Artificial Light-harvesting Systems Research Articles

Cascade Energy Transfer in Biopolymer-Templated Multi-Chromophoric Assemblies: Ratiometric Temperature Sensing.

Natural light-harvesting complexes collect energy from sunlight and transfer it to the reaction center through a cascade of energy and electron transfer steps. Artificial light-harvesting systems functioning in aqueous media mimic natural photosynthetic systems. However, their design remains a challenging task as closely packed antenna chromophores often undergo severe self-quenching. Herein, we report luminescent co-assemblies between cationic pyrene-appended imidazolium amphiphiles and two anionic biopolymeric scaffolds, heparin and DNA in aqueous media. These co-assemblies served as excellent platforms for constructing artificial light-harvesting systems as upon co-embedding of multiple external dyes, highly efficient single-step and cascade energy transfer was observed from the pyrene donors to the acceptor dyes. Most notably, the efficiency of the energy transfer process was possible to modulate by employing multiple stimuli such as pH and temperature, and this resulted in the generation of multi-color luminescent materials in solution and film states, and they were also exploited in ratiometric temperature sensing. Their stimuli-responsive luminescence in the solid state was found to be advantageous for encryption studies.

Construction of an Artificial Light-Harvesting System Based on an Aggregation-Induced Emission Type Multiperformance Supramolecular Fluorescent Gel

Construction of an Artificial Light-Harvesting System Based on an Aggregation-Induced Emission Type Multiperformance Supramolecular Fluorescent Gel

In Situ Synthesis of AIEgen-based Porous Organic Polymer Films by Interfacial Amino-yne Click Polymerization for Efficient Light-Harvesting.

We developed a catalyst-free, atom-economical interfacial amino-yne click polymerization to in situ synthesize new aggregation-induced emission luminogen (AIEgen)-based free-standing porous organic polymer films at room temperature. The crystalline properties of POP films were confirmed by powder X-ray diffraction and high-resolution transmission electron microscopy. The good porosity of these POP films was proved by their N2 uptake experiments. The thickness of POP films can be easily regulated from 16 nm to ≈1 μm by adjusting monomer concentration. More importantly, these AIEgen-based POP films show bright luminescence with high absolute photoluminescent quantum yields up to 37.8 % and good chemical and thermal stability. The AIEgen-based POP film can encapsulate an organic dye (e.g., Nile red) to further form an artificial light-harvesting system with a large red-shift (Δλ=141 nm), highly efficient energy-transfer ability (ΦET =91 %), and high antenna effect (11.3).

Water-soluble phosphate-pillar[5]arene (WPP5)-based artificial light-harvesting system for photocatalytic cross-coupling dehydrogenation

A novel water-soluble phosphate-pillar[5]arene (WPP5)-based artificial light-harvesting system (LHS) was successfully fabricated through the supramolecular assembly of phenyl-pyridyl-acrylonitrile derivative (PBT), WPP5, and organic pigment Eosin Y (ESY). Initially, after host–guest interaction, WPP5 could bind well with PBT and form WPP5 ⊃ PBT complexes in water, which further assembled into WPP5 ⊃ PBT nanoparticles. WPP5 ⊃ PBT nanoparticles performed an outstanding aggregation-induced emission (AIE) capability because of the J-aggregates of PBT in WPP5 ⊃ PBT nanoparticles, which were appropriate as fluorescence resonance energy transfer (FRET) donors for artificial light-harvesting. Moreover, due to the emission region of WPP5 ⊃ PBT overlapped well with the UV–Vis absorption of ESY, the energy of WPP5 ⊃ PBT (donor) could be significantly transferred to ESY (acceptor) via FRET process in WPP5 ⊃ PBT-ESY nanoparticles. Notably, the antenna effect (AEWPP5⊃PBT-ESY) of WPP5 ⊃ PBT-ESY LHS was determined to be 30.3, which was much higher than that of recent artificial LHSs for photocatalytic cross-coupling dehydrogenation (CCD) reactions, suggesting a potential application in photocatalytic reaction. Furthermore, through the energy transfer from PBT to ESY, the absolute fluorescence quantum yields performed a remarkable increase from 14.4% (for WPP5 ⊃ PBT) to 35.7% (for WPP5 ⊃ PBT-ESY), further confirming their FRET processes in WPP5 ⊃ PBT-ESY LHS. Subsequently, in order to output the harvested energy for catalytic reactions, WPP5 ⊃ PBT-ESY LHSs were used as photosensitizers to catalyze the CCD reaction of benzothiazole and diphenylphosphine oxide. Compared to free ESY group (21%), a significant cross-coupling yield of 75% in WPP5 ⊃ PBT-ESY LHS was observed, because more UV region energy of PBT was transferred to ESY for CCD reaction, which suggested more potential in improving the catalytic activity of organic pigment photosensitizers in aqueous systems.

A Membrane-Associated Light-Harvesting Model is Enabled by Functionalized Assemblies of Gene-Doubled TMV Proteins.

Photosynthetic light harvesting requires efficient energy transfer within dynamic networks of light-harvesting complexes embedded within phospholipid membranes. Artificial light-harvesting models are valuable tools for understanding the structural features underpinning energy absorption and transfer within chromophore arrays. Here, a method for attaching a protein-based light-harvesting model to a planar,fluidsupported lipid bilayer (SLB) is developed. The protein model consists of the tobacco mosaic viral capsid proteins that are gene-doubled to create a tandem dimer (dTMV). Assemblies of dTMV break the facial symmetry of the double disk to allow for differentiation between the disk faces. A single reactive lysine residue is incorporated into the dTMV assemblies for the site-selective attachment of chromophores for light absorption. On the opposing dTMV face, a cysteine residue is incorporated for the bioconjugation of a peptide containing a polyhistidine tag for association with SLBs. The dual-modified dTMV complexes show significant association with SLBs and exhibit mobility on the bilayer. The techniques used herein offer a new method for protein-surface attachment and provide a platform for evaluating excited state energy transfer events in a dynamic, fully synthetic artificial light-harvesting system.

Artificial Light-Harvesting System Based on Zinc Porphyrin and Benzimidazole: Construction, Resonance Energy Transfer, and Amplification Strategy for Electrochemiluminescence

Constructing robust and efficient luminophores is of significant importance in the development of electrochemiluminescence (ECL) amplification strategies. Inspired by the resonance energy transfer in natural light-harvesting systems, we propose a novel ECL amplification system based on ECL resonance energy transfer (ECL-RET), which integrates two luminophores, benzimidazole (BIM) and zinc(II) tetrakis(4-carboxyphenyl)porphine (ZnTCPP), into one framework. Through disassembling and reconstruction processes, numerous BIM surround ZnTCPP in the constructed ZIF-9-ZnTCPP. Combined with the overlapped spectra between the emission of BIM and the absorption of ZnTCPP, the energy of multiple BIM (donor) can be concentrated to a single ZnTCPP (acceptor) to amplify the ECL emission of the acceptor. This work provides a convenient way to design an efficient ECL-RET system, which initiates a brand-new chapter in the development of ECL amplification strategies.

The Materials and Application of Artificial Light Harvesting System Based on Supramolecular Self‐assembly

AbstractSupramolecular self‐assembly is the process of forming aggregates with a certain microscopic arrangement by using intermolecular interactions to join. Due to the dynamic controllability of supramolecular systems, many supramolecular systems with different functions can be precisely constructed through the design and modification of molecules. The world is now facing a crisis caused by energy problems, and the use of solar energy, especially how to achieve efficient collection of light energy like photosynthesis in nature, has become a challenge. Scientists have come up with the idea of using the tunable nature of supramolecular structure and function to construct artificial light harvesting systems, and have developed a series of ALHS based on this. Currently, ALHS have been applied to imaging, sensors, photoelectric conversion and molecular recognition, laying the foundation for the development and efficient use of light energy. This paper will review the mechanism and method of constructing ALHS based on Supramolecular Self‐assembly, the current hot materials for constructing ALHS and their characteristics, as well as the prospects and applications.

Fluorescent Nanoassemblies in Water Exhibiting Tunable LCST Behavior and Responsive Light Harvesting Ability.

Responsive fluorescent nanomaterials have been received considerable attention in recent years. In this work, a bola-type amphiphilic molecule, CSO, was synthesized which contains a hydrophobic cyanostilbene core and hydrophilic oligo(ethylene glycol) (OEG) coils at both sides. The cyanostilbene group is aggregation-induced emission (AIE) active, while the OEG coils are thermo-responsive. As a result, the CSO molecules can self-assemble into blue-fluorescent nanoassemblies with lower critical solution temperature (LCST) behavior in aqueous media. It is noteworthy that the LCST behavior can be reversibly regulated with changes in concentration and the introduction of K+ . Intriguingly, fluorescence of CSO assembly shows a blue-shift upon heating. Finally, by employing CSO as a light capturing antenna and energy donor, an artificial light harvesting system with tunable emission and thermo-responsive characteristics was fabricated. This study not only demonstrates an integrated approach to create responsive fluorescent nanomaterials, but also shows great potential for producing luminescent materials and mimicking photosynthesis in nature.

Electronic Energy Migration in Microtubules.

The repeating arrangement of tubulin dimers confers great mechanical strength to microtubules, which are used as scaffolds for intracellular macromolecular transport in cells and exploited in biohybrid devices. The crystalline order in a microtubule, with lattice constants short enough to allow energy transfer between amino acid chromophores, is similar to synthetic structures designed for light harvesting. After photoexcitation, can these amino acid chromophores transfer excitation energy along the microtubule like a natural or artificial light-harvesting system? Here, we use tryptophan autofluorescence lifetimes to probe energy hopping between aromatic residues in tubulin and microtubules. By studying how the quencher concentration alters tryptophan autofluorescence lifetimes, we demonstrate that electronic energy can diffuse over 6.6 nm in microtubules. We discover that while diffusion lengths are influenced by tubulin polymerization state (free tubulin versus tubulin in the microtubule lattice), they are not significantly altered by the average number of protofilaments (13 versus 14). We also demonstrate that the presence of the anesthetics etomidate and isoflurane reduce exciton diffusion. Energy transport as explained by conventional Förster theory (accommodating for interactions between tryptophan and tyrosine residues) does not sufficiently explain our observations. Our studies indicate that microtubules are, unexpectedly, effective light harvesters.

Construction of Artificial Light-Harvesting Systems Based on Aggregation-Induced Emission Type Supramolecular Self-Assembly Metallogels.

A method for preparing new artificial light-harvesting systems (ALHSs) based on supramolecular metallogels was proposed. Various metal ions were introduced into a solution of a bi-benzimidazole compound (P) in ethylene glycol, and P exhibited high selectivity toward Al3+, as indicated by the noticeable red shift (49 nm) observed in the fluorescence spectra of P after the addition of Al3+. Interestingly, the gelator, P, could self-assemble into a stable supramolecular gel (P-gel) that exhibits strong aggregation-induced emission in ethylene glycol. Thus, two ALHSs were successfully prepared in a gel environment. The P-Al3+ assembly acts as the donor in the ALHSs, while BODIPY 505/515 (BDP) and rhodamine 6G (Rh6G), which are loaded onto the P-Al3+ assembly, act as acceptors. In these two diverse systems, the occurrence of an energy transfer process is confirmed from the P-Al3+ assembly to BDP and Rh6G. The findings of this study will enable the design and fabrication of ALHSs.

An efficient strategy based on polyelectrolyte of constructing a sequential energy transfer artificial light-harvesting system for photocatalysis

In this work, an efficient artificial light-harvesting system with a two-step sequential energy transfer process was first constructed based on the polyelectrolyte material sodium carboxymethyl cellulose (CMC) and AIE molecule cyano-substituted amphiphilic hydroquinone derivative (PPTA) in an aqueous solution. The energy harvested by the two fluorescent dyes EY and SR101 from the supramolecular assembly PPTA-CMC was fully used for photochemical catalysis for the dehalogenation of α-bromoacetophenone, cross dehydrogenation coupling reaction (CDC), and alkylation of C–H bonds of phenyl vinyl sulfone (PVS) and tetrahydrofuran (THF) in the aqueous medium.

Construction of an efficient artificial light-harvesting system based on hyperbranched polyethyleneimine and improvement of photocatalytic performance.

An artificial light-harvesting system (ALHS) was developed in aqueous solution by employing the electrostatic co-assembly of a tetraphenylethylene derivative modified with two sulfonate groups (TPE-BSBO) and hyperbranched polyethyleneimine (PEI) as the energy donors, and 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (DBT) as the energy acceptors. The ALHS exhibits not only high efficiency in energy transfer and conversion but also a significant enhancement in the generation of reactive oxygen species (ROS), especially superoxide anion radicals (O2˙-), facilitating its utilization in photocatalytic oxidation reactions.

A cavitand-based supramolecular artificial light-harvesting system with sequential energy transfer for photocatalysis.

A novel artificial light-harvesting system, featuring sequential energy transfer processes, has been successfully constructed, which demonstrated white light emission through a precise adjustment of the donor-acceptor ratio. To better mimic natural photosynthesis, the system is employed as a nanoreactor for the photocatalysis of a cross-dehydrogenative coupling (CDC) reaction in aqueous solution.

A supramolecular artificial light-harvesting system based on a luminescent platinum(II) metallacage.

A trigonal luminescent metallacage was constructed by the coordination-driven self-assembly of m-pyridine-modified tetraphenylene ligands with organic Pt(II) acceptors, which exhibited excellent Aggregation-Induced Emission (AIE) properties. An efficient artificial light-harvesting system was successfully constructed by selecting the metallacage as the donor and the hydrophobic fluorescent dye Nile Red (NiR) as the donor molecule in a system of acetone/water (1/9, v/v), The absorption spectra of NiR and the emission spectra of the metallacage showed considerable overlap, achieving energy transfer from the metallacage to NiR.

A novel strategy of constructing an artificial light-harvesting system based on a supramolecular organic framework for photocatalysis

A supramolecular organic framework was fabricated through encapsulation-enhanced donor–acceptor interaction for the construction of artificial light-harvesting systems for photocatalysis.

Artificial supramolecular light-harvesting systems based on a pyrene derivative for photochemical catalysis

A supramolecular polymer based on NPyP and CB[8] was constructed via host–guest interactions with the AIE effect for artificial light-harvesting energy transfer and photocatalysis.

An artificial light-harvesting system constructed from a water-soluble metal-organic barrel for photocatalytic aerobic reactions in aqueous media.

An artificial light-harvesting system constructed from a water-soluble host-guest complex can be regarded as a high-level conceptual model of its biological counterpart and can convert solar energy into chemical energy in an aqueous environment. Herein, a water-soluble metal-organic barrel Ga-tpe with twelve sulfonic acid units was obtained by subcomponent self-assembly between Ga3+ ions and tetra-topic ligands with tetraphenylethylene (TPE) cores. By taking advantage of host-guest interactions, cationic dye rhodamine B (RB) was constrained in the pocket of Ga-tpe to promote the Förster resonance energy transfer (FRET) process for efficient photocatalytic aerobic oxidation of sulfides and cross-dehydrogenative coupling (CDC) reaction in aqueous media.

A temperature-responsive artificial light-harvesting system in water with tunable white-light emission

A tadpole-type amphiphilic monomer containing cyanostilbene and oligo(ethylene glycol) chains has been designed and synthesized, which can be used to construct a thermo-responsive light-harvesting system in water with tunable white-light emission.

An efficient hierarchical self-assembly approach to construct structurally diverse two-step sequential energy-transfer artificial light-harvesting systems

This research provides an efficient hierarchical self-assembly approach to construct artificial LHSs featuring excellent energy transfer efficiency and high antenna effects with diverse architectures.

A pillar[5]arene-based artificial light-harvesting system with red emission for high-resolution imaging of latent fingerprints

An artificial LHS with red emission based on pillar[5]arene was fabricated using 1% Nile red as the energy acceptor. The prepared powder was successfully used for high-contrast fluorescence imaging of latent fingerprints.