On anti-stokes luminescence from Rhodamine 6G in ethanol solutions

Anti-Stokes luminescence form Rhodamine 6G ethanol solutions excited by a He-Ne laser is observed to be strongly temperature dependent. A theoretical model is proposed for the absorption line shape on the long wavelength side of the pure electronic transition which fits the absorption and luminescence data. Vavilov's law is found to hold even when the absorption coefficient is 10^-6 times the peak absorption coefficient for the Rhodamine 6G dye solution. Another luminescence peak at 6650 Å is observed which is attributed to impurity fluorescence. It could not be related to photochemical products.     

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。     

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.     

Passive mode-locking of flashlamp pumped Rhodamine dye-lasers

A simple dye-laser system is described in which Rhodamine dyes are pumped by a co-axial linear air flashlamp in a cylindrical elliptical pumping reflector. Output pulses lasting up to 1.5sec and containing up to 250 mJ energy, have been successfully mode-locked to produce 100% modulated pulse trains. Employing a diffraction grating as cavity reflector to tune the laser frequency, in each case, for maximum absorption by the same Q-switching dye, successful mode-locking has been achieved with both Rhodamine B and Rhodamine 6G. Time resolved emission spectra have been recorded with an image tube streak camera and the effect of resonant reflectors has been studied.This work was described in a paper presented at the IEEE Conference on Laser Engineering and Applications, Washington, May 1969.     

Protein adsorption drastically reduces surface‐enhanced Raman signal of dye molecules

There is an increasing interest in developing surface enhancement Raman spectroscopy methods for intracellular biomolecule and for in vitro protein detection that involve dye or protein–dye conjugates. In this work, we have demonstrated that protein adsorption on silver nanoparticle (AgNP) can significantly attenuate the surface‐enhanced Raman spectroscopy (SERS) signal of dye molecules in both protein/dye mixtures and protein/dye conjugates. SERS spectra of 12 protein/dye mixtures were acquired using 4 proteins [bovine serum albumin (BSA), lysozyme, trypsin, and concanavalin A] and three dyes [Rhodamine 6G, adenine, and fluorescein isothiocyanate (FITC)]. Besides the protein/dye mixtures, spectra were also obtained for the free dyes and four FITC‐conjugated proteins. While no SERS signal was observed in protein/FITC mixtures or conjugates, a significantly reduced SERS intensity (up to 3 orders of magnitude) was observed for both R6G and adenine in their respective protein mixtures. Quantitative estimation of the number of dye molecules absorbed onto AgNP implied that the degree of R6G SERS signal reduction in the R6G/BSA sample is 2 to 3 orders of magnitude higher than what could be accounted for by the difference in the amount of the absorbed dyes. This finding has significant implications for both intracellular SERS analyses and in vitro protein detection using SERS tagging strategies that rely on Raman dyes as reporter molecules. Copyright © 2009 John Wiley & Sons, Ltd.     

Spectroscopic and lasing properties of Xanthene dyes encapsulated in silica and polymeric matrices

The photo-physical properties of Xanthene dyes: Basic Rhodamine Yellow (BRY), Rhodamine590perchlorate (R590p), SulforhodamineB (SRB) doped in tetramethylorthosilicate (TMOS) and poly-methylmethacrylate (PMMA) are observed. The various parameters viz. full-width at half-maxima (FWHM), peak emission wavelength, quantum yield and excited state lifetime at different concentrations ranging from ∼0.05 to ∼1 mM of the dye under excitation by Copper Vapor Laser (CVL) of high repetition rate (∼5.6 kHz) of are investigated. In order to identify photostability in dyes, normalized photostability has been studied and found that silica gel samples containing dye are more stable than that of polymeric samples. This has been further understood in terms of number density of unbleached dye molecules that infers that photobleaching of dye molecules is not prominent at higher concentrations in glassy solid matrices. Pump intensity dependent optical gain of the samples has also been reported and efforts have been made to study the efficiency of solid-state laser samples in a cavity for the performance of the dye laser.     

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.     

罗丹明101染料的光谱特性研究

观测了罗丹明101染料在甲醇和酸性甲醇溶液巾的稳态吸收、稳态荧光和时间分辨荧光光谱,得到了吸收与荧光光谱的特征信息以及荧光寿命;通过拉曼光谱、红外光谱和密度泛函理论计算,对罗丹明101染料分子的振动模式进行了指认.研究结果全面系统地表征了罗丹明101染料的光谱特征以及分子结构和振动信息,为罗丹明101染料在染料敏化太阳能电池和生物荧光标记等方面的应用研究提供了依据.     

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-Kinetic Properties of Laser Dyes in Active Elements on the Basis of Sol-Gel Matrices

The absorption and photoluminescence spectra as well as the photoluminescence lifetimes of laser dyes (Phenylamine 430, Rhodamine 6G, Rhodamine 6G zwitterion, Rhodamine 4C, and Rhodamine 101) in new matrices are studied. These matrices represent the hybrid of two types of porous glasses (microporous and sol-gel glass). Chemical transformations of the dye molecules in the matrices are not found. The dye dimers mentioned above are also absent for concentrations up to 10^-4 M. The luminescence efficiencies of the dyes in the matrix and in the ethanol solutions are compared. The difference in concentration dependences of the photoluminescence spectrum of Rhodamine 6G in the matrix and ethanol solution is found and discussed. The collective emission of the dyes in new matrices is observed at a power density of exciting radiation of 10²⁵ cm^-2s^-1 and a concentration of 10^-4 M. The energies and collective emission spectra of the dyes in the matrix are compared with those in the solutions.     

Transient excited singlet state absorption in Rhodamine 6G

Transient excited singlet state absorption (ESSA) has been studied in Rhodamine 6G in ethanol using a nitrogen laser and nitrogen laser-pumped dye laser. Broad absorption with several submaxima and possible shoulders, which represent the vibrational structure, has been observed in Rhodamine 6G in the region, 4175–4640 Å. The position of the lowest vibrational level of the first excited singlet stateS ₁ has been determined from the crossing point of the long and short wavelength spectral wings of absorption and fluorescence respectively. The energy level scheme of the molecule has been obtained with the help of the absorption and fluorescence spectra recorded. The observed structure in ESSA has been tentatively interpreted to be due to transitions from the different vibrational levels ofS ₁ to one or more vibrational levels of the upper singlet electronic stateS ₄.     

Spectral–Luminescent and Generation Characteristics of a Gel–Like Gelatin Doped with a Dye

We present the results of comparative measurements of spectral–luminescent characteristics of Rhodamine 6G and Rhodamine C in water and water–gelatin solutions. We found that gelatin added to a water solution disaggregates the molecules of the dye. The maxima of the absorption and luminescence spectra of the solution shift then to the longwave region. The quantum yield of luminescence and the efficiency of generation of the solutions investigated are measured. The generation intensity of the gel is shown to depend on its composition and the dye selected. Measurement of spectral–luminescent characteristics of water–gelatin solutions makes it possible to select dyes that would generate most efficiently in gel solutions.     

Cucurbit[7]uril Disrupts Aggregate Formation Between Rhodamine B Dyes Covalently Attached to Glass Substrates

Dye aggregation is detrimental to the performance of high optical density dye-doped photonic materials. To overcome this challenge, the ability of cucurbit[7]uril (CB7) as a molecular host to disrupt aggregate formation on glass substrates was examined. Rhodamine B was covalently attached to glass slides by initially coating the surface with azidohexylsiloxane followed by copper-catalyzed “click” triazole formation with rhodamine B propargyl ester. The absorption and emission spectra of rhodamine B coated slides in water indicated diverse heterogeneous properties as surface dye density varied. Fluorescence quenching due to dye aggregation was evident at high surface dye density. Addition of aqueous cucurbit[7]uril (CB7) to the surface-tethered dyes perturbed the spectra to reveal a considerable reduction in heterogeneity, which suggested that the presence of a surface in close proximity does not significantly impair CB7’s ability to complex with tethered rhodamine B.     

Two Photon Spectroscopy Can Serve as a Marker of Protein Denaturation Pathway

Rhodamine group of molecules are widely used dyes for imaging of biological molecules. Application of these dyes however includes a limitation that these molecules absorb in the visible range of the spectrum, which does not fall in the ‘biologically transparent window’ (BTW). Two photon absorption (TPA) process could come up with an alternate solution to this as these dyes could be excited in the near infrared (NIR) window to extract similar information. To validate this we have investigated TPA cross section (TPACS, σ₂) of two rhodamine dyes, namely Rhodamine 6G (R6G), Rhodamine B (RhB), site selectively bound with a model protein, bovine serum albumin (BSA), by exciting at 800 nm. Two photon spectroscopy and imaging confirms the binding of the dye to the protein. The decreases in TPACS with increasing temperature at a fixed BSA concentration excellently follows the temperature induced structural transition of BSA as the protein transforms from a molten globule to unfolded conformation beyond 60 °C, which has previously been established through circular dichroism (CD) measurements. The thus established resemblance in TPACS and CD measurement trends thus strongly affirms the suitability of TPA process in protein imaging and as an alternative marker to tracking its conformational transformations using NIR radiation.     

A combined theoretical and experimental study of the ultrafast photophysics of Rhodamine B

The ultrafast dynamics of zwitterionic and cationic Rhodamine B in ethanol have been investigated using TDDFT calculations and ultrafast transient absorption spectroscopy. The calculations show that the zwitterionic form exhibits an electronically excited dark state which could potentially quench the initially photoexcited state, while in the case of cationic form the lowest excited lying dark state is outside the energy region of interest and cannot explain its quenching. Due to similarities in the relaxation dynamics of the two molecules, it is suggested that the electronically excited dark state may not play such an important role in the quenching process of this dye as previously proposed. Experimental evidence presented suggests that a quenching mechanism is active on the picosecond timescale for both forms of Rhodamine B.     

Silver nanoparticle size–dependent measurement of quantum efficiency of Rhodamine 6G

The plasmonic absorption band of silver nanoparticles in the visible range of electromagnetic spectrum has been successfully exploited to alter the emission characteristics of the Rhodamine 6G dye molecule. The influence of the nanoparticle size on the fluorescence quantum yield of Rhodamine 6G is interrogated via steady state fluorescence as well as dual beam thermal lens technique. The potential of the thermal lens technique that probe nonradiative path in contrast to radiative path exhibited in the fluorescence spectra as a complementary method to measure the quantum yield of a dye molecule is exploited. Analysis of the results clearly indicates that the particle size and the spectral overlap between the emission spectra of Rhodamine 6G, and absorption spectra of the silver nanoparticles determine the quantum yield value of dye–nanoparticle mixture.     

Photo-physical properties and quantum yield of some laser dyes in new polymer host

The field of laser dyes-active solid polymer materials is a promising field and quite competitive with liquid dye lasers. This paper investigates some photo-physical parameters of pyromethene (PM-567, PM-597) and Rhodamine B dyes incorporated into glycidyl methacrylate (GMA) promising polymeric host matrix. These parameters are: absorption and emission cross-sections, fluorescence lifetime and quantum yield, in addition to FT-Raman spectra as an indication for binding the dye molecules with the backbones of GMA polymeric chain.     

Pinacyanol as a mode-locking saturable absorber for Rhodamine dye lasers

The absorption recovery time of the ground state of pinacyanol (S₁ → S₀) can be varied through the choice of solvent from 10 ps in methanol to 300 ps in glycerol. We show that mode-locking of Rhodamine 6G and Rhodamine B dye lasers can be achieved using methanol, DMSO or glycerol solutions.     

A non-mixing technique for enhancement of the tuning range of Rhodamine 6G using Rhodamine B

An optical scheme for extension of spectral tuning range of Rhodamine 6G by Rhodamine B is reported. The dye solutions are kept separately in a specially designed coupled resonator. The tuning range of Rhodamine 6G dye laser is extended from 564–609 to 564–645 nm.     

胶束中的若丹明6G荧光增强和激光行为

使用阴离子表面活性剂十二烷基硫酸钠 (SDS)有效的增强了若丹明 6G染料水溶液的荧光 ,在若丹明 6G浓度分别为 5 47× 10 -7和 5 47× 10 -4 mol·L-1时 ,最大增强比率分别为 1 95和 9 7。在后一浓度下SDS的加入使若丹明 6G染料激光阈值降低 ,能量转化效率提高。不加SDS时的激光阈值功率密度约为 6 5MW·cm-2 ,加入 4 1× 10 -2 mol·L-1的SDS后 ,激光阈值功率密度降为 0 8MW·cm-2 。泵浦光功率密度为 6 5MW·cm-2 时 ,能量转化效率达到 2 5 %。同时还观察到SDS的加入使溶液吸收谱、荧光谱和染料激光发生了红移。对以上现象的物理机制进行了讨论。