Förster Resonance Energy Transfer Rate Research Articles

Förster Resonance Energy Transfer Sensitized Singlet Fission in BODIPY‐Pentacene Dimer Conjugates

AbstractIn the present work, the energy donor 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) is used for the first time in combination with a pentacene dimer (Pnc2) to provide the conjugate BODIPYPnc2 that features absorption throughout a large part of the solar spectrum. Upon photoexcitation, the singlet excited state energy of BODIPY is transferred to the pentacene dimer via intramolecular Förster resonance energy transfer (FRET). Subsequently, the pentacene dimer undergoes intramolecular singlet fission. In this process, a singlet correlated triplet pair is generated from the first singlet excited state via coupling to an intermediate state. The results show that solvent polarity has an influence on the system, with the largest FRET rate (i.e., 7.46 × 1011 s−1) being obtained in the most polar solvent (namely, benzonitrile) along with the largest triplet quantum yield (i.e., 207 ± 20%).

Computation of Förster Resonance Energy Transfer in Lipid Bilayer Membranes.

Calculations of Förster Resonance Energy Transfer (FRET) often neglect the influence of different chromophore orientations or changes in the spectral overlap. In this work, we present two computational approaches to estimate the energy transfer rate between chromophores embedded in lipid bilayer membranes. In the first approach, we assess the transition dipole moments and the spectral overlap by means of quantum chemical calculations in implicit solvation, and we investigate the alignment and distance between the chromophores in classical molecular dynamics simulations. In the second, all properties are evaluated integrally with hybrid quantum mechanical/molecular mechanics (QM/MM) calculations. Both approaches come with advantages and drawbacks, and despite the fact that they do not agree quantitatively, they provide complementary insights on the different factors that influence the FRET rate. We hope that these models can be used as a basis to optimize energy transfers in nonisotropic media.

Mechanism of Ir(ppy)3 Guest Exciton Formation with the Exciplex-Forming TCTA:TPBI Cohost within a Phosphorescent Organic Light-Emitting Diode Environment.

Cohosts based on hole transporting and electron transporting materials often act as exciplexes in the form of intermolecular charge transfer complexes. Indeed, exciplex-forming cohosts have been widely developed as the host materials for efficient phosphorescent organic light-emitting diodes (OLEDs). In host–guest systems of OLEDs, the guest can be excited by two competing mechanisms, namely, excitation energy transfer (EET) and charge transfer (CT). Experimentally, it has been reported that the EET mechanism is dominant and the excitons are primarily formed in the host first and then transferred to the guest in phosphorescent OLEDs based on exciplex-forming cohosts. With this, exciplex-forming cohosts are widely employed for avoiding the formation of trapped charge carriers in the phosphorescent guest. However, theoretical studies are still lacking toward elucidating the relative importance between EET and CT processes in exciting the guest molecules in such systems. Here, we obtain the kinetics of guest excitation processes in a few trimer model systems consisting of an exciplex-forming cohost pair and a phosphorescent guest. We adopt the Förster resonance energy transfer (FRET) rate constants for the electronic transitions between excited states toward solving kinetic master equations. The input parameters for calculating the FRET rate constants are obtained from density functional theory (DFT) and time-dependent DFT. The results show that while the EET mechanism is important, the CT mechanism may still play a significant role in guest excitations. In fact, the relative importance of CT over EET depends strongly on the location of the guest molecule relative to the cohost pair. This is understandable as both the coupling for EET and the interaction energy for CT are strongly influenced by the geometric constraints. Understanding the energy transfer pathways from the exciplex state of cohost to the emissive state of guest may provide insights for improving exciplex-forming materials adopted in OLEDs.

Fluorescence lifetime imaging of metMyoglobin formation due to nitric oxide stress.

Myoglobin is a protein that is expressed quite unevenly among different cell types. Nevertheless, it has been widely acknowledged that the Fe3+ state of myoglobin, metmyoglobin (metMb) has a broad functional role in metabolism, oxidative/nitrative regulation and gene networks. Accordingly, real-time monitoring of oxygenated, deoxygenated and metMb proportions- or, more broadly, of the mechanisms by which metMb is formed, presents a promising line of research. We had previously introduced a Förster resonance energy transfer (FRET) method to read out the deoxygenation/oxygenation states of myoglobin, by creating the targetable oxygen (O2) sensor Myoglobin-mCherry. In this sensor, changes in myoglobin absorbance features that occur with lost O2 occupancy -or upon metMb production- control the FRET rate from the fluorescent protein to myoglobin. When O2 is bound, mCherry fluorescence is only slightly quenched, but if either O2 is released or met is produced, FRET will increase- and this rate competing with emission reduces both emission yield and lifetime. Nitric oxide (NO) is an important signal (but also a toxic molecule) that can oxidize myoglobin to metMb with absorbance increases in the red visible range. mCherry thus senses both met and deoxygenated myoglobin, which cannot be easily separated at hypoxia. In order to dissect this, we treat cells with NO and investigate how the Myoglobin-mCherry lifetime is affected by generating metMb. More discriminatory power is then achieved when the fluorescent protein EYFP is added to Myoglobin-mCherry, creating a sandwich probe whose lifetime can selectively respond to metMb while being indifferent to O2 occupancy.

Förster Resonance Energy Transfer Rate and Efficiency in Plasmonic Nanopatch Antennas

AbstractSuccessful control of Förster resonance energy transfer (FRET) through the engineering of the local density of optical states (LDOS) will allow us to develop novel strategies to fully exploit this phenomenon in key enabling technologies. Here we present an experimental and theoretical study on the effect of the LDOS on the FRET rate and efficiency in plasmonic nanopatch antennas formed between a gold nanoparticle and an extended silver film. Our results reveal that plasmonic nanopatch antennas of similar levels of LDOS exhibit comparable levels of FRET rate and FRET efficiency, demonstrating that LDOS plays an important part in controlling both FRET rate and efficiency. Our findings contribute to the ongoing debate about the relation between the FRET process and the LDOS, as well as directly impacting the development of novel FRET based light harvesting and sensing devices.

Förster Resonance Energy Transfer in Linear DNA Multifluorophore Photonic Wires: Comparing Dual versus Split Rail Building Block Designs

AbstractDNA scaffolds provide a means to precisely organize chromophores into large biomimetic exciton networks and direct energy transport for nanoscale sensing and light‐harvesting applications. Here, a functional building block of minimal complexity that maximizes the Förster resonance energy transfer (FRET) efficiency is sought. Using a model system consisting of three FRET steps in a 4‐dye cascade: Cy3→Cy3.5→Cy5→Cy5.5, we evaluate how this building block employs multiple interacting versus redundant FRET pathways. Variants of a dual rail design, where one or two copies of each dye are aligned in rigid linear parallel rows, are compared to a split rail format, where varying degrees of spacing are introduced between the rows. The FRET processes are assessed via steady‐state, time‐resolved, and single‐molecule spectroscopy. Experiments and simulation reveal the dual rail design as more efficient than the split rail and suggest the design principle that efficient FRET networks must balance the increase in FRET rate from multiple interacting pathways with undesirable fluorescence quenching between dyes in close proximity. Hybrid fluorophore combinations are identified as a strategy to mitigate this quenching, leading to optimized dual rails capable of 50% end‐to‐end efficiency. These insights can help guide the design of functional photonic wires based on DNA scaffolds.

Förster Resonance Energy Transfer and the Local Optical Density of States in Plasmonic Nanogaps.

Förster resonance energy transfer (FRET) is a fundamental phenomenon in photosynthesis and is of increasing importance for the development and enhancement of a wide range of optoelectronic devices, including color-tuning LEDs and lasers, light harvesting, sensing systems, and quantum computing. Despite its importance, fundamental questions remain unanswered on the FRET rate dependency on the local density of optical states (LDOS). In this work, we investigate this directly, both theoretically and experimentally, using 30 nm plasmonic nanogaps formed between a silver nanoparticle and an extended silver film, in which the LDOS can be controlled using the size of the silver nanoparticle. Experimentally, uranin-rhodamine 6G donor-acceptor pairs coupled to such nanogaps yielded FRET rate enhancements of 3.6 times. This, combined with a 5-fold enhancement in the emission rate of the acceptor, resulted in an overall 14-fold enhancement in the acceptor's emission intensity. By tuning the nanoparticle size, we also show that the FRET rate in those systems is linearly dependent on the LDOS, a result which is directly supported by our finite difference time domain (FDTD) calculations. Our results provide a simple but powerful method to control FRET rate via a direct LDOS modification.

Cavity-enhanced energy transfer between nano-emitters and monolayer graphene

Photonic cavities have been shown to efficiently control and enhance the Förster resonance energy transfer (FRET) between point-like donors and acceptors. In this work, we experimentally implemented photonic cavity control of the energy transfer between point-like donors and two-dimensional acceptors, using an integrated system combining an Al/SiO2 cavity with nano-emitters and graphene. We demonstrate that the Al/SiO2 cavity can control energy transfer between nanodiamond nitrogen-vacancy (NV) centers and monolayer graphene by tuning the thickness of the SiO2 layer, providing a two-fold enhancement of both the FRET efficiency and rate. Our results of point-to-layer FRET systems pave the way for a graphene-integrated dielectric cavity platform for application in enhanced light–matter interaction and photodetection devices.

Impact of a charged neighboring particle on Förster resonance energy transfer (FRET)

Förster resonance energy transfer (FRET) is an important physical phenomenon which demands precise control over the FRET rate for its wide range of applications. Hence, enhancing the FRET rate using different techniques has been extensively studied in the literature. Research indicates that introducing additional particles to a system consisting of a donor-acceptor pair can change the behaviour of FRET in the system. One such technique is to utilize the collective oscillations of the surface electrons of a neighboring electrically-neutral metal nanoparticle (MNP). However, the perceived changes on the FRET rate between the donor and the acceptor, when the MNP carries excess electrical charges are yet unknown. In this paper, we study these changes by introducing a charged MNP, in the proximity of an excited donor and a ground state acceptor. We deploy the classical Green’s tensor to express the FRET rate in the system. We consider an effective dielectric response for the MNP, which accounts for the extraneous surface charge effects. We analyze the electrical potential at the acceptor position due to the changed dipole moment of the donor molecule as a result of the electric field induced at the donor position, and obtain the FRET rate of the system. This model considers arbitrary locations and orientations of the two molecular dipole moments with regard to the position of the spherical MNP. We present the enhancement of the FRET rate, predominantly caused by both the surface plasmon excitations and the extraneous surface electrical charges carried by the neighboring MNP. We obtain the results by varying the separation distance between the molecules and the MNP, the transition frequency of the donor-acceptor pair and the size of the metallic sphere. Specifically, we demonstrate that a donor-acceptor pair placed in the vicinity of an electrically-charged Silver MNP exhibits a remarkable improvement in the FRET rate. Furthermore, the aggregate FRET enhancement is determined by other characteristics such as the location of the donor, transition frequency, separation distances and the radius of the MNP. In essence, these findings reveal an approach to realize the enhanced FRET rate in a larger span in a more controlled manner that is desirable in many FRET-based applications including spectroscopic measurements.

Plasmon-Coupled Förster Resonance Energy Transfer between Silicon Quantum Dots

The distance dependence of localized surface plasmon (LSP)-coupled Förster resonance energy transfer (FRET) between Si quantum dots (QDs) is experimentally and theoretically investigated utilizing core–shell nanostructures. The dependence of the energy transfer efficiency, rate, and characteristic distance, as well as the enhancement of the acceptor emission, on the shell thickness is examined. Compared to the structure without assistance of LSP from silver nanoparticles (Ag NPs), the FRET rate is enhanced by a factor of 15, and the Förster radius increases by 50% as a result of plasmon-coupling to the Si QDs and the FRET-assisted exciton transfer from the donors to the acceptors. The potential to tune the characteristic energy transfer distance has implications for applications in nanophotonic devices or sensors.

Orientation-Controlled Nonradiative Energy Transfer to Colloidal Nanoplatelets: Engineering Dipole Orientation Factor.

We proposed and showed strongly orientation-controlled Förster resonance energy transfer (FRET) to highly anisotropic CdSe nanoplatelets (NPLs). For this purpose, we developed a liquid-air interface self-assembly technique specific to depositing a complete monolayer of NPLs only in a single desired orientation, either fully stacked (edge-up) or fully nonstacked (face-down), with near-unity surface coverage and across large areas over 20 cm2. These NPL monolayers were employed as acceptors in an energy transfer working model system to pair with CdZnS/ZnS core/shell quantum dots (QDs) as donors. We found the resulting energy transfer from the QDs to be significantly accelerated (by up to 50%) to the edge-up NPL monolayer compared to the face-down one. We revealed that this acceleration of FRET is accounted for by the enhancement of the dipole-dipole interaction factor between a QD-NPL pair (increased from 1/3 to 5/6) as well as the closer packing of NPLs with stacking. Also systematically studying the distance-dependence of FRET between QDs and NPL monolayers via varying their separation (d) with a dielectric spacer, we found out that the FRET rate scales with d-4 regardless of the specific NPL orientation. Our FRET model, which is based on the original Förster theory, computes the FRET efficiencies in excellent agreement with our experimental results and explains well the enhancement of FRET to NPLs with stacking. These findings indicate that the geometrical orientation of NPLs and thereby their dipole interaction strength can be exploited as an additional degree of freedom to control and tune the energy transfer rate.

Förster Resonance Energy Transfer inside Hyperbolic Metamaterials

The ability to control Forster resonance energy transfer (FRET) between emitters via the design of nanostructured materials with appropriate electromagnetic properties is important in the development of fast and enhanced sources of illumination, high-efficiency photovoltaic devices, and biomedical applications, such as nanorulers. While the engineering of the local density of states allows an efficient control over the spontaneous emission rate, its influence on the FRET process has been an ongoing debate and has led to disparate experimental and theoretical results. Here, we experimentally demonstrate an increase in the FRET rate for donor–acceptor (D–A) pairs separated by fixed distances (3.4, 6.8, and 10.2 nm) located inside a hyperbolic metamaterial comprised of an array of gold nanorods. While the modification of the local density of states surrounding the D–A pairs strongly influences the FRET rate, leading to a 13-fold increase inside the metamaterial, the FRET efficiency is shown to remain mostly ...

Fundamental figures of merit for engineering Förster resonance energy transfer.

Over the past 15 years there has been an ongoing debate regarding the influence of the photonic environment on Förster resonance energy transfer (FRET). Disparate results corresponding to enhancement, suppression and null effect of the photonic environment have led to a lack of consensus between the traditional theory of FRET and experiments. Here we show that the quantum electrodynamic theory (QED) of FRET near an engineered nanophotonic environment is exactly equivalent to an effective near-field model describing electrostatic dipole-dipole interactions. This leads to an intuitive and rigorously exact description of FRET, previously unavailable, bridging the gap between experimental observations and theoretical interpretations. Furthermore, we show that the widely used concept of Purcell factor variation is only important for understanding spontaneous emission and is an incorrect figure of merit (FOM) for analyzing FRET. To this end, we analyze the figures of merit which characterize FRET in a photonic environment 1) the FRET rate enhancement factor (FET), 2) FRET efficiency enhancement factor (Feff) and 3) Two-point spectral density (SEE) which is the photonic property of the environment governing FRET analogous to the local density of states that controls spontaneous emission. Counterintuitive to existing knowledge, we show that suppression of the Purcell factor is in fact necessary for enhancing the efficiency of the FRET process. We place fundamental bounds on the FRET figures of merit arising from material absorption in the photonic environment as well as key properties of emitters including intrinsic quantum efficiencies and orientational dependence. Finally, we use our approach to conclusively explain multiple recent experiments and predict regimes where the FRET rate is expected to be enhanced, suppressed or remain the same. Our work paves for a complete theory of FRET with predictive power for designing the ideal photonic environment to control FRET.

Near-Unity Efficiency Energy Transfer from Colloidal Semiconductor Quantum Wells of CdSe/CdS Nanoplatelets to a Monolayer of MoS2.

A hybrid structure of the quasi-2D colloidal semiconductor quantum wells assembled with a single layer of 2D transition metal dichalcogenides offers the possibility of highly strong dipole-to-dipole coupling, which may enable extraordinary levels of efficiency in Förster resonance energy transfer (FRET). Here, we show ultrahigh-efficiency FRET from the ensemble thin films of CdSe/CdS nanoplatelets (NPLs) to a MoS2 monolayer. From time-resolved fluorescence spectroscopy, we observed the suppression of the photoluminescence of the NPLs corresponding to the total rate of energy transfer from ∼0.4 to 268 ns-1. Using an Al2O3 separating layer between CdSe/CdS and MoS2 with thickness tuned from 5 to 1 nm, we found that FRET takes place 7- to 88-fold faster than the Auger recombination in CdSe-based NPLs. Our measurements reveal that the FRET rate scales down with d-2 for the donor of CdSe/CdS NPLs and the acceptor of the MoS2 monolayer, d being the center-to-center distance between this FRET pair. A full electromagnetic model explains the behavior of this d-2 system. This scaling arises from the delocalization of the dipole fields in the ensemble thin film of the NPLs and full distribution of the electric field across the layer of MoS2. This d-2 dependency results in an extraordinarily long Förster radius of ∼33 nm.

FRET enhancement close to gold nanoparticles positioned in DNA origami constructs.

Here we investigate the energy transfer rates of a Förster resonance energy transfer (FRET) pair positioned in close proximity to a 5 nm gold nanoparticle (AuNP) on a DNA origami construct. We study the distance dependence of the FRET rate by varying the location of the donor molecule, D, relative to the AuNP while maintaining a fixed location of the acceptor molecule, A. The presence of the AuNP induces an alteration in the spontaneous emission of the donor (including radiative and non-radiative rates) which is strongly dependent on the distance between the donor and AuNP surface. Simultaneously, the energy transfer rates are enhanced at shorter D-A (and D-AuNP) distances. Overall, in addition to the direct influence of the acceptor and AuNP on the donor decay there is also a significant increase in decay rate not explained by the sum of the two interactions. This leads to enhanced energy transfer between donor and acceptor in the presence of a 5 nm AuNP. We also demonstrate that the transfer rate in the three "particle" geometry (D + A + AuNP) depends approximately linearly on the transfer rate in the donor-AuNP system, suggesting the possibility to control FRET process with electric field induced by 5 nm AuNPs close to the donor fluorophore. It is concluded that DNA origami is a very versatile platform for studying interactions between molecules and plasmonic nanoparticles in general and FRET enhancement in particular.

Interaction and energy transfer studies between bovine serum albumin and CdTe quantum dots conjugates: CdTe QDs as energy acceptor probes.

In this paper, a systematic investigation of the interaction of bovine serum albumin (BSA) with water-soluble CdTe quantum dots (QDs) of two different sizes capped with carboxylic thiols is presented based on steady-state and time-resolved fluorescence measurements. Efficient Förster resonance energy transfer (FRET) was observed to occur from BSA donor to CdTe acceptor as noted from reduction in the fluorescence of BSA and enhanced fluorescence from CdTe QDs. FRET parameters such as Förster distance, spectral overlap integral, FRET rate constant and efficiency were determined. The quenching of BSA fluorescence in aqueous solution observed in the presence of CdTe QDs infers that fluorescence resonance energy transfer is primarily responsible for the quenching phenomenon. Bimolecular quenching constant (kq ) determined at different temperatures and the time-resolved fluorescence data provide additional evidence for this. The binding stoichiometry and various thermodynamic parameters are evaluated by using the van 't Hoff equation. The analysis of the results suggests that the interaction between BSA and CdTe QDs is entropy driven and hydrophobic forces play a key role in the interaction. Binding of QDs significantly shortened the fluorescence lifetime of BSA which is one of the hallmarks of FRET. The effect of size of the QDs on the FRET parameters are discussed in the light of FRET parameters obtained.

Simultaneously giant enhancement of Förster resonance energy transfer rate and efficiency based on plasmonic excitations

By using an exact multiscattering electromagnetic Green's function method, we present rigorous calculations on the rate and efficiency of F\"orster resonance energy transfer (FRET) from a donor to an acceptor when they are located in the hotspots of nanoparticle clusters. A nonlocal effect has been considered by using a hydrodynamic model. It is found that the FRET rate and efficiency can be enhanced simultaneously by more than 9 and 3 orders of magnitude, respectively, due to the strong coupling plasmon resonances originating from collective excitations of nanoparticle clusters. The physical origins for these phenomena have been disclosed. Two opposite phenomena, the energy transfer rate being independent or dependent on the local density of optical states (LDOS), have been observed in the same system under different conditions. These findings not only help us to understand the unresolved debate on how the FRET rate depends on the LDOS, but also provide a way to realize ultrafast the energy transfer process with ultrahigh efficiency.

Failure of the IDA in FRET Systems at Close Inter-Dye Distances Is Moderated by Frequent Low κ(2) Values.

Förster resonance energy transfer (FRET) is analyzed in terms of distance- and orientation-dependent interactions between the transition dipole moments of the involved donor and acceptor molecules. However, the ideal dipole approximation (IDA) is known to fail at short donor-acceptor distances. In this work, we model FRET in a Cy5- and Alexa Fluor 488-labeled double-stranded RNA by means of combined molecular dynamics (MD) simulations and quantum-chemical calculations involving the IDA as well as the more sophisticated monomer transition density (MTD) approach. To this end, the relaxed ground-state geometries of the dyes were fitted to the MD-based structures. Although substantial deviations between IDA and MTD results can be observed for individual snapshots, the statistical impact of the failure on the FRET rates is negligible in the chosen examples. Our results clearly demonstrate that the IDA-based Förster model can still be applied to systems with small donor-acceptor distances, provided that the dyes are not trapped in arrangements with a high IDA failure and that the distribution of the relative transition dipole orientations is fairly isotropic.

Förster resonance energy transfer rate in any dielectric nanophotonic medium with weak dispersion

Motivated by the ongoing debate about nanophotonic control of Förster resonance energy transfer (FRET), notably by the local density of optical states (LDOS), we study FRET and spontaneous emission in arbitrary nanophotonic media with weak dispersion and weak absorption in the frequency overlap range of donor and acceptor. This system allows us to obtain the following two new insights. Firstly, we derive that the FRET rate only depends on the static part of the Green function. Hence, the FRET rate is independent of frequency, in contrast to spontaneous-emission rates and LDOS that are strongly frequency dependent in nanophotonic media. Therefore, the position-dependent FRET rate and the LDOS at the donor transition frequency are completely uncorrelated for any nondispersive medium. Secondly, we derive an exact expression for the FRET rate as a frequency integral of the imaginary part of the Green function. This leads to very accurate approximation for the FRET rate that features the LDOS that is integrated over a huge bandwidth ranging from zero frequency to far into the UV. We illustrate these general results for the analytic model system of a pair of ideal dipole emitters—donor and acceptor—in the vicinity of an ideal mirror. We find that the FRET rate is independent of the LDOS at the donor emission frequency. Moreover, we observe that the FRET rate hardly depends on the frequency-integrated LDOS. Nevertheless, the FRET is controlled between inhibition and 4×enhancement at distances close to the mirror, typically a few nm. Finally, we discuss the consequences of our results to applications of Förster resonance energy transfer, for instance in quantum information processing.

Observation of an Ultrafast Exciton Hopping Channel in Organic Semiconducting Crystals

One of the major challenges in using organic semiconductors for photovoltaics is their extremely short exciton diffusion length. Recently, a number of studies have shown that the exciton transport range within the first few picoseconds after photoexcitation can be comparable to the exciton’s diffusion length over its entire lifetime. The origin of this fast transport channel is often attributed to the large spatial coherent size of the exciton right after photoexcitation. Here we observe an ultrafast exciton hopping channel in titanyl phthalocyanine crystals even though the exciton coherent size is a few times smaller than the transport range. This channel operates only within the first few picoseconds after photoexcitation and has a hopping rate that is an order of magnitude faster than the typical Forster resonance energy transfer rate. Resonant Raman spectroscopy shows that the optically excited exciton is strongly mixed with the macrocycle vibrational mode of the phthalocyanine molecules. A hypothesis...