Perspective of energy transfer from light energy into biological energy

Energy has always been the most concerned topic in the world due to the large consumption. Various types of energy have been exploited and developed to enhance the output amount so that high requirements can be met. Like the hydro-energy, wind energy, and tidal energy, light energy as a renewable, clean, and widespread energy can be easily harvested. In microcosmic scale, some specific proteins and enzymes in green plants and bacteria play an important role in light harvest and energy conversion via photosynthesis. Inspired by the biomimetic sparks,these bioactive macromolecules and some artificially synthetic unites have been integrated together to improve the light-harvesting, and enhance their utilization efficiency. In this feature article, we primarily discuss that how to create the bio-inorganic hybrid energy converted system via biomimetic assembly strategy and artificially achieve the transformation from light into bioenergy, meanwhile highlight some promising works.

Multistep Desolvation as a Fundamental Principle Governing Peptide Self-Assembly Through Liquid-Liquid Phase Separation

Biomolecular self-assembly based on peptides and proteins is a general phenomenon encountered in natural and synthetic systems.Liquid–liquid phase separation(LLPS)is intimately involved in biomolecular self-assembly,yet the key factors at a molecular scale activating or modulating such a process remain largely elusive.Herein,we discovered in our experiments that multistep desolvation is fundamental to the formation and evolution of peptide-rich droplets:The first step was partial desolvation of peptides to form peptide clusters,and the second step was selective desolvation of hydrophobic groups within clusters to trigger LLPS and the formation of peptiderich droplets,followed by complete desolvation of droplets,initiating the nucleation of peptide selfassembly.Manipulation of the degree of desolvation at different stages was an effective strategy to control the self-assembly pathways and polymorphisms.This study sheds light on the molecular origin of LLPS-mediated self-assembly distinct from classical one-step self-assembly and paves the way for the precise control of supramolecular self-assembly.

Assembled Photosensitizers Applied for Enhanced Photodynamic Therapy

Photodynamic therapy(PDT)has emerged as an efficient method for cancer therapy.However,traditional photosensitizers(PSs)always have low bioavailability.For example,hydrophobic PSs tend to aggregate in cells and lead to aggregation-induced quenching;while hydrophilic PSs that have good solubility in water systems can hardly penetrate into cells whose membranes are lipophilic.To overcome these drawbacks,suitable PSs that meet the requirements of PDT are needed.Numerous investigations have been introduced,especially the molecular-assembly technique that can increase the bioavailability of PSs during the tumor therapy process.Besides,increasing the quantum yield of reactive oxygen species(ROS)by adjusting the PS triplet state lifetime as well as developing aggregation-induced emission(AIE)agents can also improve the PDT effect.This review summarizes the molecular-assembly technique to obtain intelligent PSs to achieve high PDT efficiency.First,increasing the quantum yield of ROS by decreasing the energy gap between S_(1)and T_(1)states or increasing the spin–orbit coupling Hamiltonian are introduced.Second,we present the bioavailability of traditional PSs by improving the amphiphilicity of the PSs or using intelligent nanostructures.Then,the AIE PSs that can form ROS in the aggregated state under irradiation are described.Finally,the perspective and challenges of PDT are discussed.

AIEgen-lipid structures:Assembly and biological applications

Aggregation-induced emission(AIE)molecules possess notable advantages outperforming traditional aggregation caused quenching(ACQ)materials on various aspects.They are rapidly developed these years.More and more AIE luminogens(AIEgens)are designed to possess multifunctions such as the abilities of near-infrared two-photon absorption and reactive oxygen species(ROS)generation,which could be used for deep tissue imaging and photodynamic therapy.The AIEgens exhibit great potential in biological application field.However,despite the photophysics stability and ROS generation ability in aggregated states are favorable conditions,their applications in biological field are retarded by uncontrolled size,single imaging mode,low targeting efficiency,and also poor biocompatibility and dispersibility in physiological environment.The combination of AIEgen and lipid is a straightforward,promising,and intensively used way to solve the above problems.Due to the special amphipathic property of lipid,which results from a hydrophilic head and hydrophobic tail structure,there are various possibilities of combination modes between lipid and AIEgen.Even a little procedure or condition change during the synthesis process will impact the structure of obtained product,which can further influence its application.Herein,we summarize the synthesis methods of different AIEgen-lipid compounds with diverse structures and properties,as well as their biological applications in this contribution,which has not been presented before,being aimed at serving as a synthesis and application reference for these promising AIEgen-lipid compounds applied in biological region.

Catalase-Conjugated Rose Bengal Biological Nanoparticles with Mitochondrial Selectivity Toward Photodynamic Therapy

Photodynamic therapy(PDT)has emerged as an efficient treatment for cancers in recent years.However,PDT is limited by low utilization of photosensitizers and tumor hypoxia.The short lifetime and diffusion radius of singlet oxygen(^(1)O_(2))further decrease the anticancer effect of PDT.Herein,we design and synthesize diameter-controllable photosensitizer nanoparticles(NPs)which can specifically accumulate on the mitochondria of cancer cells and increase the O_(2) concentrations nearby to enhance PDT efficacy.Catalase(CAT)molecules are initially conjugated with rose bengal(RB)via amide bonds and then self-assembled into CAT-RB NPs.The NPs show excellent enzyme activity in catalyzing the decomposition of hydrogen peroxide into O_(2),which makes the yield of 1O21.65-fold higher than that of free RB.The intracellular uptake efficiency of NPs is increased by up to 150 times compared with pure RB.After endocytosis,the NPs mainly located at mitochondria and ^(1)O_(2) can directly destroy mitochondria under irradiation,thereby greatly decreasing the production of adenosine triphosphate and further leading to the apoptosis of cancer cells.Moreover,CAT-RB NPs can accumulate in tumors and show excellent PDT effects in vivo.This work opens a unique path to break through the current limitations of PDT in cancer treatment.

Enhanced Bioenergy Transformation by Metal-Free Electrozyme-Based Mitochondrion Nanoarchitectonics

Herein,we couple a synthetic electrozyme in a supramolecule-assembled nanoarchitecture to achieve enhanced bioenergy transformation by mimicking mitochondrial oxidative phosphorylation.Different from the natural counterpart,the metal-free electrozyme is a semiconducting polymer deposited on an electrode.The wellmatched electrocatalytic property of the electrozyme permits oxidization of reduced nicotinamide adenine dinucleotide(NADH)to release protons under a much lower electric potential.As a consequence,the generated proton gradient drives rotary catalysis of adenosine 5′-triphosphate(ATP)synthase reconstituted in a lipid membrane to produce ATP.Remarkably,electrochemical bioenergy conversion of NADH to ATP is accomplished with much higher efficiency in such a bio-like system compared with the natural mitochondria.This work integrates synthetic and natural catalytic chemistry to facilitate enhanced bioenergy transformation,thereby greatly improving prospects in ATP-fueled bioapplications.

Assembly of CdTe Quantum Dots and Photosystem II Multi- layer Films with Enhanced Photocurrent

Photosystem II （PSII） is a photoactive protein that can drive water oxidation under light irradiation. Recently, PSII has been broadly investigated with the high demand on the bioenergy. Here, we demonstrate a facile approach for the fabrication of a photoactive electrode by the integration of PSII with quantum dots （QDs）/polyelectrolyte multilayers. The assembled QDs and PSII film with a polyelectrolyte based substrate via layer-by-layer assembly can remain the photoactivity of the PSII and broaden the absorption spectrum of PSII to produce a high photocur- rent yield. The co-assembly exhibits an obviously enhanced photocurrent under UV light irradiation. The proposed strategy can be considered for the reference and usage of PSII toward the solar energy conversion.

Reconstitution of Motor Proteins through Molecular Assembly

What is the most favorite and original chemistry developed in your research group?The most favorite and original chemistry developed in my research group is about the reconstitution of motor proteins in artificially designed and assembled units.It is based on the molecular assembly technique,but the method is different from the conventional approach.

Gas-Induced Phase Transition of Dipeptide Supramolecular Assembly

The manipulation of supramolecular assembly enables single-component architectures to possess diverse structures and functions.Here,we report directed phase transitions of dipeptide supramolecular gel to crystals with excellent selectivity and tunable mechanical properties.To be specific,lamellar-to-orthorhombic rearrangement of dipeptide molecules in the supramolecular assembly was guided by application of ammonia gas,while lamellar-tohexagonal realignment was generated upon water vapor exposure of the assembly.Importantly,this crystal phase control originated from distinct gas-mediated reconstitution of hydrogen-bonding interactions,which endowed the dipeptide materials with remarkably modulated stiffness.The selective phase transformation offers a simple and effective platform for self-assembling peptide crystals with diverse long-range-ordered structures from a single gel-state aggregation.This work opens up new perspectives on peptide-based biomaterials via gas-directed hydrogen-bonding chemistry.

Black Phosphorus Nanosheets Enhance Photophosphorylation by Positive Feedback

We construct a natural-artificial hybrid architecture containing black phosphorus nanosheets(BPNS)to enhance photosynthesis of chloroplast in a positive-feedback manner.In this architecture,oxygen yielded by photosynthesis during water splitting by photosystemⅡpromotes the photoreaction of BPNS to produce proton and inorganic phosphate(Pi).Further,transmembrane proton gradient is increased to drive ATP synthase to synthesize ATP.Meanwhile,additional photogenerated electrons produced by BPNS are transferred to the photosynthesis process.As a consequence,photosynthesis performed by chloroplast is improved.Quantitatively,photophosphorylation efficacy of the hybrid system is increased by 1.89 times in the case of Pi deficiency.This work offers a new path to enhance solar-to-chemical energy conversion,holding promise in boosting natural photosynthesis.