An Aggregation-Induced Emissive Platinum(II) Metallacycle as the Energy Donor of Rhodols for Ratiometric Detection of Hydrazine.

Industry-produced hydrazine (N2H4) is released into the environment, posing a major risk to human health and the ecosystem. Therefore, it is imperative to develop an effective and convenient method for the detection of N2H4. Herein, artificial light-harvesting systems (ALHSs) for N2H4 detection were constructed by applying an aggregation-induced emission-active platinum(II) metallacycle (TPEMc) as the energy donor and rhodols (P1, P2, and P3) as the energy acceptors. The ratiometric fluorescence probes based on ALHSs for N2H4 showed obvious signal amplification and lower limits of detection compared to those of rhodols (P1, P2, P3) alone. The TPEMc-rhodols systems clearly demonstrated a noticeable increase in fluorescence intensity at 550 nm and an obvious fluorescent color shift from cyan to yellow in the presence of N2H4. Fascinatingly, N2H4 could be visually and quantitatively detected in water by the TPEMc-rhodol systems paired with smartphone RGB analysis. Therefore, the combination of platinum(II) metallacycle with rhodols is a promising strategy for simple, sensitive, and visual detection of N2H4.

Photon upconversion crystals doped bacterial cellulose composite films as recyclable photonic bioplastics.

Biopolymers currently utilized as substitutes for synthetic polymers in photonics applications are predominantly confined to linear optical color responses. Herein we expand their applications in non-linear optics by integrating with triplet-triplet annihilation photon upconversion crystals. A photon upconverting biomaterial is prepared by cultivating Pd(II) meso-tetraphenyl tetrabenzoporphine: 9,10-diphenyl anthracene (sensitizer: annihilator) crystals on bacterial cellulose hydrogel that serves both as host and template for the crystallization of photon upconversion chromophores. Coating with gelatin improves the material's optical transparency by adjusting the refractive indices. The prepared material shows an upconversion of 633 nm red light to 443 nm blue light, indicated by quadratic to linear dependence on excitation power density (non-linearly). Notably, components of this material are physically dis-assembled to retrieve 66 ± 1% of annihilator, at the end of life. Whereas, the residual clean biomass is subjected to biodegradation, showcasing the sustainability of the developed photonics material.

Structural and spectroscopic characterization of the peridinin-chlorophyll a-protein (PCP) complex from Heterocapsa pygmaea (HPPCP).

Light harvesting proteins are optimized to efficiently collect and transfer light energy for photosynthesis. In eukaryotic dinoflagellates these complexes utilize chlorophylls and a special carotenoid, peridinin, and arrange them for efficient excitation energy transfer. At the same time, the carotenoids protect the system by quenching harmful chlorophyll triplet states. Here we use advanced spectroscopic techniques and X-ray structure analysis to investigate excitation energy transfer processes in the major soluble antenna, the peridinin chlorophyll a protein (PCP) from the free living dinoflagellate Heterocapsa pygmaea. We determined the 3D-structure of this complex at high resolution (1.2 Å). For better comparison, we improved the reference structure of this protein from Amphidinium carterae to a resolution of 1.15 Å. We then used fs and ns time-resolved absorption spectroscopy to study the mechanisms of light harvesting, but also of the photoprotective quenching of the chlorophyll triplet state. The photoprotection site was further characterized by Electron Spin Echo Envelope Modulation (ESEEM) spectroscopy to yield information on water molecules involved in triplet-triplet energy transfer. Similar to other PCP complexes, excitation energy transfer from peridinin to chlorophyll is found to be very efficient, with transfer times in the range of 1.6-2.1 ps. One of the four carotenoids, the peridinin 614, is well positioned to quench the chlorophyll triplet state with high efficiency and transfer times in the range of tens of picoseconds. Our structural and dynamic data further support, that the intrinsic water molecule coordinating the chlorophyll Mg ion plays an essential role in photoprotection.

Structure-based validation of recombinant light-harvesting complex II.

Light-harvesting complex II (LHCII) captures sunlight and dissipates excess energy to drive photosynthesis. To elucidate this mechanism, the individual optical properties of pigments in the LHCII protein must be identified. In vitro reconstitution with apoproteins synthesized by Escherichia coli and pigment-lipid mixtures from natural sources is an effective approach; however, the local environment surrounding each pigment within reconstituted LHCII (rLHCII) has only been indirectly estimated using spectroscopic and biochemical methods. Here, we used cryo-electron microscopy to determine the 3D structure of the rLHCII trimer and found that rLHCII exhibited a structure that was virtually identical to that of native LHCII, with a few exceptions: some C-terminal amino acids were not visible, likely due to aggregation of the His-tags; a carotenoid at the V1 site was not visible; and at site 614 showed mixed occupancy by both chlorophyll a and b molecules. Our observations confirmed the applicability of the in vitro reconstitution technique.

Chlorophyllase (PsCLH1) and light-harvesting chlorophyll a/b binding protein 1 (PsLhcb1) and PsLhcb5 maintain petal greenness in Paeonia suffruticosa 'Lv Mu Yin Yu'.

INTRODUCTION: Green flowers are not an adaptive trait in natural plants due to the challenge for pollinators to discriminate from leaves, but they are valuable in horticulture. The molecular mechanisms of green petals remain unclear. Tree peony (Paeonia suffruticosa) is a globally cultivated ornamental plant and considered the 'King of Flowers' in China. The P. suffruticosa 'Lv Mu Yin Yu (LMYY)' cultivar with green petals could be utilized as a representative model for understanding petal-specific chlorophyll (Chl) accumulation and color formation. OBJECTIVES: Identify the key genes related to Chl metabolism and understand the molecular mechanism of petal color changes. METHODS: The petal color parameter was analyzed at five developmental stages using a Chroma Spectrophotometer, and Chl and anthocyanin accumulation patterns were examined. Based on comparative transcriptomes, differentially expressed genes (DEGs) were identified, among which three were functionally characterized through overexpression in tobacco plants or silencing in 'LMYY' petals. RESULTS: During flower development and blooming, flower color changed from green to pale pink, consistent with the Chl and anthocyanin levels. The level of Chl demonstrated a similar pattern with petal epidermal cell striation density. The DEGs responsible for Chl and anthocyanin metabolism were characterized through a comparative transcriptome analysis of flower petals over three critical developmental stages. The key chlorophyllase (PsCLH1) and light-harvesting chlorophyll a/b binding protein 1 (PsLhcb1) and PsLhcb5 influenced the Chl accumulation and the greenness of 'LMYY' petals. CONCLUSION: PsCLH1, PsLhcb1, and PsLhcb5 were critical in accumulating the Chl and maintaining the petal greenness. Flower color changes from green to pale pink were regulated by the homeostasis of Chl degradation and anthocyanin biosynthesis. This study offers insights into underlying molecular mechanisms in the green petal and a strategy for germplasm innovation.

Artificial light harvesting system of CM6@Zn-MOF nanosheets with highly enhanced photoelectric performance.

As donors for effective energy transfer, metal-organic frameworks (MOFs) have attracted the attention of many experts in the field of artificial light-harvesting materials. This study introduces a novel two-dimensional Zn-MOF, synthesized using flexible 1,3-phenyldiacetic acid (H2mpda) and rigid 1,3,5-tris(1-imidazolyl)benzene (tib) as organic ligands. Through atomic force microscopy (AFM), we have determined the monolayer thickness of this novel material to be 5 nm. Achieving two-dimensional Zn-MOF nanosheets with large BET surface area was made possible by employing ultrasonic stripping techniques. The fluorescence emission spectrum of Zn-MOF nanosheets overlaps with the UV-vis absorption spectrum of coumarin 6 (CM6), so they can be used as a donor and acceptor for fluorescence resonance energy transfer (FRET) to construct an artificial light-harvesting system (ALHS). Compared with single crystal Zn-MOF, CM6@Zn-MOF(2) has a larger BET surface area (41 m2/g), higher quantum yield (Φfl, 30.56 %), narrower energy gap (Eg, 2.87 eV), and the light-harvesting range extends to the visible green light area. Notably, CM6@Zn-MOF(2) demonstrates a robust photocurrent response, characterized by a photocurrent on/off ratio (Ilight/Idark) of 21, and a maximum photocurrent density that surpasses that of pure Zn-MOF (2.25:1). This study successfully designed a high-performance photoelectric conversion material CM6@Zn-MOF(2), which laid a certain theoretical foundation for new artificial optical acquisition systems and electrochemical material selection.

Development of artificial photosystems based on designed proteins for mechanistic insights into photosynthesis.

This review aims to provide an overview of the progress in protein-based artificial photosystem design and their potential to uncover the underlying principles governing light-harvesting in photosynthesis. While significant advances have been made in this area, a gap persists in reviewing these advances. This review provides a perspective of the field, pinpointing knowledge gaps and unresolved challenges that warrant further inquiry. In particular, it delves into the key considerations when designing photosystems based on the chromophore and protein scaffold characteristics, presents the established strategies for artificial photosystems engineering with their advantages and disadvantages, and underscores the recent breakthroughs in understanding the molecular mechanisms governing light-harvesting, charge separation, and the role of the protein motions in the chromophore's excited state relaxation. By disseminating this knowledge, this article provides a foundational resource for defining the field of bio-hybrid photosystems and aims to inspire the continued exploration of artificial photosystems using protein design.

Optimizing photosynthetic light-harvesting under stars: simple and general antenna models.

In the next 10-20 years, several observatories will aim to detect the signatures of oxygenic photosynthesis on exoplanets, though targets must be carefully selected. Most known potentially habitable exo-planets orbit cool M-dwarf stars, which have limited emission in the photosynthetically active region of the spectrum (PAR, 400 < λ < 700 nm) used by Earth's oxygenic photoautotrophs. Still, recent experiments have shown that model cyanobacteria, algae, and non-vascular plants grow comfortably under simulated M-dwarf light, though vascular plants struggle. Here, we hypothesize that this is partly due to the different ways they harvest light, reflecting some general rule that determines how photosynthetic antenna structures may evolve under different stars. We construct a simple thermodynamic model of an oxygenic antenna-reaction centre supercomplex and determine the optimum structure, size and absorption spectrum under light from several star types. For the hotter G (e.g. the Sun) and K-stars, a small modular antenna is optimal and qualitatively resembles the PSII-LHCII supercomplex of higher plants. For the cooler M-dwarfs, a very large antenna with a steep 'energy funnel' is required, resembling the cyanobacterial phycobilisome. For the coolest M-dwarfs an upper limit is reached, where increasing antenna size further is subject to steep diminishing returns in photosynthetic output. We conclude that G- and K-stars could support a range of niches for oxygenic photo-autotrophs, including high-light adapted canopy vegetation that may generate detectable bio-signatures. M-dwarfs may only be able to support low light-adapted organisms that have to invest considerable resources in maintaining a large antenna. This may negatively impact global coverage and therefore detectability.

Spectral modulation of B850 bacteriochlorophyll a in light-harvesting complex 2 from purple photosynthetic bacterium Thermochromatium tepidum by detergents and calcium ions.

Spectral variations of light-harvesting (LH) proteins of purple photosynthetic bacteria provide insight into the molecular mechanisms underlying spectral tuning of circular bacteriochlorophyll (BChl) arrays, which play crucial roles in photoenergy conversion in these organisms. Here we investigate spectral changes of the Qy band of B850 BChl a in LH2 protein from purple sulfur bacterium Thermochromatium tepidum (tepidum-LH2) by detergents and Ca2+. The tepidum-LH2 solubilized with lauryl dimethylamine N-oxide and n-octyl-ß-D-glucoside (LH2LDAO and LH2OG, respectively) exhibited blue-shift of the B850 Qy band with hypochromism compared with the tepidum-LH2 solubilized with n-dodecyl-ß-D-maltoside (LH2DDM), resulting in the LH3-like spectral features. Resonance Raman spectroscopy indicated that this blue-shift was ascribable to the loss of hydrogen-bonding between the C3-acetyl group in B850 BChl a and the LH2 polypeptides. Ca2+ produced red-shift of the B850 Qy band in LH2LDAO by forming hydrogen-bond for the C3-acetyl group in B850 BChl a, probably due to a change in the microenvironmental structure around B850. Ca2+-induced red-shift was also observed in LH2OG although the B850 acetyl group is still free from hydrogen-bonding. Therefore, the Ca2+-induced B850 red-shift in LH2OG would originate from an electrostatic effect of Ca2+. The current results suggest that the B850 Qy band in tepidum-LH2 is primarily tuned by two mechanisms, namely the hydrogen-bonding of the B850 acetyl group and the electrostatic effect.

Integrated transcriptomic and metabolomic analysis reveals the effects and potential mechanism of hydrogen peroxide on pigment metabolism in postharvest broccoli.

To understand the effects and related potential mechanism of H2O2 on pigment metabolism in postharvest broccoli, an integrated analysis of transcriptome and metabolome was performed. Results suggested that 65 differentially expressed genes and 26 differentially accumulated metabolites involved in chlorophyll, carotenoid, and flavonoid metabolism were identified. H2O2 treatment delayed the decrease of chlorophyll content by upregulating the expressions of chlorophyll synthetic genes, thylakoid synthetic genes, and 15 light-harvesting complex genes compared with the control and diphenylene iodonium treatments. H2O2 treatment decreased the accumulation of 11 flavonoids and 5 flavonols by downregulating the flavonoid synthetic genes. In addition, H2O2 treatment promoted carotenoid biosynthesis to eliminate reactive oxygen species in thylakoids, thereby protecting chlorophyll molecules from degradation. The inhibition of flavonoids and flavonols accumulation and chlorophyll decrease was the crucial reason for the delayed yellowing in H2O2 treatment. This study provides a new method and theoretical support for delaying the yellowing process in postharvest broccoli.

Ozone priming enhanced low temperature tolerance of wheat (Triticum aestivum L.) based on physiological, biochemical and transcriptional analyses.

Low temperature significantly inhibits the plant growth in wheat (Triticum aestivum L.), prompting the exploration of effective strategies to mitigate low temperature stress. Several priming methods enhance low temperature stress tolerant, however, the role of ozone priming remains unclear in wheat. Here we found ozone priming alleviated low temperature stress in wheat. Transcriptome analysis showed that ozone priming positively modulated 'photosynthesis-antenna proteins' pathway in wheat under low temperature. Which was confirmed by the results of the ozone-primed plants had higher trapped energy flux and electron transport flux per reaction, and less damage to chloroplasts than non-primed plants under low temperature. Ozone priming also mitigated the overstimulation of glutathione metabolism and induced the accumulation of total ascorbic acid and glutathione, maintained redox homeostasis in wheat under low temperature. Moreover, gene expressions and enzyme activities in glycolysis pathways were upregulated in ozone priming comparing with non-priming after the low temperature stress. Furthermore, exogenous antibiotics significantly increased low temperature tolerance, which further proved that the inhibition of ribosome biogenesis by ozone priming was involved in low temperature tolerance in wheat. In conclusion, ozone priming enhanced wheat low temperature tolerance through promoting light-harvesting capacity, redox homeostasis, and carbohydrate metabolism, as well as inhibiting ribosome biogenesis.

A quick comparison model on optimizing the efficiency of photovoltaic panels in collecting solar radiation.

Few scholars study light efficiency of solar-cell arrays in theory, while it is difficult to experimentally determine the maximum capacity of a photovoltaic panel to collect solar radiation. This paper proposes a solar energy comparison model (SECM), considering the sunshine duration changes every day to optimize the solar radiation collection model in an ideal state for a whole year, which is easy to use, and can quickly obtain the optimal tilt angle of photovoltaic panels and the solar radiation collecting efficiency enhancement of intelligent light tracking photovoltaic panels. The results show that the sunshine duration is an important factor affecting the solar radiation received by photovoltaic panels. In regions from 66°34'N to 66°34'S, intelligent light tracking photovoltaic panels can increase the collected solar radiation by at least 63.55%, up to 122.51% compared to stationary photovoltaic panels during the effective light time, which is much higher than what most people generally thought. And the advantage of intelligent light tracking photovoltaic panels is more obvious in high latitudes, with a longer and more variable sunshine duration. These findings provide a theoretical basis for the solar radiation collection and photovoltaic panels.

A Simple Expression for the Screening of Excitonic Couplings between Chlorophylls as Inferred for Photosystem I Trimers.

The Coulomb coupling between transition densities of the pigments in photosynthetic pigment-protein complexes, termed excitonic coupling, is a key factor for the description of optical spectra and energy transfer. A challenging question is the quantification of the screening of the excitonic coupling by the optical polarizability of the environment. We use the equivalence between the sophisticated quantum chemical polarizable continuum (PCM) model and the simple electrostatic Poisson-TrEsp approach to analyze the distance and orientation dependence of the dielectric screening between chlorophylls in photosystem I trimers. On the basis of these calculations we find that the vacuum couplings Vmn(0) and the couplings in the dielectric medium Vmn=fmnVmn(0) are related by the empirical screening factor fmn=0.60+39.6θ(|κmn|-1.17)exp(-0.56Rmn/Å), where κmn is the usual orientational factor of the dipole-dipole coupling between the pigments, Rmn is the center-to-center distance, and the Heaviside-function θ(|κmn|-1.17) ensures that the exponential distance dependence only contributes for in-line type dipole geometries. We are confident that the present expression can be applied also to other pigment-protein complexes with chlorophyll or related pigments of similar shape. The variance between the Poisson-TrEsp and the approximate coupling values is found to decrease by a factor of 8 and 3-4 using the present expression, instead of an exponential distance dependent or constant screening factor, respectively, assumed previously in the literature.

Helicene Covalent Organic Frameworks for Robust Light Harvesting and Efficient Energy Transfers.

Helicenes represent a class of fascinating π compounds with fused yet folded backbones. Despite their broad structural diversity, harnessing helicenes to develop well-defined materials is still a formidable challenge. Here we report the synthesis of crystalline porous helicene materials by exploring helicenes to synthesize covalent 2D lattices and layered π frameworks. Topology-directed polymerization of [6]helicenes and porphyrin creates 2D covalent networks with alternate helicene-porphyrin alignment along the x and y directions at a 1.5-nm interval and develops [6]helicene frameworks through reversed anti-AA stack along the z direction to form segregated [6]helicene and porphyrin columnar π arrays. Notably, this π configuration enables the frameworks to be highly red luminescent with benchmark quantum yields. The [6]helicene frameworks trigger effieicnt intra-framework singlet-to-singlet state energy transfer from [6]helicene to porphyrin and facilitate intermolecular triplet-to-triplet state energy transfer from frameworks to molecular oxygen to produce reactive oxygen species, harvesting a wide range of photons from ultraviolet to near-infrared regions for light emitting and photo-to-chemical conversion. This study introduces a new family of extended frameworks, laying the groundwork for exploring well-defined helicene materials with unprecedented structures and functions.

Tunable multicolor supramolecular assemblies based on phosphorescence cascade energy transfer for photocatalytic organic conversion and anti-counterfeiting.

Making full use of the captured energy by phosphorescence light-harvesting systems (PLHSs) and the tunable photoluminescence in energy transfer process to realize the multiple applications is still the challenge of PLHSs research. In this study, we have successfully constructed a highly effective PLHS with tunable multicolor luminescence and efficient conversion of photosensitizer types, which can further be used in photocatalytic organic conversion, information anti-counterfeiting and storage. The supramolecular polymer of BDBP-CB[8], which is generated by cucurbit[8]uril (CB[8]) and 4-(4-bromophenyl)-pyridine derivative (BDBP), realizes a phosphorescence emission and a change in luminescence color. Notably, white light emission was achieved and the logic gate systems were constructed utilizing the application of adjustable luminescence color. More interestingly, PLHS can be constructed by employing BDBP-CB[8] as energy donors, Sulforhodamine 101 (SR101) and Cyanine5 (Cy5) as energy acceptors, which results in a remarkably tunable multicolor photoluminescence to achieve the information storage. Furthermore, we have also found that BDBP-CB[8] can serve as type II photosensitizer for the effective production of singlet oxygen (1O2) during the photooxidation process of styrene in aqueous environments, attaining a remarkable output rate reaching as high as 89 %. Particularly, compared with 1O2 produced by type II photosensitizer BDBP-CB[8], the construction of PLHS can effectively convert type II photosensitizer to type I photosensitizer and efficiently generate superoxide anion radical (O2•-), which can be used for photocatalytic cross-dehydrogenative coupling (CDC) reaction in the aqueous solution with a yield of 90 %. Thus, we have created a PLHS that not only achieves tunable multicolor emission for information anti-counterfeiting and storage, but also realizes the conversion of reactive oxygen species (ROS) for different types photocatalytic oxidation reactions.

Molecular events accompanying aggregation-induced energy quenching in fucoxanthin-chlorophyll proteins.

In high light, the antenna system in oxygenic photosynthetic organisms switches to a photoprotective mode, dissipating excess energy in a process called non-photochemical quenching (NPQ). Diatoms exhibit very efficient NPQ, accompanied by a xanthophyll cycle in which diadinoxanthin is de-epoxidized into diatoxanthin. Diatoms accumulate pigments from this cycle in high light, and exhibit faster and more pronounced NPQ. The mechanisms underlying NPQ in diatoms remain unclear, but it can be mimicked by aggregation of their isolated light-harvesting complexes, FCP (fucoxanthin chlorophyll-a/c protein). We assess this model system by resonance Raman measurements of two peripheral FCPs, trimeric FCPa and nonameric FCPb, isolated from high- and low-light-adapted cells (LL,HL). Quenching is associated with a reorganisation of these proteins, affecting the conformation of their bound carotenoids, and in a manner which is highly dependent on the protein considered. FCPa from LL diatoms exhibits significant changes in diadinoxanthin structure, together with a smaller conformational change of at least one fucoxanthin. For these LL-FCPa, quenching is associated with consecutive events, displaying distinct spectral signatures, and its amplitude correlates with the planarity of the diadinoxanthin structure. HL-FCPa aggregation is associated with a change in planarity of a 515-nm-absorbing fucoxanthin, and, to a lesser extent, of diadinoxanthin. Finally, in FCPb, a blue-absorbing fucoxanthin is primarily affected. FCPs thus possess a plastic structure, undergoing several conformational changes upon aggregation, dependent upon their precise composition and structure. NPQ in diatoms may therefore arise from a combination of structural changes, dependent on the environment the cells are adapted to.

Martini 3 Coarse-Grained Model for the Cofactors Involved in Photosynthesis.

As a critical step in advancing the simulation of photosynthetic complexes, we present the Martini 3 coarse-grained (CG) models of key cofactors associated with light harvesting (LHCII) proteins and the photosystem II (PSII) core complex. Our work focuses on the parametrization of beta-carotene, plastoquinone/quinol, violaxanthin, lutein, neoxanthin, chlorophyll A, chlorophyll B, and heme. We derived the CG parameters to match the all-atom reference simulations, while structural and thermodynamic properties of the cofactors were compared to experimental values when available. To further assess the reliability of the parameterization, we tested the behavior of these cofactors within their physiological environments, specifically in a lipid bilayer and bound to photosynthetic complexes. The results demonstrate that our CG models maintain the essential features required for realistic simulations. This work lays the groundwork for detailed simulations of the PSII-LHCII super-complex, providing a robust parameter set for future studies.

Structural and spectroscopic insights into fucoxanthin chlorophyll a/c-binding proteins of diatoms in diverse oligomeric states.

Diatoms, a group of prevalent marine algae, contribute significantly to global primary productivity. Their substantial biomass is linked to enhanced absorption of blue-green light underwater, facilitated by fucoxanthin chlorophyll (Chl) a/c-binding proteins (FCPs), which exhibit oligomeric diversity across diatom species. Using mild clear native PAGE analysis of solubilized thylakoid membranes, we displayed monomeric, dimeric, trimeric, tetrameric, and pentameric FCPs in diatoms. Mass spectrometry analysis revealed that each oligomeric FCP has a specific protein composition, and together they constitute a large Lhcf family of FCP antennas. In addition, we resolved the structures of the Thalassiosira pseudonana FCP (Tp-FCP) homotrimer and the Chaetoceros gracilis FCP (Cg-FCP) pentamer by cryoelectron microscopy at 2.73-Å and 2.65-Å resolution, respectively. The distinct pigment compositions and organizations of various oligomeric FCPs affect their blue-green light-harvesting, excitation energy transfer pathways. Compared with dimeric and trimeric FCPs, the Cg-FCP tetramer and Cg-FCP pentamer exhibit stronger absorption by Chl c, redshifted and broader Chl a fluorescence emission, and more robust circular dichroism signals originating from Chl a-carotenoid dimers. These spectroscopic characteristics indicate that Chl a molecules in the Cg-FCP tetramer and Cg-FCP pentamer are more heterogeneous than in both dimers and the Tp-FCP trimer. The structural and spectroscopic insights provided by this study contribute to a better understanding of the mechanisms that empower diatoms to adapt to fluctuating light environments.

Enhancing Efficiency of Dye Sensitized Solar Cells by Coinage Metal Doping of Cyanidin-Silver Trimer Hybrids at TiO2 Support Based on Theoretical Study.

Identification of a natural-based sensitizer with optimal stability and efficiency for dye-sensitized solar cell (DSSC) application remains a challenging task. Previously, we proposed a new class of sensitizers based on bio-nano hybrids. These systems composed of natural cyanidin dyes interacting with silver nanoclusters (NCs) have demonstrated enhanced opto-electronic and photovoltaic properties. In this study, we explore the doping of silver nanocluster within a cyanidin-Ag3 hybrid employing Density Functional Theory (DFT) and its time-dependent counterpart (TDDFT). Specifically, we investigate the influence of coinage metal atoms (Au and Cu) on the properties of the cyanidin-Ag3 system. Our findings suggest that cyanidin-Ag2Au and cyanidin-AgAuCu emerge as the most promising candidates for improved light harvesting efficiency, increased two-photon absorption, and strong coupling to the TiO2 surface. These theoretical predictions suggest the viability of replacing larger silver NCs with heterometallic trimers such as Ag2Au or AgAuCu, presenting new avenues for utilizing bio-nano hybrids at the surface for DSSC application.

Geometry, reactivity descriptors, light harvesting efficiency, molecular radii, diffusion coefficient, and oxidation potential of RE(I)(CO)3Cl(TPA-2, 2'-bipyridine) in DSSC application: DFT/TDDFT study.

Dye-sensitized solar cells (DSSCs) are an excellent alternative solar cell technology that is cost-effective and environmentally friendly. The geometry, reactivity descriptors, light-harvesting efficiency, molecular radii, diffusion coefficient, and excited oxidation state potential of the proposed complex were investigated. The calculations in this study were performed using DFT/TDDFT method with B3LYP functional employed on the Gaussian 09 software package. The calculations were used the 6-311 + + G(d, p) basis set for the C, H, N, O, Cl atoms and the LANL2DZ basis set for the Re atom, with the B3LYP functional.. The balance of hole and electron in this complex has increased the efficiency and lifetime of DSSCs for photovoltaic cell applications. The investigated compound shows that the addition of the TPA substituent marginally changes the geometric structures of the 2, 2'-bipyridine ligand in the T1 state. As EDsubstituents were added to the compound, the energy gap widened and moved from ELUMO (- 2.904 eV) (substituted TPA) to ELUMO (- 3.122 eV) (unsubstituted). In the studying of solvent affects; when the polarity of the solvent decreases, red shifts appears in the lowest energy an absorption and emission band. Good light-harvesting efficiency, molecular radii, diffusion coefficient, excited state oxidation potential, emission quantum yield, and DSSC reorganization energy, the complex is well suited for use as an emitter in dye-sensitized solar cells. Among the investigated complexes mentioned in literature, the proposed complex was a suitable candidate for phosphorescent DSSC.