Strong excitonic interactions are a key design strategy in photosynthetic light harvesting, expanding the spectral cross-section for light absorption and creating considerably faster and more robust excitation energy transfer. These molecular excitons are a direct result of exceptionally densely packed pigments in photosynthetic proteins. The main light-harvesting complexes of diatoms, known as fucoxanthin-chlorophyll proteins (FCPs), are an exception, displaying surprisingly weak excitonic coupling between their chlorophyll (Chl) a's, despite a high pigment density. Here, we show, using single-molecule spectroscopy, that the FCP complexes of Cyclotella meneghiniana switch frequently into stable, strongly emissive states shifted 4-10 nm toward the red. A few percent of isolated FCPa complexes and ∼20% of isolated FCPb complexes, on average, were observed to populate these previously unobserved states, percentages that agree with the steady-state fluorescence spectra of FCP ensembles. Thus, the complexes use their enhanced sensitivity to static disorder to increase their light-harvesting capability in a number of ways. A disordered exciton model based on the structure of the main plant light-harvesting complex explains the red-shifted emission by strong localization of the excitation energy on a single Chl a pigment in the terminal emitter domain due to very specific pigment orientations. We suggest that the specific construction of FCP gives the complex a unique strategy to ensure that its light-harvesting function remains robust in the fluctuating protein environment despite limited excitonic interactions.
In the major peripheral plant light-harvesting complex LHCII, excitation energy is transferred between chlorophylls along an energetic cascade before it is transmitted further into the photosynthetic assembly to be converted into chemical energy. The efficiency of these energy transfer processes involves a complicated interplay of pigment-protein structural reorganization and protein dynamic disorder, and the system must stay robust within the fluctuating protein environment. The final, lowest energy site has been proposed to exist within a trimeric excitonically coupled chlorophyll (Chl) cluster, comprising Chls a610-a611-a612. We studied an LHCII monomer with a site-specific mutation resulting in the loss of Chls a611and a612, and find that this mutant exhibits two predominant overlapping fluorescence bands. From a combination of bulk measurements, single-molecule fluorescence characterization, and modeling, we propose the two fluorescence bands originate from differing conditions of exciton delocalization and localization realized in the mutant. Disruption of the excitonically coupled terminal emitter Chl trimer results in an increased sensitivity of the excited state energy landscape to the disorder induced by the protein conformations. Consequently, the mutant demonstrates a loss of energy transfer efficiency. On the contrary, in the wild-type complex, the strong resonance coupling and correspondingly high degree of excitation delocalization within the Chls a610-a611-a612 cluster dampens the influence of the environment and ensures optimal communication with neighboring pigments. These results indicate that the terminal emitter trimer is thus an essential design principle for maintaining the efficient light-harvesting function of LHCII in the presence of protein disorder.
Experimental and theoretical foundations for femtosecond time-resolved circular dichroism (TRCD) spectroscopy of excitonic systems are presented. In this method, the system is pumped with linearly polarized light and the signal is defined as the difference between the transient absorption spectrum probed with left and with right circularly polarized light. We present a new experimental setup with a polarization grating as key element to generate circularly polarized pulses. Herein the positive (negative) first order of the diffracted light is left-(right-)circularly polarized and serves as a probe pulse in a TRCD experiment. The grating is capable of transferring ultrashort broadband pulses ranging from 470 nm to 720 nm into two separate beams with opposite ellipticity. By applying a specific chopping scheme we can switch between left and right circular polarizations and detect transient absorption (TA) and TRCD spectra on a shot-to-shot basis simultaneously. We perform experiments on a squaraine polymer, investigating excitonic dynamics, and we develop a general theory for TRCD experiments of excitonically coupled systems that we then apply to describe the experimental data in this particular example. At a magic angle of 54.7° between the pump-pulse polarization and the propagation direction of the probe pulse, the TRCD and TA signals become particularly simple to analyze, since the orientational average over random orientations of complexes factorizes into that of the interaction with the pump and the probe pulse, and the intrinsic electric quadrupole contributions to the TRCD signal average to zero for isotropic samples. Application of exciton theory to linear absorption and to linear circular dichroism spectra of squaraine polymers reveals the presence of two fractions of polymer conformations, a dominant helical conformation with close interpigment distances that are suggested to lead to short-range contributions to site energy shifts and excitonic couplings of the squaraine molecules, and a fraction of unfolded random coils. Theory demonstrates that TRCD spectra of selectively excited helices can resolve state populations that are practically invisible in TA spectroscopy due to the small dipole strength of these states. A qualitative interpretation of TRCD and TA spectra in the spectral window investigated experimentally is offered. The 1 ps time component found in these spectra is related to the slow part of exciton relaxation obtained between states of the helix in the low-energy half of the exciton manifold. The dominant 140 ps time constant reflects the decay of excited states to the electronic ground state.
- Publication type
- Journal Article MeSH
A comparative two-photon excitation spectroscopic study of the exciton structure of the core antenna complex (LH1) and its subunit B820 was carried out. LH1 and its subunit B820 were isolated from cells of the carotenoid-less mutant G9 of Rhodospirillum rubrum. The measurements were performed by two-photon pump-probe spectroscopy. Samples were excited by 70 fs pulses at 1390 nm at a frequency of 1 kHz. Photoinduced absorption changes were recorded in the spectral range from 780 to 1020 nm for time delays of the probe pulse relative to the pump pulse in the - 1.5 to 11 ps range. All measurements were performed at room temperature. Two-photon excitation caused bleaching of exciton bands (k = 0, k = ± 1) of the circular bacteriochlorophyll aggregate of LH1. In the case of the B820 subunit, two-photon excitation did not cause absorption changes in this spectral range. It is proposed that in LH1 upper exciton branch states are mixed with charge-transfer (CT) states. In B820 such mixing is absent, precluding two-photon excitation in this spectral region. Usually, CT states are optically "dark", i.e., one photon-excitation forbidden. Thus, their investigation is rather complicated by conventional spectroscopic methods. Thus, our study provides a novel approach to investigate CT states and their interaction(s) with other excited states in photosynthetic light-harvesting complexes and other molecular aggregates.
Photosynthetic proteins have evolved over billions of years so as to undergo optimal energy transfer to the sites of charge separation. On the basis of spectroscopically detected quantum coherences, it has been suggested that this energy transfer is partially wavelike. This conclusion depends critically on the assignment of the coherences to the evolution of excitonic superpositions. We demonstrate that, for a bacterial reaction center protein, long-lived coherent spectroscopic oscillations, which bear canonical signatures of excitonic superpositions, are essentially vibrational excited-state coherences shifted to the ground state of the chromophores. We show that the appearance of these coherences arises from a release of electronic energy during energy transfer. Our results establish how energy migrates on vibrationally hot chromophores in the reaction center, and they call for a reexamination of claims of quantum energy transfer in photosynthesis.
Chlorosomes from green photosynthetic bacteria belong to the most effective light-harvesting antennas found in nature. Quinones incorporated in bacterichlorophyll (BChl) c aggregates inside chlorosomes play an important redox-dependent photo-protection role against oxidative damage of bacterial reaction centers. Artificial BChl c aggregates with and without quinones were prepared. We applied hole-burning spectroscopy and steady-state absorption and emission techniques at 1.9 K and two different redox potentials to investigate the role of quinones and redox potential on BChl c aggregates at low temperatures. We show that quinones quench the excitation energy in a similar manner as at room temperature, yet the quenching process is not as efficient as for chlorosomes. Interestingly, our data suggest that excitation quenching partially proceeds from higher excitonic states competing with ultrafast exciton relaxation. Moreover, we obtained structure-related parameters such as reorganization energies and inhomogeneous broadening of the lowest excited state, providing experimental ground for theoretical studies aiming at designing plausible large-scale model for BChl c aggregates including disorder.
- MeSH
- Absorption MeSH
- Bacterial Proteins analysis chemistry MeSH
- Bacteriochlorophylls analysis chemistry MeSH
- Fluorescence MeSH
- Oxidation-Reduction MeSH
- Spectrum Analysis methods MeSH
- Temperature MeSH
- Vitamin K 2 chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
Photosystems, the machines of photosynthesis, are highly complex and energetically disordered pigment-protein structures. Yet, they perform their function, be it highly efficient energy transfer and charge separation or the ability to switch between light-harvesting and photoprotective states, extremely well. In this opinioned review we describe the interplay of disorder and exciton delocalization in photosynthetic light harvesting. By discussing recent research advances on grounds of well-established concepts, we demonstrate that not only is the excitation delocalization a robust phenomenon, but that it in fact enables the light-harvesting function in the disordered environment.
A systematic study of photothermally stimulated defects creation processes is carried out by the thermally stimulated luminescence (TSL) method for a large number of undoped and doped PbWO4 crystals under irradiation at 80-180 K in the 3.4-4.3 eV energy range. The activation energy Ea for the regular exciton state disintegration is found to be approximately 0.1 eV. For defect-related states disintegration, Ea varies in the crystals studied from 0.03 to 0.36 eV. The origin of the defect-related states is discussed. The conclusion is made that not only a release of charge carriers but also charge transfer processes take place under UV irradiation of PbWO4 crystals.
The potential of organic semiconductor based devices for light generation is demonstrated by the commercialisation of display technologies using organic light emitting diode (OLED). In OLED, organic materials plays an important role of emitting light once the current is passed through. However OLED have drawbacks whereby it suffers from photon loss and exciton quenching. Organic light emitting transistor (OLET) emerged as a new technology to compensate the efficiency and brightness loss encountered in OLED. The structure has combinational capability to switch the electronic signal such as the field effect transistor (FET) as well as to generate light. Different colours of light could be generated by using different types of organic material. The light emission could also be tuned and scanned in OLET. The studies carried out in this paper focuses on investigation of fabricated MEH-PPV based OLED and also OLET via current voltage characteristics. These studies will continue with a view to develop an optimised MEH-PPV based OLET.
- MeSH
- Equipment Failure Analysis MeSH
- Equipment Design MeSH
- Electric Conductivity MeSH
- Transistors, Electronic * MeSH
- Organic Chemicals chemistry MeSH
- Lighting instrumentation MeSH
- Semiconductors * MeSH
- Electron Transport MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Review MeSH
