Energy transfer in nucleic acid-dye complexes

Energy and exciton transfer in DNA-acridine orange complexes after dye laser excitation have been investigated. The energy transfer from the DNA-bases to the dye molecules and the exciton transfer along the DNA chain depend on the base composition and sequence of the DNA and the exciting wavelength.     

Violet-to-red photoluminescence of spiro-TAD organic films doped with different organic dyes

Photoluminescence (PL) and photoluminescence excitation (PLE) spectra of undoped spiro-TAD films and spiro-TAD films doped either by the organic dyes coumarin 7 or DCM as well as by both of these dyes simultaneously were investigated at different dye concentrations. A widened PL spectrum caused by doping was encountered and violet-to-red emission was obtained. It was established that excitation of the dyes is realized most efficiently through spiro-TAD. The overall integral PL intensity of the coumarin 7 doped films increased with dye concentration due to the suppression of nonradiative recombination in the film caused by a transfer of spiro-TAD excitation energy to the dye molecules. Mainly radiative energy transfer from semiconductor to dye molecules occurs in the case of DCM doping. No mutual influence on the luminescence of both dyes in the spiro-TAD film was observed and as a consequence, the PL band intensity of each dye can be adjusted separately.     

Laser performance and photostability of Rhodamin B in solid host matrices

Laser dye Rhodamine B was incorporated at different concentrations in GMA polymer, sol–gel glass and organic–inorganic hybrid material synthesized using the sol–gel process. The amplified spontaneous emission (ASE) was studied using Nd-YAG laser of 532 nm. The effect of laser excitation in transfer pumping configuration and the influence of dye concentration on the ASE were studied. Also, the gain and the energy conversion efficiencies were investigated. Relatively high efficiencies (to ～48%) were obtained with good photostabilities where a decrease to ～30% of the initial amplified spontaneous emission output energy were observed after pumping by 35000 shots at relatively high repetition rate (10 Hz) and energy (15 mJ). The composition and the properties of the matrix were found that optimize the laser performance and photostability of an investigated dye.     

Energy migration in DNA evaluated by the sensitized fluorescence of an intercalation dye

An equation is obtained to calculated the efficiency of energy migration along a biopolymer with transfer of excitation to a fluorescence dye using excitation and absorption spectra. With the aid of bromoethydium intercalating into DNA-phage it is shown that in a solution at room temperature energy is transferred to it only from one or two neighboring nucleotides. The low efficiency of energy migration in relation to DNA under these conditions is explained by the low probability of each event of “cold” and “hot” migration. Institute of Cell Biophysics of the Russian Academy of Sciences, Pushchino, 142292, Moscow Region, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 5, pp. 794–798, September–October, 1998.     

合成双分子膜三元体系的激发态能量转移

在４ （４’ 癸氧基 ４ 氧基联苯）丁基三甲基溴化铵双分子膜体系内,通过静电相互作用使达旦黄、荧光黄和四苯基卟啉磺酸阴离子键合在囊泡表面;研究了达旦黄给体通过荧光黄传递到四苯基卟啉磺酸阴离子受体的三元激发态能量转移。能量转移的结果改善了光的输出,扩展了光波的输出范围。     

Thionine Interaction to DNA: Comparative Spectroscopic Studies on Double Stranded Versus Single Stranded DNA

Interaction of thionine with double stranded and single stranded calf thymus DNA has been studied by absorbance, fluorescence, competition dialysis, circular dichroism and isothermal titration calorimetry. Binding to the native double stranded DNA conformation induced strong quenching in fluorescence spectrum of thionine. Linear Scatchard plots indicated the binding to be of one type and the affinity values evaluated to be of the order of 10⁵ M⁻¹ with double stranded DNA. Fluorescence quenching was much weaker with single stranded DNA and the binding affinity was about one order lower. Ferrocyanide quenching studies revealed that the fluorescence emission of dye molecules bound to the double stranded DNA was quenched much less compared to those bound to the single stranded DNA. Furthermore, there was significant emission polarization for the bound dye molecules and strong energy transfer from the DNA base pairs to the dye molecules indicating intercalative binding to ds DNA. Salt dependence of the binding phenomenon revealed that electrostatic forces played a significant role in the binding process. The intercalation of the dye molecules to double stranded DNA and simple stacking to single strands was proved from these fluorescence techniques. Support to the fluorescence results have been derived from absorption, circular dichroic and dialysis results. Calorimetric studies suggested that the binding to ds DNA conformation was both enthalpy and entropy favoured while that to ss DNA was predominantly entropy favoured.     

Effect of high-pressure water-vapor annealing on energy transfer in dye-impregnated porous silicon

We have studied the effect of high-pressure water-vapor annealing (HWA) on the excitation energy transfer from Si nanocrystals to dye molecules in porous Si layers. Efficient photoluminescence, originating from both RhB molecules and Si nanocrystals, was observed. The behavior of the polarization memory of the photoluminescence showed the presence of energy transfer from the surface-passivated Si nanocrystals to RhB molecules. The fact that HWA, which is an effective method to stabilize and enhance the emission from Si nanocrystals in porous Si, does not suppress the energy transfer is an important result since it makes possible the realization of stable Si/dye-nanocomposite functional devices.     

Study of the dissipation of vibrational energy excess using pulse fluorometry

The dependence of the emission anisotropy decay of dye fluorescence versus excitation wavelength was measured in order to study the relaxation of the vibrational energy excess. The results of these measurements allow the conclusion (in accordance with earlier findings) that the heat transfer in the solvent is a fast enough process not to influence Brownian rotations of dye molecules.     

Influence of nonradiative excitation-energy transfer on the dye laser active-medium gain-coefficient dichroism

The excitation power dependences of the luminescence polarization degree and of the anisotropy of the stimulated emission from glycerin solutions of rhodamine 6G at different dye concentrations have been obtained experimentally. It is shown that the anisotropy of the stimulated emission is determined by the dichroism of induced absorption in the range of low concentrations and by the development of excitation-energy migration into the generation channel. The complex character of the behavior of the fluorescence polarization degree is explained by the competition between several processes of excitation-energy transformation — nonradiative energy transfer and directed energy transfer to excimers with an increase in the dye concentration and in the excitation power.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 63–66, January–February, 2005.     

Influence of experimental parameters on dominant energy transfer mechanisms

Three pairs of dyes which operate as efficient energy transfer dye lasers in ethanol have been investigated to understand the dominant energy transfer mechanisms taking place in them. Special attention is given to the experimental configuration which is expected to influence the energy transfer rate constants over an order of magnitude or two. Fluorescence lifetimes have also been studied using time correlated single photon counting technique. It is found that apart from the excitation source and the concentration of dyes, the experimental configuration has a crucial role to play in determining the dominant energy transfer mechanism.     

Processes of electronic excitation energy transfer between luminescent dye molecules in microheterogeneous systems based on polymer micellar solutions

The processes of electronic excitation energy transfer (EEET) between different-type dye molecules in polymer micellar solutions with different polyelectrolyte concentration have been analyzed. The possibility of regulating the EEET efficiency between dye molecules due to change of the structure of polymer micellar complexes has been established. The results presented are explained from the viewpoint of the fractal character of distribution of interacting particles. The experimental dependence of the fractal dimension of the distribution of dye molecules in polymer micellar solutions on the polyelectrolyte concentration has been obtained.     

Fluorescence and Laser Emission from Coumarin-Acridine Orange Mixtures

The sensitized fluorescence and laser emissions of dye mixtures; (I) coumarin 102 (donor) and acridine orange (acceptor) and (II) coumarin 47 (donor) and acridine orange (acceptor) with Hg-lamp and N₂ laser, have been measured as a function of dye concentration and of the pump power (N₂ laser). Acridine orange which does not lase by itself on excitation with N₂ laser, lases efficiently in the presence of 7-amino-coumarins via singlet-singlet energy transfer. Energy transfer rate constants and critical distances have been estimated from fluorescence intensity and lifetime measurements. The performance of energy transfer dye lasers (ETDLs) are discussed in terms of spectral characteristics of the dyes and their penetration depths.     

Two-Photon Excited Fluorescence Energy Transfer: A Study Based on Oligonucleotide Rulers

The use of two-photon excitation of fluorescence for detection of fluorescence resonance energy transfer (FRET) was studied for a selected fluorescent donor–acceptor pair. A method based on labeled DNA was developed for controlling the distance between the donor and the acceptor molecules. The method consists of hybridization of fluorescent oligonucleotides to a complementary single-stranded target DNA. As the efficiency of FRET is strongly distance dependent, energy transfer does not occur unless the fluorescent oligonucleotides and the target DNA are hybridized. A high degree of DNA hybridization and an excellent FRET efficiency were verified with one-photon excited fluorescence studies. Excitation spectra of fluorophores are usually wider in case of two-photon excitation than in the case of one-photon excitation [1]. This makes the selective excitation of donor difficult and might cause errors in detection of FRET with two-photon excited fluorescence. Different techniques to analyze the FRET efficiency from two-photon excited fluorescence data are discussed. The quenching of the donor fluorescence intensity turned to be the most consistent way to detect the FRET efficiency. The two-photon excited FRET is shown to give a good response to the distance between the donor and the acceptor molecules.     

吖啶橙-罗丹明B二聚体能量转移体系在DNA测定中的应用及机理研究

首次研究了吖啶橙 罗丹明B二聚体能量转移体系作为荧光探针用于DNA的测定 ,并对其机理进行了探讨。用于鲱鱼精DNA和小牛胸腺DNA的测定 ,线性范围分别为 0 33～ 1 33mg·L- 1 ,0 33～ 3 33mg·L- 1 ,检测限分别为 1 6 3× 10 - 3mg·L- 1 ,1 5 2× 10 - 3mg·L- 1 。对 1 0 0mg·L- 1 鲱鱼精DNA和小牛胸腺DNA的测定 ,相对标准偏差分别为 2 4 %和 2 0 %。     

Temperature and Base Sequence Dependence of 2-Aminopurine Fluorescence Bands in Single- and Double-Stranded Oligodeoxynucleotides

Fluorescence excitation spectra of 2-aminopurine (2AP) incorporated into single-stranded DNA di- and trinucleotides, as well as into single- and double-stranded pentanucleotides, have been measured as a function of temperature from 5 to 65 °C. Spectral shifts have been precisely quantitated through difference spectroscopy and spectral fits. G(2AP)C and C(2AP)G oligonucleotides have relatively blue-shifted excitation spectra (especially the former) compared to the 2AP free base. The position of the excitation peak of 2AP free base is temperature independent, those of (2AP)T, G(2AP)C, C(2AP)G and TT(2AP)TT shift about 0.4 nm to the blue from 5 to 65 °C, though the spectra of the G-C-containing oligomers also change shape. The temperature dependence of the A(2AP)T spectral position is 2.5-times stronger, and just rises to that of the free base at high temperature. On the other hand, the decrease of yield with increasing temperature is smallest for A(2AP)T, even compared to the free base. The dominant effect when A neighbors 2AP appears to be temperature-dependent stacking with accompanying energy transfer, while in G- and C-containing trinucleotides a temperature-independent interaction keeps the 2AP excitation spectrum blue-shifted. The effect of double strand formation appears to be small compared to stacking interactions. These spectra can be useful in identifying base neighbors and structures of 2AP in unknown 2AP-labeled DNA.     

香豆素440/荧光素钠/藏红混合染料体系的光谱研究

通过对C440/Fl.Na/Saf.-T三元混合染料体系的荧光光谱研究,了解到这三种染料之间有较充分的能量转移。又通过对C440/Fl.Na和Fl.Na/Saf.-T两个混合染料体系的荧光寿命测量,讨论了分子间能量转移过程和机理,并做了一些定量的分析。     

Spectroscopic Characterization of the Interaction of Phenosafranin and Safranin O with Double Stranded, Heat Denatured and Single Stranded Calf Thymus DNA

Interaction of phenosafranin and safranin O with double stranded, heat denatured and single stranded calf thymus DNA has been studied by fluorescence, absorbance and circular dichroic techniques. Binding to the double stranded and heat denatured DNA conformations induced strong quenching in the fluorescence spectra of both dyes. Linear Scatchard plots indicated the binding to be of one type and the affinity evaluated to be of the order of 10(5) M(-1) with double stranded and heat denatured DNAs. Fluorescence quenching was much weaker with the single stranded DNA and the binding affinity was one order lower. Ferrocyanide quenching studies revealed that the fluorescence emission of the dye molecules bound to the double stranded and heat denatured DNAs was quenched much less compared to that bound to the single stranded DNA. Further, there was significant emission polarization for the bound dyes and strong energy transfer from the DNA base pairs to the dye molecules indicating intercalative binding. Salt dependence of the binding phenomenon revealed that electrostatic forces have significant role in the binding process. The intercalation of these molecules to double stranded and heat denatured DNA and simple stacking to single strands was proved by these fluorescence techniques. Support to the fluorescence results have been derived from absorption and circular dichroic results. Phenosafranin was revealed to be a stronger binding species compared to safranin O.     

Synchronously pumped double mode-locking of a rhodamine 6G-Cresyl violet mixture

Rhodamine 6G-Cresyl violet dye mixtures are synchronously pumped to obtain double mode-locking. Subpicosecond pulses are obtained at two wavelengths in an experimental setup that is easy to implement into existing conventional synchronously pumped systems. In addition, the excitation mechanisms of the secondary dye are discussed and evidence for resonant energy transfer is presented.     

Columinescence of dye molecules in nanostructures of metal ion complexes

The mechanism of columinescence (fluorescence sensitization) of dyes incorporated in nanostructures of metal complexes is studied. It is shown for the first time that the columinescence of dyes is due to the transfer of excitation energy from ligands and metal ions of complexes that form nanostructures. It is proven that the dye columinescence of rhodamine 6G (R6G) molecules incorporated into nanostructures of Al(DBM)₃phen, Al(DBM) _n (OH)_{6 ? 2n} , and Eu(DBM)₃phen (DBM is dibenzoylmethane) nanostructures is completely determined by the singlet excitation energy migration from ligands to R6G molecules. It is shown that, at small concentrations of R6G, the R6G columinescence intensity is lower in nanostructures of metal complexes with a high probability of S-T conversion and that this difference disappears at large concentrations of R6G. In the case of Nile blue (whose S ₁ level lies below the ⁵ D ₀ level of Eu(III)) incorporated in nanostructures of Eu(DBM)₃phen complexes, as well as in nanostructures of Al(DBM)₃phen and Gd(DBM)₃phen complexes with admixture of Eu complexes, we observed the S-S energy transfer from DBM to NB in addition to the delayed sensitized fluorescence of NB previously observed in nanostructures of Eu complexes, which was caused by the energy transfer from the ⁵ D ₀ level of Eu(III) to NB. At dye concentrations below 100 nM, the efficiency of NB sensitization due to the migration of singlet excitation energy from DBM is lower than in the case of the energy transfer from Eu(III) ions, while, at large concentrations of the dye, the S-S energy transfer successfully competes with the sensitization of NB by Eu(III) ions. The use of dye columinescence makes it possible to easily determine dye concentrations of 2–100 nM in solutions with standard spectrofluorimeters.     

Optical properties of Eu-doped zinc borate glasses

Photoluminescence, absorption and optical excitation spectra of undoped and Eu³⁺-doped binary zinc borate glasses of varied composition prepared by the melt quenching technique in air atmosphere were investigated. From photoluminescence measurements it was found that growing Eu³⁺ concentration leads to gradual disappearance of the broadband glass emission in the near-UV spectral range, while the red Eu³⁺ emission at 613 nm shows a considerable increase. This result together with excitation spectra suggests that the Eu³⁺ ions are excited via energy transfer from the initially excited glassy host. The glass composition strongly affects the position of the excitation maximum in the UV energy range.