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.     

Luminescence quenching kinetics upon diffusion-accelerated dipole-dipole energy transfer for a realistic condensed-matter model

The hard-sphere model is considered as a more realistic condensed-matter model. In this model, the radial distribution function of molecules in a medium, used for calculations of luminescence decay kinetics, takes into account the short-range order in fluids and has the shape of damped oscillations. It is assumed that the motion of donor and acceptor molecules in a solution for the lifetime of the excited state of the donor is described by the diffusion equation, while the luminescence quenching occurs due to the long-range dipole-dipole energy transfer. It is shown that, if diffusion coefficients are small, the kinetics determined in this study hardly differs at all from the traditional kinetics. At intermediate and large diffusion coefficients, this difference becomes significant and should be taken into account in estimating the Förster energy transfer radius and diffusion coefficients from experimental luminescence decay curves.     

5,10-二(对-氨基)四苯基卟啉和吖啶黄之间激发能量的传递

利用Forster能量传递机制,研究了氯仿溶液中吖啶黄向5、10-二(对-氨基)四苯基卟啉(简称TBP)的激发能量传递和TBP.浓度变化时对能量传递速度常数的影响.实验结果表明,吖啶黄和TBP之间具备能量共振传递的条件,并且计算了能量共振传递的临界距离为0.42nm、传递效率为0.72和传递速度常数为1.42×107s-1.这些数据对复合膜光电转换器件的设计将具有重要意义.     

Study of energy transfer in a solution of coumarin 460 and rhodamine 6G by time-resolved laser-induced fluorescence spectroscopy

A multi-photon fast analog technique has been used to study nonradiative energy transfer from coumarin 460 to rhodamine 6G molecules. At low acceptor concentrations (<10^-2 mol/1) the fluorescence decay from coumarin deviates markedly from monoexponential behavior. The complex decay of the donor fluorescence reflects the time-dependent population of donor-acceptor pairs. Various energy transfer kinetics were investigated. The donor decay was found to be consistent with Förster kinetics and the critical energy transfer radius was found to be (5.46±0.10) nm.     

Determination of the Efficiency and Energy Transfer Rate in the Fluorescence of a Single Donor–Acceptor Pair Attached to a Biomolecule

Resonance energy transfer from a single donor molecule to a single acceptor molecule (Förster resonance energy transfer) is currently used to determine the microscopic parameters describing interconformational changes in a protein molecule to which this single donor–acceptor pair is attached. A recently developed method makes it possible to intricately search for such parameters using a formula for the efficiency of Förster resonance energy transfer, which is the sum of several Gaussians. Another simpler method for the determination of the desired parameters of interconformational transitions has been proposed in this work on the basis of statistical processing of fluctuating tracks of fluorescence of a single donor–acceptor pair attached to a protein molecule.     

仿生色素薄膜的荧光光谱研究

本文利用柱层析法从天然产物中提取分离了叶绿素a(Chl-a)和胡罗h素C(Car),并按Langmuir-Blodgett单分子膜技术制备了Chl-a单分子膜、Chl-a与Car的混合单分子膜。实验中还引入了硬脂酸起辅助支撑作用,选用的硬脂酸与Chl-a的摩尔比为10:1。挂膜载片为经过疏水处理的玻璃片。为制作模仿天然光合膜集光天线系统的功能,我们以Car为给体Chl-a为受体,Caf与Chl-a的摩尔比为5:1、50:1和125:1;这里选用的比例远大于集光天线的色素比例。用荧光光谱的测量发现,L-B膜内的色素分子有特殊的集聚态,这种状态有助于实现高效的激子转移。作者指出,由于二维的L-B膜上会发生Frster型和激子型两种能量转移的协同作用,所以在Car与Chl-a的摩尔比125:1时Chl-a的荧光无相应衰减。Chl-a单分子膜的荧光带为677nm和766nm。吸附在层析纸上Chl-a的荧光,仅长波带有明显位移。     

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%.     

Sensitized Luminescence Kinetics as a Tool for Identification of Nonradiative Energy Transfer

Optics and Spectroscopy - A simple equation is proposed for calculating the sensitized luminescence kinetics of acceptors caused by nonradiative excitation energy transfer (Förster Resonance...     

Förster resonance energy transfer in hybrid associates of colloidal Ag<Subscript>2</Subscript>S quantum dots with thionine molecules

Nonradiative resonance energy transfer in hydrophilic hybrid associates of thionine molecules (TH⁺) with colloidal Ag₂S quantum dots (QDs) with average diameter of 3.5 nm was studied. Photoluminescence spectra and its decay shown that for these systems the supplemental photosensitization of recombination luminescence of Ag₂S QDs (1200 nm) from the region of TH⁺ fluorescence (618 nm) is possible. It was found that the average lifetime of TH⁺ molecules luminescence is shortened during their association with Ag₂S QDs. Approximation of luminescence decay by stretched exponent with value of parameter β =?0.5 indicates on the inductive-resonance dipole-dipole (Förster) mechanism of nonradiative energy transfer (FRET). The efficiency of FRET was 0.29–0.41.     

Photoluminescence of Er<Superscript>3+</Superscript> ions in layers of quasi-ordered silicon nanocrystals in a silicon dioxide matrix

The spectra and kinetics of photoluminescence from multilayered structures of quasi-ordered silicon nanocrystals in a silica matrix were studied for undoped samples and samples doped with erbium. It was shown that the optical excitation energy of silicon nanocrystals could be effectively transferred to Er³⁺ ions, which was followed by luminescence at a wavelength of 1.5 µm. The effectiveness of energy transfer increased as the size of silicon nanocrystals decreased and the energy of exciting light quanta increased. The excitation of erbium luminescence in the structures was explained based on dipole-dipole interaction (the Förster mechanism) between excitons in silicon nanocrystals and Er³⁺ ions in silica surrounding them.     

Model for photosynthetic light harvesting system: Energy transfer in anthracene- and biphenyl-cholorophyll derivatives

An intramolecular energy transfer from the ultraviolet absorbing donor to the pyro-pheophorbide a moiety occurs with high efficiency in model antenna compounds composed of 4-phenylbenzoic acid or anthracenecarboxylic acid and pyropheophorbide a. The energy transfer mechanism involves a Förster tyoe dipole-dipole coupling between the donor transition dipole(s) and the acceptor transition dipole(s) represented by the Soret band of the pyropheophorbide a moiety.     

Abrupt change of luminescence spectrum in single-layer phosphorescent polymer light emitting diode

PVK-based single-layer phosphorescent polymer OLEDs (organic light emitting diodes) with different rubrene concentrations were fabricated and examined for the Förster energy transfer from phosphorescent FIrpic dye to rubrene. We found out that at a certain rubrene concentration the energy transfer occurs abruptly and the transfer shows an abnormal evolution of electroluminescence (EL) spectrum due to the coincidence of peak wavelengths of bis[(4,6-difluorophenyl)-pyridinato-N,C^2′](picolinate) iridium(III) (FIrpic) emission and 5,6,11,12-tetraphenylnaphthacene (rubrene) absorption. With the calculation of Förster radius and average distance between FIrpic molecules, we have related the calculated ratio between the number of FIrpic molecules within to that out of Förster radius with the degree of Förster energy transfer from EL spectra measured in the experiment. Experimental results were found to fit well with the predicted results especially at low rubrene concentrations.     

Energy migration and transfer between chromophores embedded in Gaussian space

We have used a Monte Carlo method to investigate energy migration and transfer between chromophores embedded in Gaussian space. In using this method we have obtained fluorescence quantum yields, fluorescence depolarization, and the respective decay profiles of donor fluorescence. It was shown that all photophysical observables are dependent upon the number of donor and acceptor chromophores and upon the Förster radii ratio. The latter feature is particularly interesting, and it indicates the existence of correlations between donor and acceptor chromophores. It was shown that the excitation of the donor chromophore at the origin leads to different values of observables, in comparison with an excitation of a randomly selected donor chromophore. The results presented show the importance of the averaging procedures needed to be developed while dealing with specific distribution functions, as, for example, in the case of energy migration and trapping in aromatic polymers and copolymers.     

Using single donor–acceptor pairs to study the conformational dynamics of macromolecules

It is shown that in the presence of triplet levels of donor and acceptor molecules, the formula for function E(R) describing the dependence of efficiency E of Förster energy transfer on donor–acceptor distance R differs considerably from the one commonly used in experimental works.     

Influence of donor-donor transport on excitation energy transfer

Energy migration and transfer from acriflavine to rhodamine B and malachite green in poly (methylmethacrylate) have been investigated using the decay function analysis. It is found that the influence of energy migration in energy transfer can be described quite convincingly by making use of the theories of Loring, Andersen and Fayer (LAF) and Huber. At high acceptor concentration direct donor-acceptor transfer occurs through Förster mechanism.     

Microspectroscopic Study of Liposome-to-cell Interaction Revealed by Förster Resonance Energy Transfer

We report the Förster resonance energy transfer (FRET)-labeling of liposomal vesicles as an effective approach to study in dynamics the interaction of liposomes with living cells of different types (rat hepatocytes, rat bone marrow, mouse fibroblast-like cells and human breast cancer cells) and cell organelles (hepatocyte nuclei). The in vitro experiments were performed using fluorescent microspectroscopic technique. Two fluorescent dyes (DiO as the energy donor and DiI as an acceptor) were preloaded in lipid bilayers of phosphatidylcholine liposomes that ensures the necessary distance between the dyes for effective FRET. The change in time of the donor and acceptor relative fluorescence intensities was used to visualize and trace the liposome-to-cell interaction. We show that FRET-labeling of liposome vesicles allows one to reveal the differences in efficiency and dynamics of these interactions, which are associated with composition, fluidity, and metabolic activity of cell plasma membranes.     

The effect of the size of polymer chain on the energy transfer between chromophores bound to the ends of the chain

The dependence of the luminescence quantum yield of linear polymer molecules that contain chromophores at the ends on the number of units of polymer chain is studied. Numerical calculations for the dipole-dipole energy transfer between chromophores show that an increase in the chain length by a factor of 2 leads to a several-fold increase in the luminescence quantum yield depending on the ratio of the Förster radius to the radius of polymer coil. An approximate formula is derived for the adequate analysis of the dependence at the Förster radius that is significantly less than the radius of polymer coil. The dependence of the luminescence quantum yield of linear polymer molecules on the length of the statistical segment (unit) at a constant total length of the chain is also studied.     

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。     

A Novel Water-soluble Ratiometric Fluorescent Probe Based on FRET for Sensing Lysosomal pH

A new ratiometric fluorescent probe based on Förster resonance energy transfer (FRET) for sensing lysosomal pH has been developed. The probe (RMPM) was composed of imidazo[1,5-α]pyridine quaternary ammonium salt fluorophore as the FRET donor and the rhodamine moiety as the FRET acceptor. It’s the first time to report that imidazo[1,5-α]pyridine quaternary ammonium salt acts as the FRET donor. The ratio of fluorescence intensity of the probe at two wavelengths (I₄₂₄/I₅₈₁) changed significantly and responded linearly toward minor pH changes in the range of 5.4–6.6. It should be noted that it’s rare to report that a ratiometric pH probe could detect so weak acidic pH with pKa = 6.31. In addition, probe RMPM exhibited excellent water-solubility, fast-response, all-right selectivity and brilliant reversibility. Moreover, RMPM has been successfully applied to sensing lysosomal pH in HeLa cells and has low cytotoxicity.     

Fluorescence Quenching Study on the Interaction between Quercetin and Lipoxygenase

The interaction between quercetin and lipoxygenase was investigated by fluorescence spectroscopy. The analysis of the emission quenching at different temperatures revealed that the quenching mechanism correspond to a static process and, as consequence, a complex quercetin-lipoxygenase is formed. The thermodynamic parameters ΔG, ΔH and ΔS were calculated to be?32.57 kJmol^?1,?3.21 kJmol^?1 and 87.14 Jmol^?1K^?1 respectively, which suggest that hydrophobic forces plays a major role in the stabilization of the complex quercetin-lipoxygenase. The distance, r, between donor (lipoxygenase) and acceptor (quercetin) was calculated to be 3.84 nm based on Förster’s non-radiative energy transfer theory. The results obtained from the evaluation of three dimensional florescence spectra suggest a conformational modification of the protein in the region of the coupling with quercetin.