Search NASA⌕ Search

SEARCH · Search NASA

Results for “Light harvesting complexes”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Computing the Relative Affinity of Chlorophylls a and b to Light-Harvesting Complex II

In plants and algae, the primary antenna protein bound to photosystem II is light-harvesting complex II (LHCII), a pigment–protein complex that binds eight chlorophyll (Chl) a molecules and six Chl b molecules. Chl a and Chl b differ only in that Chl a has a methyl group (–CH 3 ) on one of its pyrrole rings, while Chl b has a formyl group (–CHO) at that position. This blue-shifts the Chl b absorbance relative to Chl a . It is not known how the protein selectively binds the right Chl type at each site. Knowing the selection criteria would allow the design of light-harvesting complexes that bind different Chl types, modifying an organism to utilize the light of different wavelengths. The difference in the binding affinity of Chl a and Chl b in pea and spinach LHCII was calculated using multiconformation continuum electrostatics and free energy perturbation. Both methods have identified some Chl sites where the bound Chl type ( a or b ) has a significantly higher affinity, especially when the protein provides a hydrogen bond for the Chl b formyl group. However, the Chl a sites often have little calculated preference for one Chl type, so they are predicted to bind a mixture of Chl a and b . The electron density of the spinach LHCII was reanalyzed, which, however, confirmed that there is negligible Chl b in the Chl a -binding sites. Finally, it is suggested that the protein chooses the correct Chl type during folding, segregating the preferred Chl to the correct binding site.

chemical calculations↗
DOE OSTI2020

Variable optical properties of light-harvesting complex II revisited

Understanding photosynthetic light harvesting requires knowledge of the molecular mechanisms that dissipate excess energy in thylakoids. However, it remains unclear how the physical environment of light-harvesting complex II (LHCII) influences the process of chlorophyll de-excitation. Here, we demonstrate that protein-protein interactions between LHCIIs affect the optical properties of LHCII and thus influence the total energy budget. Aggregation of LHCII in the dark altered its absorption properties, independent of the amount of prior light exposure. We also revisited the triplet excited state involved in light-induced fluorescence quenching and found another relaxation pathway involving emission in the green region, which might be related to triplet excited energy transfer to neighboring carotenoids and annihilation processes that result in photoluminescence. LHCII- containing liposomes with different protein densities exhibited altered fluorescence and scattering properties. Our results suggest that macromolecular reorganization affects overall optical properties, which need to be addressed to compare the level of energy dissipation.

Iwai, Masakazu↗
DOE OSTI2025

Switchable client specificity in a dual functional chaperone coordinates light-harvesting complex biogenesis

The proper assembly of light-harvesting complexes (LHCs) is critical for photosynthesis and requires the biogenesis of light-harvesting chlorophylla,b-binding proteins (LHCPs) to be coordinated with chlorophyll (Chl) biosynthesis. The mechanism underlying this coordination is not well understood. Here, we show that a conserved molecular chaperone, chloroplast signal recognition particle 43-kDa protein (cpSRP43), provides a molecular thermostat that helps maintain this coordination. cpSRP43 undergoes a conformational rearrangement between a well-folded closed state and a partially disordered open state. Closed cpSRP43 is dedicated to the biogenesis of LHCPs, whereas open cpSRP43 protects multiple Chl biosynthesis enzymes from heat-induced destabilization. Rising temperature shifts cpSRP43 to the open state, enabling it to protect heat-destabilized Chl biosynthesis enzymes. Our results reveal the molecular basis of a posttranslational mechanism for the thermoadaptation of LHC biogenesis. They also demonstrate how an adenosine triphosphate–independent chaperone uses conformational dynamics to switch its activity and client selectivity, thereby adapting to different proteostatic demands under shifting environmental conditions.

Science & Technology - Other Topics↗
DOE OSTI2019

Mesophyll-specific phytochromes impact chlorophyll light-harvesting complexes (LHCs) and non-photochemical quenching

Phytochromes regulate light-dependent plastid development and plant growth and development. Prior analyses demonstrated that phytochromes regulate expression of Sigma factor 2 (SIG2), which is involved in plastid transcription and coordinates expression of plastid- and nuclear-encoded genes involved in plastid development, as well as plant growth and development. Mutation of SIG2 impacts distinct aspects of photosynthesis, resulting in elevated levels of cyclic electron flow and nonphotochemical quenching (NPQ). As we initially identified SIG2 expression as misregulated in a line lacking phytochromes in mesophyll tissues (i.e., CAB3::pBVR lines), here we report on an investigation of whether photosynthetic parameters such as NPQ are also disrupted in CAB3::pBVR lines. We determined that a specific parameter of NPQ, i.e., energy-dependent quenching (qE) which is a rapidly induced photoprotective mechanism that dissipates stressful absorption of excess light energy during photosynthesis, is disrupted when mesophyll phytochromes are significantly depleted. The observed reduction in NPQ levels in strong CAB3::pBVR lines is associated with a reduction in the accumulation of Lhcb1 proteins and assembly or stability of light-harvesting complexes (LHCs), especially trimeric LHC. These results implicate mesophyll-localized phytochromes in a specific aspect of phytochrome-mediated NPQ, likely through regulation of chlorophyll synthesis and accumulation and the associated impacts on chlorophyll-protein complexes. Finally, this role is distinct from the impact of mesophyll phytochrome-dependent control of SIG2 and associated NPQ regulation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

The role of mixed vibronic Q y -Q x states in green light absorption of light-harvesting complex II

The importance of green light for driving natural photosynthesis has long been underappreciated, however, under the presence of strong illumination, green light actually drives photosynthesis more efficiently than red light. This green light is absorbed by mixed vibronic Q y -Q x states, arising from chlorophyll (Chl)-Chl interactions, although almost nothing is known about these states. Here, we employ polarization-dependent two-dimensional electronic-vibrational spectroscopy to study the origin and dynamics of the mixed vibronic Q y -Q x states of light-harvesting complex II. We show the states in this region dominantly arise from Chl b and demonstrate how it is possible to distinguish between the degree of vibronic Q y versus Q x character. We find that the dynamics for states of predominately Chl b Q y versus Chl b Q x character are markedly different, as excitation persists for significantly longer in the Q x states and there is an oscillatory component to the Q x dynamics, which will be discussed. Our findings demonstrate the central role of electronic-nuclear mixing in efficient light-harvesting and the different functionalities of Chl a and Chl b .

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

A bottom-up perspective on photodynamics and photoprotection in light-harvesting complexes using anti-Brownian trapping

Single-molecule fluorescence spectroscopy allows direct, real-time observation of dynamic photophysical changes in light harvesting complexes. The Anti-Brownian ELectrokinetic (ABEL) trap is one such single-molecule method with useful advantages. This approach is particularly well-suited to make detailed spectroscopic measurements of pigment-protein complexes in solution phase because it enables extended-duration single-molecule observation by counteracting Brownian motion. This Perspective summarizes recent contributions by the authors and others that have utilized the unique capabilities of the ABEL trap to advance our understanding of phycobiliproteins and the phycobilisome complex, the primary light-harvesting apparatus of cyanobacteria. Monitoring the rich spectroscopic data from these measurements, which include brightness, fluorescence lifetime, polarization, and emission spectra, among other measurable parameters, has provided direct characterization of pigments and energy transfer pathways in the phycobilisome, spanning scales from single pigments and monomeric phycobiliproteins to higher order oligomers and protein-protein interactions of the phycobilisome complex. Importantly, new photophysical states and photodynamics were observed to modulate the flow of energy through the phycobilisome and suggest a previously unknown complexity in phycobilisome light harvesting and energy transport with a possible link to photoadaptive or photoprotective functions in cyanobacteria. Here, beyond deepening our collective understanding of natural light-harvesting systems, these and future discoveries may serve as inspiration for engineering improved artificial light-harvesting technologies.

14 SOLAR ENERGY↗
DOE OSTI2018

Delocalized excitons in natural light-harvesting complexes

Natural organisms such as photosynthetic bacteria, algae, and plants employ complex molecular machinery to convert solar energy into biochemical fuel. An important common feature shared by most of these photosynthetic organisms is that they capture photons in the form of excitons typically delocalized over a few to tens of pigment molecules embedded in protein environments of light harvesting complexes (LHCs). Delocalized excitons created in such LHCs remain well protected despite being swayed by environmental fluctuations and are delivered successfully to their destinations over 100 nanometer distances in about 100 ps times. Decades of experimental and theoretical investigation have produced a large body of information offering insight into major structural, energetic, and dynamical features contributing to LHCs’ extraordinary capability to harness photons using delocalized excitons. The objective of this review is (i) to provide a comprehensive account of major theoretical, computational, and spectroscopic advances that have contributed to this body of knowledge, and (ii) to clarify the issues concerning the role of delocalized excitons in achieving efficient energy transport mechanisms. The focus of this review is on three representative systems: the Fenna-Matthews-Olson complex of green sulfur bacteria, the light harvesting 2 complex of purple bacteria, and phycobiliproteins of cryptophyte algae. Although we offer a more in-depth and detailed description of theoretical and computational aspects, major experimental results and their implications are also assessed in the context of achieving excellent light-harvesting functionality. Future theoretical and experimental challenges to be addressed in gaining a better understanding and utilization of delocalized excitons are also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

AlphaFold and Structural Mass Spectrometry Enable Interrogations on the Intrinsically Disordered Regions in Cyanobacterial Light-harvesting Complex Phycobilisome

Intrinsically disordered proteins/regions (IDPRs) are a very large and functionally important class of proteins that participate in weak multivalent interactions in protein complexes. They are recalcitrant for interrogations using X-ray crystallography and cryo-EM. The IDPRs observed at the interface of the photosynthetic pigment protein complexes (PPCs) remain much less clear, e.g., the major cyanobacterial light-harvesting complex (PBS) contains an unstructured PB-loop insertion in the phycocyanobilin domain (PB domain) of ApcE (the largest polypeptide in PBS). Here, a joint platform is built to probe such structural domains. This platform is characterized by two-round progressive justifications of in silico models by using the structural mass spectrometry data. First, the AlphaFold-generated 3D structure of the PB domain (containing PB-loop) was justified in the context of PBS. Second, docking the AlphaFold-generated ApcG (a ligand) into the first-step justified structure (a receptor). The final ligand-receptor complex was then subjected to a second-round justification, again, by using unequivocal isotopically-encoded cross-links identified in LC-MS/MS. This work reveals a full-length PB-loop structure modelled in the PBS basal cylinder, free from any spatial conflicts against the other subunits in PBS. The structure of PB domain highlights the close associations of the intrinsically disordered PB-loop with its binding partners in PBS, including ApcG, another IDPR. The PB-loop region involved in the binding of photosystem II (PSII) is also discussed in the context of excitation energy transfer regulation. Finally, this work calls attention to the highly disordered, yet interrogatable interface between the light-harvesting antenna complexes and the reaction centers.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Vibronic coupling in light-harvesting complex II revisited

A growing body of work has pointed to vibronic mixing as a crucial design principle for efficient energy and charge transfer in natural and artificial systems.= Notable among these studies was the recent observation of vibronically promoted ultrafast energy flow in the major antenna complex of green plants and algae light-harvesting complex II (LHCII)—the most abundant membrane protein on the Earth—via the emerging experimental technique two-dimensional electronic-vibrational (2DEV) spectroscopy. This spectroscopy, which correlates electronic and nuclear degrees-of-freedom, shows promise for providing mechanistic insight into vibronic coupling; however, explicit theoretical input is necessary to extract such a detail. In a separate paper, we have developed a heterodimer model that describes various forms of vibronic coupling—which were speculated to be present in LHCII—resulting from diagonal electron–phonon coupling giving Franck–Condon (FC) activity and the nuclear dependence of the electronic transition dipole moment giving Herzberg–Teller (HT) activity. Here, we draw connections between this theoretical work and recent experimental studies in order to demonstrate how HT activity is leveraged in the function of LHCII.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Anionic Lipids Regulate the Light-Harvesting Complex 1-Reaction Center Photocycle in Purple Bacteria

Photosynthetic purple bacteria can capture and convert sunlight with a remarkable, nearly 100% quantum efficiency. The light-harvesting complex 1-reaction center (LH1-RC) core complex is the membrane complex fundamentally responsible for solar energy conversion. LH1-RC has a highly conserved surrounding lipid composition known to favor anionic lipids for an unknown function. Here, in this work, we compared experimentally the rate of LH1-to-RC energy transfer in detergent, membrane nanodiscs with varying lipid compositions, purified membrane fragments, and live cells. The energy transfer rate indicated that RC turnover decreased in neutral lipids, yet was partially restored in anionic lipids, revealing an unexpected lipid dependence. In complementary molecular dynamics simulations, the anionic lipid cardiolipin showed electrostatic interactions with LH1-RC that may mediate quinone exchange, providing a mechanism for the observed lipid dependence. Overall, these results revealed that anionic lipids facilitate LH1-RC redox cycling, identifying a functional role for membrane composition in photosynthetic solar energy conversion.

bacteria↗
DOE OSTI2019

Assessing density functional theory in real-time and real-space as a tool for studying bacteriochlorophylls and the light-harvesting complex 2

We use real-time density functional theory on a real-space grid to calculate electronic excitations of bacteriochlorophyll chromophores of the light-harvesting complex 2 (LH2). Comparison with Gaussian basis set calculations allows us to assess the numerical trust range for computing electron dynamics in coupled chromophores with both types of techniques. Tuned range-separated hybrid calculations for one bacteriochlorophyll as well as two coupled ones are used as a reference against which we compare results from the adiabatic time-dependent local density approximation (TDLDA). The tuned range-separated hybrid calculations lead to a qualitatively correct description of the electronic excitations and couplings. They allow us to identify spurious charge-transfer excitations that are obtained with the TDLDA. When we take into account the environment that the LH2 protein complex forms for the bacteriochlorophylls, we find that it substantially shifts the energy of the spurious charge-transfer excitations, restoring a qualitatively correct electronic coupling of the dominant excitations also for TDLDA.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Coupled charge and energy transfer dynamics in light harvesting complexes from a hybrid hierarchical equations of motion approach

Here, we describe a method for simulating exciton dynamics in protein–pigment complexes, including effects from charge transfer as well as fluorescence. The method combines the hierarchical equations of motion, which are used to describe quantum dynamics of excitons, and the Nakajima–Zwanzig quantum master equation, which is used to describe slower charge transfer processes. We study the charge transfer quenching in light harvesting complex II, a protein postulated to control non-photochemical quenching in many plant species. Using our hybrid approach, we find good agreement between our calculation and experimental measurements of the excitation lifetime. Furthermore, our calculations reveal that the exciton energy funnel plays an important role in determining quenching efficiency, a conclusion we expect to extend to other proteins that perform protective excitation quenching. This also highlights the need for simulation methods that properly account for the interplay of exciton dynamics and charge transfer processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Vibronic mixing enables ultrafast energy flow in light-harvesting complex II

Since the discovery of quantum beats in the two-dimensional electronic spectra of photosynthetic pigment-protein complexes over a decade ago, the origin and mechanistic function of these beats in photosynthetic light-harvesting has been extensively debated. The current consensus is that these long-lived oscillatory features likely result from electronic-vibrational mixing, however, it remains uncertain if such mixing significantly influences energy transport. Here, we examine the interplay between the electronic and nuclear degrees of freedom (DoF) during the excitation energy transfer (EET) dynamics of light-harvesting complex II (LHCII) with two-dimensional electronic-vibrational spectroscopy. Particularly, we show the involvement of the nuclear DoF during EET through the participation of higher-lying vibronic chlorophyll states and assign observed oscillatory features to specific EET pathways, demonstrating a significant step in mapping evolution from energy to physical space. These frequencies correspond to known vibrational modes of chlorophyll, suggesting that electronic-vibrational mixing facilitates rapid EET over moderately size energy gaps.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Multiscale cyclic dynamics in light harvesting complex in presence of vibrations and noise

Starting from the many-body Schrödinger equation, in this work we derive a new type of Lindblad master equations describing a cyclic exciton/electron dynamics in the light harvesting complex and the reaction center. These equations resemble the master equations for the electric current in mesoscopic systems, and they go beyond the single-exciton description by accounting for the multi-exciton states accumulated in the antenna, as well as the charge-separation, fluorescence and photo-absorption. Although these effects take place on very different timescales, their inclusion is necessary for a consistent description of the exciton dynamics. Our approach reproduces both coherent and incoherent dynamics of exciton motion along the antenna in the presence of vibrational modes and noise. We applied our results to evaluate energy (exciton) and fluorescent currents as functions of sunlight intensity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Biomimetic Light Harvesting Complexes Based on Self-Assembled Dye-DNA Nanostructures (Final Technical Report)

A fundamental limitation in the development of artificial molecular light harvesting structures is that generally if one places pigment molecules close enough to achieve very high energy transfer efficiency and absorbance cross section, the dyes interact in such a way that self-quenching occurs. This limits both the optical cross section and the overall efficiency of light capture in such systems. Nature overcomes this problem and achieves efficient energy transfer without self-quenching by controlling the environment, vibration characteristics, orientation and dynamics of the pigments involved in light harvesting. Natural light harvesting systems have evolved highly intricate chromophore architectures of protein-bound organic molecules that absorb and funnel solar energy with high efficiency and fast transfer rates using elegant excitonic circuitries. Nature achieves this precise control over the properties of pigment complexes by using specific proteins as templates to guide the formation of very well-defined pigment aggregates, groups of pigment molecules that are in close enough contact to undergo excitonic interactions resulting in new electronic properties that were not present in the monomer. In synthetic systems, pigment aggregates are well known, and J-aggregates and H-aggregates have been long studied for their unique properties. In Nature, the chlorosomes of green bacteria form what appear to be classical J-aggregates and the light harvesting complexes of purple nonsulfur bacteria form ring structures that have many of the properties of J-aggregates such as a red-shifted absorbance spectrum and excited states that are delocalized over multiple pigment molecules. These photosynthetic systems leverage the spectral and enhanced transport properties of J-like aggregates to achieve fast exciton transport within the antenna and thus high light-harvesting efficiency. The close interaction of the pigments results in substantial electronic coupling that lifts the degeneracy of excitonic states and therefore modifies the absorption and emission spectra of the monomer. In the case of J-aggregation, lower energy excitonic states acquire significant oscillator strength, resulting in a characteristic bathochromic shift of the absorption and fluorescence and often superradiant delocalized exciton states.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Observation of dissipative chlorophyll-to-carotenoid energy transfer in light-harvesting complex II in membrane nanodiscs

Abstract Plants prevent photodamage under high light by dissipating excess energy as heat. Conformational changes of the photosynthetic antenna complexes activate dissipation by leveraging the sensitivity of the photophysics to the protein structure. The mechanisms of dissipation remain debated, largely due to two challenges. First, because of the ultrafast timescales and large energy gaps involved, measurements lacked the temporal or spectral requirements. Second, experiments have been performed in detergent, which can induce non-native conformations, or in vivo, where contributions from homologous antenna complexes cannot be disentangled. Here, we overcome both challenges by applying ultrabroadband two-dimensional electronic spectroscopy to the principal antenna complex, LHCII, in a near-native membrane. Our data provide evidence that the membrane enhances two dissipative pathways, one of which is a previously uncharacterized chlorophyll-to-carotenoid energy transfer. Our results highlight the sensitivity of the photophysics to local environment, which may control the balance between light harvesting and dissipation in vivo.

59 BASIC BIOLOGICAL SCIENCES↗