Radiative energy transfer II. The effect of radiative transfer on the monomer to excimer ratio in a binary system

The equations derived in part I of this series to obtain the correction for radiative energy transfer when the observation of the fluorescence emission is made from the same face of the cell where excitation takes place are applied to the case where pyrene (Py) is the energy donor and 9,10-diphenylanthracene (DPA) is the energy acceptor. It is shown that the magnitude of the correction is quite large and that to neglect it could lead to important errors, when analysing the results regarding the possibility of a nonradiative energy transfer from Py excimers. Different methods of correcting the overall energy transfer efficiencies already published are critically reviewed.     

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.     

具有电子推拉结构的多支化分子的光物理特性的研究

利用稳态光谱和飞秒时间分辨荧光亏蚀的技术,研究了不同溶剂中一系列有分子内电荷转移特性的分子的结构与光物理性质的关系,研究体系为三苯胺作为电子给体,2,1,3-苯并噻二唑作为受体的单支分子及其对应的两支和三支分子. 并结合TD-DFT计算进一步解释了实验中所观察到的现象. 三个分子相似的吸收和荧光光谱以及强的溶剂依赖光谱特性表明两支与三支分子激发态与单支分子相似,表明激发态都定域在其中一支上. 激发时多支分子内发生多维电荷转移,然后快速地定域到某一支上发射. 另一方面多支分子相对于单支分子吸收和发射光谱的红     

Nonradiative and radiative Förster energy transfer between quantum dots

We theoretically study nonradiative and radiative energy transfer between two localized quantum emitters, a donor (initially excited) and an acceptor (receiving the excitation). The rates of nonradiative and radiative processes are calculated depending on the spatial and spectral separation between the donor and acceptor states and for different donor and acceptor lifetimes for typical parameters of semiconductor quantum dots. We find that the donor lifetime can be significantly modified only due to the nonradiative Förster energy transfer process at donor–acceptor separations of approximately 10 nm (depending on the acceptor radiative lifetime) and for the energy detuning not larger than 1–2 meV. The efficiency of the nonradiative Förster energy transfer process under these conditions is close to unity and decreases rapidly with an increase in the donor–acceptor distance or energy detuning. At large donor–acceptor separations greater than 40 nm, the radiative corrections to the donor lifetime are comparable with nonradiative ones but are relatively weak.     

Langmuir-Blodgett单分子膜功能体系的研究——(Ⅰ)膜系间敏化荧光的Förster机制

利用L-B技术制作L-B功能单分子膜。以两种花菁染料作给体和受体,用硬脂酸单分子膜作隔离夹层。在这种体系中的能量转移是Förster机制,有效距离为～100。     

Dually fluorescent silica nanoparticles

The cationic dyes 9-aminoacridine (9AA) and safranine (Sf) were entrapped into silica spheres of about 0.2 μm diameter prepared by modified Stöber method. The fluorescent materials are investigated by steady-state and time-resolved emission, in addition of confocal fluorescence microscopy. Silica particles containing 9-aminoacridine (SP9AA) and safranine (SPSf) or both dyes (SPSf9AA) are emissive particles. When both dyes are present in the same particle but loaded in sequential stages 9AA emission is quenched as a consequence of energy transfer from 9AA (donor) to Sf (acceptor). This result suggests that particle growing processes where the acceptor is incorporated first into the core do not prevent donor/acceptor pairs to be close due to an overlay of the concentration gradients of both dyes in a radial core-shell like distribution.     

Time-gated microscopic energy transfer measurements for probing mitochondrial metabolism

Spectroscopic and microscopic methods for probing mitochondrial malfunction were established using cultivated endothelial cells from the calf aorta and various inhibitors of the respiratory chain, which is located at the inner mitochondrial membrane. Time-gated fluorescence spectroscopy was used to measure autofluorescence of the coenzyme NADH as well as “energy transfer efficacy” from excited NADH molecules (energy donor) to the mitochondrial marker rhodamine-123 (energy acceptor). Autofluorescence usually exhibited a weak increase after specific inhibition of enzyme complexes of the respiratory chain. In contrast, a pronounced increase in energy transfer efficacy was observed after inhibition of the same enzyme complexes. The detection of donor (NADH) and acceptor (R123) fluorescence in different nanosecond time gates following the exciting laser pulses enhances selectivity and improves quantification of energy transfer measurements. Therefore, timegated energy transfer spectroscopy is suggested to be an appropriate tool for probing mitochondrial malfunction.     

表面增强的分子间能量转移效应

研究了粗糙金属银表面对分子间能量转移效应的影响，实验观察到吸附分子增强的敏化荧光，结合表面局域电磁理论分析表明，吸附于银表面的分子间非辐射能量转移率被增强１０＾２倍，证实了表面增强的分子间能量转移效应的存在。     

Effects of Internal Rotations on the Time-Resolved Fluorescence in a Bichromophoric Protein System Under the Energy Transfer Interaction

Effects of internal rotations of chromophores under the energy transfer interaction in proteins on the time-resolved fluorescence were examined by numerical calculations. Expressions used for the calculations are based on the approximations that the energy transfer takes place according to Foöurster's mechanism and the rotational motions of the energy donor and acceptor along the surfaces of cones are described by a set of rotational diffusion equations. The intensity decay of the donor depended a little on the rotational diffusion coefficient of the donor in some cases, while that of the acceptor did very little. Anisotropy of the donor decayed faster as the diffusion coefficient of the donor increased. Anisotropy decay of the acceptor markedly depended not only on the mutual configuration of the pair in the protein, but also on the diffusion coefficient of the donor. The dependence of the time-resolved fluorescence on the diffusion coefficient of the acceptor was not as great as that of the donor.     

Enhanced Emission Induced by FRET from a Long-Lifetime, Low Quantum Yield Donor to a Long-Wavelength, High Quantum Yield Acceptor

We report observation of high quantum yield, long-lifetime fluorescence from a red dye BO-PRO-3 excited by resonance energy transfer (RET). The acceptor fluorescence was highly enhanced upon binding to the donor-labeled DNA. A ruthenium complex (Ru) was chosen as a donor in this system because of its long fluorescence lifetime. Both donor and acceptor were non-covalently bound to DNA. Emission from the donor-acceptor system (DA) at wavelengths exceeding 600 nm still preserves the long-lifetime component of the Ru donor, retaining average fluorescence lifetimes in the range of 30–50 ns. Despite the low quantum yield of the Ru donor in the absence of acceptor, its overall quantum yield of the DA pair was increased by energy transfer to the higher quantum yield acceptor BO-PRO-3. The wavelength-integrated intensity of donor and acceptor bound to DNA was many-fold greater than the intensity of the donor and acceptor separately bound to DNA. The origin of this effect is due to an efficient energy transfer from the donor, competing with non-radiative depopulation of the donor excited state. The distinctive features of DA complexes can be used in the development of a new class of engineered luminophores that display both long lifetime and long-wavelength emission. Similar DA complexes can be applied as proximity indicators, exhibiting strong fluorescence of adjacently located donors and acceptors over the relatively weak fluorescence of separated donors and acceptors.     

Vectorial photoinduced electron transfer in phospholipid vesicles and LB bilayers

Summary Photoinduced electron transfer (PET) was studied in phospholipid vesicles and in Langmuir-Blodgett bilayers in the attempt to produce a model for electron transfer processes in biological media. Spatial organization of the reaction centers in lipid membranes needs to be controlled in order to provide high efficiency of light-to-chemical energy conversion. We designed a phospholipid system where the donor is localized in the inner bilayer whereas the acceptor is at the polar groups-water interface. We used dipalmitoylphosphatidic acid vesicles containing low molar fractions of dipalmitoylphosphatidylcholine with pyrene (donor) bound to one of the alkyl chains. Methylviologen (acceptor) was added to the external aqueous phase; upon photoexcitation of the donor we observed the electron transfer to take place in a unidirectional manner from the inside of the bilayer to the interface. Information about the location of the donor was obtained studying the photophysical properties of the pyrene chromophore in vesicles and in LB layers. The photoinduced electron transfer reaction was evidenced by quenching of pyrene fluorescence in the presence of increasing concentrations of acceptor, the process was studied both with steady-state and time-resolved fluorescence emission. Fluorescence intensity was found to decrease with increasing concentration of methylviologen, similar results were obtained for vesicles and LB layers of analog composition immersed in a methylviologen solution. Lifetimes of the excited species were found to be of the same order of magnitude in vesicle and LB-layer systems. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Fluorescence quenching of 9-cyanoanthracene in presence of zinc tetraphenylporphyrin in a polar liquid medium

Steady-state and time-resolved techniques are used to study photoinduced electron and/or excitational energy transfer processes involved within a novel donor (zinc tetraphenylporphyrin)-acceptor (9-cyanoanthracene) system in a polar liquid medium (acetonitrile) at the ambient temperature (300 K). After photoexcitation of 9-cyanoanthracene, its fluorescence emission as well as lifetime are found to be quenched in presence of zinc tetraphenylporphyrin. The fluorescence quenching is ascribed to be due to the combined effect of electron transfer from zinc tetraphenylporphyrin to 9-cyanoanthracene and energy transfer (radiative as well as non-radiative) from 9-cyanoanthracene to zinc tetraphenylporphyrin. The highly exergonic values of Gibbs free energy change for both forward electron transfer reaction (−1.15 eV) and charge recombination reaction (−1.94 eV) indicate the possibilities of occurrences of these two processes in the Marcus inverted region. The fluorescence quenching rate due to photoinduced electron transfer reaction is found to be close to the diffusion-controlled limit within the present donor-acceptor system upon excitation of the acceptor molecules.     

Energy transfer from Sm3+ to Er3+ in zinc phosphate glass

A study of energy transfer from samarium to erbium ions in zinc phosphate glass has been performed for a range of donor (1.0 wt% fixed) and acceptor concentrations ranging from 0.2 wt% to 1.2 wt%. The intensity of emission spectra of Sm³⁺ ions in the presence of Er³⁺ ions shows an overall decrease, thereby suggesting a non radiative energy transfer from Sm³⁺ ions to Er³⁺ ions. The interaction mechanism between the donor and acceptor ions is found to be mainly electric dipole-dipole in nature. The parameters required for the quantitative study of energy transfer e.g. energy transfer efficiencies, transfer probabilities, critical transfer distances have been computed.     

pH-Dependent fluorescence and singlet energy transfer in water-soluble polymers containing eosin and phenol red chromophores

The pH-dependent fluorescence and energy transfer properties of water-soluble polyacrylamide labeled with a donor (eosin) and acceptor (phenol red) were studied. Eosin emission intensity decreases with pH increases. This observation corresponds to the expectation that the fluorescence intensity of eosin should diminish with pH increases resulting from increased spectral overlap between dyes. The lower energy transfer efficiency compared to a pH sensor made with the same polymer, but with a cross-linker, can be explained by the larger distances between the two chromophores resulting from conformational flexibility and electrostatic repulsion of the chromophore ions.     

Time-resolved spectra of coumarin 30-rhodamine 6G dye mixture

The effect of acceptor concentration on the energy transfer from Coumarin 30 (donor) to Rhodamine 6G (acceptor) has been studied. The nature of energy transfer reaction has been studied through lifetime measurements by recording the time-resolved fluorescence decay curves. The energy transfer parameters calculated were used to confirm the occurrence of energy transfer on the basis of the emission-reabsorption effect.     

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.     

香豆素、罗丹明衍生物和DCM激光染料分子间的激发能传递

通过考察香豆素4-DCM、香豆素481-DCM、否豆素540A-罗丹明6G、香豆素540A-罗丹明640在乙醇、乙二醇等极性溶剂中的激发光谱和荧光发射光谱,研究了它们之间的激发能传递过程。     

金属卟啉分子组装体系中的三线态能量传递

利用稳态和瞬态光谱技术研究了人工组装锌卟啉(ZnP)-苯桥(BB)-铁卟啉(Fe(Cl)P)超分子体系中给体三线态到受体的能量传递及其机理。结果表明体系中存在着由给体ZnP三线态向受体Fe(Cl)P的超快能量传递过程,在室温和低温下通过激发给体ZnP,其单线态的激发能经由系间窜越过程使其三线态布居,在受体Fe(Cl)P存在的情况下,位于给体三线态的激发能经由桥联分子B传递到受体Fe(Cl)P,室温下传递速率为7.2×105s-1。由于体系中给体到受体之间的空间距离约为2.5nm,由给体-受体直接耦合引起的传递机理可以排除,由桥联分子媒介的超交换机理是该能量传递过程的主要物理机理。     

Energy transfer from acraflavine to rhodamine B in methanol and glycerol:water solution

Excitation energy transfer from acraflavine to rhodamine B in methanol at 300 K is found to be through the mechanism of exciton migration even though the acceptor concentration is about 10 times the donor concentration. The transfer is more efficient at 230 K. In glycerol: water solvent at 300 K the energy migration has been found to persist even upto the acceptor concentration about 50 times the donor concentration. Our results agree with those of Bojarski [2] in as much as the energy migration has been observed even though the acceptor concentration is greater than the donor concentration, but differ in the sense that the migration does not cease at the acceptor concentration 3 times the donor as observed by Bojarski. These effects have been attributed to facilitation of the exciton migration as in glassy media reported by us previously [14,15]. By a quantitative analysis of acceptor emission, we have concluded that the quantum efficiency of transfer is unity. Part of the acraflavine band has been found to transfer radiatively also.     

CdTe量子点与罗丹明B水溶液体系下的双光子激发荧光共振能量转移

采用时间分辨荧光光谱技术研究了在双光子激发下不同尺寸的量子点与罗丹明B 之间的荧光共振能量转移. 研究结果表明, 在800 nm的双光子激发条件下, 体系间能量转移效率随着供体吸收光谱与受体荧光光谱的光谱重叠程度增加而增加; 理论分析表明, 供体和受体间的Förster半径增加是导致其双光子能量转移效率增大的物理原因. 同时, 研究了罗丹明B浓度对荧光共振能量转移效率的影响. 研究结果表明, 量子点的荧光寿命随着罗丹明B浓度的增加而减小; 量子点与罗丹明B之间的荧光共振能量转移效率随着罗丹明B浓度的增加而增加; 当罗丹明B浓度为3.0×10^-5 mol·L^-1时, 双光子荧光共振能量转移效率为40.1%.