Nanoarchitectonics of Vesicle Microreactors for Oscillating ATP Synthesis and Hydrolysis.

We construct a compartmentalized nanoarchitecture to regulate bioenergy level. Glucose dehydrogenase, urease and nicotinamide adenine dinucleotide are encapsulated inside through liquid-liquid phase separation. ATPase and glucose transporter embedded in hybrid liposomes are attached at the surface. Glucose is transported and converted to gluconic acid catalyzed by glucose dehydrogenase, resulting in an outward proton gradient to drive ATPase for ATP synthesis. In parallel, urease catalyzes hydrolysis of urea to generate ammonia, which leads to an inward proton gradient to drive ATPase for ATP hydrolysis. These processes lead to a change of the direction of proton gradient, thus achieving artificial ATP oscillation. Importantly, the frequency and the amplitude of the oscillation can be programmed. The work explores nanoarchitectonics integrating multiple components to realize artificial and precise oscillation of bioenergy level.

Light-triggered AND logic tetrapeptide dynamic covalent assembly.

We demonstrate light-triggered dynamic covalent assembly of a linear short tetrapeptide containing two terminal cysteine residues in an AND logic manner. A photobase generator is introduced to accomplish light-mediated pH regulation to increase the reduction potential of thiols in the tetrapeptide, which activates its oxidative polymerization through disulfide bonds. Interestingly, it is elucidated that under light irradiation, mere co-existence of photobase generator and the oxidizing agent permits the polymerization performance of this tetrapeptide. Hence, a light-triggered AND logic dynamic covalent assembly of a tetrapeptide is achieved. Further, upon redox response, the reversible aggregation and disaggregation can be transformed for numerous times due to the dynamic covalent feature of disulfide bond. As a comparison, no assembly occurs for a short peptide containing one terminal cysteine residue under the same stimuli condition. This work offers a new approach to remotely control programmable molecular assembly of short linear peptides based on dynamic covalent bond, holding great potential in wide bioapplications.

Nanoarchitectonics with a Membrane-Embedded Electron Shuttle Mimics the Bioenergy Anabolism of Mitochondria.

Enhanced bioenergy anabolism through transmembrane redox reactions in artificial systems remains a great challenge. Here, we explore synthetic electron shuttle to activate transmembrane chemo-enzymatic cascade reactions in a mitochondria-like nanoarchitecture for augmenting bioenergy anabolism. In this nanoarchitecture, a dendritic mesoporous silica microparticle as inner compartment possesses higher load capacity of NADH as proton source and allows faster mass transfer. In addition, the outer compartment ATP synthase-reconstituted proteoliposomes. Like natural enzymes in the mitochondrion respiratory chain, a small synthetic electron shuttle embedded in the lipid bilayer facilely mediates transmembrane redox reactions to convert NADH into NAD+ and a proton. These facilitate an enhanced outward proton gradient to drive ATP synthase to rotate for catalytic ATP synthesis with improved performance in a sustainable manner. This work opens a new avenue to achieve enhanced bioenergy anabolism by utilizing a synthetic electron shuttle and tuning inner nanostructures, holding great promise in wide-range ATP-powered bioapplications.

Photozyme-Catalyzed ATP Generation Based on ATP Synthase-Reconstituted Nanoarchitectonics.

We demonstrate that ATP synthase-reconstituted proteoliposome coatings on the surface of microcapsules can realize photozyme-catalyzed oxidative phosphorylation. The microcapsules were assembled through layer-by-layer deposition of semiconducting graphitic carbon nitride (g-C3N4) nanosheets and polyelectrolytes. It is found that electrons from polyelectrolytes are transferred to g-C3N4 nanosheets, which enhances the separation of photogenerated electron-hole pairs. Thus, the encapsulated g-C3N4 nanosheets as the photozyme accelerate oxidation of glucose into gluconic acid to yield protons under light illumination. The outward transmembrane proton gradient is established to drive ATP synthase to synthesize adenosine triphosphate. With such an assembled system, light-driven oxidative phosphorylation is achieved. This indicates that an assembled photozyme can be used for oxidative phosphorylation, which creates an unusual way for chemical-to-biological energy conversion. Compared to conventional oxidative phosphorylation systems, such an artificial design enables higher energy conversion efficiency.

Long afterglow particle enables spectral and temporal light management to boost photosynthetic efficiency.

Herein, we develop a strategy of matched spectral and temporal light management to improve photosynthetic efficiency by co-assembling natural thylakoid membrane (TM) with artificial long afterglow particle (LAP). To be specific, LAP with excellent stability and biocompatibility possesses the capabilities of light conversion and storage, optically-matched with the absorption of TM. These favorable features permit LAP as an additional well-functioned light source of photosynthesis performed by TM. As a consequence, enhanced photosynthesis is achieved after co-assembly, compared with pure TM. Under light, the rates of electron transfer, oxygen yield and adenosine triphosphate (ATP) production in this biohybrid architecture are boosted owing to down-conversion fluorescence emission from LAP. Under dark, persistent phosphorescence emission in charged LAP facilitates continual photosynthesis of TM, while that of pure TM almost stops immediately. This proof-of-concept work opens a new route to augment the photosynthetic efficiency of green plants by utilizing precise light-managed materials.

Super Light-Sensitive Photosensitizer Nanoparticles for Improved Photodynamic Therapy against Solid Tumors.

Photodynamic therapy (PDT) is an effective method for superficial cancer treatment. However, the limited light intensity in tissues, tumor hypoxia, and the low accumulation efficiency of photosensitizers (PSs) in tumors are still major challenges. Herein, we introduce super light-sensitive PS nanoparticles (designated HR NPs) that can increase singlet oxygen (1 O2 ) production and improve PS accumulation in tumors. HR NPs have the ability to produce a large amount of 1 O2 under ultralow power density light (0.05 mW cm-2 ) irradiation. More significantly, HR NPs have a long circulating time in tumor-bearing mice and can accumulate in tumors with high efficiency. When irradiated by light with a suitable wavelength, the nanoparticles exhibit excellent antitumor efficacy. This work will make it possible to cure solid tumors by PDT by enhancing the therapeutic effects.

A polyaniline surface-modified Prussian blue analogue cathode for flexible aqueous Zn-ion batteries.

Aqueous Zn-ion batteries have gained popularity due to their low cost and high safety, but their low energy density limits their application scenarios. Although the Prussian blue analogue (PBA) has the characteristics of high redox potential, the poor capacity and cycling performance restrict its further development. Here, we propose a modification strategy of a polyaniline (PANI) coating on zinc ferricyanide (ZnHCF). The PANI coating inhibits the dissolution of ZnHCF and enables the Zn-ion battery to present two long-flat discharge voltage platforms as well as a high capacity of 150 mA h g-1, which provides a new idea for the development of high-performance PBA battery materials. Meanwhile, owing to the spring-like structure, the battery has a high stretchability of 600% and maintains stable electrochemical properties during stretching.

Oriented Nanoarchitectonics of Bacteriorhodopsin for Enhancing ATP Generation in a Fo F1 -ATPase-Based Assembly System.

Energy conversion plays an important role in the metabolism of photosynthetic organisms. Improving energy transformation by promoting a proton gradient has been a great challenge for a long time. In the present study, we realize a directional proton migration through the construction of oriented bacteriorhodopsin (BR) microcapsules coated by Fo F1 -ATPase molecular motors through layer-by-layer (LBL) assembly. The changes in the conformation of BR under illumination lead to proton transfer in a radial direction, which generates a higher proton gradient to drive the synthesis of adenosine triphosphate (ATP) by Fo F1 -ATPase. Furthermore, to promote the photosynthetic activity, optically matched quantum dots were introduced into the artificial coassembly system of BR and Fo F1 -ATPase. Such a design creates a new path for the use of light energy.

Ultra-High-Capacity and Dendrite-Free Zinc-Sulfur Conversion Batteries Based on a Low-Cost Deep Eutectic Solvent.

Traditional cathodes for aqueous Zn-ion batteries are afflicted by a limited specific capacity and fearful Zn dendrites. Herein, these troubles are disposed of with a conversion-type Zn-S battery and low-cost deep eutectic solvent (DES). By utilizing the optimized electrolyte, the symmetrical Zn battery can stably cycle over 3920 h, which also confers on the Zn-S battery an ultrahigh specific capacity of ∼846 mA h gS-1 and energy density of 259 W h kg-1 at 0.5 A g-1. Importantly, the conversion chemistry of S and ZnS is responsible for the superior anti-self-discharge behavior (capacity retention: 94.58 and 68.58% after standing for 72 and 288 h versus Zn//VO2 battery: 76.82 and 47.80% after resting for 24 and 72 h versus Zn//MnO2 battery: 95.96 and 91.57% after resting for 24 and 72 h, respectively). This work is the first authentication of Zn-S batteries based on a newly developed low-cost DES-based electrolyte, which meanwhile settles the deep-rooted low specific capacity and infamous Zn dendrite issues in conventional (de)intercalation Zn-ion batteries.

Boric Acid-Fueled ATP Synthesis by Fo F1 ATP Synthase Reconstituted in a Supramolecular Architecture.

Significant strides toward producing biochemical fuels have been achieved by mimicking natural oxidative and photosynthetic phosphorylation. Here, different from these strategies, we explore boric acid as a fuel for tuneable synthesis of energy-storing molecules in a cell-like supramolecular architecture. Specifically, a proton locked in boric acid is released in a modulated fashion by the choice of polyols. As a consequence, controlled proton gradients across the lipid membrane are established to drive ATP synthase embedded in the biomimetic architecture, which facilitates tuneable ATP production. This strategy paves a unique route to achieve highly efficient bioenergy conversion, holding broad applications in synthesis and devices that require biochemical fuels.

Co-assembled Supramolecular Gel of Dipeptide and Pyridine Derivatives with Controlled Chirality.

It is commonly considered that amyloid-ß (Aß) fibrils are heavily involved in the neurological diseases. Establishing an external model based on the core recognition motif (diphenylalanine, FF) of Aß would be of significance in understanding the assembly and disassembly of Aß fibrils in living system. Herein, supramolecular gels with structure transition from amyloid-like ß-sheet to different supramolecular helices were obtained through the co-assembly of a N-fluorenylmethoxycarbonyl-protected L-FF (L-FmocFF) with achiral pyridine derivatives. It is found that the different stacking modes (H- or J-aggregates) of additives and the microenvironment of chiral carbon play vital roles for the selectively chiral transfer or amplification of L-FmocFF. The dynamic process of helix formation was also captured. This work provides a convenient co-assembly way to explore the structure basis of Aß fibrils with a controlled chirality.

A Dipeptide-Based Hierarchical Nanoarchitecture with Enhanced Catalytic Activity.

Achieving synthetic architectures with simple structures and robust biomimetic catalytic activities remains a great challenge. Herein, we explore a facile supramolecular assembly approach to construct a dipeptide-based hierarchical nanoarchitecture with enhanced enzyme-like catalytic activity. In this nanoarchitecture, nanospheres are put in a chain-like arrangement through coordination-driven directional self-assembly. The reversible transformation of anisotropic nanochains to isotropic nanospheres switches biomimetic activity. Notably, the assembled nanoarchitecture exhibits a high enzyme-like activity and remarkable long-term stability to promote hydroquinone oxidation, superior to the natural counterpart. This work will pave the way to develop reversible and reusable supramolecular biocatalysts with ordered hierarchical structures for accelerating chemical transformations.

Self-Assembled Dipeptide Aerogels with Tunable Wettability.

Constructing supramolecular materials with tunable properties and functions is a great challenge due to the complex competition between multiple assembly pathways. Herein, we report that dipeptides can self-assemble into aerogels with entirely different surface wettability through precisely controlling the assembly pathways. Charged groups or aromatic residues are selectively exposed on the surface of their nanoscale building blocks which results either in a superhydrophilic or highly hydrophobic surface. With this special property, single component dipeptide aerogels can play diverse roles in medical care applications. This study suggests great promise in the synthesis of supramolecular materials with different targeted functions from the same molecular unit.

Insight into the efficiency of oxygen introduced photodynamic therapy (PDT) and deep PDT against cancers with various assembled nanocarriers.

Photodynamic therapy (PDT) has been used in the treatment of cancers and other benign diseases for several years in clinic. However, the hypoxia of tumors and the penetration limitation of excitation light to tissues can dramatically reduce the efficacy of PDT to cancers. To overcome these drawbacks, various assembled nanocarriers such as nanoparticles, nanocapsules, nanocrystals, and so on were introduced. The assembled nanocarriers have the ability of loading photosensitizers, delivering O2 into tumors, generating O2 in situ in tumors, as well as turning near-infrared (NIR) light, X-rays, and chemical energy into ultraviolet or visible light. Therefore, it is easy for the nanocarriers to improve the hypoxia microenvironment or increase the treatment depth of cancers, which will improve the efficiency of PDT to some degree. In recent years, a number of investigations were focused on these subjects. We will summarize the advances of nanocarriers in PDT, especially in O2 introduction PDT and deep PDT. The perspectives, challenges, and potential in translation of PDT will also be discussed. This article is categorized under: Therapeutic Approaches and Drug Discovery > Emerging Technologies Biology-Inspired Nanomaterials > Lipid-Based Structures Therapeutic Approaches and Drug Discovery > Nanomedicine for Oncologic Disease.

Solvent-tunable dipeptide-based nanostructures with enhanced optical-to-electrical transduction.

We explore a facile approach to construct dipeptide-based building blocks containing π-conjugated bridges by using biocross-linkers. Well-defined nanostructures can be assembled and tuned by using different solvents. Compared to pristine units, such dipeptide-based assemblies exhibit structure-dependent and remarkably enhanced optoelectronic properties.

The Ultrafast Assembly of a Dipeptide Supramolecular Organogel and its Phase Transition from Gel to Crystal.

A gel-to-crystal phase transition of a dipeptide supramolecular assembly mediates active water transportation in oils. The addition of water into ultrafast-assembling dipeptide organogels can induce a lamellar-to-hexagonal structural transformation of dipeptide molecular arrangement. Consequently, a phase transition from gel to crystal occurs and in turn water is transported in the dipeptide crystal via well-defined channels. On a macroscopic scale, water transport in the bulk system exhibits an anisotropic characteristic, which can be tuned by the presence of ions in the Hofmeister series. These favorable features enable the automatic separation of dispersed nanoparticles from dissolved electrolytes in aqueous solution. These findings demonstrate the potential of this assembled system for active filtration without external pressure.

Assembled Vitamin B2 Nanocrystals with Optical Waveguiding and Photosensitizing Properties for Potential Biomedical Application.

Great success has been achieved in recent years in the development of synthetic or assembled nanobiomaterials. Among these, biomolecule-based nanoarchitectures with special optical property are of particular interest. Here, we demonstrate that vitamin B2 nanocrystals assembled as nanorods can be obtained with precise control. Excitingly, such one-dimensional nanostructures not only exhibit intrinsic optical waveguiding properties but also the ability to sensitize oxygen to produce reactive oxygen species. With these properties, we applied the obtained vitamin B2 nanorods under remotely localized light illumination into single tumour cells in vitro for anticancer photodynamic therapy. Further, vitamin B2 nanorods were explored for in vivo photodynamic therapy by using a tumour model. With such bionanostructures, new features and functions of vitamin B2 and its derivatives have been developed.

Nanozyme-Catalyzed Cascade Reactions for Mitochondria-Mimicking Oxidative Phosphorylation.

Multiple-enzyme-involving cascade reactions that yield bioenergy are necessary in natural oxidative phosphorylation. However, in vitro applications are hampered by the sensitivity of catalytic activity to environmental adaptation. Herein, we explore nanozyme-catalyzed cascade reactions in an assembled hybrid architecture for mitochondria-mimicking oxidative phosphorylation. Hollow silica microspheres containing trapped gold nanoparticles were synthesized to promote two enzyme-like catalytic reactions that transform glucose into gluconic acid in the presence of oxygen. The resulting transmembrane proton gradient drives natural ATP synthase reconstituted on the surface to convert ADP and inorganic phosphate into ATP. The assembled architecture possesses high activity for oxidative phosphorylation, comparable to that of natural mitochondria. This study provides a new natural-artificial hybrid prototype for exploring bioenergy supply systems and holds great promise for ATP-powered bioapplications.

Proton-consumed nanoarchitectures toward sustainable and efficient photophosphorylation.

At present, photophosphorylation in natural or artificial systems is accomplished by the production of protons or their pumping across the biomembranes. Herein, different from this strategy above, we demonstrate a designed system which can effectively enhance photophosphorylation by photo-induced proton-scavenging through molecular assembly. Upon the introduction of photobase generators, a (photo-) chemical reaction occurs to produce hydroxyl ions. Accompanying the further extramembranous acid-base neutralization reaction, an outbound flow of protons is generated to drive the reconstituted adenosine triphosphate (ATP) synthase to produce ATP. That is, contrary to biochemistry, the proton gradient to drive photophosphorylation derives from the scavenging of protons present in the external medium by hydroxyl ions, produced by the partially photo-induced splitting of photobase generator. Such assembled system holds great potential in ATP-consuming bioapplications.

Supramolecularly Assembled Nanocomposites as Biomimetic Chloroplasts for Enhancement of Photophosphorylation.

Prototypes of natural biosystems provide opportunities for artificial biomimetic systems to break the limits of natural reactions and achieve output control. However, mimicking unique natural structures and ingenious functions remains a challenge. Now, multiple biochemical reactions were integrated into artificially designed compartments via molecular assembly. First, multicompartmental silica nanoparticles with hierarchical structures that mimic the chloroplasts were obtained by a templated synthesis. Then, photoacid generators and ATPase-liposomes were assembled inside and outside of silica compartments, respectively. Upon light illumination, protons produced by a photoacid generator in the confined space can drive the liposome-embedded enzyme ATPase towards ATP synthesis, which mimics the photophosphorylation process in vitro. The method enables fabrication of bioinspired nanoreactors for photobiocatalysis and provides insight for understanding sophisticated biochemical reactions.