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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 that multistep desolva-tion is fundamental to the formation and evolution of peptide-rich droplets. The first step is partial desolvation of peptides to form peptide clusters, and the second step is selective desolvation of hydrophobic groups within clusters to trigger LLPS and the formation of peptide-rich droplets, followed by the complete desolvation of droplets, initiating the nucleation of peptide self-assembly. Manipulation of the degree of desolvation at different stages is an effective strategy to control the self-assembly pathways and polymorphisms. This study sheds light on the molecular origin of LLPS-mediated self-assembly dis-tinct from classical one-step self-assembly and paves the way for the precise control of supramolecular self-assembly.

Development of peptide-based supramolecular materials with hierarchical morphology and tunable guest loading displays broad potential as drug carrier in view of biocompatibility and biodegradability. Herein, we report a facile Schiff base nanoarchitectonic for supramolecular assembly of diphenylalanine (FF) metastable gel. The addition of trace glutaraldehyde (GA)/H

An overview of chromopeptide self-assembly is presented to systematically understand this kind of newly emerging peptide building block.

Ordered assemblies of the peptide diphenylalanine (FF) are produced and deposited on planar substrates. The FF aggregate growth is achieved through precipitation from aqueous ammonia solutions induced by solvent evaporation. The applied dip-coating technique confines the FF assembly growth to a narrow zone near the three-phase contact. The growth was observed online by optical microscopy and was investigated systematically as a function of the process parameters. Depending on the external gas flow (to influence solvent evaporation), the withdrawal speed, the initial FF, and the initial ammonia concentrations, FF forms long, straight, and rigid microfibers and/or shorter, curved nanofibers. Under certain process conditions, the FF fibers can also aggregate into stripes. These can be deposited as large arrays of uniform stripes with regular widths and spacings. Scenarios leading to the various types of fibers and the stripe formation are presented and discussed in view of the experimental findings.

Understanding the exact localization of nanoparticles within cell is of particular importance for rational design of high-effective nanomedicines. In the present study, direct stochastic optical reconstruction microscopy (dSTORM) is employed to elucidate the precise localization of nanoparticles within cells owing to its superiority of nanometric resolution, multicolour ability and minimal invasiveness. The localization of the Cy5 labelled mesoporous silica nanoparticles (MSNs-Cy5) in MCF-7 cells are monitored by dSTORM and conventional fluorescence microscopy, respectively. The dSTORM images demonstrate much higher spatial resolution for locating MSNs-Cy5 within cells compared to that of the conventional fluorescence images. Moreover, the distribution of MSNs-Cy5 within three cell lines over time are obtained. For the MCF-7 and HeLa cells, MSNs-Cy5 nanoparticles distribute nearly all around the cytoplasm after 5 h incubation. In contrast, MSNs-Cy5 nanoparticles within NIH 3T3 cells are quite different that they are found to be either attached to or embedded into cell membranes, without penetrating into the cytoplasm. Overall, we provide a practical method to reveal the in situ precise imaging of nanoparticles in cells with nanometric resolution precision. This method may open up new opportunities for organelle-specific targeting drug delivery to achieve maximum therapeutic benefit.

Peptide self-assemblies show intriguing and tunable physicochemical properties, and thus have been attracting increasing interest over the last two decades. However, the micro/nano-scale dimensions of the self-assemblies severely restrict their extensive applications. Inspired by nature, to genuinely realize the practical utilization of the bio-organic super-architectures, it is beneficial to further organize the peptide self-assemblies to integrate the properties of the individual supermolecules and fabricate higher-level organizations for smart functional devices. Therefore, cumulative studies have been reported on peptide microfabrication giving rise to diverse properties. This review summarizes the recent development of the microfabrication of peptide self-assemblies, discussing each methodology along with the diverse properties and practical applications of the engineered peptide large-scale, highly-ordered organizations. Finally, the current limitations of the state-of-the-art microfabrication strategies are critically assessed and alternative solutions are suggested.

Hypothesis In view of the photothermal effect of polydopamine (PDA) nanoparticles and their internal D-π-D structures during assembly, the two-photon excited properties of PDA were studied toward the biomedical application. Further, the PDA molecules were coordinated with Mn2+ and the assembled nanoparticles were covered by cancer cell membranes, the complex system could be used directly for the treatment of cancer with photothermal and chemodynamic therapy. Experiments The two-photon excited PDA-Mn2+ nanoparticles were used for the photothermal therapy combined with chemodynamic therapy. The complexes were coated with cancer cell membranes in order to enhance the tumor homologous efficiency. Multi-modal bioimaging and anti-tumor detections were carried out both in vitro and in vivo. Findings PDA nanoparticles were demonstrated to have both good two-photon excited fluorescence and photothermal efficiency. The assembled nanoparticles modified with Mn2+ and cancer cell membranes have an obvious targeting and synergetic anti-cancer efficiency. The system creates a simple way for a precise operation with multi-modal imaging function.

The manipulation of supramolecular assembly enables single-component architectures to possess diverse structures and functions. Here, we report directed phase transitions of dipeptide supramolecula...

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 (

Control of symmetry breaking of materials provides large opportunities to regulate their properties and functions. Herein, we report breaking the symmetry of layered dipeptide crystals by utilizing CO

As a good alternative for natural enzyme, enzyme mimics with artificial functional materials have attracted considerable attention. However, it remains a great challenge to develop a facile method to design laccase mimic with high catalytic activity, long-term stability and reusability. In this report, we propose the one-pot synthesis of reusable paper filter templated Cu-doped polydopamine membranes (PF@PDA/Cu) with laccase-like activity. Compared with the natural laccase, the PF@PDA/Cu membrane exhibits enhanced catalytic activity for the chemical conversion of hydroquinone into benzoquinone. Interestingly, these membranes present good tolerance to high temperature and the catalytic activity increases with the increase of temperature. Moreover, these membranes could be stored for 7 days and recycled for 5 times with negligible loss of catalytic activity. This work provides a promising paradigm for rational design and practical applications of metal-loading PDA materials based on one-pot synthesis methodology.

Dynamic covalent chemistry (DCC) is fascinating because of its dual nature. It perfectly combines the reversible nature of noncovalent bonds with the robustness of covalent bonds, effectively enhancing the stability of assemblies and meanwhile giving rise to unprecedented properties. Therefore, integration of DCC with supramolecular chemistry has emerged as a versatile and an extraordinarily useful approach in directing peptide assembly. This Minireview focuses on a recent strategy, which exploits dynamic Schiff base chemistry in combination with supramolecular chemistry, to mediate dipeptide assembly toward nanoarchitectonics. Diversified structures, new emergent properties, and their related applications are highlighted. Lastly, the opportunities and prospects in this exciting field are also introduced.

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.

Polydopamine nanoparticles were used to stabilize a nano-Pt catalyst to relieve tumour hypoxia in photodynamic therapy (PDT). Polydopamine not only provides a platform for carrying nano-Pt and photosensitizers but is also used as a photothermal reagent for photothermal therapy (PTT). The system presented an enhanced anti-tumor therapy effect through a combined PDT and PTT mechanism.

Covalently triggered peptide self-assembly is achieved through sequential integration of spontaneous covalent reaction and noncovalent interactions, thus both enhancing the physiological stability and extending unexpected functionality of the resulting peptide-based assemblies, different from popular supramolecular peptide self-assembly merely associated with noncovalent interactions. This review summarizes the recent progress on the development of covalently triggered peptide self-assembly for cancer theranostics. Especially, we propose the fundamental design principle of covalently triggered peptide self-assembly for constructing a variety of peptide-based assemblies including nanoparticles, nanofibers, hollow nanospheres, and other nanoarchitectures. Subsequently, the discussion is anchored in an overview of representative covalently assembled peptide-based nanodrugs for the cancer theranostics. Finally, the challenges and perspectives on the clinical potential of the covalently assembled peptide-based nanodrugs are highlighted. This review will provide new insights into construction of peptide-based nanodrugs through combination of covalent reaction and noncovalent self-assembly and prompt their clinical applications in cancer diagnosis and therapeutics.

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 FoF1-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 FoF1-ATPase. Furthermore, to promote the photosynthetic activity, optically matched quantum dots were introduced into the artificial coassembly system of BR and FoF1-ATPase. Such a design creates a new path for the use of light energy.

peer-reviewed Molecular stacking modes, generally classified as H-, J-, and X-aggregation, play a key role in determining the optoelectronic properties of organic crystals. However, the control of stacking transformation of a specific molecule is an unmet challenge, and a priori prediction of the performance in different stacking modes is extraordinarily difficult to achieve. In particular, the existence of hybrid stacking modes and their combined effect on physicochemical properties of molecular crystals are not fully understood. Herein, unexpected stacking transformation from H- to J- and X-aggregation is observed in the crystal structure of a small heterocyclic molecule, 4,4'-bipyridine (4,4'-Bpy), upon coassembly with N-acetyl-l-alanine (AcA), a nonaromatic amino acid derivative. This structural transformation into hybrid stacking mode improves physicochemical properties of the cocrystals, including a large red-shifted emission, enhanced supramolecular chirality, improved thermal stability, and higher mechanical properties. While a single crystal of 4,4'-Bpy shows good optical waveguiding and piezoelectric properties due to the uniform elongated needles and low symmetry of crystal packing, the significantly lower band gap and resistance of the cocrystal indicate improved conductivity. This study not only demonstrates cocrystallization-induced packing transformation between H-, J-, and X-aggregations in the solid state, leading to tunable mechanical and optoelectronic properties, but also will inspire future molecular design of organic functional materials by the coassembly strategy. ACCEPTED peer-reviewed

Incorporation of non-equilibrium actions in the sequence of self-assembly processes would be an effective means to establish bio-like high functionality hierarchical assemblies. As a novel methodology beyond self-assembly, nanoarchitectonics, which has as its aim the fabrication of functional materials systems from nanoscopic units through the methodological fusion of nanotechnology with other scientific disciplines including organic synthesis, supramolecular chemistry, microfabrication, and bio-process, has been applied to this strategy. The application of non-equilibrium factors to conventional self-assembly processes is discussed on the basis of examples of directed assembly, Langmuir-Blodgett assembly, and layer-by-layer assembly. In particular, examples of the fabrication of hierarchical functional structures using bio-active components such as proteins or by the combination of bio-components and two-dimensional nanomaterials, are described. Methodologies described in this review article highlight possible approaches using the nanoarchitectonics concept beyond self-assembly for creation of bio-like higher functionalities and hierarchical structural organization.

Inspired by the self-assembly phenomena in nature, the instructed self-assembly of exogenous small molecules in a biological environment has become a prevalent process to control cell fate. Despite mounting examples of versatile bioactivities, the underlying mechanism remains less understood, which is in large hindered by the difficulties in the identification of those dynamic assemblies in situ. Here, with direct stochastic optical reconstruction microscopy, we are able to elucidate the dynamic morphology transformation of the enzyme-instructed supramolecular assemblies in situ inside cancer cells with a resolution below 50 nm. It indicates that the assembling molecules endure drastically different pathways between cell lines with different phosphatase activities and distribution. In HeLa cells, the direct formation of intracellular supramolecular nanofibers showed slight cytotoxicity, which was due to the possible cellular secretory pathway to excrete those exogenous molecules assemblies. In contrast, in Saos-2 cells with active phosphatase on the cell surface, assemblies with granular morphology first formed on the cell membranes, followed by a transformation into nanofibers and accumulation in cells, which induced Saos-2 cell death eventually. Overall, we provided a convenient method to reveal the in situ dynamic nanomorphology transformation of the supramolecular assemblies in a biological environment, in order to decipher their diverse biological activities.

Molecular assemblies of cationic dipeptide-gold nanoparticle (CDP-AuNP) hybrid microspheres were used to modify cholesterol oxidase electrodes for high-sensitivity cholesterol detection. The cationic dipeptide used here serves as a functional molecule for adsorbing chloroauric acid based on electrostatic interactions and assembly into spherical structures, providing a platform for loading gold nanoparticles (AuNPs), increasing the immobilization load of the enzyme and maintaining the activity of the enzyme as a result of excellent biocompatibility. Moreover, the CDP-AuNP modified cholesterol oxidase electrode has a higher electrocatalytic activity to cholesterol with obvious enhancement in the current response, exhibiting a current response 13 times higher than that of the controlled electrode. The outstanding biocompatibility and increased enzyme load by hybrid microspheres and the good charge-transfer ability of AuNPs in the peptide-based electrode indicate a very attractive perspective in the field of biodevices.

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 F

Dopamine-based materials have attracted considerable interests due to their unique physicochemical properties including versatile adhesion property, high chemical reactivity, strong photothermal conversion capacity, excellent biocompatibility and biodegradability, etc. Since the discovery of oxidative self-polymerization of dopamine for preparation of polydopamine, different strategies have been employed to construct fruitful polydopamine-based materials, such as nanoparticles, core/shell nanoparticles, microcapsules, films, and hydrogels. Moreover, one-pot polydopamine-assisted co-deposition could facilitate the incorporation of functional molecules into the materials during the formation process of polydopamine, thus greatly simplifying the functionalization procedure of polydopamine. This chapter is devoted to introduce recent development in dopamine-based materials and their applications. First, an overview of the different methodologies for fabrication of dopamine-based materials is summarized. We outline various polydopamine-based materials constructed with different preparation strategies and novel materials prepared via the co-assembly strategy. Thereafter, we focus on the recent advances of emerging applications of dopamine-based materials in various fields ranging from cancer theranostics, bioimaging, self-adhesive bioelectronics to removal of heavy metal ions. Finally, we discuss the critical unsolved challenges in this field and some potential opportunities for future research.

Dopamine-based materials have attracted widespread interest due to the outstanding physicochemical and biological properties. Since the first report on polydopamine (PDA) films, great efforts have been devoted to develop new fabrication strategies for obtaining novel nanostructures and desirable properties. Among them, one-pot co-assembly strategy offers a unique pathway for integrating multiple properties and functions into dopamine-based platform in a single simultaneous co-deposition step. This review focuses on the state of the art development of one-pot multicomponent self-assembly of dopamine-based materials and summarizes various single-step co-deposition approaches, including PDA-assisted adaptive encapsulation, co-assembly of dopamine with other molecules through non-covalent interactions or covalent interactions. Moreover, emerging applications of dopamine-based materials in the fields ranging from sensing, cancer therapy, catalysis, oil/water separation to antifouling are outlined. In addition, some critical remaining challenges and opportunities are discussed to pave the way towards the rational design and applications of dopamine-based materials.

Hierarchical self-assembly and crystallization with long-range ordered spatial arrangement is ubiquitous in nature and plays an essential role in the regulation of structures and biological functions. Inspired by the multiscale hierarchical structures in biology, tremendous efforts have been devoted to the understanding of hierarchical self-assembly and crystallization of biomolecules such as peptides and amino acids. Understanding the fundamental mechanisms underlying the construction and organization of multiscale architectures is crucial for the design and fabrication of complex functional systems with long-range alignment of molecules. This Review summarizes the typical examples for hierarchically oriented organization of peptide self-assembly and discusses the thermodynamic and kinetic mechanisms that are responsible for this specific hierarchical organization. Most importantly, we propose the concept of hierarchically oriented organization for self-assembling peptide crystals, distinct from the traditional growth mechanism of supramolecular polymerization and crystallization based on the Ostwald ripening rule. Finally, we assess critical challenges and highlight future directions towards the mechanistic understanding and versatile application of the hierarchically oriented organization mechanism. Hierarchical self-assembly and crystallization is ubiquitous in nature and is of key importance for creation of complex superstructures. Herein, Yuan and co-workers propose that hierarchically oriented organization guides the formation of such complex systems, especially in supramolecular peptide crystals.

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.

Nature makes use of molecular machines to perform intricate functions in every significant biological process and to power macroscopic motion in organisms. Biomolecular motor proteins perform crucial tasks such as cell division, intracellular transport and mechanical actuation in biological cells. The rotary motor FoF1-ATPase is one of the most extensively studied biomolecular machines as a result of its vital physiological function. Research on the function of FoF1-ATPase can help to better understand the underlying biological processes and may also result in the development of biological molecular motor-based devices or even inspire the creative design and construction of artificial molecular machines. Recent advances in nanoscience and biotechnology have enabled engineering experiments with FoF1-ATPase that have achieved notable success. In this Review, we first outline the reconstitution of FoF1-ATPase into simple liposomes and polymersomes and then focus on recent progress in the reconstitution of FoF1-ATPase on layer-by-layer-assembled systems. The elaborate structural designs utilized in layer-by-layer-assembled systems to better mimic natural cell structures are introduced. The rational integration of functional components to achieve stimuli-responsive ATP syntheses from FoF1-ATPase-based biomimetic systems is highlighted. Finally, we address some remaining key challenges and speculate on future directions for the field. FoF1-ATPase is a vital molecular machine in organisms responsible for the catalytic synthesis of the basic energy unit ATP. In this Review, the development of FoF1-ATPase reconstitution into artificial architectures is discussed ultimately leading to the development of stimuli-responsive ATP synthesis.

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.

We report a thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brush functionalized Janus Au-Pt bimetallic micromotor capable of modulating the direction of motion with the change of the ambient temperature. The PNIPAM@Au-Pt micromotor moved along the Au-Pt direction with a speed of 8.5 μm s-1 in 1.5 % H2 O2 at 25 °C (below the lower critical solution temperature (LCST) of PNIPAM), whereas it changed the direction of motion (i.e., along the Pt-Au direction) and the speed decreased to 2.3 μm s-1 at 35 °C (above LCST). Below LCST, PNIPAM brushes grafted on the Au side were hydrophilic and swelled, which permitted the electron transfer and proton diffusion on the Au side, and thus the motion is regarded as a self-electrophoretic mechanism. However, PNIPAM brushes above LCST became hydrophobic and collapsed, and thus the driving mechanism switched to the self-diffusiophoresis like that of Pt-modified Janus silica motors. These motors could reversibly change the direction of motion with the transition of the hydrophobic and hydrophilic states of the grafted PNIPAM brushes. Such a thermoresponsive polymer brush functionalization method provides a new strategy for engineering the kinematic behavior of phoretically driven micro/nanomotors.

We report a novel nanophotosensitizer via one-step covalent assembly of dopamine and genipin. This is the first report unveiling the photodynamic effect of dopamine-based materials. These nanophotosensitizers can also act as pH-responsive drug nanocarriers via a catechol-boronate linkage, thus achieving combined PDT and chemotherapy for highly efficient cancer treatment.

Photosystem II (PSII) is a fascinating photosynthesis-involved enzyme, participating in sunlight-harvest, water splitting, oxygen release, and proton/electron generation and transfer. Scientists have been inspired to couple PSII with synthetic hierarchical structures via biomimetic assembly, facilitating attainment of natural photosynthesis processes, such as photocatalytic water splitting, electron transfer and ATP synthesis, in vivo. In the past decade, there has been significant progress in PSII-based biomimetic systems, such as artificial chloroplasts and photoelectrochemical cells. The biomimetic assembly approach helps PSII gather functions and properties from synthetic materials, resulting in a complex with partly natural and partly synthetic components. PSII-based biomimetic assembly offers opportunities to forward semi-biohybrid research and synchronously inspire optimization of artificial light-harvest micro/nanodevices. This review summarizes recent studies on how PSII combines with artificial structures via molecular assembly and highlights PSII-based semi-natural biosystems which arise from synthetic parts and natural components. Moreover, we discuss the challenges and remaining problems for PSII-based systems and the outlook for their development and applications. We believe this topic provides inspiration for rational designs to develop biomimetic PSII-based semi-natural devices and further reveal the secrets of energy conversion within natural photosynthesis from the molecular level., This review collects the recent contributions on PSII coupling with artificial structures via molecular assembly, and highlights how PSII-based semi-natural systems realize enhanced photosynthesis.

Hypothesis Crystalline self-assemblies of diphenylalanine (FF) are since long back considered to be related to Alzheimer's disease. An improved understanding of the mechanism behind the formation of such structures can lead to strategies for investigating the dynamic processes of assembly and disassembly of FF. Experiment The assembly, disassembly and reassembly of FF crystals are influenced by the solvent composition and can be triggered by evaporation of solvent. In this work these processes are directly monitored, and the structures obtained are analyzed. Findings The role of the solvent for assembly, disassembly and reassembly of diphenylalanine crystals has been demonstrated. The initial crystal structure formed via self-assembly of FF monomers can be transformed into needle-like crystals and further to hollow hexagonal microtubes through evaporation of the solvent. It is shown that all the assembly-disassembly processes are spontaneous and driven by thermodynamics. It is also found that some of the crystalline structures exhibit optical waveguiding properties.

A novel peptide nanodrug composed of three functional motifs, bis(pyrene), FFVLK and CREKA, was used as a two-photon excited photosensitizer for precise photodynamic therapy (PDT). The system presented excellent two-photon imaging ability, tumor target effect and high reactive oxygen species productivity for improving treatment precision and efficiency in PDT.

As low‐molecular‐weight hydrogelators, dipeptide hydrogel materials are suited for embedding multiple organic molecules and inorganic nanoparticles. Herein, a simple but precisely controllable method is presented that enables the fabrication of dipeptide‐based hydrogels by supramolecular assembly inside microfluidic channels. Water‐soluble quantum dots (QDs) as well as premixed porphyrins and a dipeptide in dimethyl sulfoxide (DMSO) were injected into a Y‐shaped microfluidic junction. At the DMSO/water interface, the confined fabrication of a dipeptide‐based hydrogel was initiated. Thereafter, the as‐formed hydrogel flowed along a meandering microchannel in a continuous fashion, gradually completing gelation and QD entrapment. In contrast to hydrogelation in conventional test tubes, microfluidically controlled hydrogelation led to a tailored dipeptide hydrogel regarding material morphology and nanoparticle distribution., A dipeptide hydrogel was obtained by dynamic assembly in the confined space of continuous‐flow microfluidics. Organic porphyrins and inorganic quantum dots (QDs) were integrated in the system for energy transfer, and dynamic structural control over hydrogel formation and QD integration occurred within the microchannel network (see picture).

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.

The dynamic Schiff base bond is exploited to construct monodisperse dopamine-based nanoparticles with autofluorescence and pH-sensitivity. This allows facile monitoring and pH-responsive drug release in the acidic tumor microenvironment. Anticancer drugs doxorubicin and a photosensitizer chlorin e6 are further loaded into the nanoparticles and synergistic anticancer efficacy is achieved.