Light-harvesting Activity Research Articles

The Orange Carotenoid Protein Triggers Cyanobacterial Photoprotection by Quenching Bilins via a Structural Switch of Its Carotenoid.

Cyanobacteria were the first microorganisms that released oxygen into the atmosphere billions of years ago. To do it safely under intense sunlight, they developed strategies that prevent photooxidation in the photosynthetic membrane, by regulating the light-harvesting activity of their antenna complexes-the phycobilisomes-via the orange-carotenoid protein (OCP). This water-soluble protein interacts with the phycobilisomes and triggers nonphotochemical quenching (NPQ), a mechanism that safely dissipates overexcitation in the membrane. To date, the mechanism of action of OCP in performing NPQ is unknown. In this work, we performed ultrafast spectroscopy on a minimal NPQ system composed of the active domain of OCP bound to the phycobilisome core. The use of this system allowed us to disentangle the signal of the carotenoid from that of the bilins. Our results demonstrate that the binding to the phycobilisomes modifies the structure of the ketocarotenoid associated with OCP. We show that this molecular switch activates NPQ, by enabling excitation-energy transfer from the antenna pigments to the ketocarotenoid.

Modified successive ionic layer adsorption and reaction for interconnected bismuth vanadate nanograins: Highly active visible light harvesting photoanodes

A modified successive ionic layer adsorption and reaction (SILAR) method is developed for depositing interconnected bismuth vanadate (BiVO4) nanoparticles with improved visible light harvesting activity. Facile control of preparative parameters like deposition cycles, anionic precursor, pH and deposition temperature significantly altered BiVO4 surface morphology. BiVO4 thin films prepared with Na3VO4 anionic precursor show dispersed nanoparticles type morphology and that deposited with NaVO3 precursor displays 3D interconnected nanoparticles morphology. The BiVO4 photoanodes with 3D interconnected nanoparticles morphology exhibits an excellent photocurrent density of 5.19 mA cm−2 at 1.23 V vs. RHE with superior photostability and improved applied bias photon to current efficiency (ABPE) (1.50 %) compared to dispersed nanostructured BiVO4 photoanodes. The excellent photoelectrochemical (PEC) characteristics of BiVO4 photoanodes with 3D interconnected nanoparticle morphology can be ascribed to porous morphology, optimum thickness, narrow band gap energy and favorable electronic band structure for water splitting. The current study illustrates the usefulness of the modified SILAR approach for depositing 3D interconnected BiVO4 nanoparticle morphology in a single step that is superior and efficient to previously reported multistep processes.

Functional Coupling of Biohybrid Photosynthetic Antennae and Reaction Center Complexes: Quantitative Comparison with Native Antennae.

Light-harvesting (LH) complexes in photosynthetic organisms absorb photons within limited wavelength ranges over a broad solar spectrum. Extension of the LH wavelength has been realized by attaching artificial fluorophores to LH complexes (biohybrid LH complexes) for complementing the limited-wavelength regions. However, how efficiently such fluorophores in biohybrid LH complexes function to drive the photocatalytic reaction center (RC) has not been quantitatively evaluated, specifically in comparison with native LH antenna complexes. In this study, we prepared various biohybrid LH1-RC complexes (from Rhodopseudomonas palustris), to quantitatively evaluate the LH activity of the attached external chromophores through a photocurrent generation reaction by LH1-RC on an electrode. For a direct comparison of the LH activity among the LH chromophores that were examined, we introduced the k1 term, which represents the extent of the functional coupling of LH and the photochemical reactions in the RC. We determined that the hydrophobic fluorophore ATTO647N attached to LH1 possesses the highest LH activity among the examined hydrophilic fluorophores such as Alexa647, and its activity is comparable to that of native LH1(-RC). The LH activity of LH2 (from Rhodoblastus acidophilus strain 10050) and its biohybrid LH2s were examined for the comprehensive assessment of their LH activity.

Transplanting experiment and transcriptome sequencing reveal the potential ecological adaptation to plateau environments in the allopolyploid Isoetes sinensis

Relatively high frequencies of polyploidy are generally found in high-altitude regions. However, more diploid than polyploid species of Isoetes are distributed in plateau environments in China. The low-altitude species Isoetes sinensis originates from the allopolyploidization between a plateau parent and another low altitude species. To study potential ecological adaptation to plateau environments in the allopolyploid I. sinensis, we transplanted individuals of I. sinensis to different altitudes. RNA sequencing was performed to elucidate the molecular response of this species’ ecological adaptation to plateaus. More unique differentially expressed genes (DEGs) were detected in individuals transplanted to the Qinghai–Tibet Plateau (QTP) than elsewhere, such as genes for ribosomal proteins (RPs) and succinate dehydrogenase (SDH), which helped them adapt to higher altitudes under both terrestrial and submerged conditions. In both terrestrial and submerged conditions, the expression of a large number of genes changed to help plants adapt to exposure to the high levels of ultraviolet (UV) radiation on plateaus, such as the genes associated with the accumulation of flavonoids, decreasing chlorophyll content, and reducing light harvesting activity. The expression of vacuolar-type H+-transporting ATPase (V-ATPase) and phosphoenolpyruvate carboxylase (PEPC) increased with altitude, revealing that the intensity of the crassulacean acid metabolism (CAM) of I. sinensis might be positively associated with altitude. In general, our results reveal that although I. sinensis only lives at low altitudes, it can still adapt to plateau stress by regulating the expression of certain key genes. The potential ecological adaptation to plateau environments in the allopolyploid I. sinensis may have been inherited from the plateau parent.

Enhanced light harvesting and photocurrent generation activities of biohybrid light–harvesting 1–reaction center core complexes (LH1-RCs) from Rhodopseudomonas palustris

A light harvesting system that effectively drives photocatalytic component is essential for converting solar light into chemical energy. Here we addressed the extension of light harvesting activity and presented a quantitative analysis of the functional linkage between light harvesting and a photocatalytic reaction of biohybrid light-harvesting 1–reaction center core complex (LH1-RC from Rhodopseudomonas palustris). Light harvesting wavelengths were extended by a series of fluorophores (Alexa647, 680, 750, and ATTO647N), which were covalently attached to LH1-RC (LH1-RC-Fluors). Femtosecond transient absorption spectroscopy revealed ultrafast excitation energy transfer (EET) from the fluorophores to bacteriochlorophyll a pigments in LH1 (B875), followed by charge separation in RC. The rate of EET increased with increase in the spectral overlap between the emission bands of the fluorophores and the absorption band of B875. The attachment of the external light harvesting fluorophores boosted the maximum yield of charge separation and photocurrent generation activity. We discussed the effects of the number of fluorophores attached to LH1-RC and location of the fluorophores in a lipid bilayer environment on light harvesting activity.

The Effect of Cu and Ga Doped ZnIn2S4 under Visible Light on the High Generation of H2 Production

A Cu+ and Ga3+ co-doped ZnIn2S4 photocatalyst (Zn(1−2x)(CuGa)xIn2S4) with controlled band gap was prepared via a simple one-step solvothermal method. Zn(1−2x)(CuGa)xIn2S4 acted as an efficient photocatalyst for H2 evolution under visible light irradiation (λ > 420 nm; 4500 µW/cm2). The effects of the (Cu and Ga)/Zn molar ratios of Zn(1−2x)(CuGa)xIn2S4 on the crystal structure (hexagonal structure), morphology (microsphere-like flower), optical property (light harvesting activity and charge hole separation ability), and photocatalytic activity have been investigated in detail. The maximum H2 evolution rate (1650 µmol·h−1·g−1) was achieved over Zn0.84(CuGa)0.13In2S4, showing a 3.3 times higher rate than that of untreated ZnIn2S4. The bandgap energy of Zn(1−2x)(CuGa)xIn2S4 decreased from 2.67 to 1.90 eV as the amount of doping Cu+ and Ga3+ increased.

A Key Role of Xanthophylls That Are Not Embedded in Proteins in Regulation of the Photosynthetic Antenna Function in Plants, Revealed by Monomolecular Layer Studies.

The main physiological function of LHCII (light-harvesting pigment-protein complex of photosystem II), the largest photosynthetic antenna complex of plants, is absorption of light quanta and transfer of excitation energy toward the reaction centers, to drive photosynthesis. However, under strong illumination, the photosynthetic apparatus faces the danger of photodegradation and therefore excitations in LHCII have to be down-regulated, e.g., via thermal energy dissipation. One of the elements of the regulatory system, operating in the photosynthetic apparatus under light stress conditions, is a conversion of violaxanthin, the xanthophyll present under low light, to zeaxanthin, accumulated under strong light. In the present study, an effect of violaxanthin and zeaxanthin on the molecular organization and the photophysical properties of LHCII was studied in a monomolecular layer system with application of molecular imaging (atomic force microscopy, fluorescence lifetime imaging microscopy) and spectroscopy (UV-Vis absorption, FTIR, fluorescence spectroscopy) techniques. The results of the experiments show that violaxanthin promotes the formation of supramolecular LHCII structures preventing dissipative excitation quenching while zeaxanthin is involved in the formation of excitonic energy states able to quench chlorophyll excitations in both the higher (B states) and lower (Q states) energy levels. The results point to a strategic role of xanthophylls that are not embedded in a protein environment, in regulation of the photosynthetic light harvesting activity in plants.

Extension of Light-Harvesting Ability of Photosynthetic Light-Harvesting Complex 2 (LH2) through Ultrafast Energy Transfer from Covalently Attached Artificial Chromophores.

Introducing appropriate artificial components into natural biological systems could enrich the original functionality. To expand the available wavelength range of photosynthetic bacterial light-harvesting complex 2 (LH2 from Rhodopseudomonas acidophila 10050), artificial fluorescent dye (Alexa Fluor 647: A647) was covalently attached to N- and C-terminal Lys residues in LH2 α-polypeptides with a molar ratio of A647/LH2 ≃ 9/1. Fluorescence and transient absorption spectroscopies revealed that intracomplex energy transfer from A647 to intrinsic chromophores of LH2 (B850) occurs in a multiexponential manner, with time constants varying from 440 fs to 23 ps through direct and B800-mediated indirect pathways. Kinetic analyses suggested that B800 chromophores mediate faster energy transfer, and the mechanism was interpretable in terms of Förster theory. This study demonstrates that a simple attachment of external chromophores with a flexible linkage can enhance the light harvesting activity of LH2 without affecting inherent functions of energy transfer, and can achieve energy transfer in the subpicosecond range. Addition of external chromophores, thus, represents a useful methodology for construction of advanced hybrid light-harvesting systems that afford solar energy in the broad spectrum.

Morphology, photosynthesis, and internal structure alterations in field apple leaves under hidden and acute zinc deficiency

In the field, apple trees (Malus domestica L.) do not exhibit visible deficient symptoms when affected by hidden zinc (Zn) deficiency, while internal injury in the leaves may prior occurred. We named the leaves on Zn deficient trees without and with visible rosette symptoms as ‘hidden rosette leaves’ and ‘rosette leaves’, respectively. The healthy leaves of normal trees were named ‘normal leaves’ and selected as the control. The changes in leaf photosynthesis, physiology and internal structure were analyzed to elucidate the damage mechanism of Zn deficiency in apple leaves. We found that the reduction in photosynthesis under Zn deficiency was primarily due to non-stomatal limitation, in particular the changes in photosystem II (PS II). Zinc deficiency significantly reduced chlorophyll content in the hidden rosette leaves without obvious changes to chloroplasts and grana number. The intrinsic efficiency of PS II (Fv′/Fm′), actual photochemical efficiency of PS II (ϕPS II) and electron transport rate (ETR) were all significantly decreased in both hidden rosette leaves and rosette leaves, while a further significant increase in the minimal fluorescence (Fo) along with reductions in maximum photochemical efficiency of PSII (Fv/Fm) and photochemical quenching (qP) occurred in rosette leaves. These results indicate that the decrease in chlorophyll content and inhibition of PS II light-harvesting activity may account for the photosynthesis reduction during the initial stage of Zn deficiency. As Zn deficiency aggravated, cellular deficient characteristics like abnormal cell arrangements and disorganization of thylakoids became more exaggerated; visible external symptoms of Zn deficiency appeared with internal alterations, including photosynthetic apparatus damage accompanied by subsequent chloroplast and grana disintegration. We concluded that the PS II activity was relatively sensitive to Zn deficiency, hence the chlorophyll fluorescence parameters like Fv′/Fm′ and ϕPS II may be used as predictive indictors for hidden Zn deficiency on apple trees.

Natural light harvesting systems: unraveling the quantum puzzles

In natural light harvesting systems, the sequential quantum events of photon absorption by specialized biological antenna complexes, charge separation, exciton formation and energy transfer to localized reaction centers culminates in the conversion of solar to chemical energy. A notable feature in these processes is the exceptionally high efficiencies ( $$>$$ 95 %) at which excitation is transferred from the illuminated protein complex site to the reaction centers. The high speed of excitation propagation within a system of interwoven biomolecular network structures, is yet to be replicated in artificial light harvesting complexes. A clue to unraveling the quantum puzzles of nature may lie in the observations of long lived coherences lasting several picoseconds in the electronic spectra of photosynthetic complexes, which occurs even in noisy environmental baths. However the exact nature of the association between the high energy propagation rates and strength of quantum coherences remains largely unsolved. A number of experimental and theoretical studies have been devoted to unlocking the links between quantum processes and information protocols, in the hope of finding the answers to nature’s puzzling mode of energy propagation. This review presents recent developments in quantum theories, and links information-theoretic aspects with photosynthetic light-harvesting processes in biomolecular systems. There is examination of various attempts to pinpoint the processes that underpin coherence features arising from the light harvesting activities of biomolecular systems, with particular emphasis on the effects that factors such non-Markovianity, zeno mechanisms, teleportation, quantum predictability and the role of multipartite states have on the quantum dynamics of biomolecular systems. A discussion of how quantum thermodynamical principles and agent-based modeling and simulation approaches can improve our understanding of natural photosynthetic systems is included.

Donor-Linked Di(perylene bisimide)s: Arrays Exhibiting Fast Electron Transfer for Photosynthesis Mimics

The first example of donor-linked di(perylene bisimide)s is reported. UV-vis absorption spectra of these newly synthesized dyads showed intense absorption across the entire visible region, demonstrating their excellent light-harvesting activities. The severe fluorescence quenching event probed by steady-state fluorescence spectroscopy and the free-energy calculations suggested the possibility of electron transfer (ET) in these arrays upon photoexcitation. Further femtosecond transient absorption spectra clarified that the fluorescence quenching was due to fast intramolecular ET. The rate of the charge separation (CS) was found to be as high as 10(12) s(-1) in CH(2)Cl(2). It was suggested that the large ET driving forces, strong donor-acceptor electronic coupling, and relatively small reorganization energy of diPBI accounted for the rapid ET process in a synergic manner. The fate of the generated radical ion pair depended on the solvent used. Rapid charge recombination to ground state occurred for the dyads in polar CH(2)Cl(2) and for diPBI-TPA in nonpolar toluene. However, sufficient (3)diPBI* population was attained via efficient spin-orbit coupled intersystem crossing from the charge-separated state for diPBI-PdTPP in toluene. These photophysical properties are interpreted as the cooperation between thermodynamic feasibility and kinetic manipulation.

Porphyrin Light‐Harvesting Arrays Constructed in the Recombinant Tobacco Mosaic Virus Scaffold

We have demonstrated the construction of multiple porphyrin arrays in the tobacco mosaic virus (TMV) supramolecular structures by self-assembly of recombinant TMV coat protein (TMVCP) monomers, in which Zn-coordinated porphyrin (ZnP) and free-base porphyrin (FbP) were site-selectively incorporated. The photophysical properties of porphyrin moieties incorporated in the TMV assemblies were also characterized. TMV-porphyrin conjugates employed as building blocks self-assembled into unique disk and rod structures under the proper conditions as similar to native TMV assemblies. The mixture of a ZnP donor and an FbP acceptor was packed in the TMV assembly and showed energy transfer and light-harvesting activity. The detailed photophysical properties of the arrayed porphyrins in the TMV assemblies were examined by time-resolved fluorescence spectroscopy, and the energy transfer rates were determined to be 3.1-6.4x10(9) s(-1). The results indicate that the porphyrins are placed at the expected positions in the TMV assemblies.

Dendritic multiporphyrin arrays as light-harvesting antennae: effects of generation number and morphology on intramolecular energy transfer.

A series of star- and cone-shaped dendritic multiporphyrin arrays, (nPZn)4PFB and (nPZn)1PFB, respectively, that contain energy-donating dendritic zinc porphyrin (PZn) wedges of different numbers (n = 1, 3, and 7) of the PZn units, attached to an energy-accepting free-base porphyrin (PFB) core, were synthesized by a convergent growth approach. For the cone-shaped series ((nPZn)1PFB), the efficiency of energy transfer (phi ENT) from the photoexcited PZn units to the focal PFB core, as evaluated from the fluorescence lifetimes of the PZn units, considerably decreased as the generation number increased: (1PZn)1PFB (86%), (3PZn)1PFB (66%), and (7PZn)1PFB (19%). In sharp contrast, the star-shaped series ((nPZn)4PFB) all showed high phi ENT values: (1PZn)4PFB (87%), (3PZn)4PFB (80%), and (7PZn)4PFB (71%). Energy transfer efficiencies of (3PZn)4-ester-PFB, (1PZn)4-ester-PFB, and (3PZn)1-ester-PFB, whose dendritic PZn wedges are connected by an ester linkage to the PFB core, were almost comparable to those of the corresponding ether-linked versions. Fluorescence depolarization (P) studies showed much lower P values for star-shaped (7PZn)4PFB and (3PZn)4PFB than cone-shaped (7PZn)1PFB and (3PZn)1PFB, respectively, indicating a highly efficient energy migration among the PZn units in the star-shaped series. Such a morphology-assisted photochemical event is probably responsible for the excellent light-harvesting activity of large (7PZn)4PFB molecules.

Evolution of O2 in Brown Algal Chloroplasts

A METHOD IS DESCRIBED FOR THE ISOLATION OF PHOTOSYNTHETICALLY ACTIVE CHLOROPLASTS FROM FOUR SPECIES OF BROWN ALGAE: Fucus vesiculosis, Nereocystis luetkeana, Laminaria saccharina, and Macrocystis integrifolia. When compared to lettuce and spinach chloroplasts, the algal chloroplasts all showed lower activities for both photosystems II and I. Chloroplasts from all the plants produced H(2)O(2), with photosystem I functioning as the O(2) reductant in the light. In contrast to the green plants, however, brown algal chloroplasts strongly reduced O(2) under conditions where both photosystems II and I remain active. Relative variable fluorescence values were lower both in intact plants and chloroplasts of the brown algae than for either spinach or lettuce. It is suggested that although light harvesting activities appear similar in all the plants, details of electron transport in brown algae may differ from those of green plants.