银/二氧化钛核壳纳米颗粒对碲化镉纳米晶的荧光增强研究

利用新合成的复合纳米结构银/二氧化钛核壳纳米颗粒,研究了金属银纳米颗粒对碲化镉纳米晶层荧光的增强情况.结果表明,这种新型复合金属纳米结构能极大地增强发光纳米晶层的荧光强度.银/二氧化钛核壳纳米颗粒是以水合肼、硝酸银和四异丙氧基钛为原材料,利用胶体化学法在水溶液中合成.透射电子显微镜图片表明这种新合成的银/二氧化钛纳米材料基本上呈球形,有较为明显的核壳结构,中间黑色的核是银纳米颗粒,外层颜色较浅部分是二氧化钛壳层.另外,包裹二氧化钛壳层后,银纳米颗粒的表面等离子吸收带从409 nm红移至430 nm,也证实了这种新型核壳纳米材料的形成.将此合成方法得到的银/二氧化钛纳米颗粒和碲化镉纳米晶用旋转涂覆方法进行直接组合后,得到了银纳米颗粒对碲化镉纳米晶荧光的明显增强,并对其增强的物理过程进行了讨论.这种能够增强荧光团发光的新型复合银纳米结构将在发光器件、荧光成像、生物探测等方面具有一定的应用价值.     

pH-dependent fluorescence property of methyl red isomers in silver colloids

We report the use of silver (Ag) colloids in the spectroscopic differentiation of methyl red (MR) isomers (o-MR, m-MR, p-MR) by fluorescence techniques. Under different pH conditions, the formation of MR-Ag complex has an impact on the fluorescence band shapes and peak position shift, which are distinctive between MR isomers. The fluorescence quenching between 400 and 414 nm accompanied by simultaneous enhancement between 510 and 541 nm changes with pH are closely related to energy transfer efficiency and the interaction between the MR isomers and the Ag surface.     

甲基橙溶液的pH值对纳米银荧光增强效应的影响

研究了甲基橙溶液的pH对纳米银荧光增强效应的影响.当pH 1.5和2.1时,纳米银对溶液的吸收光谱影响甚小.当pH 3.1时,吸收峰蓝移26 nm,且强度明显降低.当pH值在3.8～8.2范围时,不仅吸收峰蓝移而且在426～456 nm出现宽吸收带.在任何pH值的甲基橙溶液中加入纳米银,S2→S0跃迁荧光发射带强度下降,但下降比率受pH值影响不大;S1→S0跃迁荧光发射带强度增强,其增强比率受pH值影响较大.当pH 2.1时,荧光增强比率最大;当pH 4.8时,荧光增强比率最小.分析认为,pH值对甲基橙溶液光谱性质的影响与不同pH值条件下甲基橙分子结构的改变以及分子在纳米银粒子表面不同的吸附方式、介质环境等因素相关,尤其与甲基橙分子与纳米银粒子间的距离密切相关.     

Optical properties and ultrafast electron dynamics in gold–silver alloy and core–shell nanoparticles

Silver and gold are the two most popular metals used for many nanoparticle applications, such as surface enhanced Raman scattering or surface enhanced fluorescence, in which the local field enhancement associated with the excitation of the localized surface-plasmon–polariton resonance (SPR) is exploited. Therefore, tunability of the SPR over a wide energy range is required. For this purpose we have investigated core–shell nanoparticles composed of gold and silver with different shell thicknesses as well as the impact of alloying on these nanoparticles due to a tempering process. The nanoparticles were prepared by subsequent deposition of Au and Ag atoms or vice versa on quartz substrates followed by diffusion and nucleation. Their linear extinction spectra were measured as a function of shell thickness and annealing temperature. It turned out that different gold shell thicknesses on silver cores allow a tuning of the SPR position from 2.79 to 2.05 eV, but interestingly without a significant change on the extinction amplitude. Heating of core–shell nanoparticles up to only 540 K leads to the formation of alloy nanoparticles, accompanied by a back shift of the SPR to 2.60 eV. Calculations performed in quasi-static approximation describe the experimental results quite well and prove the structural assignments of the samples. In additional experiments, we applied the well-established persistent spectral hole burning technique to the alloy nanoparticles in order to determine the ultrafast dephasing time T ₂. We obtained a dephasing time of T ₂=(8.1±1.6) fs, in good agreement with the dephasing time of T _2,∞=8.9 fs, which is already included in the dielectric function of the bulk.     

Study of concentration-dependent quantum yield of Rhodamine 6G by gold nanoparticles using thermal-lens technique

Tailoring optical properties of the dye molecules using metal nanoparticles is a burgeoning area of research. In this work, we report our results on the studies of how the absorption and emission behavior of Rhodamine 6G dye is tailored using gold nanoparticles. Furthermore, the influence of dye concentration on these properties for a given concentration of nanoparticles in the dye-nanoparticle mixture is investigated. In addition, the difference between the concentration-dependent fluorescence quantum yield of the dye molecules is measured in the absence and presence of nanoparticles using the dual-beam thermal-lens technique. Our absorption spectral studies show additional spectral features due to nanoparticle aggregation on interaction with cationic Rhodamine 6G dye. Dye concentration-dependent steady-state fluorescence studies in the presence of nanoparticles indicate a blue shift in peak fluorescence emission wavelength. The quantum yield value measured using thermal-lens technique exhibit a non-monotonic behavior with dye concentration with substantial quenching for lower dye concentrations. The results are interpreted in terms of dye–nanoparticle interaction and the formation of dye shell around the nanoparticle.     

两种纳米粒子的自组装及表面增强拉曼光谱研究

在氨基硅烷化的单晶硅片表面通过静电自组装技术组装上金和金核铂壳两种纳米粒子,通过改变基底浸泡在溶胶中的时间控制基底上纳米粒子的密度。用扫描电子显微镜(SEM)对基底表面上的形貌进行表征,结果表明纳米粒子呈亚单层二维阵列分布。以吡啶(Py)为探针分子,用波长为632.8 nm的激发光作为激发光源,研究纯金和金铂复合基底上的表面增强拉曼光谱(SERS)行为。数据显示在金纳米粒子之间引入金核铂壳纳米粒子后,Py的两个特征峰的频率没有明显变化,但谱峰的强度却变弱了,其SERS信号衰减最大可至原来的24%。这是由于引入的铂的d态电子使金的等离子体激发猝灭,从而破坏了电磁场增强,使金的SERS信号衰减。     

Luminescence of Nile red as indicator of composition of nanoparticles from diketonate complexes of trivalent metals

We study the sensitization of fluorescence of Nile red in nanoparticles formed in aqueous solutions of complexes of Al, In, Sc, and Lu with DBM, DBM, and phen and of complexes of In with MBTA and phen. We show that, at concentrations of Nile red of 2–50 nM and complexes of 10–30 μM, the fluorescence intensity of Nile red in aqueous solutions increases by 1.5–2 orders of magnitude compared to its fluorescence in H₂O. We find that, at these concentrations of Nile red in solutions of complexes Al, the dye is completely contained in nanoparticles from these complexes. We show that Nile red molecules are inhomogeneously distributed in nanoparticles from complexes and, upon the completion of the formation of nanoparticles, dye molecules tend to be localized in regions of nanoparticles formed from diketonate complexes M(diketone)₃phen (M is Lu or In) and Al(DBM)₃. Upon the localization of Nile red in these regions, the maximum of its fluorescence spectrum shifts toward ∼600 nm and, upon the penetration of Nile red into nanoparticles from Sc complexes, the shift of the maximum of its fluorescence spectrum compared to the spectrum in water does not exceed 10 nm. The shifts of the spectra are collated with the ability of ions to form diketonate and hydroxy diketonate complexes. We demonstrate that the fluorescence of Nile red is efficiently sensitized, not only upon its penetration into nanoparticles formed from complexes, but also upon its adsorption on the nanoparticle surface when Nile red molecules are introduced in solutions of already formed nanoparticles.     

Spectral narrowing and lasing threshold in self-assembled active photonic crystal

Laser-induced emission from rhodamine-B dye embedded in pseudo band gap opaline photonic crystals is discussed. The photonic crystals are fabricated using rhodamine-B doped polystyrene colloids and show 65% reflectance at the stop band centered at 604 nm. The reflectance of the crystal is increased to 74% by coating with a thin layer of gold. Both spontaneous and stimulated emissions of the dye are observed in the photonic stop band environment by exciting the crystal with the second harmonic (532 nm) of a Q-switched Nd:YAG laser. The thin layer of gold functioned as a high reflecting end mirror to the dye-doped cavity when the crystal is pumped from the substrate side. Angle-dependent suppression at the stop band wavelength is observed in the spontaneous emission of the dye. Spectrally narrow stimulated emission and lasing is achieved in the gold coated dyed PhC at a threshold pump power of 60 mW in a selective direction of 22° from the direction of excitation. By studying emission from several photonic crystals with different number of layers, it is concluded that a sharp threshold for lasing is not observed in uncoated photonic crystals when they contained fewer than 30 ordered layers and lesser than 70% reflectance.     

金纳米粒子掺杂DNA-CTMA-DPFP薄膜的表面增强拉曼散射特性

采用柠檬酸三钠还原氯金酸和离子交换法制备金纳米粒子掺杂DNA-CTMA材料,利用钯催化反应合成9,9-二乙基-2,7-二-(4-吡啶)芴荧光染料(DPFP),将DPFP与DNA-CTMA混合后,旋凃制备金纳米粒子掺杂的DNA-CTMA-DPFP薄膜样品。通过吸收光谱、荧光光谱和拉曼光谱的测量,研究了薄膜样品的光学特性和表面增强拉曼散射(SERS)特性。实验结果表明,薄膜样品在300～360 nm的吸收主要来自DPFP,在500～700 nm的吸收来自样品中金纳米粒子的局域表面等离子共振;样品在370,386,408 nm处的荧光峰分别对应DPFP的S₁₀-S₀₀、S₁₀-S₀₁和S₁₀-S₀₂能级的电子振动跃迁;在785 nm激光激发下,薄膜样品的拉曼散射主要来自DPFP分子,随着金纳米粒子掺杂比的增大,DPFP分子的拉曼散射峰强度逐渐增强。因此,金纳米粒子掺杂DNA-CTMA薄膜适合作为多种染料分子的SERS基底。     

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     

Metal-Enhanced Fluorescence from Gold Surfaces: Angular Dependent Emission

The first observation of Metal-Enhanced Fluorescence (MEF) from large gold colloids is presented. Gold colloids, 40 and 200 nm diameter, were deposited onto glass substrates in a homogeneous fashion. The angular-dependent fluorescence emission of FITC-HSA, adsorbed onto gold colloids, was measured on a rotating stage which was used to evaluate MEF at all spatial angles. The emission intensity of FITC-HSA was found to be up to 2.5-fold brighter than the emission on bare glass substrates at an angle of 270 degrees. This is explained by the Radiating Plasmon Model, whereby the combined system, composed of the fluorophore and the metal colloids, emits with the photophysical characteristics of the fluorophore, after the excitation and the partial radiationless energy transfer between the excited states of the fluorophore and the surface plasmons of the gold colloids. The fluorescence enhancement was found to be higher with 200 nm gold colloids as compared to 40 nm colloids due to the increased contribution of the scattering portion of the 200 nm gold colloid extinction spectrum. These observations suggest that gold colloids could be used in MEF applications, offering more stable surfaces than the commonly used silvered surfaces, for applications requiring longer term storage and use.     

SERS studies of isolated and agglomerated gold nanoparticles functionalized with a dicarboxybipyridine‐trimercaptotriazine‐ruthenium dye

A dicarboxybipyridine‐trimercaptotriazine ruthenium complex, primarily designed for dye solar cells, has been successfully employed for generating electrostatically stabilized gold colloids, because of its high negative charge and capability of binding to gold nanoparticles via the sulfur groups. Surprisingly, a strong surface‐enhanced Raman scattering enhancement has been observed for the isolated nanoparticles, exceeding those recorded after inducing agglomeration. Such unusual response has been ascribed to the predominant contribution of the charge‐transfer and resonance Raman mechanisms, more than compensating for the lack of the local hot spots, in relation to the agglomerated systems. Copyright © 2014 John Wiley & Sons, Ltd.     

纳米银组装结构上罗丹明B的表面增强荧光效应

采用表面自组装技术,在玻璃表面构筑银纳米粒子的二维组装结构。银纳米粒子组装结构的表面等离子共振光谱中偶极子表面等离子体共振对组装结构更为敏感而表现出较大位移。组装银纳米粒子可极大增强罗丹明B的荧光。荧光的表面增强效应主要来自银纳米粒子对荧光分子所处区域的局部电磁场增强,银纳米粒子的表面分子修饰对其表面增强效应有较大的影响。     

Nonlinear Excitation of Tryptophan Emission Enhanced by Silver Nanoparticles

We measured and analyzed the behavior of the fluorescence of tryptophan water solutions with and without silver nanoparticles, excited by one, two and three photon processes. Two different colloids with silver nanoparticles with distinct diameters (0.65 nm and 9 nm) were used in the experiments. Fluorescence quenching was observed with one and two photon excitation. However, upon three-photon excitation, significant fluorescence enhancement was observed in the colloid. In this case excitation of the amino acid is assisted by the nonlinear absorption of infrared light by the silver nanoparticles. In this paper we are proposing a new way to explore metallic nanoparticles to enhance autofluorescence of biomolecules.     

Near-infrared surface-enhanced Raman spectroscopy of chemisorbed compounds on gold colloids

Near-infrared surface-enhanced Raman scattering (SERS) spectra have been measured for strongly chemisorbed compounds, such as 4-mercaptopyridine and thiophenol, on gold colloids in mixed solvents of ethanol and water using a diode laser as an excitation source. From UV-vis spectroscopy, the aggregated gold colloids show a broad absorbance band through the visible to the near-infrared after adding chemisorbing compounds. The absorption maximum is located in the range 750–850 nm, permitting the use of a near-IR source (826 nm) for the first time in SERS of gold colloid systems. The estimated enhancement is on the order of 10⁵. Transmission electron microscopy of aggregated gold particles revealed a cluster morphology. The aggregated mixed-solvent colloids were more stable than those prepared in water, and were useful in dissolving compounds with poor water solubility.     

Nanostructures of gold coated iron core-shell nanoparticles and the nanobands assembled under magnetic field

Pure metal iron nanoparticles are unstable in the air. By a coating iron on nanoparticle surface with a stable noble metal, these air-stable nanoparticles are protected from the oxidation and retain most of the favorable magnetic properties, which possess the potential application in high density memory device by forming self-assembling nanoarrays. Gold-coated iron core-shell structure nanoparticles (Fe/Au) synthesized using reverse micelles were characterized by transmission electron microscopy (TEM). The average nanoparticle size of the core-shell structure is about 8 nm, with about 6 nm diameter core and 1∼2 nm shell. Since the gold shell is not epitaxial growth related to the iron core, the morié pattern can be seen from the overlapping of iron core and gold shell. However, the gold shell lattice can be seen by changing the defocus of TEM. An energy dispersive X-ray spectrum (EDS) also shows the nanoparticles are air-stable. The magnetic measurement of the nanoparticles also proved successful synthesis of gold coated iron core-shell structure. The nanoparticles were then assembled under 0.5 T magnetic field and formed parallel nanobands with about 10 μm long. Assembling two dimensional ordered nanoarrays are still under going. Received 29 November 2000     

Size effects on the magnetic and optical properties of CuO nanoparticles

Optical and magnetic studies on CuO nanoparticles prepared by a chemical route are reported and the effect of size variation on these properties is discussed. SEM images show that the nanoparticles are interlinked into microspheres with the cages containing visible nanoscale holes. Diffuse reflectance spectroscopy indicates a consistent red shift in the fundamental band gap (indirect band gap) from 1.23 to 1 eV as the size decreases from 29 to 11 nm. This observed red shift is attributed to the presence of defect states within the band gap. A clear blue shift is observed in the direct band gap of these nanoparticles presumably due to the quantum confinement effects. Air-annealed samples show a paramagnetic response whereas particles annealed in a reducing atmosphere show additionally a weak ferromagnetic component at room temperature. For both types of particles, the paramagnetic and ferromagnetic moments, respectively, increase with decreasing size. The role of oxygen vacancies is understood to relate to the generation of free carriers mediating ferromagnetism between Cu spins. AC susceptibility measurements show both the antiferromagnetic transitions of CuO including the one at 231 K which is associated with the onset of the spiral antiferromagnetic phase transition.     

银纳米颗粒对胆固醇荧光的增强效用研究

在传统荧光光谱技术的基础上,结合金属纳米颗粒的增强荧光技术,探索提高荧光光谱技术检测人全血溶液中胆固醇含量的精度和分辨率的方法。实验研究方面,采用波长为407 nm的激光作为激发光,照射加入一定量银纳米颗粒作为荧光增强剂的人全血溶液,研究了银纳米颗粒对人全血溶液在可见光波段的荧光增强作用。结果表明,胶体状态的银纳米颗粒可以显著增强低浓度的人全血溶液荧光光谱的强度,且不同位置荧光发射峰的荧光增强效率随银胶加入量的增加均呈现先增后减的趋势,但不同峰位置的最强增强效率对应的银胶加入量不同。理论分析方面,根据实验结果及胆固醇分子和银纳米颗粒在溶液中的分布情况,建立了分子间距模型,并根据模型计算得出胆固醇分子和银纳米粒子之间的最佳增强荧光效果间距在12.19～25 nm范围内,这个结果和其他文献中的理论值吻合较好。综上所述,使用银纳米颗粒可实现全血溶液荧光的增强,研究结果为提高检测血液中多种物质的灵敏度和精度提供了有价值的参考作用。     

Surface Plasmon Resonance and Field Enhancement of Au/Ag Alloyed Hollow Nanoshells

We investigate the nanostructure, surface plasmon resonance （SPR） absorption and nonlinear enhancement of Au/Ag alloyed hollow nanoshells prepared by the replacement reaction of Ag nanoparticles in a HAuCI4 aqueous solution. As the volume of HAuCl4 increases from OmL to 0.S mL, the SPR band of the Au/Ag alloyed nanoshells is tuned from 430nm to 780nm, and the third-order nonlinear optical susceptibility is enhanced nearly by an order of magnitude, which indicates a large enhancement of local field in the Au/Ag alloyed hollow nanoshells with hole defects.     

银粒子的表面修饰及荧光表面增强效应

采用表面化学修饰制备了Ag-SiO2核-壳纳米粒子,发现SiO2包裹壳层形状随其厚度而改变,包裹初期SiO2壳层依托银核的形状生长,随着壳层厚度增加则趋于热力学稳定的球状。银纳米粒子的表面等离子体共振可由SiO2包裹壳层厚度调变,银核吸收谱峰随壳层厚度增大而红移。Ag-SiO2核-壳纳米粒子可极大增强罗丹明6G的荧光强度,且表面增强效应与壳层的厚度密切相关。