光谱特性

以钛酸四丁酯(TBTi)为前驱体,利用微波高压反应法合成了纳米二氧化钛溶胶,并与Ti(SO4)2水解法制备出的二氧化钛纳米微粒对比.考察了两种前驱体制备的二氧化钛纳米微粒荧光光谱及共振散射光谱特性,用TBTi制备的二氧化钛纳米微粒在320 nm有一个共振散射峰,在470 nm有一个同步散射峰,在360,400和470 nm处有三个荧光发射峰;用Ti(SO4)2制备的二氧化钛纳米微粒在340 nm有个共振散射峰,在470 nm有一个同步散射峰,400和470 nm处有两个荧光发射峰.反应条件对共振散射强度的影响与其对荧光的影响变化趋势一致,但共振散射光强度较荧光强度强得多.     

氧化镁单晶纳米片的简单合成

报道了一种简单的由单质镁两步制备大量氧化镁单晶纳米片的合成方法．实验中先由镁粉在不加任何助剂的条件下,于180℃水热反应36h制备了反应前驱物Mg(OH)2,再由新制备的氢氧化镁在400℃下焙烧4h获得该氧化镁单晶纳米片．粉末衍射分析表明所制备氧化镁纳米晶为立方结构．扫描电镜分析显示这些纳米晶为片状形貌,其平均厚度约为80nm,宽度为2-6μm．高分辨透射电镜照片显示,氧化镁纳米片中有大量孔状形貌存在,同时电了衍射花样显示,该氧化镁纳米片具有单晶特性．室温荧光光谱显示纳米片在416nm附近有一个强而宽的蓝色荧光峰,在559nm附近有一个相对较弱而宽的绿色荧光峰．BET测试表明该纳米片有较大的表面积(127.21m2/g)．产物表征和实验过程分析显示,片状纳米晶的形成是由前驱物形貌的模板作用所致,而其孔状形貌是由前驱物失水所形成．     

小尺寸铕(Ⅲ)配合物荧光纳米颗粒的制备

利用再沉淀法分别制备出了小尺寸(~10nm)纯相和杂相的Eu³⁺配合物荧光纳米颗粒。所制备的纯相的荧光纳米颗粒在水溶液中容易聚集,并且荧光猝灭严重。相比较而言,掺有适量疏水性硅烷的杂相纳米颗粒则具有较强的荧光、均匀的尺寸和良好的分散性。硅烷在碱性环境下(pH=9)迅速地水解,而后在纳米微粒的表面形成二氧化硅薄层。亲水的二氧化硅薄层消除了Eu³⁺配合物纳米颗粒间的疏水相互作用,进而防止了纳米颗粒的聚集,从而导致了杂相荧光纳米颗粒发光性能的提高。     

反应前驱物中n(S)∶n(Cd)对CdS薄膜结构及发光特性的影响

采用化学水浴以CdCl2·H2O、CS( NH2)2、NH4Cl、NH3·H2O和去离子水作为反应前驱物制备CdS纳米晶薄膜.采用扫描电镜( SEM)、X射线衍射(XRD)、透射光谱和稳态荧光光谱,研究了反应前驱物中不同的n(S)∶n(Cd)对所制备的CdS薄膜的形貌、结构和光学性能的影响.结果表明:反应前驱物中n(S...     

CdS纳米颗粒填充的自支撑多孔硅光致发光特性

为了研究CdS纳米颗粒填充的自支撑多孔硅的光致发光特性,选用电阻率为0.01~0.02Ω·cm的P型硅片,先采用二步阳极氧化法制备自支撑多孔硅,再利用电泳法将CdS纳米颗粒填充入该自支撑多孔硅中.采用扫描电子显微镜、X射线能谱分析、X射线衍射分析、光致发光谱分析对所制备样品的形貌、相结构、组份及发光性能进行研究.实验结果表明:自支撑多孔硅内部成功填充了CdS纳米颗粒,该CdS纳米颗粒衍射峰为(210);CdS纳米颗粒填充的自支撑多孔硅光致发光峰峰位发生红移,且从570nm转移到740nm;电泳时间直接影响CdS纳米颗粒的填充量,导致相关的发光峰强度及发光峰位明显不同.     

单分散银纳米颗粒的超声辅助制备及表面拉曼与荧光增强效应

以硝酸银和甲硼烷叔丁胺络合物分别为反应前驱物和还原剂,在油胺油酸体系中,利用超声辅助方法在室温下制备出粒径为3.4 nm的单分散银纳米颗粒．通过XRD、TEM和EDX对产物进行表征,结果显示产物具有典型的面心立方结构,单分散特征明显、尺寸分布均匀,且最可几尺寸为3.4 nm．超声反应时间、油胺和油酸的用量及其比例对银纳米晶的形貌和尺寸有重要影响,其中油胺溶剂的使用是控制单分散银纳米晶尺寸的关键．同时,研究显示单分散银纳米颗粒对罗丹明6G模型分子具有很强的拉曼增强效应;双光子荧光照片显示其具有很好的荧光增强效应．     

铽共聚荧光高分子的发光性能研究

以合成的铽三元荧光配合物为原料,采用键合法制备了16种绿色荧光高分子.通过荧光光谱分析研究它们的性能.结果表明,所有绿色荧光高分子的发光特性与铽三元荧光配合物的发光特性基本相似,均发出了铽离子的特性光,荧光表现为绿色.采用散点图和列表法研究了绿色荧光高分子化合物的荧光强度与铽三元荧光配合物单体量间的关系.结果表明,绿色荧光高分子的荧光强度与铽三元荧光单体量间不成线性关系.     

介电泳技术制备具有分子荧光增强效应的电极间纳米间隙结构

将单个核壳结构纳米颗粒放置在金属纳米电极之间制备了纳米尺度间隙结构.利用介电泳技术,本文可控地将蛋白质层包裹的SiO₂@Au核壳结构纳米颗粒定位放置在被荧光分子覆盖的纳米电极之间,从而得到了夹在纳米颗粒和金属纳米电极之间的纳米间隙结构.初步的光致发光测量表明,制备的纳米间隙结构可以有效地增强间隙中分子的荧光信号.这一结果为后续实现基于纳米间隙电极的电致分子荧光奠定了基础.     

Ag@SiO2纳米复合物对羧酸铕配合物的荧光增强

分别以苯氧乙酸和对苯二甲酸为阴离子配体,以邻菲罗啉为中性配体,稀土铕离子为中心体,合成了两种三元稀土铕配合物Eu(Phen)L3(L=苯氧乙酸)和Eu2(Phen)2L3’(L’=对苯二甲酸)。利用还原法制备纳米银溶胶,采用改进的Stber法在银纳米颗粒外面包裹二氧化硅,通过控制正硅酸四乙酯(TEOS)的滴加时间和滴加量以控制二氧化硅壳层的生长厚度,得到Ag@SiO2核壳结构颗粒。通过该核壳结构颗粒与DMF溶解的稀土铕配合物的相互作用,得到核壳型Ag@SiO2荧光纳米复合物。结果表明,所得纳米银粒径为50 nm左右,包覆的SiO2壳层厚度约为12 nm。SiO2包覆的纳米银对两种铕配合物的荧光发射有明显的增强作用。     

乳化-前驱物热分解法制备纳米氧化锌

以 Zn(NO3 ) 2 · 6 H2 O、Na2 CO3 - Na HCO3 为原料 ,阴离子表面活性剂为乳化剂 ,有机溶剂为分散剂 ,采用乳化法制备前驱物 ,热分解前驱物得到纳米 Zn O;XRD物相分析表明 ,产物为标准六方晶系 ;Raman光谱表明产物是 Zn O晶体 ;并通过 TG- DTA确定前驱物分解成纳米 Zn O的最佳温度为 30 0℃。     

掺杂4-苯基卟啉的聚苯乙烯／二氧化硅复合纳米微球的制备

采用溶胶-凝胶法,首先利用苯乙烯与3-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)化学反应合成共聚前驱物,利用TEOS在一定的条件下水解与缩合,一步合成了有机-无机复合纳米微球。用扫描电镜、红外光谱对共聚物及复合纳米粒子进行了表征。将非水溶性发光材料四苯基卟啉掺杂其中,制备出荧光复合纳米粒子。该粒子表现出了良好的发光性能,染料泄漏与猝灭几乎为零,可以作为一种新型的高效率的生物标记材料。     

Synthesis of Eu(III): naphtoyltrifluoroacetone:trioctylphosphineoxide complex-doped silica fluorescent nanoparticles through a new approach

In this study, a new approach for the preparation of a fluorescent europium(III) complex-doped silica nanoparticles has been developed. The synthesis process involved the following steps: (1) preparing silica nanoparticles by water-in-oil microemulsion method, (2) dyeing the spherical silica particles by europium(III): naphtoyltrifluoroacetone (NTA):trioctylphosphineoxide (TOPO), (3) adsorbing polyvinylpyrrolidone (PVP) onto the core structure and growing silica on PVP surface. The as-prepared nanoparticles exhibited stronger emission intensity, higher photo- and chemical stability. Despite the fact that europium(III) complex was doped into the nanoparticles, its fluorescence properties such as a wide Stokes shift, a narrow emission peak, and long fluorescence lifetime, were retained. The nanoparticles are uniform in shape and size (50 ± 5 nm in diameter). This study could provide new avenue for the fabrication of Eu: NTA:TOPO-based nanoparticles, facilitating their application in bioassay issues.     

近红外染料Yb(P4)(CoP) 掺杂 PS/SiO2复合纳米荧光标记物的制备及其性能

利用苯乙烯与3-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)化学反应合成共聚前驱物, 再采用凝胶-溶胶法,与四乙氧基硅烷在一定的条件下共同水解与缩合,合成了近红外染料 合镱(Ⅲ)掺杂的聚苯乙烯/二氧化硅复合纳米粒子。这种制备染料掺杂复合纳米粒子的方法既克服了传统物理包埋方法染料容易泄漏的问题,又不受到化学键合方法对近红外染料分子性质的限制。用扫描电子显微镜表征该复合纳米粒子呈球形,大小均匀,直径约100 nm。所制得的纳米粒子荧光性质稳定,受外界环境的影响小,具潜在生物亲和性,是一种新型的近红外荧光标记物。     

Behaviour of Fluorescence Emission of Cyanine Dyes,Cyanine Based Fluorescent Nanoparticles and CdSe/ZnS Quantum Dots in Water Solution Upon Specific Thermal Treatments

Fluorescence techniques are widely used as detection methods in a wide range of biological imaging and analytical applications. The purpose of this work is to determine a measurement method which leads to a comparison between different classes of fluorophores in term of stability of the fluorescence signal upon thermal treatment cycles. This kind of investigation can determine whether the fluorophore performance is affected by heating/cooling cycles and to what extent. The fluorophores considered in this work were organic fluorophores belonging to the family of indocyanine dyes (IRIS3 by Cyanine Technologies S.p.A.) in their molecular form or encapsulated within silica nanoparticles, and CdSe/ZnS carboxyl quantum dots (Qdots 565 ITK by Invitrogen). The NIST Standard Reference Material® SRM 1932 fluorescein solution was used in the certified concentration as reference material in order to evaluate the repeatability of the used spectrofluorimeter. The proposed measurement protocol allows to characterize all kind of fluorophores upon thermal treatments. This allows direct comparison of their performance under temperature changes, giving useful guidelines for the selection of the most suitable fluorophore for the envisaged application. Moreover the method appears to be a promising tool for the characterisation of reference fluorescent materials. The experimental results demonstrate that each fluorophore class shows a specific behaviour. The experimental data analysis points out an important hysteresis effect for quantum dots that was not detected for cyanine molecules and was only slightly detected for cyanine doped silica nanoparticles.     

Electromagnetic interaction of fluorophores with designed two-dimensional silver nanoparticle arrays

We study the fluorescence enhancement of dye molecules adsorbed on regular two-dimensional arrays of designed silver nanoparticles. The silver particles show two orthogonal optical resonances at different wavelengths because of their elongated shape. The short-wavelength resonance was designed to fit to the absorption maximum of the fluorophore. When the excitation light drives the short-wavelength resonance, the measured fluorescence intensity is strongly enhanced compared to that for the orthogonal particle orientation. This shows directly a strong electromagnetic coupling between the nanoparticles and the fluorophore. Additionally enhanced photochemical bleaching is observed due to the interaction of fluorophores with the particles. Using a rate model describing the fluorescence enhancement and the bleaching enhancement, an average value for the particle-induced increase in the radiative fluorescence rate is obtained, together with a lower limit for the averaged particle-induced field intensity enhancement factor. Received: 3 July 2001 / Revised version: 3 September 2001 / Published online: 15 October 2001     

Synthesis and characterisation of highly fluorescent core–shell nanoparticles based on Alexa dyes

Current and future developments in the emerging field of nanobiotechnology are closely linked to the rational design of novel fluorescent nanomaterials, e.g. for biosensing and imaging applications. Here, the synthesis of bright near infrared (NIR)-emissive nanoparticles based on the grafting of silica nanoparticles (SNPs) with 3-aminopropyl triethoxysilane (APTES) followed by covalent attachment of Alexa dyes and their subsequent shielding by an additional silica shell are presented. These nanoparticles were investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM) and fluorescence spectroscopy. TEM studies revealed the monodispersity of the initially prepared and fluorophore-labelled silica particles and the subsequent formation of raspberry-like structures after addition of a silica precursor. Measurements of absolute fluorescence quantum yields of these scattering particle suspensions with an integrating sphere setup demonstrated the influence of dye labelling density-dependent fluorophore aggregation on the signaling behaviour of such nanoparticles.     

One-step synthesis of dye-incorporated porous silica particles

Fluorescent nanoparticles have a variety of biomedical applications as diagnostics and traceable drug delivery agents. Highly fluorescent porous silica nanoparticles were synthesized in a water/oil phase by a microemulsion method. What is unique about the resulting porous silica nanoparticles is the combination of a single-step, efficient synthesis and the high stability of its fluorescence emission in the resulting materials. The key of the success of this approach is the choice of a lipid dye that functions as a surrogate surfactant in the preparation. The surfactant dye was incorporated at the interface of the inorganic silica matrix and organic environment (pore template), and thus insures the stability of the dye?Csilica hybrid structure. The resulting fluorescent silica materials have a number of properties that make them attractive for biomedical applications: the availability of various color of the resulting nanoparticle from among a broad spectrum of commercially dyes, the controllablity of pore size (diameters of ~5?nm) and particle size (diameters of ~40?nm) by adjusting template monomer concentration and the water/oil ratio, and the stability and durability of particle fluorescence because of the deep insertion of surfactant??s tail into the silica matrix.     

A Comparative Study of Fluorescein Isothiocyanate-Encapsulated Silica Nanoparticles Prepared in Seven Different Routes for Developing Fingerprints on Non-Porous Surfaces

Preparation of fluorescein isothiocyanate (FITC)-encapsulated silica nanoparticles (F-SiNPs) via seven different approaches to be used as developing agents for fingerprints detection is presented in this report. In this study, the suitability of each synthesis route toward incorporation of the selected fluorophore into silica matrix and its efficiency in fingerprints detection were systematically studied. The composition of the particles was designed to examine the hydrophobic and dipole-dipole interactions between the silicate backbone and both of the fluorescent reporter molecules and the fingerprint residues. F-SiNPs were prepared with two conventional sol-gel approaches; the Stöber method and the water in oil reverse microemulsion (WORM) method. The alkoxysilane precursor, tetraethoxyorthosilicate (TEOS) and its binary mixtures with phenyltriethoxysilane (PTEOS) or 3-aminopropyl triethoxysilane (APTES) have been used in preparing the F-SiNPs to study the effect of nanoparticles composition on fingerprints development. In addition, FITC was conjugated with APTES so it can be covalently bonded to the silica matrix and to be compared with non-covalently FITC-doped SiNPs. Moreover, the enhancement effect of introducing polyvinylpyrrolidone (PVP) onto the surface of the less hydrophobic F-SiNP on fingerprints detection on different non-porous surfaces was also investigated. The mean diameters of the F-SiNPs were between 4.1?±?0.6 and 110.4?±?31.1 nm as obtained from the TEM size measurement for the nanoparticles prepared by the WORM and Stöber methods, respectively. The obtained results clearly highlight the advantages of using a mixture of TEOS and PTEOS alkoxysilane precursors in preparing F-SiNPs with remarkable encapsulation efficiency and clear detection of fingerprints due to efficient embedding of the fluorophore inside the silica network even without conjugation. It was also observed that both the Stöber and WORM methods can be used in preparing the F-SiNPs developing agents and that PVP coated particles did not show any significant enhancement in fingerprints visualization.     

Synthesis of intrinsic fluorescent polypyrrole nanoparticles by atmospheric pressure plasma polymerization

Intrinsic fluorescent polypyrrole (ppy) nanoparticles with different shapes were fabricated by atmospheric pressure plasma polymerization. Gradient electrical field and polarization of active particles in the plasma induce change of shape of nanoparticles from spherical to rod, when the plasma power varied from 5 W to 10 W. Both X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) results suggest that the atmospheric pressure plasma polymerization process (APPP) at the power of 5 W and 10 W can help to preserve the integrity of the structure of monomer due to the predominant role of radical polymerization in APPP at these powers. However, when the plasma power increased to 20 W, the ring structure of some pyrroles was destroyed, owing to existence of higher energy species. The polypyrrole nanoparticles exhibit the peak fluorescence around 415 nm. Fluorescent results show that the fluorescent properties of polypyrrole nanoparticles are related to the particle size of the polymer. The bigger particles would have more enlarged room for exciton diffusion, resulting in lower fluorescence intensity and red shift of the fluorescent peak.     

Reduced Lifetimes are Directly Correlated with Excitation Irradiance in Metal-Enhanced Fluorescence (MEF)

We describe a fundamental observation in Metal-Enhanced Fluorescence (MEF), which has become a leading technology in the life sciences today, namely, how the lifetime of fluorophores near-to metallic plasmon-supporting silver islands/nanoparticles, modulates as a function of excitation power irradiance. This finding is in stark contrast to that observed in classical far-field fluorescence spectroscopy, where excitation power does not influence fluorophore radiative decay/lifetime.