Fluorescence and photodissociation of rhodamine 575 cations in a quadrupole ion trap

The fluorescence and photodissociation of rhodamine 575 cations confined to a quadrupole ion trap are observed during laser irradiation at 488 nm. The kinetics of photodissociation is measured by time-dependent mass spectra and time-dependent fluorescence. The rhodamine ion signal and fluorescence decay are studied as functions of buffer gas pressure, laser fluence, and irradiation time. The decay rates of the ions in the mass spectra agree with decay rates of the fluorescence. Some of the fragment ions also fluoresce and further dissociate. The photodissociation rate is found to depend on the incident laser fluence and buffer gas pressure. The implications of rapid absorption/fluorescence cycling for photodissociation of dye-labeled biomolecular ions under continuous irradiation are discussed.     

Triangular Rhodamine Triads and Their Intrinsic Photophysics Revealed from Gas-Phase Ion Fluorescence Experiments

When ionic dyes are close together, the internal Coulomb interaction may affect their photophysics and the energy-transfer efficiency. To explore this, we have prepared triangular architectures of three rhodamines connected to a central triethynylbenzene unit (1,3,5-tris(buta-1,3-diyn-1-yl)benzene) based on acetylenic coupling reactions and measured fluorescence spectra of the isolated, triply charged ions in vacuo. We find from comparisons with previously reported monomer and dimer spectra that while polarization of the π-system causes redshifted emission, the separation between the rhodamines is too large for a Stark shift. This picture is supported by electrostatic calculations on model systems composed of three linear and polarizable ionic dyes in D_3h configuration: The electric field that each dye experiences from the other two is too small to induce a dipole moment, both in the ground and the excited state. In the case of heterotrimers that contain either two rhodamine 575 (R575) and one R640 or one R575 and two R640, emission is almost purely from R640 although the polarization of the π-system expectedly diminishes the dipole-dipole interaction.     

Study on the Catalytic Determination of Vanadium (V) Using the Rhodamine 6G-Periodate Redox Reaction and its Analytical Application

 A fluorescence quenching method for the determination of vanadium (V) based on the vanadium- catalyzed oxidation of rhodamine 6G (R6G) with periodate in the presence of ethylenediaminetetraacetic acid disodium salt (EDTA) in sulfuric acid medium is described. The fluorescence was measured with excitation and emission wavelengths of 525 and 555 nm, respectively. The calibration graph for vanadium (V) had linear ranges of 3.0 × 10⁻⁹–1.5 × 10⁻⁸ mol/l and 1.5 × 10⁻⁸–4.0 × 10⁻⁸ mol/l, respectively. The detection limit was 1.7 × 10⁻⁹ mol/l. The proposed method was successfully applied to the determination of vanadium (V) in river water, rain water and cast iron samples. Received June 29, 2001 Revision October 9, 2001     

Photodissociation and collisional cooling of rhodamine 575 cations in a quadrupole ion trap

The photodissociation of rhodamine 575 cations held in a quadrupole ion trap is studied using 514 nm light as a function of buffer gas pressure, irradiation time, and laser fluence. The laser-induced photodissociation decays of rhodamine ions have lifetimes on the order of seconds for the range of pressures and powers investigated and exhibit strong nonlinear pressure dependence. Dissociation mechanisms are considered that involve the sequential absorption of multiple photons and several collisional deactivation steps.     

新型双发色团染料荧光光谱及其寿命的研究

有效的染料激光操作需要较高的荧光量子效率,若丹明是在500~700 nm光谱区中一类最重要的激光染料.然而,染料的基态分子和三线态对辐射能量的吸收将会大大降低激光输出效率,再者,由于若丹明类染料在紫外区的吸收系数较小,为了有效吸收泵浦能量(如用XeCI准分子激光,308 nm),就必须使用高浓度染料溶液,在这种情况下,若丹明类染料较小的Stokes位移就势必造成基态分子更大的重复吸收,即造成更大的谐振腔损耗^[1].     

Hybrid Rhodamine Fluorophores in the Visible/NIR Region for Biological Imaging

Fluorophores and probes are invaluable for the visualization of the location and dynamics of gene expression, protein expression, and molecular interactions in complex living systems. Rhodamine dyes are often used as scaffolds in biological labeling and turn‐on fluorescence imaging. To date, their absorption and emission spectra have been expanded to cover the entire near‐infrared region (650–950 nm), which provides a more suitable optical window for monitoring biomolecular production, trafficking, and localization in real time. This review summarizes the development of rhodamine fluorophores since their discovery and provides strategies for modulating their absorption and emission spectra to generate specific bathochromic‐shifts. We also explain how larger Stokes shifts and dual‐emissions can be obtained from hybrid rhodamine dyes. These hybrid fluorophores can be classified into various categories based on structural features including the alkylation of amidogens, the substitution of the O atom of xanthene, and hybridization with other fluorophores.     

Spectroscopic studies of rhodamine 6G dispersed in polymethylcyanoacrylate

We report here electronic absorption, fluorescence and resonance Raman studies of rhodamine 6G laser dye dispersed in the polymethylcyanoacrylate matrix. In the electronic absorption and fluorescence spectra of dispersed rhodamine 6G, band maxima are red shifted compared to solution. Raman spectra show some new bands. These spectral changes arise due to matrix effect and interaction between rhodamine 6G and the host material involving amine group of rhodamine.     

Effect of poly-HEMA hydrophilic gel environment on the photo-physical behavior of rhodamine dyes

The absorption spectra of rhodamine B (RB) chloride, rhodamine 6G (R6G) tetrafluoroborate and rhodamine 6G chloride in poly-2-hydroxyethyl methacrylate hydrogel (PHEMA) matrix were studied using absorption spectroscopy in the visible region. The transport and aggregative properties of these ionic dyes in aqueous solution across the hydrophilic gel were also investigated. The similarities of absorption spectra of RB in aqueous solutions and in hydrogel host suggest that the hydrogel framework has a minor effect in their absorption spectra. In contrast, there is a relatively strong interaction or electrostatic forces between R6G dyes and the hydrogel matrix. The permeability of R6G chloride through hydrogel host is seen to be markedly higher than RB chloride and R6G tetrafluoroborate.     

Synthesis and characterization of structure optimized film doped with Rhodamine 6G

Amplified spontaneous emission (ASE) property of a red dye rhodamine 6 g (R6G) doped into a highly ordered mesoporous SBA-15 film and a planar waveguide poly (4-vinylphenol) (P4VP) film were studied and compared. Regular morphology and mesoporous structure have been evidenced from the photographs, TEM and Nitrogen adsorption–desorption characterizations. A narrower, higher peak was observed in emission spectra from the meso-structured SBA-15 film doping with R6G (R6G/SBA-15) compared with the photoluminescence (PL) spectrum that of R6G in C₂H₅OH (R6G/C₂H₅OH) solution, was abruptly narrowed down to a line-width of about 9.8 nm when pumping at an energy of 0.12 mJ pulse⁻¹, which indicates a favorable ASE property in R6G/SBA-15 film. Comparing the P4VP film spin-coating with R6G (R6G/P4VP), the R6G/SBA-15 film exhibited a much narrower and stronger emission spectrum when it is pumped by the 355 nm pulsed source at the same pumping energy, which means that the meso-structure of the SBA-15 film can optimize ASE property of the material. The threshold was easily obtained by R6G/SBA-15 film at 0.02 mJ pulse⁻¹, and it was lower than that of R6G/P4VP film. The optimized ASE property owes much to the effects of the better spatial confinement of the molecules in the ordered mesoporous structure of SBA-15 film.     

Coumarin Modified Rhodamine Derivative： Fluorescent Chemosensor Selectively Recognizing Al^3＋ and Ca^2＋

A fluorescent probe with a coumarin moiety bound to rhodamine 6G hydrazide（l） was synthesized. Its sensing behavior toward various metal ions was investigated with fluorescence methods. Compound I displays different fluorescence emission responses to Al^3＋ and Ca^2＋ at the same excitation wavelength in the visible light region, while no changes occur after the addition of other metal ions. The binding ratios of the complexs of 1-Al^3＋ and 1-Ca^2＋ are both 2：1 according to the Job plot and high resolution mass spectrometer（HRMS） experiments. Moreover, emission spectrum of 1-Ca^2＋ complex and absorption spectrum of the rbodamine dyes overlap largely. When Al^3＋ was added to the 1-Ca2＋ system, calcium in complex 1-Ca2＋ can be displaced by Al^3＋, resulting in the output of another ratiometric sensing signal, which demonstrates that the 1-Ca^2＋ complex can be served as a new and effective fluorescence resonance energy transfer（FRET） donor for rhodamine derivatives.     

Photoresponse and anisotropy of rhodamine dye intercalated in ordered clay layered films

In order to elaborate organized two-dimensional arrangements of fluorescent dyes in host solid layered materials, rhodamine 6G (R6G) is encapsulated in supported thin films of laponite (Lap) clay. Clay films are elaborated by the spin-coating technique and their surface morphology is analyzed by scanning electron (SEM) and atomic force (AFM) microscopies. The internal order of the stacked clay layers is checked by X-ray diffraction technique (DRX). The thermostability of R6G in the Lap films is discussed on the basis of several thermogravimetric and calorimetric techniques (TG, DTA and DSC). The R6G adsorbed species in Lap films are characterized by absorption and fluorescence (steady-state and time-resolved) spectroscopies. Monomers, dimers and higher-order aggregates are identified for very low (<0.1%), moderate (1–25%) and high (>40% of the total cation exchange capacity, CEC, of the clay) dye content, respectively. Both non-fluorescence H-type and fluorescent J-type aggregates of R6G in Lap films are characterized.Absorption and fluorescence techniques with linearly polarized light are applied to evaluate the anisotropic photoresponse of R6G in Lap films, from which the preferential orientation of dye molecules with respect to the clay layers can be evaluated. The validity of the newly established fluorescence polarization is contrasted with the well-established absorption polarization method, and the emission spectroscopy with linearly polarized light can be applied to establish the preferential orientation of fluorophore molecular probes incorporated in any rigid and ordered 2D host materials, including monolayers and biological membranes.     

Fluorescent properties of cationic-anionic polymethine dyes

The fluorescence spectra were studied and the quantum yields of the fluorescence of a number of cationic-anionic polymethine dyes were measured in polar, low-polarity, and nonpolar solvents. It was shown that the fluorescence spectra of cationic-anionic dyes in polar solvents, like the absorption spectra, represent the sum of the fluorescence spectra of the corresponding cationic and anionic dyes. For dyes in which the absorption bands of the anion and cation are close and a new short-wave band arises in the ion pairs, excitation into this band virtually does not lead to fluorescence, which is a consequence of the forbidden nature of the long-wave transition that arises as a result of the interaction of the chromophores. For a number of cationic-anionic dyes in ion pairs an energy transfer is observed: When an ion possessing short-wave absorption is excited, an ion with long-wave absorption fluoresces.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2532–2539, November, 1992.     

Luminescence Spectroscopy of Rhodamine Homodimer Dications in Vacuo Reveals Strong Dye-Dye Interactions

Being alone or together makes a difference for the photophysics of dyes but for ionic dyes it is difficult to quantify the interactions due to solvent screening and nearby counter ions. Gas-phase luminescence experiments are desirable and now possible based on recent developments in mass spectrometry. Here we present results on tailor-made rhodamine homodimers where two dye cations are separated by methylene linkers, (CH₂)_n. In solution the fluorescence is almost identical to that from the monomer whereas the emission from bare cation dimers redshifts with decreasing n. In the absence of screening, the electric field from the charge on one dye is strong enough to polarize the other dye, both in the ground state and in the excited state. An electrostatic model based on symmetric dye responses (equal induced-dipole moments in ground state) captures the underlying physics and demonstrates interaction even at large distances. Our results have possible implications for gas-phase Förster Resonance Energy Transfer.     

A novel fluorescent sensor for Sn4+ detection: Dark resonance energy transfer from silole to rhodamine

A novel dark resonance energy transfer (DRET) off–on cassette SR1 was constructed by coupling a silole donor with a rhodamine acceptor. Due to the intramolecular rotations of the phenyl rings, the silole fluorophore served as a dark donor in solution state and fluorescence leakage from the donor emission could be avoided. Binding with Sn⁴⁺ ion induced the ring‐opening of the rhodamine acceptor, thus increase the overlapping between the emission spectra of the donor and absorption spectra of the acceptor. DRET was turned on and energy was transferred from the silole donor to the rhodamine acceptor. Emission from the rhodamine acceptor was achieved with a large Stokes shift up to 198 nm. The sensor showed good sensitivity and selectivity towards Sn⁴⁺ to other metal ions in methanol aqueous solution through the formation of a 1:1 complex between SR1 and Sn⁴⁺. This research provides a new approach for the development of rhodamine‐based sensors towards metal ions with large Stokes shifts.     

Trace Determination of Rhodamine B and Rhodamine 6G Dyes in Aqueous Samples by Solid‐phase Extraction and High‐performance Liquid Chromatography Coupled with Fluorescence Detection

A simple and reliable method was developed to detect two basic synthetic dyes, rhodamine B (RB) and rhodamine 6G (R6G), in wastewater and surface water samples by high performance liquid chromatography with fluorescence detection (HPLC‐FLD). These dyes have been reported to be both mutagenic and carcinogenic in various organisms. The contents of these two dyes in water samples were extracted by Oasis HLB solid‐phase extraction (HLB‐SPE), and were then determined by an isocratic HPLC using an Atlantis® T3‐C18 column. Water samples at various pH conditions and the compositions of eluents for SPE were evaluated. The results indicate that the proposed method is precise and sensitive in analyzing these two basic synthetic dyes, and the limits of quantitation were 1.5 ng/L for RB and 0.3 ng/L for R6G in 100 mL of water samples. The recovery of analytes in spiked surface water and municipal wastewater treatment plant (WWTP) effluent samples ranged from 61 to 90% with the precision (RSD) ranging from 2 to 12%. The concentrations of analytes were detected in various water samples ranging from 0.7 to 81 ng/L.     

Study of fluorescent aggregates of polymethine dyes

Absorption, fluorescence, and fluorescence excitation spectra have been studied for a number of anionic, cationic, and cationic-anionic polymethine dyes in low-polar and nonpolar solvents, as well as in binary mixtures of solvents differing in polarity. For most of the dyes studied, fluorescent aggregates have been found to form. Their broad fluorescence bands are located in the long-wave region with respect to those of the initial dyes. The quantum yield of the aggregate fluorescence is normally higher than that of the initial dyes. Fluorescence excitation spectra of some cationic-anionic dyes in nonpolar solvents disagree with their absorption spectra because of contact and solvent-separated ion pairs simultaneously present in the solution.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 69–75, January, 1993.     

Synthesis of a Far‐Red Photoactivatable Silicon‐Containing Rhodamine for Super‐Resolution Microscopy

The rhodamine system is a flexible framework for building small‐molecule fluorescent probes. Changing N‐substitution patterns and replacing the xanthene oxygen with a dimethylsilicon moiety can shift the absorption and fluorescence emission maxima of rhodamine dyes to longer wavelengths. Acylation of the rhodamine nitrogen atoms forces the molecule to adopt a nonfluorescent lactone form, providing a convenient method to make fluorogenic compounds. Herein, we take advantage of all of these structural manipulations and describe a novel photoactivatable fluorophore based on a Si‐containing analogue of Q‐rhodamine. This probe is the first example of a “caged” Si‐rhodamine, exhibits higher photon counts compared to established localization microscopy dyes, and is sufficiently red‐shifted to allow multicolor imaging. The dye is a useful label for super‐resolution imaging and constitutes a new scaffold for far‐red fluorogenic molecules.     

Fluorescence of sanguinarine: fundamental characteristics and analysis of interconversion between various forms

The quaternary isoquinoline alkaloid, sanguinarine (SG) plays an important role in both traditional and modern medicine, exhibiting a wide range of biological activities. Under physiological conditions, there is an equilibrium between the quaternary cation (SG⁺) and a pseudobase (SGOH) forms of SG. In the gastrointestinal tract, SG is converted to dihydrosanguinarine (DHSG). All forms exhibit bright fluorescence. However, their spectra overlap, which limited the use of powerful techniques based on fluorescence spectroscopy/microscopy. Our experiments using a combination of steady-state and time-resolved techniques enabled the separation of individual components. The results revealed that (a) the equilibrium constant between SG⁺ and SGOH is pK _a = 8.06, while fluorescence of DHSG exhibited no changes in the pH range 5–12, (b) the SGOH has excitation/emission spectra with maxima at 327/418 nm and excited-state lifetime 3.2 ns, the spectra of the SG⁺ have maxima at 475/590 nm and excited-state lifetime 2.4 ns. The DHSG spectra have maxima at 327/446 nm and 2-exponential decay with components 4.2 and 2.0 ns, (c) NADH is able to convert SG to DHSG, while there is no apparent interaction between NADH and DHSG. These techniques are applicable for monitoring the SG to DHSG conversion in hepatocytes.     

Solid-emissive rhodamine: hydrogen bonding-assisted efficient intermolecular fluorescence resonance energy transfer in the solid state

Solid-emissive rhodamine complexes are obtained by mixing commercial rhodamine B (RhB) with the recently developed solid-emissive boron 2-(2′-pyridyl)imidazole (BOPIM) derivatives. The formation of intermolecular hydrogen bonds between RhB and BOPIM dyes plays a key role in the emission of RhB in the solid state. The disappearance of emissions from BOPIM dyes indicates the occurrence of efficient intermolecular fluorescence resonance energy transfer (FRET). The hydrogen bond also helps prevent the intermolecular interaction between the carboxyl moieties on RhB to alleviate concentration-induced fluorescence quenching because the emission of the complexes can be directly lightened by excitation at the RhB absorption (510 nm). Our results indicate that intermolecular FRET assisted by non-covalent interactions can be an efficient tool for constructing red or near-infrared solid emitters.     

多枝罗丹明酰肼类荧光探针的研究进展与应用

罗丹明以其良好的光稳定性、光物理性质和荧光效应得到了人们的极大重视。 基于罗丹明的螺环衍生物与被检测物质作用开环而产生荧光响应的特性,将两个或多个罗丹明母体单元构筑到包含特异性的识别单元的探针分子中,形成多枝的罗丹明酰肼类荧光探针,不仅可以弥补单分子探针的某些功能缺陷,而且可以使其具有更高灵敏度、更高选择性和可靠性,更加有利于分析检测。 本文着重从设计原理、识别性能、应用范围等方面介绍了多枝罗丹明探针在Hg2+、Cu2+、Fe3+和Al3+等离子检测中发展趋势,并展望了这类荧光探针在活细胞金属离子光学成像的应用前景。