Electronic Energy Migration Research Articles

Sub-8-fs pulses in the visible to near-infrared by a degenerate optical parametric amplifier.

This work presents a single-stage optical parametric amplifier (OPA) operating at degeneracy (DOPA) and pumped by the third harmonic of a Yb:KGW laser system. This DOPA exploits the broad amplification bandwidth that occurs with type-I phase-matching in β-barium borate (BBO) when signal and idler overlap in the spectrum. The output pulses span from 590 to 780 nm (1.59-2.10 eV) with 7.75-fs duration after compression. Ultrashort pulses with similar bandwidths in this spectral window complement the existing array of optical parametric amplifiers that cover either the visible or the near-IR spectral regions with sub-10-fs pulses. This source of ultrashort optical pulses will enable the application of sophisticated spectroscopy techniques to the study of electronic coherences and energy migration pathways in biological, chemical, and condensed matter systems.

In-cell structural dynamics of an EGF receptor during ligand-induced dimer-oligomer transition.

The epidermal growth factor receptor (EGFR) is a membrane protein that regulates cell proliferation, differentiation and survival, and is a drug target for cancer therapy. Ligand-induced activation of the EGFR kinase is generally regarded to require ligand-bound-dimers, while phosphorylation and down-stream signalling is modulated by oligomers. Recent work has unveiled changes in EGFR dynamics from ligand-induced dimerization in membranes extracted from cells, however, less is known about the changes in EGFR dynamics that accompany the ligand-induced oligomerization in a live cell environment. Here, we determine the dynamics of a c-terminal GFP tag attached to EGFR in the unliganded dimer and in the liganded oligomers. By means of the single-frequency polarized phasor ellipse approach we extracted two correlation times on the sub-nanosecond and super-nanosecond timescales, respectively. EGF binding to the EGFR-GFP dimer lengthened the sub-nanosecond correlation time (from 0.1 to 1.3ns) and shortened the super-nanosecond correlation time (from 210 to 56ns) of the c-terminal GFP probe. The sub-nanosecond depolarization processes were assigned to electronic energy migration between proximal GFPs in the EGFR dimer or oligomer, while the super-nanosecond correlation times were assigned to nanosecond fluctuations of the GFP probe in the EGFR complex. Accordingly, these results show that ligand binding increased the average separation between the c-terminal tags and increased their rotational mobility. We propose that the dynamics are linked to an inhibitory function of the c-terminal tail in the un-liganded dimer and to the requirement of facile stochastic switching between kinase activation and cytoplasmic adaptor/effector binding in the active oligomers.

Solid-State Emission from Mono- and Bichromophoric Boron Dipyrromethene (BODIPY) Derivatives and Comparison with Fluid Solution.

The syntheses and crystal structures of sterically crowded mono- and bichromophoric BODIPY-based dyes are reported. The "monomeric" compound is weakly fluorescent in the liquid phase due to fast internal conversion associated with rotation of aryl rings at the boron atom. The side-by-side "dimer" exhibits weak excitonic coupling between the dipyrrin units and is much more emissive in fluid solution. Solid samples of both molecular entities are strongly fluorescent under near-UV illumination. Thus, the mono-chromophore exhibits dual fluorescence from what appears to be a mixture of crystalline and possibly amorphous (or interfacial regions) distributions. The bi-chromophore packs in the crystal as pairs of chromophores with each unit being provided by a different molecule. This leads to excitonic splitting and the formation of a strong H-band in the absorption spectrum. Fluorescence occurs from the corresponding J-species and also from what appears to be an aggregated state associated with interfacial areas. Both bulk and interface-bound states show relatively long-lived fluorescence while the crystal structures indicate the likelihood for fast electronic energy migration between molecules.

Using fluorescence detected two-dimensional spectroscopy to investigate initial exciton delocalization between coupled chromophores.

Förster theory describes electronic exciton energy migration in molecular assemblies as an incoherent hopping process between donor and acceptor molecules. The rate is expressed in terms of the overlap integral between donor fluorescence and acceptor absorption spectra. Typical time scales for systems like photosynthetic antennae are on the order of a few picoseconds. Prior to transfer, it is assumed that the initially excited donor molecule has equilibrated with respect to the local environment. However, upon excitation and during the equilibration phase, the state of the system needs to be described by the full density matrix, including coherences between donor and acceptor states. While being intuitively clear, addressing this regime experimentally has been a challenge until the recently reported advances in fluorescence detected two-dimensional spectroscopy. Here, we demonstrate using fourth order perturbation theory the conditions for the presence of donor-acceptor coherence induced cross-peaks at zero waiting time between the first and the second pair of pulses. The approach is illustrated for a heterodimer model which facilitates an analytical solution.

Energy migration processes in phosphate nanocrystals: Size and dimensionality dependence

Peculiarities of electronic excitation energy migration in phosphate nanocrystals with three-dimensional (EuPO4) and one-dimensional (EuP3O9) arrangement of regular ions under variation of concentration of both energy traps (Nd3+ ions) and scattering centres (La3+ ions) are discussed in the paper. Processes of energy migration in both EuPO4 and EuP3O9 nanocrystals are phonon-assisted ones due to absence of resonance between energy levels of adjacent Eu3+ ions. The distance of energy migration for both EuPO4 and EuP3O9 nanocrystals was found to be equal to tens of nanometres, however, for EuPO4 nanocrystals energy migration leads to stronger quenching of Eu3+ luminescence. For 10 nm EuPO4 nanocrystals sufficient hampering of energy migration is observed due to the depletion of the low-energy phonon spectrum as a result of the phonon confinement effect.

Temperature-dependent conformations of exciton-coupled Cy3 dimers in double-stranded DNA.

Understanding the properties of electronically interacting molecular chromophores, which involve internally coupled electronic-vibrational motions, is important to the spectroscopy of many biologically relevant systems. Here we apply linear absorption, circular dichroism, and two-dimensional fluorescence spectroscopy to study the polarized collective excitations of excitonically coupled cyanine dimers (Cy3)2 that are rigidly positioned within the opposing sugar-phosphate backbones of the double-stranded region of a double-stranded (ds)-single-stranded (ss) DNA fork construct. We show that the exciton-coupling strength of the (Cy3)2-DNA construct can be systematically varied with temperature below the ds-ss DNA denaturation transition. We interpret spectroscopic measurements in terms of the Holstein vibronic dimer model, from which we obtain information about the local conformation of the (Cy3)2 dimer, as well as the degree of static disorder experienced by the Cy3 monomer and the (Cy3)2 dimer probe locally within their respective DNA duplex environments. The properties of the (Cy3)2-DNA construct we determine suggest that it may be employed as a useful model system to test fundamental concepts of protein-DNA interactions and the role of electronic-vibrational coherence in electronic energy migration within exciton-coupled bio-molecular arrays.

Exciton Relaxation in Highly Rigid Conjugated Polymers: Correlating Radiative Dynamics with Structural Heterogeneity and Wavefunction Delocalization

Conjugated polymers are promising materials for solar cells and other electronic applications due to facile charge and electronic energy migration along the conjugated backbone. Torsional defects due to rotation around single bonds on the backbone are known to decrease the effective conjugation length of these materials, limiting their ability to shuttle charge and electronic energy. We investigated the radiative emission dynamics of a recently synthesized rigid conjugated ladder polymer (LP1) and nonrigid control (CP1) with a similar carbazole backbone moiety. LP1 was prepared using a recently reported synthesis under thermodynamic control, leading to a low backbone defect density. We find that the singlet emission lifetime of LP1 is longer than that of any previously reported ladder conjugated polymer, which we attribute to its low defect density. Further, the emission contains a large-amplitude long component with a lifetime that lasts as long as 5 ns. Our results imply that careful control of defects ...

Functional interpretation of the role of cyclic carotenoids in photosynthetic antennas via quantum chemical calculations

In the paper positions of the energy levels of the first three excited states of cyclic carotenoids are calculated. The pigments studied include the representatives of β-carotene homologous series containing 5, 7, 9 and 11 conjugated bonds, as well as xanthophylls: zeaxanthin, violaxanthin, lutein, canthaxanthin, astaxanthin and auroxanthin. The results are obtained using quantum chemistry computational methods. The data obtained are discussed in relation to biological functions of carotenoids and their role in the processes related to electronic excitation energy migration involving chlorophyll and oxygen molecules.

Luminescence of Ln3+ lanthanide complexes in polymer matrices

The photoluminescence properties of Tb3+ and Eu3+ complexes with polymer ligands containing various kinds of complexing groups—namely, carboxyl (5–20 mol %), pyridylquinoline (5 mol %), or pyridylnaphthyl (5 and 10 mol %) groups—in solution and block are considered. The chemical structure of a neutral comonomer (methyl methacrylate; styrene; isopropyl-, phenyl-, or benzylmethacrylamide; and N-vinylamides) in polymer ligands is varied. The intensity of photoluminescence is dependent not only on the chemical nature of a complexing group but also the chemical nature of a neutral comonomer and a spacer. Variation in the nature of a comonomer and a ligand makes it possible to prepare complexes in which a high luminescence of a low-molecular-mass complex is preserved and advantages inherent in a polymer complex are acquired. The effect of the nature of the polymer matrix (photoactive and photoinert) on the efficiency of electronic-excitation energy transfer is ascertained. The data on the photoluminescence of metal-polymer complexes that are based on polymer ligands containing vinylcarbozole units and that possess hole conductivity make it possible to regard them as materials for electroluminescence. The intensity of photoluminescence of these complexes is related to the competition of oppositely directed photophysical processes in a macromolecule: formation of excimers and migration of electronic excitation energy. An analysis of the published data and of the results of the authors shows that detailed studies of these polymer systems in solution and in matrices are needed to gain insight into the relationship between photo- and electroluminescence properties of metal-polymer complexes, because the matrix plays different roles in photoluminescence and electroluminescence (inner filter or conduction); as a consequence, the emission spectra may differ appreciably. It is shown that the efficiency of electroluminescence may be improved if the transfer of energy from the lanthanide ligand in a complex to the conducting matrix is decreased.

Luminescence and electronic excitations in Li6Gd(BO3)3: Ce3+ crystals

This paper reports on a study of the luminescence emitted by Li6Gd(BO3)3: Ce3+ crystals under selective photoexcitation to lower excited states of the host ion Gd3+ and impurity ion Ce3+ within the 100–500-K temperature interval, where the mechanisms of migration and relaxation of electronic excitation energy have been shown to undergo noticeable changes. The monotonic 10–15-fold increase in intensity of the luminescence band at 3.97 eV has been explained within a model describing two competing processes, namely, migration of electronic excitation energy over chains of Gd3+ ions and vibrational energy relaxation between the 6Ij and 6Pj levels. It has been shown that radiative transitions in Ce3+ ions from the lower excited state 5d1 to 2F5/2 and 2F7/2 levels of the ground state produce two photoluminescence bands, at 2.08 and 2.38 eV (Ce1 center) and 2.88 and 3.13 eV (Ce2 center). Possible models of the Ce1 and Ce2 luminescence centers have been discussed.

On the analyses of fluorescence depolarisation data in the presence of electronic energy migration. Part I: Theory and general description

A new and general procedure is described for a detailed analysis of time-resolved fluorescence depolarisation data in the presence of electronic energy migration. An isotropic ensemble of bifluorophoric molecules (D(1)-R-D(2)) has been studied to demonstrate its utility. Intramolecular donor-donor energy migration occurs between the two donor groups (D), which are covalently connected to a rigid linker group (R). These groups undergo restricted reorientational motions with respect to the R group. The analysis of depolarisation data basically involves the search for best-fit parameters which describe the local reorientational motions, the intermolecular D(1)-D(2) distance, as well as the mutual orientations of the donors. For this, the analysis is partly performed on the Fourier domain and the best-fit parameters are determined by using an approach based on a Genetic Algorithm. The energy migration process has been described by using Monte Carlo simulations and an extended Förster theory (EFT). It is found that the EFT provides the least time-consuming computational method. Since one-photon and two-photon excited fluorescence experiments can be applied for energy migration studies, a general and unified theoretical formulation is given.

Artificial Light-Harvesting Arrays: Electronic Energy Migration and Trapping on a Sphere and between Spheres

A sophisticated model of the natural light-harvesting antenna has been devised by decorating a C(60) hexa-adduct with ten yellow and two blue boron dipyrromethene (Bodipy) dyes in such a way that the dyes retain their individuality and assist solubility of the fullerene. Unusually, the fullerene core is a poor electron acceptor and does not enter into light-induced electron-transfer reactions with the appended dyes, but ineffective electronic energy transfer from the excited-state dye to the C(60) residue competes with fluorescence from the yellow dye. Intraparticle electronic energy transfer from yellow to blue dyes can be followed by steady-state and time-resolved fluorescence spectroscopy and by excitation spectra for isolated C(60) nanoparticles dissolved in dioxane at 293 K and at 77 K. The decorated particles can be loaded into polymer films by spin coating from solution. In the dried film, efficient energy transfer occurs such that photons absorbed by the yellow dye are emitted by the blue dye. Films can also be prepared to contain C(60) nanoparticles loaded with the yellow Bodipy dye but lacking the blue dye and, under these circumstances, electronic energy migration occurs between yellow dyes appended to the same nanoparticle and, at higher loading, to dye molecules on nearby particles. Doping these latter polymer films with the mixed-dye nanoparticle coalesces these multifarious processes in a single system. Thus, long-range energy migration occurs among yellow dyes attached to different particles before trapping at a blue dye. In this respect, the film resembles the natural photosynthetic light-harvesting complexes, albeit at much reduced efficacy. The decorated nanoparticles sensitize amorphous silicon photocells.

On the analyses of fluorescence depolarisation data in the presence of electronic energy migration. Part II: Applying and evaluating two-photon excited fluorescence

Electronic energy migration within a bifluorophoric molecule has been studied by time-resolved two-photon excited (TPE) fluorescence depolarisation experiments. Data were analysed by using a recently developed quantitative approach [O. Opanasyuk and L. B.-Å. Johansson, On the Analyses of Fluorescence Depolarisation Data in the Presence of Electronic Energy Migration. Part I: Theory and General Description, Phys. Chem. Chem. Phys., submitted]. The energy migration occurs between the 9-anthrylmethyl groups of the bifluorophoric molecule, bis-(9-anthrylmethylphosphonate) bisteroid. These groups undergo local reorientations, while overall tumbling of the bisteroid is strongly hampered in the used viscous solvent, 1,2-propanediol. To solely obtain information about local reorientations of the 9-anthrylmethyl group, also the mono-(9-anthrylmethylphosphonate) bisteroid was studied, which enabled modelling of the ordering potential shape. The analysis of data is partly performed in the Fourier domain and the best-fit parameters are determined by using an approach based on a Genetic Algorithm. The energy migration process was described by an extended Förster theory (EFT). A reasonable value of the distance between the 9-anthrylmethyl groups, as well as for the mutual orientation of the ordering potentials, is found. Furthermore, values of the two-photon tensor components were obtained.

Electronic Energy Migration in Solid versus Liquid Host Matrices for Concentrated Perylenediimide Dye Solutions

In this paper, we continue our evaluation of Forster-type theories of exciton diffusion in disordered environments. The perylenediimide dye Lumogen Red is used as a donor molecule in two different liquids, CHCl(3) and dimethylformamide, and the energy transfer to the acceptor molecule Rhodamine 700 is measured using time-resolved fluorescence decays. The exciton motion is measured over Lumogen Red concentrations ranging from 1 × 10(-4) to 5 × 10(-2) M, and the results are compared to previous results for exciton diffusion in a solid polymer. Depending on the theoretical approach used to analyze the data, we find that the energy migration in the liquids is a factor of 2-3 faster than in the solid polymer, even after taking molecular translation into account. Measurements for a Lumogen Red concentration of 10 mM in the different host environments yield diffusion constants ranging from 2.2 to 3.1 nm(2)/ns in the liquids, as compared to 1.1-1.2 nm(2)/ns in solid poly(methyl methacrylate) (PMMA). The results in the liquids are in good agreement with theoretical predictions and numerical simulations of previous workers, while the results in solid PMMA are 2-3 times slower. This discrepancy is discussed in the context of the rapid energetic averaging present in the liquid environments but absent in the solid matrix, where unfavorable configurations and low energy trapping sites are frozen in by the static disorder.

A model of dissipative energy transfer in natural and artificial photosystems

Within the Redfield theory, a model is proposed that describes dissipative dynamics of electronic excitation energy migration in natural and artificial photosystems. The model explicitly takes into account physicochemical properties of the protein environment, which allows the fitting parameters to be completely excluded from calculations. The model is used to calculate the dynamics of energy transfer in a photosystem of purple bacteria and eight model photosystems, which helped to reveal the main factors that determine the rate and efficiency of energy transfer.

Two-photon excited fluorescence depolarisation and electronic energy migration within donor–donor pairs

A unified theoretical description is presented for one- and two-photon excited fluorescence depolarisation and electronic energy migration within pairs of chromophores. Two weakly coupled donor groups are linked via a rigid macromolecule with the ability to undergo restricted reorienting motions. Describing these reorienting motions as well as their influence on the coupling is rather complex, but can be accounted for by using the extended Förster theory. Here explicit expressions have been derived for chromophores belonging to the point groups D(2h), D(2) and C(2v) when residing in uniaxial potentials (i.e. C(infinity v) symmetry). From the given basic equations, it is possible however, to derive the relevant equations for molecules of arbitrary symmetry in any uniaxial orienting potential. The expected time-resolved fluorescence anisotropy for different two-photon absorption tensors are compared for reorienting fluorophores in liquids, as well as in anisotropic systems. Simulated fluorescence depolarisation data are also displayed that mimic energy migration within pairs of two-photon excited donor molecules, which simultaneously undergo reorienting motions within effectively isotropic and uniaxially anisotropic environments. The obtained results demonstrate that the time-resolved fluorescence anisotropy strongly depends on the properties of the two-photon absorption tensor, as well as on using a linear or a circular polarisation of the excitation field.

All-optical switching based on controlled energy transfer between nanoparticles in film arrays

The potentiality to exert optical control, over the migration of electronic excitation energy between particles with suitably disposed electronic levels, affords a basis for all optical switching. Implemented in a configuration with nanoparticles arrayed in thin films, the process can offer an ultrafast parallel-processing capability. The mechanism is a near-field transfer of energy from donor nanoparticles in one layer (written into an electronically excited state by the absorption of light) to counterpart acceptors; the transfer effect proves amenable to activation by non-resonant laser radiation. The possibility of optical control arises under conditions where the donor-acceptor energy transfer is rigorously forbidden in the absence of laser light, either on the grounds of symmetry or energetics. Under such conditions, optical switching can be produced by the throughput of a single off resonant beam or, with more control options, by two coincident beams. In model electrodynamical calculations the transfer fidelity, signifying the accuracy of mapping an input to its designated output, can be identified and cast in terms of key optical and geometric characteristics. The results show that, at reasonable levels of laser intensity, cross talk drops to insignificant levels. Potential applications extend beyond simple switching into all-optical elements for logic gates and optical buffers.

Extended Förster theory for determining intraprotein distances : Part III. Partial donor–donor energy migration among reorienting fluorophores

An extended Förster theory (EFT) is derived and outlined for electronic energy migration between two fluorescent molecules which are chemically identical, but photophysically non-identical. These molecules exhibit identical absorption and fluorescence spectra, while their fluorescence lifetimes differ. The latter means that the excitation probability becomes irreversible. Unlike the case of equal lifetimes, which is often referred to as, donor-donor energy migration (DDEM), the observed fluorescence relaxation is then no longer invariant to the energy migration process. To distinguish, the present case is therefore referred to as partial donor-donor energy migration (PDDEM). The EFT of PPDEM is described by a stochastic master equation (SME), which has been derived from the stochastic Liouville equation (SLE) of motion. The SME accounts for the reorienting as well as the translational motions of the interacting chromophores. Synthetic fluorescence lifetime and depolarisation data that mimics time-correlated single photon counting experiments have been generated and re-analysed. The rates of reorientation, as well as the orientational configurations of the interacting D-groups were examined. Moreover the EFT of PPDEM overcomes the classical "kappa(2)-problem" and the frequently applied approximation of kappa(2) = 2/3 in the data analyses. An outline for the analyses of fluorescence lifetime and depolarisation data is also given, which might prove applicable to structural studies of D-labelled macromolecules, e.g. proteins. The EFT presented here brings the analyses of PDDEM data to the same level of molecular detail as that used in ESR- and NMR-spectroscopy.

Fluorescence Depolarization Studies of Filamentous Actin Analyzed with a Genetic Algorithm

A new method, in which a genetic algorithm was combined with Brownian dynamics and Monte Carlo simulations, was developed to analyze fluorescence depolarization data collected by the time-correlated single photon-counting technique. It was applied to studies of BODIPY-labeled filamentous actin (F-actin). The technique registered the local order and reorienting motions of the fluorophores, which were covalently coupled to cysteine 374 (C374) in actin and interacted by electronic energy migration within the actin polymers. Analyses of F-actin samples composed of different fractions of labeled actin molecules revealed the known helical organization of F-actin, demonstrating the usefulness of this technique for structure determination of complex protein polymers. The distance from the filament axis to the fluorophore was found to be considerably less than expected from the proposed position of C374 at a high filament radius. In addition, polymerization experiments with BODIPY-actin suggest a 25-fold more efficient signal for filament formation than pyrene-actin.

Studies of Photoinduced Electron Transfer and Energy Migration in a Conjugated Polymer System for Fluorescence “Turn-On” Chemosensor Applications

A series of poly[p-(phenyleneethynylene)-alt-(thienyleneethynylene)] (PPETE) polymers with variable percent loadings of the N,N,N'-trimethylethylenediamino group on the polymer backbone were synthesized and fully characterized. Photophysical studies show that changes in the loading of the amino group receptor on the backbone do not affect the polymer electronic structure in either the ground or excited states. The fluorescence quantum yields were found to be directly related to the loading of the amino groups and can be modeled by a Stern-Volmer type relationship. Photophysical studies related the total quenching efficiency to the inherent rate of photoinduced electron transfer (PET), the lifetime of the exciton, the rate of excitation energy migration along the polymer backbone, and the total loading of the receptor on the polymer. The role of the loading dependence on the application of these polymers as fluorescence "turn-on" sensors for toxic metal cations in dilute solution was also studied. Results showed that the fluorescence enhancement upon binding various cations was maintained even when the amino receptor loading along the polymer backbone was reduced.