Efficient Light-harvesting Systems Research Articles

Detection of 132-carboxy-chlorin produced by the in vitro BciC enzymatic hydrolysis of zinc chlorophyllide

Green photosynthetic bacteria with an efficient light-harvesting system contain special chlorophyll molecules, called bacteriochlorophylls c, d, e, in their main antennae. In the biosynthetic pathway, a BciC enzyme is proposed to catalyze the hydrolysis of the C132-methoxycarbonyl group of chlorophyllide a, but the resulting C132-carboxy group has not been detected yet because it is spontaneously removed due to the instability of the β-keto-carboxylic acid. In this study, the in vitro BciC enzymatic reactions of zinc methyl (131R/S)-hydroxy-mesochlorophyllides a were examined and a carboxylic acid possessing the C132S-OH was first observed as the hydrolyzed product of the C132-COOCH3.

Synthesis and Photophysical Properties of Light-Harvesting Gold Nanoclusters Fully Functionalized with Antenna Chromophores.

The development of efficient light-harvesting systems is important to understand the key aspects of solar-energy conversion processes and to utilize them in various photonic applications. Here, atomically well-defined gold nanoclusters are reported as a new platform to fabricate artificial light-harvesting systems. An efficient amide coupling method is developed to synthesize water-soluble Au22 clusters fully protected with pyrene chromophores by taking advantage of their facile phase-transfer reaction. The synthesized Au22 clusters with densely packed 18 pyrene chromophores (Au22 -PyB18 ) exhibit triple-emission in blue, green, and red wavelength regions arising respectively from pyrene monomer, pyrene excimer, and Au22 emission, producing bright white light emission together. The photoluminescence of Au22 is enhanced by more than tenfold, demonstrating that pyrenes at the periphery efficiently channel the absorbed energy to the luminescent Au22 at the center. A combination of femtosecond transient absorption and anisotropy measurements of Au22 -PyB18 explicitly reveals three main decay components of 220 fs, 3.5ps, and 160ps that can be assigned to energy migration between pyrenes and energy transfer processes from pyrene monomer and excimer to the central Au22 , respectively.

Artificial Light-Harvesting Metallacycle System with Sequential Energy Transfer for Photochemical Catalysis.

Highly efficient light-harvesting systems with the sequential energy transfer process are significant for utilizing solar energy in photosynthesis. Herein, we report a quadrilateral platinum(II) metallacycle containing tetraphenylethylene (M1) as a light-harvesting platform. The M1 assembly serves as an ideal donor because of the aggregation-induced emission (AIE) effect, realizing two-step sequential energy transfer from the M1 assembly to eosin Y (ESY) and then to sulforhodamine (SR101) with high efficiency. ESY was used as a bridge in a relay mode during this process. To better mimic natural photosynthesis, the M1-ESY-SR101 system was utilized as photochemical catalysis for alkylation of C-H bonds in aqueous solution, showing enhanced catalytic activity as compared with the M1-ESY system or ESY/SR101 alone.

In Vitro Hydrolysis of Zinc Chlorophyllide a Homologues by a BciC Enzyme.

Chlorosomes in green photosynthetic bacteria are the largest and most efficient light-harvesting antenna systems of all phototrophs. The core part of chlorosomes consists of bacteriochlorophyll c, d, or e molecules. In their biosynthetic pathway, a BciC enzyme catalyzes the removal of the C132-methoxycarbonyl group of chlorophyllide a. In this study, the in vitro enzymatic reactions of chlorophyllide a analogues, C132-methylene- and ethylene-inserted zinc complexes, were examined using a BciC protein from Chlorobaculum tepidum. As the products, their hydrolyzed free carboxylic acids were observed without the corresponding demethoxycarbonylated compounds. The results showed that the in vivo demethoxycarbonylation of chlorophyllide a by an action of the BciC enzyme would occur via two steps: (1) an enzymatic hydrolysis of a methyl ester at the C132-position, followed by (2) a spontaneous (nonenzymatic) decarboxylation in the resulting carboxylic acid.

Photothermal Conversion of CO2 with Tunable Selectivity Using Fe-Based Catalysts: From Oxide to Carbide

Conversion of CO2 into fuels via solar energy would be a promising strategy to reduce CO2 emissions and produce value-added carbon compounds. However, the development of efficient light-harvesting and photocatalytic systems remains a significant challenge because of scarcity of low-cost and high-efficiency catalysts in CO2 conversion. Herein, a tunable selectivity in photothermal CO2 conversion was demonstrated over a series of Fe-based catalysts developed through a simple hydrogenation/carbonization treatment with commercial Fe3O4 as a precursor. The Fe3O4 catalyst demonstrated a full selectivity toward CO (about 100%) and 11.3 mmol g–1 h–1 activity for the photothermal catalytic conversion of CO2. More importantly, the pure-phase θ-Fe3C produced remarkably high selectivity toward hydrocarbon products (>97%) and superior activity (10.9 mmol g–1 h–1) in the photothermal conversion of CO2. Meanwhile, it is found that the selectivity toward a hydrocarbon (CHx) can be modulated by the extent of hydrogenation/carbonization of the Fe3O4 precursor. In addition, we demonstrated the vital influence of the nonthermal effect on the enhanced catalytic performance with the Fe-based catalysts during the photothermal conversion of CO2.

In vitro C132-dealkoxycarbonylations of zinc chlorophyll a derivatives including C132-substitutes by a BciC enzyme

Chlorosomes in the green photosynthetic bacteria are the largest and most efficient light-harvesting antenna systems of all phototrophs. The core part of chlorosomes consists of bacteriochlorophyll c, d, e, or f molecules. In their biosynthetic pathway, a BciC enzyme catalyzes the removal of the C132-methoxycarbonyl group of chlorophyllide a. In this study, in vitro C132-dealkoxycarbonylations of zinc chlorophyll a derivatives bearing a methyl-, ethyl- or propyl-esterifying group and its methyl ester analogs with additional alkyl and hydroxy groups at the C132-position were examined using the BciC enzyme. The BciC-catalyzed reaction activity for the C132-methoxycarbonylated substrate was comparable to that for the ethoxycarbonylated compound; however, depropoxycarbonylation did not proceed. The BciC enzymatic demethoxycarbonylation of zinc methyl C132-alkylated pheophorbides a was gradually suppressed with the elongation of the alkyl chain and finally became inactive for the propyl substrate. The reaction of the C132-hydroxylated substrate (allomer) was accelerated compared to that of the C132-methyl analog possessing a similar steric size, and gave the corresponding C132-oxo product via further air-oxidation. All of the abovementioned enzymatic reactions occurred for one of the C132-epimers with the same configuration as in chlorophyllide a. The above substrate specificities and product distributions indicated the stereochemistry and size of the BciC enzymatic active site (pocket).

Global and target analysis of relaxation processes of the collapsed state of P3HT polymer nanoparticles.

Organic-inorganic heterostructure materials have received significant research interest for designing light harvesting devices because of their efficient charge separation. Here, we design organic and inorganic nano-heterostructures using conjugated polymer nanoparticles (PNPs) [poly(3-hexylthiophene-2,5-diyl), P3HT] and Au nanoparticles. We investigate the carrier relaxation processes of this heterostructure at different time scales by ultrafast transient absorption spectroscopy. The lifetime of the singlet state (S1) of the pristine polymer shortens from 480.7 ps to 2.8 ps due to the formation of nanoparticles, and the formation of a delocalized collective state (CLS) is obtained in polymer nanoparticles whose lifetime is found to be 384.6 ps. The hot and ultrafast electron transfers occur from P3HT polymer nanoparticles to Au nanoparticles and the time constants are 253 fs and 37.7 ps, respectively, which are responsible for the efficient charge separation in such heterostructures. Such a fundamental study of relaxation processes of organic-inorganic nano heterostructures is very significant for designing light harvesting systems.

A highly efficient light-harvesting system with sequential energy transfer based on a multicharged supramolecular assembly.

A supramolecular assembly was constructed by the nonconvalent interaction of pillar[5]arene (WP5) with a pyridinium modified tetraphenylethene (Py-TPE) derivative, in which Py-TPE/WP5 acted as a donor, and sulforhodamine 101 and sulfonated aluminum phthalocyanine acted as acceptors to realize a highly efficient light-harvesting system with two-step sequential energy transfer.

All Ceramic-Based Metal-Free Ultra-broadband Perfect Absorber

In this paper, we scrutinize unprecedented potential of transition metal carbides (TMCs) and nitrides (TMNs) for realization of light perfect absorption in an ultra-broad frequency range encompassing all of the visible (Vis) and near infrared (NIR) regions. For this purpose, two different configurations which are planar and trapezoidal array are employed. To gain insight on the condition for light perfect absorption, a systematic modeling approach based on transfer matrix method (TMM) is firstly utilized. Our modeling findings prove that the permittivity data of these TMCs and TMNs are closely matched with the ideal data. Thus, they can have stronger and broader absorption behavior compared to metals. Besides, these ceramic materials are preferred to metals due to the fact that they have better thermal properties and higher durability against erosion and oxidation than metals. This could provide the opportunity for design of highly efficient light harvesting systems with long-term stability. Numerical simulations are conducted to optimize the device optical performance for each of the proposed carbides and nitrides. Our findings reveal that these ceramic coatings have the broadest absorption response compared to all lossy and plasmonic metals. In planar configuration, titanium carbide (TiC) has the largest absorption bandwidth (BW) where an absorption above 0.9 is retained over a broad wavelength range of 405–1495 nm. In trapezoid architecture, vanadium nitride (VN) shows the widest BW covering a range from 300 to 2500 nm. The results of this study can serve as a beacon for the design of future high-performance energy conversion devices including solar vapor generation and thermal photovoltaics where both optical and thermal requirements can be satisfied.

Microemulsion-Assisted Self-Assembly and Synthesis of Size-Controlled Porphyrin Nanocrystals with Enhanced Photocatalytic Hydrogen Evolution.

Design and engineering of highly efficient light-harvesting nanomaterial systems to emulate natural photosynthesis for maximizing energy conversion have stimulated extensive efforts. Here we present a new class of photoactive semiconductor nanocrystals that exhibit high-efficiency energy transfer for enhanced photocatalytic hydrogen production under visible light. These nanocrystals are formed through noncovalent self-assembly of In(III) meso-tetraphenylporphine chloride (InTPP) during microemulsion assisted nucleation and growth process. Through kinetic control, a series of uniform nanorods with controlled aspect ratio and high crystallinity have been fabricated. Self-assembly of InTPP porphyrins results in extensive optical coupling and broader coverage of the visible spectrum for efficient light harvesting. As a result, these nanocrystals display excellent photocatalytic hydrogen production and photostability under the visible light in comparison with the commercial InTPP porphyrin powders.

Constructing Artificial Light-Harvesting Systems by Covalent Alignment of Aggregation-Induced Emission Molecules.

The characteristics of chloroplasts harvesting solar energy and conducting energy transfer have inspired chemists to mimic similar processes. However, accurate manipulation to gain regularly displayed antenna chromophores in mimicking chloroplasts is a great challenge. Herein, a rational design is presented that combines orderly arranged chromophores with aggregation-induced emission (AIE) to develop artificial light-harvesting systems. Tetraphenyl ethylene (TPE) molecules, which exhibited strong AIE properties, are considered as building blocks to fabricate high emissive 2D nanosheets and nanovesicles, respectively. Furthermore, the well-aligned TPE molecules are also developed as donor chromophores in light-harvesting processes. After subsequent surface modification by porphyrin molecules as acceptor chromophores, an efficient light-harvesting system has been integrally constructed. This study demonstrates a novel strategy to utilize AIE feature to mimic chloroplasts process in nature.

Influence of shape on the carrier relaxation dynamics of CsPbBr3 perovskite nanocrystals.

Lead halide perovskite nanocrystals (NCs) have recently emerged as a new class of functional materials for designing efficient light harvesting systems because of their unique photophysical properties. Here, we report the influence of different shapes on the relaxation dynamics of perovskite nanocrystals. The structural transformation of CsPbBr3 NCs from cubic shape to rod shape occurs by changing the solvent from toluene to dichloromethane (DCM). Rietveld analysis reveals that the crystallinity along with the preferred orientation (PO) of the orthorhombic phase plays a vital role for the unidirectional growth of rod shaped CsPbBr3 NCs in DCM. Time-resolved emission spectroscopy and ultrafast transient absorption spectroscopy are used to understand the photoinduced relaxation processes. Global and target analysis of femto-second transient absorption kinetics has been done to understand the individual excited-state species. The analysis reveals that trap states play an important role in the carrier relaxation dynamics of cubic and rod shaped NCs. The lifetime of the shallow trap (ST) changes from 25 ps to 45 ps and the lifetime of the deep trap (DT) state changes from 163 ps to 303 ps with changing the shape of the nanocrystals from cubic to rod. This work highlights the tuning of the crystal phase, shape and the exciton dynamics of CsPbBr3 NCs that would be beneficial for designing efficient photovoltaic devices.

Efficient Light-Harvesting Systems with Tunable Emission through Controlled Precipitation in Confined Nanospace.

Light harvesting is a key step in photosynthesis but creation of synthetic light-harvesting systems (LHSs) with high efficiencies has been challenging. When donor and acceptor dyes with aggregation-induced emission were trapped within the interior of cross-linked reverse vesicles, LHSs were obtained readily through spontaneous hydrophobically driven aggregation of the dyes in water. Aggregation in the confined nanospace was critical to the energy transfer and the light-harvesting efficiency. The efficiency of the excitation energy transfer (EET) reached 95 % at a donor/acceptor ratio of 100:1 and the energy transfer was clearly visible even at a donor/acceptor ratio of 10 000:1. Multicolor emission was achieved simply by tuning the donor/acceptor feed ratio in the preparation and the quantum yield of white light emission from the system was 0.38, the highest reported for organic materials in water to date.

Simple and Robust Panchromatic Light Harvesting Antenna Composites via FRET Engineering in Solid State Host Matrices

The efficient harvesting of incident solar radiation is an important technical challenge for future world energy and chemical needs. Luminescent solar concentrators (LSCs) can efficiently harvest solar energy and concentrate it toward a useful output, such as photovoltaic cells or a photocatalytic reactor. LSCs are planar waveguides doped with luminescent materials that emit light into waveguide modes concentrating it toward the edges. However, large scale LSCs have been limited by the reabsorption of emitted photons. To overcome this, research has turned toward creating artificial light-harvesting systems that spatially and spectrally concentrate light through different donor and acceptor chromophores. Usually these chromophores are covalently linked and synthetically complex. We report a simple, versatile, and highly efficient light-harvesting antenna system consisting of dyes suspended in a PMMA micropowder. These composites absorb light throughout the visible region of the solar spectrum, efficiently ...

Predictive modeling of broad wavelength light-harvesting performance in assemblies of multiple chromophores

Developing efficient panchromatic light harvesting systems that exploit the energy available from the entire solar spectrum in an economically feasible and scalable fashion is of great importance. Light harvesting by incorporating multiple chromophores into molecular assemblies such as micelles and vesicles is one method for accomplishing this result. In this paper, we describe panchromatic light harvesting in lipid-based vesicle bilayers that contain a random distribution of lipid-bound chromophores. Numerically exact modeling based on Förster theory is developed to establish the criteria for designing a highly efficient panchromatic light-harvesting unit. An approximate modeling method is also developed to greatly reduce the complexity of the modeling problem. Both the exact and approximate models are verified by designing and experimentally testing an efficient three-chromophore light-harvesting system. For the experiments, 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine-N-(lissamine rhodamine B sulfonyl) (Rhod) as the lowest energy chromophore, 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine-N-(7-nitro-2-1,3-benzoxadiazol-4-yl) (NBD) as an intermediate acceptor, and Marina Blue® 1,2-Dihexadecanoyl-sn-Glycero-3-Phosphoethanolamine (MB) as the highest energy absorber (donor) are selected. From chromophore concentrations and R0 values, modeling predicts an overall efficiency of energy transfer to the terminal acceptor greater than ≈0.6 across a broad excitation wavelength range of ≈250 nm. The predicted transfer efficiency is verified by the experimental results. In addition, comparison of the approximate modeling method with both the numerically exact method and experimental results confirms that the computationally efficient approximate method is sufficiently accurate to guide choices of experimental parameters such as chromophore concentration. Overall, these results show predictive design of panchromatic light-harvesting performance can be performed rapidly and efficiently using an approximate kinetic model for randomly distributed assemblies of multiple chromophores.

Structural Variations in Chlorosomes from Wild-Type and a bchQR Mutant of Chlorobaculum tepidum Revealed by Single-Molecule Spectroscopy.

Green sulfur bacteria can grow photosynthetically by absorbing only a few photons per bacteriochlorophyll molecule per day. They contain chlorosomes, perhaps the most efficient light-harvesting antenna system found in photosynthetic organisms. Chlorosomes contain supramolecular structures comprising hundreds of thousands of bacteriochlorophyll molecules, which are properly positioned with respect to one another solely by self-assembly and not by using a protein scaffold as a template for directing the mutual arrangement of the monomers. These two features-high efficiency and self-assembly-have attracted considerable attention for developing light-harvesting systems for artificial photosynthesis. However, reflecting the heterogeneity of the natural system, detailed structural information at atomic resolution of the molecular aggregates is not yet available. Here, we compare the results for chlorosomes from the wild type and two mutants of Chlorobaculum tepidum obtained by polarization-resolved, single-particle fluorescence-excitation spectroscopy and theoretical modeling with results previously obtained from nuclear-magnetic resonance spectroscopy and cryo-electron microscopy. Only the combination of information obtained from all of these techniques allows for an unambiguous description of the molecular packing of bacteriochlorophylls within chlorosomes. In contrast to some suggestions in the literature, we find that, for the chlorosomes from the wild type as well as for those from mutants, the dominant secondary structural element features tubular symmetry following a very similar construction principle. Moreover, the results suggest that the various options for methylation of the bacteriochlorophyll molecules, which are a primary source of the structural (and spectral) heterogeneity of wild-type chlorosome samples, are exploited by nature to achieve improved spectral coverage at the level of individual chlorosomes.

Highly Efficient Artificial Light-Harvesting Systems Constructed in Aqueous Solution Based on Supramolecular Self-Assembly.

Highly efficient light-harvesting systems were successfully fabricated in aqueous solution based on the supramolecular self-assembly of a water-soluble pillar[6]arene (WP6), a salicylaldehyde azine derivative (G), and two different fluorescence dyes, Nile Red (NiR) or Eosin Y (ESY). The WP6-G supramolecular assembly exhibits remarkably improved aggregation-induced emission enhancement and acts as a donor for the artificial light-harvesting system, and NiR or ESY, which are loaded within the WP6-G assembly, act as acceptors. An efficient energy-transfer process takes place from the WP6-G assembly not only to NiR but also to ESY for these two different systems. Furthermore, both of the WP6-G-NiR and WP6-G-ESY systems show an ultrahigh antenna effect at a high donor/acceptor ratio.

Interfacial Charge Transfer between Zinc Oxide Nanoparticles and Methyl Viologen: Influence of Size

AbstractThe fundamental understanding of photoinduced electron transfer (PET) between semiconductor nanocrystals and dye molecules is very important to design efficient light harvesting system based on inorganic‐organic hybrid system. Here, we have investigated the photoluminescence quenching and charge transfer process from ZnO NPs to methyl viologen (MV2+) by using steady state and time resolved spectroscopy. Absorption spectroscopic studies reveal that the charge‐transfer (CT) complex is formed between ZnO NPs and MV2+ which gives distinct size dependent CT bands. The defect emission of ZnO NPs is found to be quenched significantly after adding MV2+ molecule. The charge transfer process between ZnO NPs and MV2+ is confirmed by using laser flash photolysis and the stability of CT complexes is found to be more prominent for 6.3 nm ZnO NPs with MV2+ than 4.2 nm ZnO NPs with MV2+. The study of the electronic interaction of ZnO NPs with MV2+ is very important for further applications in organic/inorganic hybrid optoelectronic materials.

Photon Harvesting in Conjugated Polymer-Based Functional Nanoparticles.

The design of new generation light-harvesting systems based on conjugated polymer nanoparticles (PNPs) is an emerging field of research to convert solar energy into renewable energy. In this Perspective, we focus on the understanding of the light harvesting processes like exciton dynamics, energy transfer, antenna effect, charge carrier dynamics, and other related processes of conjugated polymer-based functional nanomaterials. Spectroscopic investigations unveil the rotational dynamics of the dye molecules inside of PNPs and exciton dynamics of the self-assembled structures. A detailed understanding of the cascade energy transfer for white light and singlet oxygen generation in multiple fluorophores containing a PNP system by time-resolved spectroscopy is highlighted. Finally, ultrafast spectroscopic investigations provide direct insight into the impacts of electron and hole transfer at the interface in the hybrid materials for photocatalysis and photocurrent generation to construct efficient light-harvesting systems.

In vitro enzymatic assays of photosynthetic bacterial 3-vinyl hydratases for bacteriochlorophyll biosyntheses.

A chlorosome is a large and efficient light-harvesting antenna system found in some photosynthetic bacteria. This system comprises self-aggregates of bacteriochlorophyll (BChl) c, d, or e possessing a chiral 1-hydroxyethyl group at the 3-position, which plays a key role in the formation of the supramolecule. Biosynthesis of chlorosomal pigments involves stereoselective conversion of 3-vinyl group to 3-(1-hydroxyethyl) group facilitated by a 3-vinyl hydratase. This 3-vinyl hydration also occurs in BChl a biosynthesis, followed by oxidation that introduces an acetyl group at the 3-position. Herein, we present in vitro enzymatic assays of paralogous 3-vinyl hydratases derived from green sulfur bacteria, Chlorobaculum tepidum and Chlorobaculum limnaeum, the filamentous anoxygenic phototroph Chloroflexus aurantiacus, and the chloracidobacterium Chloracidobacterium thermophilum. All the hydratases showed hydration activities. The biosynthetic pathway of BChl a and other chlorosomal pigments is discussed considering the substrate specificity and stereoselectivity of the present hydratases.