不同构型罗丹明分子拉曼光谱的密度泛函理论研究

利用密度泛函理论研究了罗丹明6G、罗丹明123和罗丹明B分子的拉曼光谱. BP86泛函计算的罗丹明系列分子的阳离子在气相中的拉曼光谱与相应的分子在水溶液中的实验光谱符合很好. 结果显示氯离子以及氢键的引入对罗丹明B分子的拉曼光谱有较明显的影响,该影响可以部分地解释罗丹明B分子在水溶液中和在金表面上拉曼光谱的不同. 精确描述罗丹明分子在金属表面的表面增强拉曼光谱,需要考虑由界面相互作用而导致的变化.     

Formation and destruction of polyelectrolyte microcapsules modified by rhodamine 6G

Polyelectrolyte capsules with Rhodamine 6G molecules included into the shell are obtained in this work. The inclusion of dye molecules into the shell can provide the destruction of capsules by photosensitization. Measurements of the dye fluorescence intensity in the shell show that the energy of photoexcited molecules is effectively dissipated by the surrounding organic matrix. The capsule suspension is laser irradiated in the absorption band of Rhodamine 6G molecules. Measurements of the size distribution of capsules before and after laser irradiation reveal that the capsules are destroyed by laser illumination.     

Nanofiltering via integrated liquid core waveguides

We demonstrate and describe how nanoporous liquid core waveguides can exclude scattering particles, making them an ideal integrated platform for analysis of turbid solutions. Milk with 0.5% fat showed an optical propagation loss of 0.05?dB/mm at 633?nm in nanoporous waveguides compared to the 10.6?dB/mm loss in standard cuvette measurements. To examine the nanofiltering effect, waveguides were infiltrated with solutions containing Rhodamine B molecules (1?nm) and 22?nm red fluorescing polystyrene beads. With fluorescence spectroscopy we show that 22?nm beads are excluded, while Rhodamine B molecules penetrate the waveguides. This is further confirmed by fluorescence microscopy, also revealing a homogenous distribution of Rhodamine in the waveguide volume.     

Rhodamine B-Coated Gold Nanoparticles as Effective “Turn-on” Fluorescent Sensors for Detection of Zinc II Ions in Water

We designed a fluorescence resonance energy transfer system consisting of fluorophore Rhodamine B and gold nanoparticles for sensing of zinc ions in aqueous solution. The electrostatic attraction between positively charged N-atoms in Rhodamine molecules and negatively charged citrate corona of gold nanoparticles led to substantial fluorescence quenching. However, the quenching is switched off in the presence of zinc ions and therefore the system can be used as an effective “turn-on” fluorescence sensor. UV-Vis absorption, fluorescence spectroscopy, and transmission electron microscopy were used for sensor evaluation. The approach of “turn-on” fluorescence has real potential for sensing metallic ions in water.     

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。     

荧光法研究几种分子在海藻酸钙空心胶囊中的缓释性能

实验中选取了带有正电罗丹明6G分子、带有负电荷荧光素分子、中性的尼罗红分子和生物分子R-藻红蛋白为模型分子.将这几种分子分别包封于海藻酸钙窄心胶囊中.实验表明囊芯分子的电性对其在海藻酸钙空心胶囊中缓释性能有影响,带有正电荷罗丹明6G分子的扩散过程中,多孔聚合物骨架扩散是主要过程.中性分子则表现出来一个膜相溶出和多孔聚合物骨架扩散共同控制的过程.带有负电荷荧光素分子,由于静电排斥作用,加剧囊芯分子的运动.从而使得荧光素分子可以直接从膜相溶出.此外.南于胶囊囊壁上带有负电,不论是带有正电荷还足带有负电荷的分子都会延长其达到扩散平衡的时间.而电中性分子由于没有库仑相互作用的影响更容易达到平衡.囊芯和囊辟相互作用强的其扩散系数小,反之其扩散系数大.R-藻红蛋白的扩散完全是一个多孔聚合物骨架扩散控制的过程.由于分子的体积比较大,因此扩散的平衡时间也比较长.     

Optical properties of Rhodamine B and Rhodamine 6G on silver surfaces

The transmission spectra of Rhodamine B and Rhodamine 6G dyes coated on silver island films for various thickness were recorded. A strong coupling between the silver particle plasma resonance and the dye molecules is observed. The absorption of dye molecules increases when the absorption band of individual dyes and silver particles overlaps. In higher silver film thicknesses, transmission increases. The theoretical calculation using Maxwell-Garnett theory and Wang and Kerker’s results qualitatively supports the observed phenomenon. A red shift in the absorption peak of dyes on silver surfaces in comparison to solution phase absorption peak indicates photobleaching.     

ZnS∶Cu-罗丹明B的荧光共振能量转移性质

为了解决现有的基于量子点荧光共振能量转移体系的生物毒性问题,选用无毒的ZnS∶Cu量子点与罗丹明B构建新型荧光共振能量转移体系。通过共沉淀法成功制备了形貌均一的ZnS∶Cu纳米晶量子点。在此基础上,测试了不同掺杂浓度的ZnS∶Cu量子点及罗丹明B的荧光光谱。然后,通过对ZnS∶Cu量子点的表面修饰构建了以ZnS∶Cu量子点为供体、罗丹明B为受体的荧光共振能量转移体系。实验结果表明:ZnS∶2%Cu量子点的发光光谱与罗丹明B的吸收光谱在481 nm处有较大重合,说明构建荧光共振能量转移的最佳铜掺杂摩尔分数为2%。通过计算发现以ZnS∶2%Cu量子点为供体、罗丹明B为受体的荧光共振能量转移体系的能量转移效率为25.8%。进一步实验结果表明,罗丹明B浓度也能够影响能量转移。     

Integral fluorescence enhancement by silver nanoparticles controlled via PMMA matrix

The metal-enhanced fluorescence is measured with different thickness of emission film. Silver nanoparticles are immobilized on glass slide by chemical self-assembly method. Rhodamine B molecules are dispersed in the polymer matrix of Poly(methyl methacrylate) (PMMA), then spin coated on prepared silver particles substrate with different thickness from 15 nm to 70 nm. The enhanced fluorescence is observed depending on the thickness of emission film since the average distance between rhodamine B molecules and silver nanoparticles is altered by the PMMA matrix. The 5-fold enhancement is attained. The experiment was explained qualitatively by an integral fluorescence enhancement.     

有机分子隔离层对机械抛光金属银表面的罗丹明6G荧光增强效应的影响

采用物理吸附法,在机械抛光纯银表面引入对巯基苯胺(p-Amiothiophenol,PATP)分子充当隔离层,运用激光光谱学方法研究隔离层对位于银表面附近的罗丹明6G(Rh6G)分子的荧光增强效应影响。实验结果表明,未经PATP分子修饰的机械抛光金属衬底对Rh6G分子表现为猝灭效应,而经过PATP分子修饰后的银表面对Rh6G分子的荧光发射具有增强效应。根据局域表面等离子共振及辐射能量转移模型对实验观测所得结果进行了分析研究,结果表明,PATP有机分子隔离层的引入有效地减小了荧光分子与金属衬底之间的无辐射能量速率,提高了荧光辐射强度。     

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.     

罗丹明B荧光增强苯受激拉曼散射研究

将液芯光纤技术与荧光增强受激拉曼散射技术相结合,能够大大增强受激拉曼散射光谱强度,降低受激拉曼散射阈值。通过对罗丹明B苯溶液在液芯光纤中的受激拉曼散射进行研究,结果表明:荧光染料Rhodamine B可以降低苯溶液的各阶受激拉曼散射阈值近一个数量级;在一定浓度范围内(10-6mol/L~10-8mol/L)各阶Stokes阈值随浓度降低而降低,并在理论上给出了解释。并且理论推导了在荧光种子作用下的四阶耦合波方程。液芯光纤中的受激拉曼光谱技术在对实现宽带受激辐射激光器、种子激光,以及生物大分子结构研究、生物分子的非生物过程研究等领域等有光明应用前景。     

Near-field scanning optical microscopy of single molecules by femtosecond two-photon excitation

We present a demonstration of near-field scanning optical microscopy of single molecules based on ultrafast two-photon-induced fluorescence. Measurements were performed by use of 100-fs pulses at 800 nm from a Ti:sapphire laser to excite the two-photon transition in Rhodamine B molecules. Although near-field probes are normally metal coated to achieve superresolution, we used uncoated tips to achieve sufficiently high optical powers to generate acceptable fluorescence emission rates. Images of single molecules demonstrate a resolution of ~175nm(< lambda/4) on a topographically smooth surface, which surpasses the apparent lambda/2 resolution limit for uncoated tips operating in the linear response regime.     

飞秒荧光亏蚀光谱技术研究液相体系取向弛豫

溶液中分子的快速弛豫过程直接反映了溶液中溶质和周围溶剂分子间的相互作用[1- 3 ] .在液相体系中分子取向通常是随机分布的 .当溶质分子被线偏振光激发至激发态时 ,其分子取向将由原来各向同性的球形分布瞬间变成各向异性的椭球分布 .由于溶质分子周围大量溶剂分子的存在 ,通过二者之间相互作用 ,激发态溶质分子在一定方向上的取向优势将很快弛豫掉 .这种溶液中的取向弛豫过程通常是几个到几百皮秒[1- 3 ] .飞秒分辨荧光亏蚀光谱原理和实验方法见文献[4 - 7] .当溶液中的溶质分子被线偏振飞秒激光脉冲激发至电子激发态时 ,经过一定的延迟…     

基于银纳米三角片与罗丹明6G的荧光共振能量转移法检测钴离子

以罗丹明6G和牛血清白蛋白的复合物为荧光探针,银纳米三角片为猝灭剂,研究了银纳米三角片与荧光复合物的荧光共振能量转移现象,建立了测定钴离子的荧光分析法。研究发现,一定浓度的荧光复合物与银纳米三角片混合后,由于荧光复合物在银纳米三角片上吸附而发生荧光共振能量转移,荧光猝灭达到80%左右。当钴离子存在时,银纳米三角片与罗丹明6G荧光共振能量转移被破坏,荧光逐渐恢复。随着钴离子浓度的增加,体系荧光值的恢复率(I/I₀)与钴离子的浓度(c_Co2+)有良好的线性关系,线性回归方程为I/I₀=1.054+21.72 c_Co2+,相关系数r2为0.996 2。通过对自然水样进行加标回收检测,实现了钴离子的定量检测,回收率在90.4%～115.1%之间。建立了一种可靠的选择性检测钴离子的荧光分析方法。     

Energy transfer between fluorescent dyes in photonic crystals

Energy transfer from fluorescein (Fl) to Rhodamine B (RhB) in the opal photonic crystals has been investigated by photoluminescence. The results show that the energy transfer can be enhanced effectively by photonic bandgaps. When the fluorescence emission wavelength of donor Fl overlaps the photonic bandgap the fluorescence intensity of the donor is suppressed, while the fluorescence intensity of acceptor RhB is obviously enhanced. This enhancement can be attributed to the inhibition of radiative emission of the donor in the photonic crystals.     

Development of temporal spectroscopic properties for Xerogel matrices doped with Rhodamine 6G dye

The solid host of a laser dye modifies its spectroscopic properties with respect to its liquid host. During the Sol-Gel process the dye molecules suffer from changing their environment. Two parameters affect this matter, the change in the concentration due to the evaporation of the solvent (drying) and the caging of dye molecules inside the pores or attachment to the silica network. Rhodamine 6G absorption and fluorescence spectra with different concentrations, during Sol-Gel time processing, have been studied. Both, absorption and fluorescence spectra of the dye in the solid host, for different concentrations, show a blue-shift relative to its liquid phase.     

Spectral-Luminescent Properties of Deposited Rhodamine 6G Films

We have investigated the absorption and fluorescence spectra of Rhodamine 6G thin (20–100 nm) films vacuum-deposited on solid dielectric substrates: quartz and borosilicate glasses and polymer films. By the absorption spectra several molecular absorption centers — monomers, dimers, and complex associates — have been revealed. For the first time luminescence of vacuum-deposited Rhodamine 6G films has been obtained and investigated. We classified it as fluorescence of plane dimers and dimers of the house-of-cards type and also as luminescence of complex associates. The dependence of the spectral composition of the films on the excitation wavelength in the 293–353 K temperature range has been studied. It has been proposed that amorphous Rhodamine 6G films obtained by the vacuum deposition method contain crystalline zones and microclusters of adsorbed water molecules.     

First Observation of Surface Plasmon-Coupled Emission Due to LED Excitation

Detection limitations for fluorescence methods are normally determined by the phenomenon itself rather than the sensitivity of the instrumentation. These limitations make it necessary to have high sensitivity, high cost equipment causing fluorescence methods to remain lab-oriented. Alleviation of the limitations can be achieved through the phenomenon of surface plasmon-coupled emission (SPCE), which displays enhanced, directional, polarized fluorescence. Here we present the excitation of SPCE from Rhodamine B with a light-emitting diode (LED). Incorporating the gains in sensitivity due to SPCE with LED excitation, it could be possible to design low-cost, high-sensitivity sensors that would allow measurements to be performed in the field.     

Fluorescence properties of the dye-intercalated smectite

The fluorescence properties of the dye Rhodamine 590 and Rhodamine 640 intercalated into montmorillonite were studied. All of the intercalation reactions were accomplished in an ethanol solution which contained the corresponding quality of Rhodamine. The TG-DTA and the X-ray diffraction data showed that the immobilization of Rhodamine depended on the amount of ethanol incorporated in the interlayer space of montmorillonite. The 14.8 Å basal spacing of products indicated a conformation of Rhodamine with the xanthene nucleus and the phenyl group positioned parallel and perpendicular to the silicate layer, respectively. Also, the infrared pleochromism, which supported the proposed orientation of the phenyl group, was observed at 1250 and 712 cm⁻¹. The main fluorescence bands of both products were observed near 600 nm when excited by the 514.5 nm line of an argon ion laser. The results indicated that the mesomeric structure determined the fluorescence behavior, which was little different for the two products owing to the environment of the interlayer. These data are briefly discussed relative to the reaction conditions utilized for the synthesis of products. Also, the results support the idea that the products have a high potential for use as a host for a tunable laser.