中文   |   English   |   Email Alert
Fig/Tab
Advanced Search
image

Controllable Assembly of Diphenylalanine Dipeptide Micro/Nano Structure Assemblies and Their Applications

Keqing Wang , Huimin Xue , Chenchen Qin , Wei Cui

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (9) : 1882 -1895.

PDF
Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (9) : 1882-1895 DOI: 10.7536/PC211206
research-article
Scan to read & Share
Controllable Assembly of Diphenylalanine Dipeptide Micro/Nano Structure Assemblies and Their Applications
Author information +
History +
PDF

Abstract

In recent years, the construction of micro/nano structure assemblies by biological assembly units has been extensively studied in the fields of bio⁃nanotechnology and other fields. Micro/nano structure assemblies with different morphologies can be obtained by a quick and simple method such as the self⁃assembly of biomolecules. Diphenylalanine dipeptide and its derivatives, as a biologically active peptide in many peptide⁃based building blocks, have good biocompatibility and characteristic for chemical modification, biological function and simple preparation. Micro/nano⁃materials with different structures based on diphenylalanine and its derivatives can be obtained by controllable assembled methods. They also have wide applications in optics, mechanical engineering, electrochemical sensing and detection areas, etc. Controlled assembly of short peptides and its derivatives can be achieved by changing the assembly conditions or introducing of exogenous small molecules. This review summaries and outlooks the controllable assembly of diphenylalanine dipeptide micro/nano structure assemblies and their applications in biomedicine, biosensor, optoelectronic materials, optical waveguides and catalysis.

Graphical abstract

Keywords

molecule assembly / diphenylalanine dipeptide / biomedicine / biosensor / optoelectronic materials

Cite this article

Download citation ▾
Keqing Wang, Huimin Xue, Chenchen Qin, Wei Cui. Controllable Assembly of Diphenylalanine Dipeptide Micro/Nano Structure Assemblies and Their Applications. Progress in Chemistry, 2022, 34(9): 1882-1895 DOI:10.7536/PC211206

登录浏览全文

4963

注册一个新账户 忘记密码

Contents

1 Introduction
2 Controllable assembly of dipeptide⁃based assemblies
2.1 Physical factors
2.2 Chemical factors
2.3 Biological factors
3 Application of dipeptide⁃based assemblies
3.1 Biomedicine
3.2 Biosensors
3.3 Optoelectronic materials
3.4 Optical waveguide
3.5 Catalysis
4 Conclusion and outlook

1 Introduction

Many important metabolic processes in biological systems are constructed by bottom-up self-assembly processes through multiple cooperative intermolecular forces, and a series of precise and dexterous biomolecular assemblies promote various biological functions such as energy conversion, material transport and information storage. From the crystal arrangement at the molecular level to the distribution of galaxies in the universe, self-assembly processes are ubiquitous in nature, such as the double helix structure of DNA, the self-assembly of phospholipids to form cell membranes, and the aggregation and folding of proteins, which are considered to be the result of the self-assembly of disordered biomolecules. Inspired by natural organisms, researchers have begun to try to build devices with atomic, molecular or nanoscale functional assemblies as primitives through a "bottom-up" approach[1,2]. Precise regulation of the dynamic process of biomolecular assembly can help to understand and understand the molecular mechanism of various biological activities. Common biological motifs play an important role at this time, and the assembly structural units can spontaneously form a stable, non-covalent aggregation system with specific structure and function by means of weak intermolecular interaction.It can not only design morphological bionic structures, but also design molecular bionic and functional bionic assemblies to meet the application needs of people in various fields. The methodological significance of self-assembly is vividly displayed in the construction of specific functional devices. These biocompatible assemblies also have excellent mechanical, optical, piezoelectric and semiconductor properties, which expand their application research in energy storage, biosensing, material science, biomedicine, artificial photosynthesis and so on[3,4].
Diphenylalanine dipeptide (FF), as an important biomolecule, is the key recognition sequence of β-amyloid protein (causing Alzheimer's disease), which plays a very important role in life activities and is used to construct micro-and nano-materials with diverse structures and functions[5,6]. The derivatives of FF mainly include aromatic group modified Fmoc FF, Nap FF, Cbz FF, CDP, Fc FF, and alkyl group modified Ac FF and Boc FF. The modification of these functional groups not only enriches the self-assembly structure of FF, but also further expands the function and application of the assembly[7⇓~9]. In order to obtain functional biological nanomaterials, it is necessary to precisely control the self-assembly conditions and processes of biomolecules, which is also one of the challenges in the field of self-assembly. Previous studies have shown that biological nanomaterials with diverse structures and functions, such as nanotubes, nanorods, nanospheres, flower-like, dendritic, vesicular structures, can be obtained by regulating intermolecular interactions (such as hydrogen bonding, electrostatic interaction, hydrophilic-hydrophobic interaction, DNA/RNA hybridization) or changing external conditions (such as pH, temperature, ionic strength, or adding organic matter and enzymes to the system)[10,11][12⇓⇓~15][16⇓⇓⇓⇓~21]. In addition, some functional nano-assembly elements such as metal nanoparticles and carbon nanotubes can also be introduced into the self-assembly system to further enrich the functions and applications of self-assembled biological nanomaterials. In this process, the interaction between biomolecules and other non-biological materials can guide the self-assembly of biomolecules and corresponding motifs into hybrid nanomaterials, and the mechanism of assembly into various nanostructures has been widely studied[22⇓⇓~25][26,27]. Among them, the interaction between molecules, the regulation of external stimuli and the design of functions are of great significance for the self-assembly of biomolecules to form functional nanomaterials and multifunctional applications[28⇓~30]. For a long time, Li Junbai's research group has used aromatic linear dipeptide diphenylalanine and its derivatives as building blocks to dynamically regulate the self-assembly process of peptide molecules and co-assembly with other guest molecules under different experimental conditions, and has also obtained a series of micro-nano assembly structures and carried out related application exploration[31⇓~33].

2 Controllable assembly of diphenylalanine dipeptide-based micro-nano materials

The mechanism of biomolecular self-assembly to form various micro-nano structures is quite complex. The internal factors affecting its assembly refer to intermolecular interactions and biomolecule-specific interactions. Intermolecular interactions mainly include hydrogen bonding, electrostatic interaction, hydrophilic-hydrophobic interaction and π-π-π interaction. Biomolecule-specific interactions include DNA base pairing, ligand-receptor binding, antigen-antibody binding, and biomolecule-polymer binding. Researchers regulate these effects by changing the assembly conditions, so as to achieve precise regulation of the structure and function of the assembly. In general, changing the assembly conditions generally includes adjusting the internal assembly environment and applying external stimuli, such as temperature, pH, solvent, ionic strength, enzyme, light, and ultrasound. Of course, one of the important ways to expand the structure and function of the assembly is to select the co-assembly components and adjust the mixing ratio of the assembly components.

2.1 Physical factors (temperature, light, ultrasound)

2.1.1 Temperature

Temperature is an important factor affecting the conformation and intermolecular interactions of biomolecules in solution, and this parameter is easy to control accurately under various conditions. Temperature is one of the most effective and universal factors regulating the self-assembly process of peptidyl molecules. Gazit team found that FF molecules themselves can be cyclized to form cyclic peptide structures at high temperatures, and the assembly of linear dipeptide molecules is transformed into the assembly of cyclic peptide molecules after cooling and deposition[34]. In addition, because most peptide-based assembly materials are temperature-responsive, the structure of the assembly can be transformed by changing the temperature. Liu et al. Realized the phase transformation of FF gel crystal by freezing treatment, and the metastable gel phase was gradually transformed into the thermodynamically stable crystal phase by multiple cycles between 77 K and room temperature[35]. It was found that the freezing treatment disrupted and re-established the balance of intermolecular interaction forces, and finally the dipeptide hexagonal crystal was obtained. The fluorescence emission of the dipeptide crystal is significantly enhanced due to the limitation of vibrational relaxation of the heavy molecular interaction of the self-assembly. At the same time, the experiment proves that this method can be used for other diphenylalanine-based organogels to achieve gel crystal transformation, indicating that freezing treatment is a universal method for regulating biomolecular assembly. These findings are helpful to further study the relationship between gelation and crystallization of self-assembled systems, so as to achieve the purpose of regulating the assembly and function of single-component materials.
He Zhimin's research team of Tianjin University has deeply studied the chiral assembly system of Fc and FF (Figure 1). By adjusting the temperature and other conditions, the diameter, pitch and chirality of the spiral assembly can be precisely controlled to obtain uniform chiral nanomaterials[36]. There are two kinds of structures in the assembly process: Twisted β sheets and Helical β sheets. The precise control of chiral assembly behavior can obtain ideal chiral materials and explore their applications.

2.1.2 Light

In addition, biological nanostructures can also be obtained by photoinduced self-assembly of biomolecules. In the process of photoinduced self-assembly, the groups responsive to light stimulation can be used as photoswitches to regulate the structure and function of nanomaterials[37]. Photoregulated peptidyl self-assembly is mainly achieved by introducing photoresponsive groups into the system as photoswitching molecules. There are two kinds of common photoswitching molecules: photoinduced cis-trans isomerization (such as azobenzene, semithioindigo, diphenylethylene) and photoinduced open-ring-closure (such as spiropyran)[38]. These photoswitch molecules can either participate in the assembly process as assembly motifs or act as external factors to induce assembly. The assembly system with photoswitch molecules is not only easier to regulate, but also easier to functionalize because of the reversibility of the assembled structure[39].
Ma et al. Used a photoisomerized azobenzene molecule (EPABS) to regulate the self-assembly process of CDP, and successfully realized the reversible transformation of the assembly structure under the alternating irradiation of visible light (dendritic structure) and ultraviolet light (vesicular structure)[37]. Under visible light irradiation, trans-EPABS and CDP form strong electrostatic interaction and π-π-interaction, and their aromatic rings stack to a certain extent, thus co-assembling to form a dendritic structure. When irradiated by UV light, the trans-EPABS was transformed into the cis-EPABS structure, and the strong hydrophilicity and high steric hindrance made the force between the cis-EPABS and CDP molecules gradually weakened or even disappeared with the UV light irradiation, which eventually led to the detachment of the cis-EABS from the assembly system and the disintegration of the co-assembly structure. At this time, CDP self-assembles to form vesicular structures.
In addition, Li et al. Also realized the reversible transformation of FF toluene gel and sol by introducing Merocyanine (MEH) into the FF self-assembly process, as shown in Figure 2[40]. After visible light irradiation, MEH will release protons into the environment, photoinduced ring closure reaction and transformation into Spiropyran (SP). When the primary amine group in the FF molecule accepts the proton, the electrostatic interaction between molecules increases, which destroys the original π-π-stacking interaction of the assembly, resulting in the gel-to-sol transition. In the dark, SP is converted to MEH, and the sol-gel transition occurs. During the whole assembly process, MEH molecules only act as an external factor to induce the assembly behavior, and do not affect the assembly of FF molecules. Biomolecular assembly induced by light stimulation has the advantages of reversibility, rapidity, non-invasiveness, remoteness and cleanness, which makes it play an important role in the research fields of light-responsive biomaterials, self-healing smart materials and injectable bio-gels.

2.1.3 Ultrasound

It has been proved that ultrasound is also one of the most effective methods to promote crystal formation[41,42]. In the process of crystal formation, the presence of ultrasound makes it easier for molecules to aggregate to form non-tubular crystals[43]. This is because the ultrasonic treatment can reduce the concentration gradient on the growth crystal plane necessary for the formation of tubular crystals[44]. Skorb et al. Used an ultrasound-assisted method to obtain dipeptide nanotube and dipeptide nanowire structures by controlling the concentration and pH, respectively[43]. In view of this, Li et al. Tried to control the morphology of FF assemblies by changing the ultrasonic time[45]. A mixture of nanofibers and microtubules was obtained when the sonication time was 1 min. When the sonication time increased to 5 min, the FF molecules were mainly assembled into microtubules with a small amount of nanofibers and microrods. When the ultrasonic time is increased to 20 min, the FF microrod structure is mainly obtained. That is to say, the increase of ultrasonic time is beneficial to the formation of FF microrods. Subsequently, hollow dipeptide microspheres with unilocular and multilocular structures were prepared by ultrasound-assisted emulsion droplet templating. The different solubilities of toluene and hexane with hexafluoroisopropanol, the ultrasound-induced emulsion droplet template, and the partial cross-linking of FF molecules by GA are the key factors for the formation of these two different types of hollow spheres. This novel surfactant-free emulsion droplet templating method assisted by ultrasound also facilitates the development of new strategies to fabricate peptide-based micro-nano materials with novel structures and functions[46].

2.2 Chemical factors (exogenous small molecules, ionic strength, solvent effect, pH)

2.2.1 Exogenous small molecule

In the process of peptide self-assembly research, researchers have found that there are still some difficulties in realizing the application of single-component peptide self-assembly in biological and related engineering fields. Considering that peptide molecules themselves are easy to modify, researchers have gradually begun to introduce functional small molecules into peptide self-assembly systems to achieve the integration and optimization of their special properties through the synergistic effect between different components.
Na et al. Co-assembled anthracene compounds with aggregation-induced luminescence with FF to obtain FF microtubules with fluorescence characteristics, and the morphology, fluorescence intensity and emission wavelength of microtubules could be regulated by changing the content of the two components[47]. Yan Xuehai's research group found that FF porphyrin was co-assembled into micellar microspheres, and the micellar microspheres contained abundant water[48]. The assembly process showed that the dipeptide was first aggregated around the porphyrin molecule in the form of J, and then the dipeptide-porphyrin ion complex was self-assembled to form nanorods, which were finally aggregated to form porous microspheres. The microsphere has a wide spectral absorption range and high photostability, and the porous and multi-cavity microsphere will be of great value in photocatalytic reactions. Ma et al. Regulated CDP assembly by using three sulfoazobenzene molecules with similar structures but slight differences in terminal groups to obtain three assemblies with urchin-like, flower-like and plate-like structures[49]. Electrostatic force and π-π-interaction are the main driving forces for the formation of the co-assembly structure. It was found that the introduction of sulfonic azobenzene molecules destroyed the original interaction between CDP molecules. Because of the slight difference in the terminal structure of the three azobenzene molecules,When they are inserted into the interlayers of CDP molecules, they overlap with the aromatic rings of CDP to different degrees, resulting in different molecular stacking modes and finally forming assemblies with different morphologies. Cationic dipeptides can also co-assemble with phosphotungstic acid to form micelles in aqueous solution through electrostatic interaction, which not only has good stimulus response to pH and temperature, but also has good encapsulation properties[50]. Octaethylplatinum and 9,10diphenylanthracene were co-assembled with FF as photosensitizer and quencher, respectively, to obtain organogels with green to blue triplet and triplet annihilation upconversion luminescence properties. The results show that the relative yield of upconversion luminescence in air is as high as 12%. At the same time, due to the introduction of photosensitizer and quencher, the π-π-interaction of the system is enhanced, and the mechanical properties of the co-assembled organogel are also significantly enhanced[51].
FF, protein and glutaraldehyde react to form Schiff base bonds, which can also be further assembled to obtain stable hydrogels. The reaction conditions are mild, and the secondary structure of the protein does not change during assembly. The dipeptide protein hydrogel is stable in neutral PBS solution. However, when the pH changes to acidic or alkaline, the gel will undergo disassembly, and at the same time, the encapsulated guest molecules in the gel will be released. It is worth noting that when hemoglobin (Hb) and glucose oxidase (GOD) as guest molecules are encapsulated in the hydrogel at the same time, FF Hb GOD hydrogel can be formed, and the enzyme reaction can occur when glucose solution is added, which makes the hydrogel bioresponsive[52]. Based on the above characteristics, the dipeptidyl stilbene protein hydrogel prepared by using the Schiff base bond has great potential for biosensors, biocatalysis and biomedicine. In view of the fact that both ends of CDP molecule contain amino groups, the assembly of CDP can also be regulated by the mild Schiff base reaction between small aldehydes and amino groups. Using CDP as the assembly motif, the monodisperse enzyme-responsive nanoparticles were also assembled by the covalent assembly method induced by small aldehyde molecules[53]. In addition to small biomolecules, the co-assembly systems of some biomacromolecules (such as chitosan, hyaluronic acid, natural polyamine, etc.) And peptide molecules can also give full play to the functionality of biomolecules and the diversity of peptide molecular assembly structures, so as to construct more applicable co-assembly materials.

2.2.2 Ionic strength

Metal ions and proteins play an important role in the regulation of the structure and function of biological tissues through the supramolecular interaction of metal ligands[4]. Studies have shown that metal ions (Cu2+,Zn2+ and Fe3+) are involved in the assembly of proteins in a variety of neurodegenerative diseases, a typical example of which is Alzheimer's disease and protein amyloidosis[54]. This is because metal ion complexation can regulate non-covalent interactions such as metal coordination bonds, hydrogen bonds, and π-π-stacking, thereby inhibiting or accelerating the formation of amyloid.
Ihee's group studied the conditions that affect the formation of FF nanowires and nanotubes[55]. It has been shown that the ionic strength in aqueous solution has a great influence on the assembly of FF. FF can form nanowires in aqueous solution at high ionic strength and nanotubes at low ionic strength. By adjusting the preparation conditions, FF nanowires can be decomposed and transformed into FF nanotubes. Gazit, an Israeli scientist, used the short peptide Fmoc and FF as a model to explore the role of metal ions in the formation of amyloid[15]. According to the different coordination characteristics of metal ions, they selected different valence metal ions (Na+,K+,Zn2+,Cu2+,Fe3+,Al3+) and explored the dynamic gelation behavior of Fmoc FF in the presence of different proportions of various metal ions. As shown in Figure 3, low concentrations of monovalent metal ions formed stronger gels, which may be due to the coordination of metal ions and Fmoc FF, which enhanced the supramolecular interaction in the gel. However, with the further increase of Na+/K+ concentration, a weak network structure was formed. For divalent metal ions, the concentration ratio also affects the assembly structure, and FmocFF/Zn2+ or FmocFF/Cu2+ forms a superhelix structure under the condition of 1 ∶ 1; 2 ∶ 1 to form a β-pleated structure; There was no self-supporting gel formation at 1:2. During the whole process, there was no gel formation in the assembly system with trivalent metal ions. These results indicate that the mechanism of peptide assembly involving different metal ions is different. In addition, due to the positive charge of the metal ion/dipeptide complex, the assembled supramolecular metallogel shows excellent DNA binding and diffusion ability in vitro, which also lays a foundation for the application of metallogel in 3D biochips, cell culture and drug delivery.

2.2.3 Solvent effect

The interaction between the solvent and the peptide molecule is essential to achieve the regulation of the self-assembly process. The polarity, aromaticity and strong hydrogen bond formation ability of the solvent itself can directly affect the assembly behavior of peptide molecules at the molecular level, so different peptidyl assembly structures can be obtained by changing the solvent.
Ihee's group has studied the formation conditions and mechanism of FF nanowires[56]. They found that FF could form monodisperse nanowires with liquid crystalline behavior after sonication in nonpolar solvent CS2 at room temperature. These nanowires formed by aromatic dipeptides are strongly rigid with an aspect ratio of up to 25.1. When the concentration of nanowires is 7 wt% ~ 10 wt%, the whole dispersion system shows optical birefringence and forms liquid crystal without phase separation. Wang et al. Found that trace solvent-bridged hydrogen bonding interactions are the key driving force for FF self-assembly to form long-range fibers[57]. They chose FF/dichloromethane as a model in which there are no hydrogen bonds or π/π interactions between FF and dichloromethane molecules. FF assembly was subsequently induced by three types of trace solvents: Ⅰ, solvents that readily form hydrogen bonding interactions with FF, including ethanol, N, N dimethylformamide, and acetone; II is a solvent having a π-π-interaction with FF, such as toluene; III is a solvent that has only van der Waals interactions with FF, such as n-hexane. The results show that the formation of directional hydrogen bonds can be successfully induced by adding a trace amount of solvent which is easy to form hydrogen bonds in the system, and the self-assembly of FF can be successfully induced to form fiber or ribbon structures. However, the addition of trace amounts of toluene and n-hexane did not induce the formation of fibrous structure.
Zhang et al. explored the gel-forming ability of Fc FF in different solvents[58]. Studies have shown that water molecules play a vital role in the self-assembly of Fc and FF to form hydrogels. In contrast, in more polar organic solvents such as acetonitrile and methanol, Fc and FF can be dissolved at high concentrations, but do not form hydrogels. In nonpolar solvents, Fc and FF can be dissolved in toluene by heating, but a large number of 4 ~ 6 μm spheres will precipitate after the solution is cooled. This may be due to the hydrogen bonding interaction between water molecules and carboxyl and amide bonds, which can drive the assembly of Fc and FF to form ordered β-fold structures, which can further form stable hydrogels through helical winding. Zhu et al. Could control the self-assembly structure of FF into organogel or flower-like microcrystals by introducing ethanol as a co-solvent to trigger the dipeptide self-assembly system[59]. For the 25% ethanol/toluene system, there is an in situ transition from gel phase to crystal phase. The polarity of the solvent as well as the ability to provide hydrogen bonds plays an important role in controlling the formation of the gel as well as the FF self-assembled structure. The present experimental results provide a deeper understanding of gel formation and the assembly process of gelling agent molecules in solution. Moreover, the molecular self-assembly structure can be regulated by simply introducing a cosolvent.

2.2.4 pH

Many studies have shown that changing the solution pH has become one of the important means to regulate the self-assembly of peptide molecules. Amino acids in peptide sequences usually contain pH-sensitive groups, and their surface charges can be significantly changed by changing the environmental pH. These changes in surface charges will further trigger changes in electrostatic interactions or hydrophilic-hydrophobic balance, making pH one of the key factors regulating the self-assembly behavior of peptide molecules.
Ulijin et al. Reported the formation of Fmoc FF hydrogel in pure water phase[60]. Fmoc FF was dissolved in alkaline aqueous solution (pH > 8) and titrated with HCl until hydrogel formation was observed. Under alkaline conditions, the carboxyl end of Fmoc is negatively charged, which increases its solubility and avoids self-assembly due to charge repulsion. When the system was titrated to pH < 8, the carboxyl end of some dipeptides began to protonate, which weakened the repulsive force between charges and formed hydrogen bonds, which was conducive to the self-assembly of Fmoc FF. Through experimental verification, the authors proposed a model of antiparallel β-sheet with Fmoc groups hanging. The four lamellae are stacked to form a cylindrical fiber with a diameter of about 3 nm, and the fiber structure is stabilized by antiparallel π π stacking of the Fmoc groups (Fig. 4). These fibers are bundled side by side to form a ribbon structure, which is finally wound to form Fmoc FF hydrogel.
Krishnan et al. explored the self-assembly behavior of FF under different pH conditions[61]. They found that when pH < 5, FF self-assembled to form nanotubes of 35 ~ 60 nm, and the size of these nanotubes changed from hundreds of nanometers to several microns with the increase of pH. However, the assemblies obtained under alkaline pH conditions are network structures formed by the stacking of large hollow tubes. In this regard, they first proposed the self-assembly mechanism of FF at acidic pH: the isoelectric point (pI) of FF is 5.68, below which the dipeptide exists mainly in the form of cations, and above which it exists in the form of anions. NH 3 + is a hydrogen bond donor, whereas —COO- is a hydrogen bond acceptor, and —NH2 and — COOH are both hydrogen bond donors and acceptors. Above the isoelectric point, the FF molecules are stacked through head-to-tail interactions due to the multiple hydrogen bonding interactions between the terminal groups —NH2 and —COO-. Below the isoelectric point, the repulsion between adjacent — NH 3 + groups restricts the stacking of FF molecules in the horizontal direction, but the stacking in the vertical direction is not hindered, so the assembly is a smaller nanotube at pH values below the isoelectric point of FF. As the pH value increases, the — NH 3 + is converted to —NH2, which increases the stacking interactions in both the horizontal and vertical directions, resulting in the formation of large, elongated nanotubes.
Tang et al. explored the effect of pH on the self-assembly behavior of Fmoc and FF[62]. Under high pH conditions, most of the molecules are ionized and dissolved in solution, so that no assembly is formed. When the pH is between 10.2 and 9.5, the assembly is paired fibrils composed of antiparallel β-sheets. At pH between 9.5 and 6.2, the peptide molecules were gradually neutralized, resulting in a decrease in the surface charge of the fibers, which enabled them to assemble laterally into rigid ribbon-like structures of larger size through hydrophobic interactions. When the pH is between 6.2 and 5.2, the peptide molecules are further neutralized, so that the ribbon structure is aggregated, and when all the Fmoc and FF molecules are neutralized, the system is subjected to phase separation, and precipitates are separated out from the solution. Adams' group found that 2NapFF could assemble into micellar aggregates at high pH and gel phase at low pH[63]. It has been shown that the change of cation concentration affects the packing mode between peptide molecules, resulting in the formation of different assembly structures.

2.3 Biological factors (enzymes)

The phenomenon of enzymatic self-assembly exists widely in organisms. Inspired by biomimetics, we can learn from the phenomenon of enzymatic self-assembly in organisms to regulate and explore the assembly behavior of dipeptides. Researchers have found that many enzymes can achieve similar assembly processes in vitro, such as phosphorylase, lipase, thermolysin, subtilisin and so on[64⇓~66]. Based on these enzymatic self-assembly systems, a variety of functional response systems with enzymes as "switches" have been designed to regulate the assembly process of dipeptides and obtain micro-nano materials with specific functions[67].
Xu Bing's research group was the first to study enzymatic supramolecular assembly, designed a new type of gelator Nap FFGEY, and constructed a dual-enzyme induction system based on kinase/phosphorylase, which can regulate the formation of supramolecular hydrogel by inducing the phosphorylation and dephosphorylation of gelator[68][69]. The addition of kinase to the hydrogel in the presence of adenosine triphosphate causes a gel-to-sol phase transition. The tyrosine residue is converted to phosphotyrosine by the kinase, making Nap FFGEY more hydrophilic; Phosphatase treatment of the transformed sol phase can restore it to a hydrogel. Subsequently, they combined lysine (K) and tyrosine phosphate (Y) with Nap FF to synthesize a D-type gelator precursor, Nap FFKY, which can be assembled into hydrogels under the induction of phosphorylase[70]. Anticancer drug paclitaxel or fluorophore 4 nitro 2, 1, 3 benzoxadiazole is connected to Nap FFKY to form fluorescent molecular aggregates inside cells through intracellular enzymatic hydrogelation, which has broad application prospects in tumor chemotherapy and cell imaging. Ulijn's team used thermolysin as an enzyme model to induce the self-assembly of a variety of Fmoc-modified amphiphilic peptide molecules, and found that the enzyme could selectively induce the formation of hydrogels through reversible hydrolysis. Analysis of the resulting Fmoc-FFF gel showed that the gel was composed of interwoven fibers with a diameter of about 10 to 20 nm[71]. In addition, they successfully used the subtilisin/thermolysin dual-enzyme system to drive the self-assembly and hydrolysis of peptide-based hydrogels[72].

3 Application of diphenylalanine dipeptidyl assembly

Peptide-based assembly micro-nano materials have been widely concerned and studied because of their advantages such as simple preparation, easy modification and good biocompatibility. The development of supramolecular chemistry and the unique dynamic and directional nature of non-covalent bonds have further promoted the tunability and intelligent response of peptide-based materials assembly[73]. This part mainly introduces the applications of peptide-based supramolecular assembly micro-nano materials in the fields of biomedicine, biosensing, optoelectronic materials, optical waveguides and catalysis.

3.1 Biomedicine

The pursuit and yearning for a healthy and happy life has always been the goal of people's life. Modern medicine has entered the era of molecular medicine, and precise diagnosis and targeted therapy are the inevitable trend of the development of contemporary medicine. The development of molecular medicine is still in the early stage, facing many bottlenecks, which requires the deep participation of molecular scientists, especially chemists. The superior biological and chemical properties of peptides show the great advantages of their self-assemblies and broad application prospects in the field of biomedicine.
Phenylalanine based materials have good biocompatibility, so they can be widely used in the field of biomedicine and serve human health. Li Junbai's research group has also been committed to the exploration of polypeptide assembly and its biological applications, and has achieved many research results, and has also made a comprehensive review of the assembly behavior and application progress based on dipeptides[74⇓~76]. Zhang et al. Found that glutaraldehyde (GA) could induce the covalent assembly of cationic diphenylalanine (CDP) to obtain monodisperse nanospheres (CDPNPs) with uniform size[53]. The nanoparticles can be loaded with doxorubicin (DOX), an anticancer drug, with a loading efficiency of more than 50%. In vitro release experiments show that DOX shows a very good sustained release performance in PBS containing trypsin. Recently, by precisely controlling the assembly path of dipeptides, solvent molecules are used to induce the orientation of dipeptide molecules, and their hydrophilic or hydrophobic groups are selectively exposed on the outer surface of the assembled nanostructure.O as to form super-hydrophilic aerogel or super-hydrophobic ice gel (the gel obtained by freeze drying is defined as ice gel), wherein the super-hydrophilic aerogel and the super-hydrophobic ice gel are respectively composed of nanofibers and nanobelts, so that the regulation of the surface hydrophilicity/hydrophobicity of the assembly is realized, and the dipeptide aerogel with adjustable interface wettability is obtained. The results showed that the properties of the constructed dipeptide assemblies, including fluorescence emission and specific surface area, were also significantly different. Further experiments confirmed that the dipeptide aerogel with controllable wettability had its special use in the field of medicine, and it was found that it had better hemostatic effect than the commercially available gelatin sponge when it was used for in vitro hemostasis (Fig. 5). This study opens up a new way for the development of peptide-based assembly materials with different properties and functions constructed by the same molecular unit, and brings new inspiration for the research and application of single-component and multi-performance supramolecular assembly materials[77].
Phototherapy is considered to be one of the effective cancer treatments because of its safety and high selectivity. The directional conversion of light energy can be realized by regulating the interaction force between peptide molecules, and the peptide-based assembly materials can effectively realize the loading and transportation of one or more photodynamic drugs, so that the peptide-based assembly materials have been widely and deeply studied in the field of photodynamic tumor therapy (PDT) and photothermal tumor therapy (PTT). Ma et al. Used the crosslinking agent glutaraldehyde to assemble with CDP to obtain an injectable nanocarrier with controllable size and structure, which was used to load the photosensitive drug Ce6 and deliver it to tumors[78]. Anti-tumor efficacy analysis showed that Ce6 encapsulated in hydrogel could inhibit tumor growth and recurrence more effectively than free Ce6, and caused little damage to important organs. Therefore, the injectable composite hydrogel is promising for the treatment of superficial tumors. Recently, pH-responsive convertible peptide-based nanoparticles have been developed for photodynamic therapy to prolong tumor retention time. When exposed to the acidic tumor microenvironment, the self-assembled peptideporphyrin nanoparticles are converted into nanofibers, and this conversion improves their singlet oxygen production capacity and enables high accumulation and long-term retention at the tumor site. A strong fluorescent signal of these nanomaterials was detected in tumor tissue after up to 7 days of administration. In addition, the peptide assemblies exhibited excellent antitumor efficacy by in vivo PDT. This in situ fiber conversion strategy may enable the design of effective stimuli-responsive biomaterials for long-term imaging and therapy[79]. Glutaraldehyde can generate an oligomer through the aldol condensation reaction of the glutaraldehyde, and then the aldehyde group of the oligomer and the amino group of CDP form an assembly unit through the action of a Schiff base to form a nanoparticle after standing, which has very good biocompatibility and biodegradability. Through phagocytosis, these nanoparticles can be taken up by cells and eventually degraded in the cell interior. The nanoparticles can be well loaded with the anti-tumor drug doxorubicin, and the loaded nanoparticles show very good anti-tumor performance even when the drug concentration is very low, based on the drug concentration[53].

3.2 Biosensing

Nanomaterials based on diphenylalanine and its derivatives with different structures can be obtained by controlled assembly, which have been widely used in the field of electrochemical biosensing because of their large specific surface area, good biocompatibility and high electron transport efficiency[74]. For the first time, Gazit group modified peptidyl nanotubes on the electrode and improved the sensitivity of electrochemical detection[80]. The detection sensitivity of the graphite electrode modified by the FF nanotube is doubled; The thiol-modified dipeptide nanotube immobilized on the gold electrode showed a 16-fold response to 10 mM H2O2 compared with the bare electrode, indicating that the FF nanotube can significantly improve the electron transport efficiency. Later, a new type of electrochemical enzyme sensor was constructed, in which glucose oxidase or alcohol dehydrogenase was immobilized on the dipeptide nanotube, and the highly sensitive detection of glucose and ethanol was achieved by differential pulse voltammetry[81]. Subsequently, many peptide-based nanomaterials have been reported to construct electrochemical sensors with improved electrochemical performance[82,83]. Gong et al. Modified FF Au nanoparticles and horseradish peroxidase on the electrode successively, and realized the detection of H2O2 by using the reducibility and catalytic activity of the modified electrode to H2O2[84]. In addition, electrochemical detection of phenylalanine dipeptide nanowires has also been reported[85]. Castillo et al. Dropped folate-modified dipeptide nanotubes onto graphene-modified electrodes to achieve early diagnosis and detection of cancer cells[86].
At present, many related reports have proved the application of dipeptide-based self-assembled structural materials in improving the performance of biosensors. Although some progress has been made, the weak conductivity of FF-based assembly materials also limits the detection performance of the constructed biosensors. Noble metal nanoparticles have many outstanding advantages, such as excellent conductivity, biocompatibility and large specific surface area. Therefore, the electrochemical properties of electrodes modified by many nanomaterials have been greatly improved. Therefore, the combination of dipeptide molecules and noble metal gold nanoparticles to obtain materials with complementary advantages also has great advantages in improving the application of dipeptide micro-nano assemblies in biosensors[87]. Recently, Wang et al. Used CDP as the assembly motif and the interaction of positive and negative charges to obtain dipeptide gold particle hybrid microspheres (CDP Au NPs) with controllable size, bioactivity and catalytic properties, and modified them with cholesterol oxidase on the electrode to obtain a biosensor for highly sensitive detection of cholesterol (Fig. 6)[88]. This composite system well represents the biocompatibility of the peptide and the catalytic performance of the gold particles. Compared with the electrode without CDP AuNPs hybrid microspheres, the sensitivity of the enzyme electrode modified by CDP AuNPs for cholesterol detection was increased by 13 times. Such assembled particles can also be used for other highly sensitive and stable electrochemical detection.
In addition to noble metal nanoparticles, graphene can also be co-assembled with peptide-based materials to obtain materials with excellent performance for biosensing. Graphene, as a material with higher conductivity and larger specific surface area than other carbon-based nanomaterials, has also attracted much attention for its application in electrochemical sensing. The functionalized nanomaterial obtained by co-assembling the graphene and the FF has complementary advantages in properties, which not only can avoid the limitation of the graphene material with a single component in the application of electrochemical sensing,For example, it tends to aggregate in aqueous solution, has weak electrochemical activity and poor biocompatibility, and can avoid the limitations of single component and weak conductivity FF in further application of electrochemical sensing[89].

3.3 Photoelectric material

With the increasing demand for environmentally friendly organic semiconductor materials, bio-inspired peptide-based semiconductor materials have gradually become the focus of attention in this field. In recent years, FF and its derivatives have been widely used in the construction of optoelectronic materials, and their photoluminescence, conductivity, piezoelectricity and energy storage properties have expanded the scope of application.
Lee et al. controlled the ratio of solvent water to hexafluoroisopropanol, FF concentration, and pulling rate by using the pulling method to obtain FF nanotubes with close packing in the same direction (fig. 7)[90]. FF nanotubes exhibit piezoelectric properties as well as unidirectional polarizability. With the help of a piezoelectric energy harvester, the FF nanotube can have a piezoelectric voltage of up to 2.8 V, a current of 37.4 nA, and a power of 8.2 nW, which is enough to power multiple LCD panels. Yang's research group assembled a vertically grown diphenylalanine microrod array through electric field control, and further prepared a diphenylalanine micro-piezoelectric generator[91]. The open-circuit voltage of the generator reaches 1.4 V, and the energy density reaches 3.3 nW/cm2. This miniature peptide-based piezoelectric device has very high stability, and the output voltage does not decrease when it is pressed 1000 times in half an hour. Heo et al. Deposited vertically aligned Cyclo FF nanowire arrays on a silicon dioxide substrate coated with a gold coating by vapor deposition[92]. The nanowire array can stably exist in water and TBS buffer, and the special stability enables the nanowire array to be successfully applied to the field of triboelectricity. A voltage of 350 V can be generated during contact with aluminum-coated PTFE, with an output current of 10 μA and a maximum power density of ~73.7 mW/m2, which is enough to light more than a hundred LED bulbs. This research provides an opportunity for the development of biocompatible energy materials. Park's group also reported that FF/Co3O4 nanowires were obtained by peptide self-assembly[93]. Peptide nanowires were obtained by treating FF membrane with aniline vapor at high temperature, and then mixed with Co3O4 nanocrystals obtained by reducing Co ions in aqueous solution with NaBH4 to finally form composite nanowires. This kind of nanowire can be used as the negative electrode of Li-ion battery, and its storage capacity for Li ions is much higher than that of pure FF nanowire, which may be widely used in the field of energy storage in the future.
Xue et al. Used the covalent reaction of CDP with genipin to obtain a heterocyclic molecule with a high degree of π conjugation (CDPG), as shown in Figure 8[94]. CDPG was assembled to form nanospheres and nanofibers in non-aromatic polar solvent and aromatic non-polar solvent, respectively. Compared with the building blocks CDP and genipin, both assemblies showed significantly enhanced photoelectric response effects. The performance of the photoelectric conversion device is enhanced by about 500 times. The experimental results show that the structure of CDPG assembly can be changed by controlling the assembly process to improve the device performance.

3.4 Optical waveguide

Optical waveguide properties are also one of the important discoveries in the development of peptide-based semiconductor materials. Li Junbai's research group started the application research of peptide-based micro-nano materials in optical waveguide in 2011, and carried out a series of leading work in this area[95,96]. Both FF and CDP can self-assemble to form microtubules, microrods or crystal sheets, and their surfaces are smooth and crystalline, so they are very suitable for optical waveguide materials. Compared with traditional silicon-based and inorganic optical fibers, peptide-based optical waveguide materials have good biocompatibility, and can be doped or modified with photosensitizers, quantum dots, rare earth ions, etc., thus expanding their applications in biological devices[76].
The highly symmetrical hexagonal microtube structure can be obtained by controlling the slow crystallization of FF by hydrothermal annealing. When the hexagonal microtube dispersion was diluted, it was found that the microtubes cracked from one end and cracked into independent nanotubes. This assembly mode of nanotubes packed into microtubes is also consistent with the FF single crystal structure information. After doping with dye, FF microtubes show good optical waveguide characteristics, which is first found in phenylalanine-based assembly systems[97].
Subsequently, diphenylalanine nanofibers, microtubules and microrods were prepared by ultrasound-assisted solvent crystallization, respectively, by adjusting and optimizing the assembly conditions (such as ultrasonic time, concentration, solvent volume ratio). Selected area electron diffraction (SAED) showed that the prepared diphenylalanine microtubules and microrods had single crystal structure and showed significant optical waveguide properties, which was relatively rare in biomolecular assembly systems. Combined with the good biocompatibility of peptide-based assemblies, the one-dimensional crystal structure of diphenylalanine dipeptide is expected to be used in medical fields such as disease diagnosis[45].
In addition, the binary solvent ammonia can also be selected as the solvent of the self-assembly system to study the assembly of FF and its optical waveguide application. The volatilization of the solution near the three-phase contact line induces the nucleation of FF crystals, while the continuous pulling system on the substrate allows the crystal to grow continuously and directionally. By controlling the temperature of the substrate, the solvent and the pulling speed of the substrate, the number and length of the aligned FF single crystals can be controlled. It not only realizes the rapid growth of ultra-long oriented FF single crystal, but also obtains FF single crystal with optical waveguide properties. Based on its ordered arrangement structure, it is expected to develop related applications in large-scale optical devices[29].
In 2019, Li et al. Obtained a hierarchically ordered FF branching structure by rapidly volatilizing the solvent with the assistance of moist airflow, as shown in Figure 9[98]. The FF-branched structure can still be obtained by introducing the dye rhodamine B (RhB) in the assembly process, and the dye-doped assembly can show fluorescence at different excitation wavelengths, which indicates that the FF-branched structure can be used as a functional fluorescent dye molecular carrier scaffold in the field of biomedical detection. Optical waveguide experiments show that the branched FF structure exhibits an optical conduction mode of single-point input, multi-point output, multi-point input and single-point output, which has great potential in the field of optical transmission devices.

3.5 Catalyze

Natural systems often have enormous molecular complexity and build exquisite architectures and functional materials through precise spatial and temporal control, and supramolecular self-assembly of peptides and proteins is one of the key factors[99,100]. In a variety of natural enzyme systems, their excellent characteristics and functions not only attract people to unlock the mysteries of nature, but also arouse great interest in green life design of advanced materials. However, natural enzymes are inherently unstable and complex, so it is desirable to develop biomimetic catalytic alternatives to natural enzymes. For this purpose, scientists have pursued the development of supramolecular nanozymes through self-assembly strategies associated with multiple noncovalent interactions. Peptides, as functional motifs of natural proteins, can be used as versatile and promising building blocks for the design of functional biomimetic nanozymes. Importantly, the mechanism of peptide-based NANase structural regulation is well defined, and their unique properties (e.g. Selectivity, autocatalysis, etc.) as fundamental biological units in living systems may provide further possibilities for modulating catalytic performance. Han et al. Reviewed the research progress of peptide-based supramolecular nanozymes, including peptide-based assembly, precise functional regulation through supramolecular noncovalent interactions, catalytic reaction, and energy conversion mechanism[101]. These previous studies can inspire the construction of a novel supramolecular nanoenzyme with high catalytic selectivity and efficiency in various applications.
Wang et al. Obtained chain-like multilevel ordered short peptide assemblies through dynamic covalent bond assembly and metal ion coordination[33]. By adjusting the pH of the assembly system, the nanochain can be disassembled to obtain a stable nanosphere structure, thereby constructing a short peptidyl nanoassembly with a reversible structure, and the structure and function of the assembly have a reversible "switch" property of ion response (fig. 10). In order to test the catalytic activity of the assembly, 2-nitro-5-thiobenzoic acid, which has a specific ultraviolet absorption at 412 nm, was used as an indicator. Laccase could catalyze the oxidation of hydroquinone to p-benzoquinone, and the product could fade the indicator after reaction with the indicator. Compared with natural laccase, the catalytic efficiency of the dipeptidyl nanoassembly as a catalyst was increased by 2 times at a specific time, showing a higher affinity with the substrate, and the biomimetic enzyme could still maintain a higher catalytic activity after 7 days of storage, and its stability was much higher than that of natural laccase. The assembly in this study has a function beyond natural laccase, which provides an important inspiration for the construction of artificial enzymes with high catalytic activity and high stability[33].
Chen et al. Described an extremely simple method to construct enzymatically active dipeptide-based nanoscale supramolecular architectures[102]. The biocatalyst is completed by the self-assembly of peptidyl units. Through the coordination with zinc ions, the peptide self-assembly process can form supramolecular β-folded ordered nanocrystals, which can be used as basic units to further construct higher-order supramolecular structures. The experimental results show that the biomimetic enzyme has significant hydrolytic activity and lasting stability. This work further illustrates the feasibility and value of using a biomimetic supramolecular assembly approach to develop next-generation biocatalysts for biotechnological applications.
In addition to the above applications, diphenylalanine dipeptidyl micro-nano materials can also be used to prepare biological templates of various materials, artificial photosynthesis, tissue repair materials, spray printing, optical manufacturing and so on.

4 Conclusion and prospect

The assembly of FF and its derivatives is a multi-factor controlled process, and the morphology and structure of the assembly are determined by the interaction between molecules and the external environment of the reaction. Through precise regulation, the assembly with specific morphology and structure can be obtained and its related application research can be carried out. By introducing functional molecules such as photosensitizers, chemicals and enzymes into the assembly system, peptide-based micro-nano materials have a wide range of applications in the field of biomedicine. The introduction of molecules with optical, electrical and magnetic properties into the assembly system can also further expand its application scope.
Supramolecular peptide co-assembly is an emerging research field, which can make up for the shortcomings of pure chemical synthesis in some aspects, such as time-consuming or difficult to achieve by chemical synthesis. Precisely designed multifunctional peptide assemblies enhance structural complexity and chemical diversity within the co-assembly system. Dynamically complex co-assembly pathways enable the formation of assemblies with tailored physical, chemical, and mechanical properties, thereby expanding the scope of nanotechnology. Moreover, this strategy can effectively extend the application range of micro-nano materials, from the fabrication of devices to the treatment of diseases. Although significant progress has been made in this field of research, the full promise of peptide supramolecular coassembly has yet to be fully realized[103]. For example, the effective cooperative assembly of multiple peptide motifs and the regulation of specific properties still face enormous challenges. In biomedical applications, due to the complexity of biological systems, there is still a gap between theoretical research and practical application. Stimulus-responsive co-assembled peptide hydrogels and nanostructures are equally important and are one of the future directions for the development of advanced functional smart nanomaterials. In addition, the study of supramolecular co-assembly between biologically significant short peptides will reveal various enigmatic non-covalent protein folding physiology, pathology, and drug design, contributing to human disease treatment and health development. In summary, biomimetic molecular materials and systems have long-term potential to lead to fundamentally new sustainable and degradable materials, dynamically tunable sensors, novel autonomous medical interventions, and new modes of energy production and conversion[104]. With the progress of nanoscience and technology, computational design and the in-depth and refined research of self-assembly and co-assembly, improved automation and artificial intelligence analysis technology can better deal with complex systems, heterogeneous and dynamic adaptive mixtures.Peptide-based systems chemistry will eventually yield new solutions and insights that have not been explored by biology, and it is believed that the inherent simplicity and versatility of supramolecular co-assembly of short peptides will make more important contributions to the development and application of nanotechnology.

References

Publishing order | Descend order by publishing year | Descend order by cited within
[1]

Goor O J G M, Hendrikse S I S, Dankers P Y W, Meijer E W. Chem. Soc. Rev., 2017, 46(21): 6621.
[2]

Tao K, Levin A, Adler-Abramovich L, Gazit E. Chem. Soc. Rev., 2016, 45(14): 3935.
[3]

Makam P, Gazit E. Chem. Soc. Rev., 2018, 47(10): 3406.
[4]

Wei G, Su Z Q, Reynolds N P, Arosio P, Hamley I W, Gazit E, Mezzenga R. Chem. Soc. Rev., 2017, 46(15): 4661.
[5]

Vestergaard M, Kerman K, Saito M, Nagatani N, Takamura Y, Tamiya E. J. Am. Chem. Soc., 2005, 127(34): 11892.
[6]

Lingenfelder M, Tomba G, Costantini G, Colombi Ciacchi L, De Vita A, Kern K. Angew. Chem., 2007, 119(24): 4576.
[7]

Adler-Abramovich L, Gazit E. Chem. Soc. Rev., 2014, 43(20): 6881.
[8]

Tao K, Yoskovitz E, Adler-Abramovich L, Gazit E. RSC Adv., 2015, 5(90): 73914.
[9]

Wu A L, Guo Y X, Li X B, Xue H M, Fei J B, Li J B. Angew. Chem. Int. Ed., 2021, 60(4): 2099.
[10]

Wang J B, Chao J, Liu H J, Su S, Wang L H, Huang W, Willner I, Fan C H. Angew. Chem. Int. Ed., 2017, 56(8): 2171.
[11]

Elsawy M A, Smith A M, Hodson N, Squires A, Miller A F, Saiani A. Langmuir, 2016, 32(19): 4917.
[12]

Wei G, Reichert J, Jandt K D. Chem. Commun., 2008(33): 3903.
[13]

Dave A C, Loveday S M, Anema S G, Jameson G B, Singh H. Biomacromolecules, 2014, 15(1): 95.
[14]

Wei G, Reichert J, Bossert J, Jandt K D. Biomacromolecules, 2008, 9(11): 3258.
[15]

Ji W, Yuan C Q, Zilberzwige-Tal S, Xing R R, Chakraborty P, Tao K, Gilead S, Yan X H, Gazit E. ACS Nano, 2019, 13(6): 7300.
[16]

Scanlon S, Aggeli A. Nano Today, 2008, 3(3/4): 22.
[17]

Yang Y L, Ulung K, Wang X M, Horii A, Yokoi H, Zhang S G. Nano Today, 2009, 4(2): 193.
[18]

Baker P A, Goltz M N, Schrand A M, Yoon D Y, Kim D S. Biosens. Bioelectron., 2014, 61: 119.
[19]

Hamley I W. Angew. Chem. Int. Ed., 2014, 53(27): 6866.
[20]

Lian M L, Chen X, Liu X J, Yi Z C, Yang W S. Sens. Actuat. B Chem., 2017, 251: 86.
[21]

Gao X, Matsui H. Adv. Mater., 2005, 17(17): 2037.
[22]

Wang J H, Ouyang Z F, Ren Z W, Li J F, Zhang P P, Wei G, Su Z Q. Carbon, 2015, 89: 20.
[23]

Kim W, ThÉvenot J, Ibarboure E, Lecommandoux S, Chaikof E. Angew. Chem. Int. Ed., 2010, 49(25): 4257.
[24]

Zou Q L, Abbas M, Zhao L Y, Li S K, Shen G Z, Yan X H. J. Am. Chem. Soc., 2017, 139(5): 1921.
[25]

Zhang Q, Li M X, Zhu C Y, Nurumbetov G, Li Z D, Wilson P, Kempe K, Haddleton D M. J. Am. Chem. Soc., 2015, 137(29): 9344.
[26]

Yang L L, Liu A J, Cao S Q, Putri R M, Jonkheijm P, Cornelissen J J L M. Chem. Eur. J., 2016, 22(44): 15570.
[27]

Zhang S G. Nat. Biotechnol., 2003, 21(10): 1171.
[28]

Hauser C A E, Zhang S G. Nature, 2010, 468(7323): 516.
[29]

Sun B B, Li Q, Riegler H, Eickelmann S, Dai L R, Yang Y, Perez-Garcia R, Jia Y, Chen G X, Fei J B, Holmberg K, Li J B. ACS Nano, 2017, 11(10): 10489.
[30]

Puiu M, Bala C. Bioelectrochemistry, 2018, 120: 66.
[31]

Xue H M, Fei J B, Wu A L, Xu X, Li J B. CCS Chem., 2021, 3(11): 8.
[32]

Sun B B, Tao K, Jia Y, Yan X H, Zou Q L, Gazit E, Li J B. Chem. Soc. Rev., 2019, 48(16): 4387.
[33]

Wang C L, Fei J B, Wang K Q, Li J B. Angew. Chem. Int. Ed., 2020, 59(43): 18960.
[34]

Adler-Abramovich L, Aronov D, Beker P, Yevnin M, Stempler S, Buzhansky L, Rosenman G, Gazit E. Nat. Nanotechnol., 2009, 4(12): 849.
[35]

Liu X C, Fei J B, Wang A H, Cui W, Zhu P L, Li J B. Angew. Chem. Int. Ed., 2017, 56(10): 2660.
[36]

Wang Y F, Qi W, Huang R L, Yang X J, Wang M F, Su R X, He Z M. J. Am. Chem. Soc., 2015, 137(24): 7869.
[37]

Ma H C, Fei J B, Li Q, Li J B. Small, 2015, 11(15): 1787.
[38]

Yao X Y, Li T, Wang J, Ma X, Tian H. Adv. Opt. Mater., 2016, 4(9): 1322.
[39]

Russew M M, Hecht S. Adv. Mater., 2010, 22(31): 3348.
[40]

Li X B, Fei J B, Xu Y Q, Li D X, Yuan T T, Li G L, Wang C L, Li J B. Angew. Chem. Int. Ed., 2018, 57(7): 1903.
[41]

Zhao Y S, Yang W S, Yao J N. Phys. Chem. Chem. Phys., 2006, 8(28): 3300.
[42]

Wang H Q, Yan X H, Li G L, Pilz-Allen C, Möhwald H, Shchukin D. Adv. Healthcare Mater., 2014, 3(6): 825.
[43]

Skorb E V, Möhwald H, Irrgang T, Fery A, Andreeva D V. Chem. Commun., 2010, 46(42): 7897.
[44]

Eddleston M D, Jones W. Cryst. Growth Des., 2010, 10(1): 365.
[45]

Li Q, Jia Y, Dai L R, Yang Y, Li J B. ACS Nano, 2015, 9(3): 2689.
[46]

Li Q, Ma H C, Jia Y, Li J B, Zhu B H. Chem. Commun., 2015, 51(33): 7219.
[47]

Na N, Mu X Y, Liu Q L, Wen J Y, Wang F F, Ouyang J. Chem. Commun., 2013, 49(86): 10076.
[48]

Zou Q L, Zhang L, Yan X H, Wang A H, Ma G H, Li J B, Möhwald H, Mann S. Angew. Chem. Int. Ed., 2014, 53(9): 2366.
[49]

Ma H C, Fei J B, Cui Y, Zhao J, Wang A H, Li J B. Chem. Commun., 2013, 49(85): 9956.
[50]

Yan X H, Zhu P L, Fei J B, Li J B. Adv. Mater., 2010, 22(11): 1283.
[51]

Liu X C, Fei J B, Zhu P L, Li J B. Chem. Asian J., 2016, 11(19): 2700.
[52]

Yuan T T, Fei J B, Xu Y Q, Yang X K, Li J B. Macromol. Rapid Commun., 2017, 38(20): 1700408.
[53]

Zhang H, Fei J B, Yan X H, Wang A H, Li J B. Adv. Funct. Mater., 2015, 25(8): 1193.
[54]

Miller Y, Ma B Y, Nussinov R. Coord. Chem. Rev., 2012, 256(19/20): 2245.
[55]

Kim J, Han T H, Kim Y I, Park J S, Choi J, Churchill D G, Kim S O, Ihee H. Adv. Mater., 2010, 22(5): 583.
[56]

Han T H, Kim J, Park J S, Park C B, Ihee H, Kim S O. Adv. Mater., 2007, 19(22): 3924.
[57]

Wang J, Liu K, Yan L Y, Wang A H, Bai S, Yan X H. ACS Nano, 2016, 10(2): 2138.
[58]

Zhang G, Zhang L W, Rao H J, Wang Y F, Li Q, Qi W, Yang X J, Su R X, He Z M. J. Colloid Interface Sci., 2020, 577: 388.
[59]

Zhu P L, Yan X H, Su Y, Yang Y, Li J B. Chem. Eur. J., 2010, 16(10): 3176.
[60]

Jayawarna V, Ali M, Jowitt T A, Miller A F, Saiani A, Gough J E, Ulijn R V. Adv. Mater., 2006, 18(5): 611.
[61]

Kumaraswamy P, Lakshmanan R, Sethuraman S, Krishnan U M. Soft Matter, 2011, 7(6): 2744.
[62]

Tang C, Smith A M, Collins R F, Ulijn R V, Saiani A. Langmuir, 2009, 25(16): 9447.
[63]

McAulay K, Ucha P A, Wang H, Fuentes-CaparrÓs A M, Thomson L, Maklad O, Khunti N, Cowieson N, Wallace M, Cui H G, Poole R J, Seddon A, Adams D J. Chem. Commun., 2020, 56(29): 4094.
[64]

Hughes M, Xu H X, Frederix P W J M, Smith A M, Hunt N T, Tuttle T, Kinloch I A, Ulijn R V. Soft Matter, 2011, 7(21): 10032.
[65]

Chronopoulou L, Lorenzoni S, Masci G, Dentini M, Togna A R, Togna G, Bordi F, Palocci C. Soft Matter, 2010, 6(11): 2525.
[66]

Zhao J, Huang R L, Qi W, Wang Y F, Su R X, He Z M. Progress in Chemistry, 2014, 26(9): 1445.
[67]

( 赵君, 黄仁亮, 齐崴, 王跃飞, 苏荣欣, 何志敏. 化学进展, 2014, 26(9): 1445.).
[68]

Williams R J, Smith A M, Collins R, Hodson N, Das A K, Ulijn R V. Nat. Nanotechnol., 2009, 4(1): 19.
[69]

Yang Z, Xu B. Adv. Mater., 2006, 18(22): 3043.
[70]

Yang Z M, Liang G L, Wang L, Xu B. J. Am. Chem. Soc., 2006, 128(9): 3038.
[71]

Li J Y, Gao Y, Kuang Y, Shi J F, Du X W, Zhou J, Wang H M, Yang Z M, Xu B. J. Am. Chem. Soc., 2013, 135(26): 9907.
[72]

Toledano S, Williams R J, Jayawarna V, Ulijn R V. J. Am. Chem. Soc., 2006, 128(4): 1070.
[73]

Das A K, Collins R, Ulijn R V. Small, 2008, 4(2): 279.
[74]

Xing R R, Zou Q L, Yan X H. Acta Phys. Chim. Sin., 2020, 36(10): 1909048.
[75]

( 邢蕊蕊, 邹千里, 闫学海. 物理化学学报, 2020, 36(10): 1909048.).
[76]

Yan X H, Zhu P L, Li J B. Chem. Soc. Rev., 2010, 39(6): 1877.
[77]

Fei J B, Li Q, Zhao J, Li J B. Progress in Chemistry, 2019, 31(1): 30.
[78]

( 费进波, 李琦, 赵洁, 李峻柏. 化学进展, 2019, 31(1): 30.).
[79]

Jia Y, Li Q, Li J B. Chin. Sci. Bull., 2017, 62(6): 469.
[80]

( 贾怡, 李琦, 李峻柏. 科学通报, 2017, 62(6): 469.).
[81]

Li X B, Li Q, Fei J B, Jia Y, Xue H M, Zhao J, Li J B. Angew. Chem. Int. Ed., 2020, 59(29): 11932.
[82]

Ma K, Xing R R, Jiao T F, Shen G Z, Chen C J, Li J B, Yan X H. ACS Appl. Mater. Interfaces, 2016, 8(45): 30759.
[83]

Sun B B, Chang R, Cao S P, Yuan C Q, Zhao L Y, Yang H W, Li J B, Yan X H, Hest J C M. Angew. Chem. Int. Ed., 2020, 59(46): 20582.
[84]

Yemini M, Reches M, Rishpon J, Gazit E. Nano Lett., 2005, 5(1): 183.
[85]

Yemini M, Reches M, Gazit E, Rishpon J. Anal. Chem., 2005, 77(16): 5155.
[86]

Adler-Abramovich L, Badihi-Mossberg M, Gazit E, Rishpon J. Small, 2010, 6(7): 825.
[87]

Huang Y, Tan J, Cui L J, Zhou Z D, Zhou S F, Zhang Z H, Zheng R, Xue Y W, Zhang M X, Li S S, Zhu N X, Liang J T, Li G Y, Zhong L P, Zhao Y X. Biosens. Bioelectron., 2018, 102: 560.
[88]

Gong Y F, Chen X, Lu Y L, Yang W S. Biosens. Bioelectron., 2015, 66: 392.
[89]

Sasso L, Vedarethinam I, EmnÉus J, Svendsen W E, Castillo-LeÓon J. J. Nanosci. Nanotech., 2012, 12(4): 3077.
[90]

Castillo J J, Svendsen W E, Rozlosnik N, Escobar P, Martínez F, Castillo-LeÓn J. Analyst, 2013, 138(4): 1026.
[91]

Huang S M, Chen G S, Ou R H, Qin S, Wang F X, Zhu F, Ouyang G F. Anal. Chem., 2018, 90(14): 8607.
[92]

Wang K Q, Li Z R, Wang C L, Zhang S, Cui W, Xu Y Q, Zhao J, Xue H M, Li J B. J. Colloid Interface Sci., 2019, 557: 628.
[93]

Si Y C, Samulski E T. Nano Lett., 2008, 8(6): 1679.
[94]

Lee J H, Heo K, Schulz-Schönhagen K, Lee J H, Desai M S, Jin H E, Lee S W. ACS Nano, 2018, 12(8): 8138.
[95]

Nguyen V, Zhu R, Jenkins K, Yang R S. Nat. Commun., 2016, 7: 13566.
[96]

Park I W, Choi J, Kim K Y, Jeong J, Gwak D, Lee Y H, Ahn Y H, Choi Y J, Hong Y J, Chung W J, Lee M, Heo K. Nano Energy, 2019, 57: 737.
[97]

Ryu J, Kim S W, Kang K, Park C B. ACS Nano, 2010, 4(1): 159.
[98]

Xue H M, Li X B, Wang K Q, Cui W, Zhao J, Fei J B, Li J B. Chem. Commun., 2019, 55(87): 13136.
[99]

Sun B B, Riegler H, Dai L R, Eickelmann S, Li Y, Li G L, Yang Y, Li Q, Fu M F, Fei J B, Li J B. ACS Nano, 2018, 12(2): 1934.
[100]

Li Q, Ma H C, Wang A H, Jia Y, Dai L R, Li J B. Adv. Opt. Mater., 2015, 3(2): 194.
[101]

Yan X H, Li J B, Möhwald H. Adv. Mater., 2011, 23(25): 2796.
[102]

Li Q, Jia Y, Yang X K, Dai L R, Das B, Acharya S, Sun B B, Yang Y, Liu X C, Ariga K, Li J B. ACS Appl. Mater. Interfaces, 2019, 11(1): 31.
[103]

Wang L, Shen G Z, Yan X H. Particuology, 2022, 64: 14.
[104]

Dong J Q, Liu Y, Cui Y. J. Am. Chem. Soc., 2021, 143(42): 17316.
[105]

Han J J, Gong H N, Ren X K, Yan X H. Nano Today, 2021, 41: 101295.
[106]

Chen Y, Yang Y Q, Orr A A, Makam P, Redko B, Haimov E, Wang Y N, Shimon L J W, Rencus-Lazar S, Ju M T, Tamamis P, Dong H, Gazit E. Angew. Chem. Int. Ed., 2021, 60(31): 17164.
[107]

Li L C, Xie L, Zheng R L, Sun R Q. Front. Chem., 2021, 9: 739791.
[108]

Sheehan F, Sementa D, Jain A, Kumar M, Tayarani-Najjaran M, Kroiss D, Ulijn R V. Chem. Rev., 2021, 121(22): 13869.

Funding

National Natural Science Foundation of China(21961142022)

National Natural Science Foundation of China(21872150)

National Natural Science Foundation of China(22072160)

PDF (12107KB)

2001

Accesses

0

Citation

Detail
Sections
Recommended

/

〈 〉

Address of Editorial Office: No. 33 Beisihuan Xilu, Zhongguancun , Beijing 100190, China
Tel: +86 10 8262 7757
Fax: +86 10 8262 7757
E-mail: progchem@mail.las.ac.cn
http://www.progchem.ac.cn
    • 　
    Copyright © Editorial Office of Progress in Chemistry