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Functional Protein Based Nanomaterials for Environmental Protection Application

Ximeng Cheng , Qingrui Zhang

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (4) : 678 -688.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (4) : 678-688 DOI: 10.7536/PC200695
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Functional Protein Based Nanomaterials for Environmental Protection Application
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Abstract

Protein is a kind of biological macromolecule with stable structure and abundant functional groups. Recently, the development of protein based nanomaterials has raised wide-spread research enthusiasm, especially in environmental remediation. Dopamine, amyloid-fibrils and protein-inorganic hybrid nanoflower are the three most representative ones. Inspired by mussels, the strong adhesive polydopamine coating forms in alkaline condition through self-polymerization, which is widely used in surface modification. Amyloid-fibrils, obtained by the heat treatment or chemical denaturation of functional protein, possess the large aspect ratio and more active sites for enhancing the decontamination. Besides, the three-dimensional structure of protein makes it easy to form hybrid nanoflower with metallic phosphate. The protein nanoflower provides high surface area for wastewater purification with the assistance of the metallic phosphate. Based on the structural properties of protein, this review summarizes the fabrication, formation mechanism and applications of above three nanomaterials in water pollution control, providing reference to the subsequent scientific study.

Contents

1 Introduction

2 Mussel-inspired dopamine coating and its application

2.1 Preparation and polymerization mechanism of dopamine

2.2 Modification and application of dopamine in environmental protection

3 The structure and environmental application of amyloid-fibrils

3.1 Physicochemical properties and fabrication of amyloid-fibrils

3.2 The environmental applications of amyloid-fibrils

4 Preparation and application of protein induced nanoflower

4.1 Formation and characterization of protein-nanoflower

4.2 Application of protein nanoflower in the field of environment protection

5 Conclusion and outlook

Graphical abstract

Keywords

nano-materials / dopamine / amyloid-fibrils / protein nanoflower / water pollution control

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Ximeng Cheng, Qingrui Zhang. Functional Protein Based Nanomaterials for Environmental Protection Application. Progress in Chemistry, 2021, 33(4): 678-688 DOI:10.7536/PC200695

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1 Introduction

Deep remediation and purification of water pollution is one of the difficulties in the field of environment. Among many treatment methods, adsorption is widely used because of its advantages of high efficiency and simplicity, in which the selection of adsorbent is particularly critical. In recent years, functional proteins as a new type of bio-based adsorption materials have attracted much attention. Protein is a kind of biomacromolecule with unique structure and rich function, which has the characteristics of abundant source, degradability and excellent environmental compatibility.The peptide chain/polypeptide formed by connecting amino acids through peptide bonds is the basic structural unit of a protein, and the peptide chain is folded into a protein molecule with a flexible three-dimensional space structure under the drive of non-covalent bonds[1]; Protein molecular chains are rich in amino, carboxyl and sulfhydryl groups, and their electrical properties can be adjusted. These abundant functional groups provide many sites for the chelation adsorption of metal ions and organic compounds[2,3]. In the past few decades, researchers have attached great importance to the application of new technologies to improve the structural characteristics of protein molecules. While improving and stabilizing the amino acid composition, they have further regulated the periodic arrangement of amino acid residues through metal coordination and chemical modification, thus modifying the functional characteristics of proteins[4]. In addition, protein molecules have diverse morphological structures and special biological activities, and are excellent templates for assisting the synthesis of biological nanocomposites with diverse functions and structures. Protein-based composites with many advantages are gradually emerging in the field of environmental remediation, especially in the field of water pollution control.
In the past five years, a large number of studies have been carried out around the characteristics of functional proteins and their environmental applications, the most representative of which is polydopamine (PDA), which is derived from the functional characteristics of mussel adhesion proteins.The unique catechol structure contributes to the construction of various adhesive functional coatings, facilitates the bonding of amino groups, mercapto groups and other active groups, and is used for the adsorption and degradation of heavy metals, organic dyes and other pollutants in water. In addition, beta-lactoglobulin (beta-LG), bovine serum albumin and the like can form ultra-high aspect ratio nanofibers through heat treatment, chemical denaturation and other ways, which is helpful to expose the structure of active amino acid groups.The deep purification of trace pollutants is further enhanced, and the three-dimensional structure of the protein is also convenient to chelate with the metal phosphate and guide the formation of a protein nanoflower structure, so that the efficient purification of pollutants in water is realized by cooperating with the metal phosphate and the protein active components. Based on the unique properties of protein, this paper reviews the structure, preparation process and application in environmental water treatment of three kinds of functional protein nanomaterials, including dopamine coating, protein starch fiber and protein guided nanoflower, in order to provide a theoretical basis and reference for related research.

2 Mussel-inspired dopamine coat and application thereof

Dopamine-like materials are a new class of functional protein materials, and their discovery stems from the strong adhesion of invertebrate mussels in humid seawater environment (Fig. 1). It was found that 3,4-Dihydroxyphenyl L-Alanine (DOPA), an amino acid with strong adhesion, existed in the byssus protein secreted by mussel, and DOPA and lysine residues in byssus protein were the main sources of mussel adhesion[5⇓~7]. In 2007, Messersmith et al. Found that the molecular structure of dopamine (DA), a neurotransmitter in the human body, is similar to that of DOPA. Under alkaline conditions, DA can oxidize and self-polymerize into a PDA coating with strong adhesion, and then functionalize the surface of membranes and other materials[8][9,10]. In addition, dopamine contains active groups such as catechol and amine, which can effectively remove heavy metal ions and various organic pollutants in polluted water[11,12].

2.1 Preparation and polymerization mechanism of dopamine

the polymerization process of dopamine is simple and the reaction conditions are mild.As a reaction monomer,the self-polymerization oxidation reaction can occur under alkaline conditions(pH>7.5)and In the presence of oxygen in the absence of light.in the polymerization process,the concentration of dopamine,deposition time and oxidant can affect the self-assembly behavior of dopamine[14]。 It was found that the deposition rate of polydopamine increased With the increase of the initial concentration of dopamine.with the increase of the initial concentration of dopamine and reaction temperature,the deposition rate of polydopamine film increased and the surface became rough[15,16]。 During the polymerization of dopamine,the thickness of the membrane was affected by the pH value.Under alkaline condition,the thickness of the membrane increases with the increase of pH value,and reaches the maximum at pH=8.5[17]。 oxidant is also a key factor In the polymerization of dopamine.Under normal conditions,oxygen can be used as Oxidant in the reaction.in addition to oxygen,ammonium persulfate,sodium periodate and metal ions are also used as oxidants to accelerate the polymerization of dopamine[18⇓~20]。 In 2017,Zhang et al.Reported the rapid deposition of polydopamine using CuSO4/H2O2as an oxidant.The PDA nanoparticles obtained were not easy to agglomerate and could be uniformly deposited into coatings with a thickness of only~75 nm for a long time[21]。 In addition,some studies have found that laccase can also be used as a biocatalyst to accelerate the oxidative polymerization of dopamine under weak acid conditions[22]。
the formation mechanism of PDA is complex,and there are many intermediates in the reaction process,so the polymerization mechanism and the exact molecular structure of dopamine are still uncertain.Some studies have shown that polydopamine formed in aqueous solution is very similar to the structure and synthesis pathway of eumelanin in vivo[23]。 As shown in fig.2,firstly,under the alkaline condition,DA undergoes an oxidation reaction,and the hydroxyl group in catechol is deprotonated to generate dopamine quinones,which undergo intramolecular cyclization,Michael addition reaction and oxidative rearrangement to generate an indole-type structure 5,6 dihydroxyindole(DHI),that DHI monome is further branched to form dim and oligomer isomers with higher degree of polymerization,and finally reacts with catechol and o-benzoquinone in a reverse direction to form PDA crosslink polymer。
in 2012,Bielawski et al.Proposed a new viewpoint on the formation process of dopamine through solid-state spectroscopy and crystallization technology.They believed that PDA is a crosslinked structure formed by monomers through strong non-covalent bond forces(including charge transfer,π-πstacking and hydrogen bonding),as shown In Figure 3.These non-covalent interactions make PDA highly stable and water-insoluble[18]。

2.2 Modification of Polydopamine and Its Application in Environmental Protection

Polydopamine has good stability and biocompatibility,and the abundant catechol,amine and aromatic groups in its structure can effectively remove target pollutants through electrostatic interaction,chelation,hydrogen bonding,π-πstacking and other effects[24,25]。 In addition,the use of dopamine to modify the surface of the material can reduce the secondary pollution to the environment,and the preparation process is green and simple,which provides a new idea for the preparation of environmentally friendly composites[26]。
Industrial wastewater contains a large number of heavy metal ions and organic dyes,which cause great harm to the environment[27,28]。 Dopamine functional materials are widely used in the field of environmental water treatment,ranging from simple PDA microspheres to various PDA coating modified composites.Farnad et al.First reported that PDA microspheres(PDA-MS)could be used as a highly selective adsorbent for the removal of copper ions from aqueous solutions[29]。 Zhang et al.Found that oxidatively self-polymerized PDA microspheres can rapidly remove Pb(Ⅱ)from water[30]。 the results of adsorption experiments show that PDA microspheres have high selectivity for Pb(II)in the presence of high concentrations of Ca(II)/Mg(II)/Na(I)(as shown in Figure 4),and can achieve rapid adsorption of Pb(II)within 1 min.The results of column adsorption experiments further verify that the actual water treatment capacity is about 200 times that of ordinary commercial ion exchange resins.Fu et al.Studied the adsorption of methylene blue(MB)on PDA microspheres[31]。 kinetic experiments showed that the adsorption of MB on PDA followed the pseudo-second-order Kinetic model,and the maximum adsorption capacity was 90.7 mg/G at 25℃.There is an electrostatic interaction between the cationic dye MB and the catechol adsorbed on the PDA microspheres,and theπ-πstacking interaction further enhances the adsorption effect.Wan et al.Used the strong adhesion of dopamine to modify the surface of electrospinning to obtain PDA-coated polyvinyl alcohol/polyacrylic acid membrane(PVA/PAA@PDA)[32]。 the composite material can adsorb 93%(50 mg/L)of methyl blue(MB)in solution within 30 min,and The maximum adsorption capacity reaches 1147.6 mg/G,which is much higher than that of unmodified PVA/PPA。
organic dyes,aromatic nitro compounds and other pollutants have the characteristics of high toxicity and difficult degradation,which seriously threaten aquatic organisms and human health.Among the existing water treatment technologies,catalytic method is one of the effective methods for decolorization and degradation of aromatic nitro compounds and Organic dye wastewater solution[33⇓~35]。 Wang et al.prepared a PDA-coated polyvinylidene fluoride(PVDF)membrane nanocomposite Au-TiO2-PDA-PVDF for the degradation of tetracycline under visible light irradiation.The study found that the dopamine coating could realize the in-situ reduction of complexed gold,and the formed composite membrane had a tetracycline degradation rate of 92%within 120 min.The degradation process followed first-order kinetics(Figure 5 )[36]。 The high photocatalytic activity and good reusability indicate that PDA can not only be used as a photosensitizer to improve the photocatalytic efficiency of the catalyst,but also be used as a bioadhesive interface to enhance the binding force between the catalyst and the membrane,thereby improving the stability of the catalyst.Tang Jing et al.Used dopamine to reduce Ag+on the surface of Fe3O4to obtain Fe3O4-PDA@Ag materials to degrade methyl orange dye[37]。 Under the same reaction conditions,the removal rate of Fe3O4-PDA@Ag microspheres was still more than 90%after six cycles 。
Therefore,dopamine can be self-assembled into a uniform and dense polydopamine coating under simple conditions,and the biomimetic modification of dopamine can be carried out without destroying the structure of the material itself.As an ideal surface cross-linking agent,dopamine has strong adhesion,unique structure and many functional groups(providing a large number of active sites),and has shown excellent performance in the deep removal and catalytic oxidation of many pollutants,such As heavy metal ions and organic dyes.As an important functional coating material,PDA has a broad application prospect in the purification of wastewater。

3 Structural and environmental applications of amyloid fibrosis

In recent years, amyloid-fibrils, as an environmentally friendly bio-nanotechnology, have attracted a large number of scholars to study in the field of environmental water treatment[38]. Early research on amyloid fibrils focused on Alzheimer's disease, Creutzfeldt-Jakob disease and other medical diseases, and its misfolding often led to tissue abnormalities[39⇓~41]. The protein amyloid fiber is a highly ordered protein self-assembly body, and amino acid groups on the surface of the protein amyloid fiber can effectively bind toxic heavy metal ions and other pollutants in water through stronger supramolecular metal-ligand interaction,Good biocompatibility and unique fibrous structure with ultra-high aspect ratio show great application potential in the field of water pollution control[42⇓~44].

3.1 Physicochemical properties and fibrosis process of protein amyloid fibrils

amyloid protein is a pair of closely linked and repeated cross-folded structures formed byβ-sheet structure,and protein monomers or polypeptide fragments can further form highly orderedβ-structure Amyloid fibers through hydrogen bonding stacking[45]。 Amyloid fibrils have a large specific surface area and an ultrahigh aspect ratio[46⇓~48]。 β-lactoglobulin(β-LG),lysozyme,bovine serum albumin,sericin and other proteins can be used to prepare amyloid fibrils.Takeβ-LG as an example:β-LG is the main component of whey protein in milk,accounting for about 50%of the total whey protein[49,50]。 β-LG contains 162 amino acid residues with molecular weight of 18.4 kDa and isoelectric point of 5.1~5.3.There are four cysteines on the surface of the fiber and two disulfide bonds in the molecule[51,52]。 β-LG generally exists in the form of dimer in solution.When there are a large number of protein aggregates in solution,the number ofβ-sheets increases,and the conformation of protein monomers rearranges accordingly,which accelerates the aggregation and precipitation of protein monomers,and then formsβ-lactoglobulin fibers[53,54]。
At present,there are two theories about the self-assembly process of protein fibrosis:one is that the use of denaturants such as guanidine hydrochloride can induce the partial unfolding of protein chain structure,theβ-sheet is rearranged to form fibers(path 1 in fig.6),and another theory is that high temperature conditions cause protein denaturation,and the hydrolyzed polypeptide fragments self-assemble to form fibers(path 2 in fig.6)[55⇓⇓⇓~59]。 Studies have also shown that the two theories can coexist in the fibrosis process of the same protein[60]。
the process of protein fibrosis is affected by many factors,such as The concentration of protein monomer,pH value of solution,temperature and salt ion concentration[61⇓~63]。 Most studies suggest that acidic conditions and low ion concentrations favor protein fibrosis.protein concentration and solvent quality have a great influence on the system's tropism(isotropic solution,fiberization or amorphous morphology),especially in the process of fiber formation at high temperature,there is a clear correlation between protein concentration and the formation rate of fiber morphology[64⇓~66]。 It is also believed that the aggregation ofβ-LG at pH=2,80℃and low ionic strength is a linear process and can be completed in multiple steps[67]。 In addition,The degree of conversion of protein to fiber varies with the time of high temperature heat treatment,as shown In fig.7.In addition to the above factors,some physical effects can also affect the fiber formation process,such as increasing the interfacial shear rate can increase the number of fiber nuclei,increasing the hydrophobicity and roughness of the material surface can also promote the growth of fibers.Starch fiber structure has ultra-high aspect ratio,which can significantly enhance the exposure sites of protein amino acid structure,and is likely to improve its functionalization efficiency.the following will systematically elaborate its environmental application performance[68,69]。

3.2 Application of starch-based fiber materials in environmental protection

Amyloid fibrils are a kind of stable protein structures.Their unique one-dimensional linear morphology,good biocompatibility and multi-level scale structure have made them have excellent properties in chemical modification.the abundant charged amino acid groups on its surface have also made great progress in The binding of metal ions,adsorption of organic pollutants and catalytic degradation[71,72]。 Bolisetty et al.Usedβ-lactoglobulin fiber and activated carbon to prepare a composite membrane with high mechanical strength for removing heavy metal ions in wastewater[73]。 They explored the removal performance of the composite membrane for Pb2+,Hg2+,Pd2+and Au2+,and the results showed that the removal efficiency of the four heavy metals was higher than 99%(Figure 8),and the amyloid fibers in the composite membrane could reduce the adsorbed gold ions to gold nanoparticles by heating or chemical reduction,which also made it possible to recycle precious metal ions.Zhang et al.prepared zirconium-based amylaceous fibrous membrane for fluoride removal and used the material for multiple filtration cycles of actual tap water and acidic wastewater,with the maximum adsorption capacity of 21.8 mg/G[74]。 XPS results showed that there was a strong interaction between the zirconium-based fiber membrane and the F-,and the specific surface area increased after the incorporation of ZrO2less than 10 nm,which further enhanced the adsorption performance of the composite membrane.Reinhold et al used amyloid fibrous carbon membrane to adsorb arsenate(+5)and arsenite(+3)in water,and the removal efficiency could reach 99%[75]。 Amyloid fibrils have a variety of binding residues,which can strongly adsorb arsenic ions through metal-ligand interactions and improve the utilization efficiency of active groups.Morshedi et al.explored the removal of azo dyes by lysozyme fibers[76]。 It was found that the adsorption capacity of enzyme fiber was much higher than that of activated carbon(11 6%~20 0%).There was no difference in cell activity when the cells were cultured with the adsorbed solution,which further verified the good adsorption performance of the enzyme fiber。
in addition,amyloid fibers can catalyze the conversion of organic dyes and aromatic compounds in water by binding metal particles.Huang et al.reduced and deposited metal Cu/Au/Ag nanoparticles on theβ-lactoglobulin fiber membrane in situ by filtration deposition method,and the membrane catalytic reactor Cu-Ag-Au@β-LGF CMR prepared could continuously catalyze the reduction of 4-nitrophenol(4-NP),as shown in Figure 9[77]。
It was found that the catalytic behavior was in accordance with the first-order kinetic model,and the catalytic rate constants were higher than those of Ag and Au nanoparticles alone,and the activity was still higher than 97%after 8 cycles of continuous catalysis.Bolisetty et al.reduced Au2+and Pd2+into nanoparticles loaded on the outer surface of amyloid fibers by means of charged amino acid groups on the surface of amyloid fibers to obtainβ-LG-Au andβ-LG-Pd,respectively[78]。 the two composite fibers can rapidly reduce 4-nitrophenol to 4-aminophenol,and the reduction rate is 1.2 times that of the metal nanoparticles alone.Feng et al.Studied the catalytic performance of amyloid fibers loaded with gold nanoparticles of different sizes for 4-nitrophenol[79]。 It was found that the activation energy was decreased and the reaction rate was increased by decreasing the size of gold nanoparticles。
the highly ordered self-assembled fiber has high thermal stability and good surface activity,and the amino acid side chain on the surface of the amyloid fiber has many potential applications in the aspect of application design chemical reaction,and more protein fiber structures with various functions and excellent performances can be obtained after further grafting modification of the amino acid R group;as a biomacromolecule,its excellent compatibility also provides a material basis for its compounding with various nanomaterials.in order to realize the practical application of these materials in environmental water treatment as soon as possible,more properties and composite materials still need to be broadened and explored。

4 Preparation and Environmental Application of Protein-guided Nanoflower Material

Biomimetic nanoflower materials with unique morphologies have always been the research focus of researchers at home and abroad. In recent years, hybrid nanoflower materials induced by protein three-dimensional structure have attracted wide attention because they have both the excellent physical and chemical properties of organic substances and the stability of inorganic substances[80⇓~82]. Nano-flower-like materials have multi-level structural conformation, large specific surface area and high porosity, and there are a considerable number of active sites on the surface, which endow hybrid nano-flower materials with excellent adsorption performance, so they are often used as adsorption materials to remove heavy metals, arsenic and other pollutants in water. At the same time, protein molecules carry abundant functional groups, and the unique amino (—NH2) and hydroxyl (-OH) in the structure further improve the activity of the material, which can effectively realize the catalytic oxidation of organic pollutants and show great application prospects in the remediation and treatment of water pollution.

4.1 Preparation and Characterization of Protein-Inorganic Hybrid Nanoflower

The preparation technology of nanoflowers has been relatively mature as early as The research stage of inorganic nanoflowers.The commonly used preparation methods of inorganic nanoflowers include vapor deposition,hydrothermal method,sol-gel method,precipitation method and so on[83]。 These methods mainly focus on the redox of metal elements In inorganic nanoflowers and the thermal decomposition of unstable components,and the whole reaction needs to be carried out at high temperature,high pressure and in some organic solvents.in order to avoid the uncontrolled growth of inorganic nanoflowers under such complex conditions,some special measures need to be taken to control the morphology of inorganic nanoflowers[84,85]。 Unlike the preparation of inorganic nanoflowers,the growth of protein-guided hybrid nanoflowers is a self-assembly process,which is simple to operate,does not require harsh experimental conditions and is pollution-free to the environment.The self-assembly method mainly utilizes protein substances such as bovine serum albumin(BSA),laccase,trypsin,catalase and the like to spontaneously combine with metal ions(Cu2+,Ca2+,Zn2+and Co2+)through non-covalent bonds to form complexes,The protein is integrated into the inorganic nano-flower structure as a functional construction unit while retaining the original biological activity,and the crystal growth is regulated to form a multi-level flower-like structure with good morphological characteristics by inducing the formation of nucleation sites of the crystal[86⇓~88]。 The self-assembly method has many advantages,so it has been adopted by many researchers。
the growth process of nanoflowers can be simply divided into three stages:the first stage is the growth of the original crystal nucleus,in which the amino and carboxyl functional groups on the surface of proteins complex with metal ions to form complexes,providing nucleation sites for the formation of crystals[89]; the second stage is the formation of independent"petals",in which the metal-protein complexes continue to agglomerate into polymers,and the"petals"are forced to appear by the dynamic control of surface crystal growth.the last stage is the nanoflower formation stage,because of anisotropy,"petals"overlap each other and adhere from inside to outside to form a nanoflower shape.During the formation of nanoflowers,there are binding sites in all directions,so the bending orientation of nanosheets is random.Some scholars have proposed that Van der Waals force,dipole force,electrostatic attraction,repulsive force,entropy effect and anisotropic polarizability are all important factors for the formation of flower-like morphology in all stages of protein nanoflower growth[90,91]。
the formation of nanoflowers will vary depending on the reaction conditions,including the concentration,type,and temperature of the protein.Many researchers have carried out related research work and found that no flower structure was formed without protease.When the concentration of protease is gradually increased,the nanoflower structure begins to appear,but interestingly,the morphological change of nanoflower is contrary to the process of flower from bud to bloom in nature:the diameter of nanoflower is gradually reduced from large to small,and the overall structure will gradually shrink[92]。
Further investigation shows that the increase of protease concentration accelerates the nucleation of crystals,which inhibits the growth of nanoflowers,reduces the diameter of nanoflowers,and makes the"flower"more compact(Fig.10)。
in the preparation process of nanoflowers,different kinds of proteins were added,and the morphology of nanoflowers was also different.Fig.11 is a scanning electron microscope image of nanoflowers respectively prepared with papain,laccase,and horseradish peroxidase(HRP)as substrates.the difference in the morphology of nanoflowers in the figure is mainly due to the difference in the structure of the added enzyme protein itself.the histidine,cysteine and methionine residues in the enzyme protein molecule will control the coordination of the protein with metal ions,and directly affect the structure and morphology of the nanoflowers[93]。 in addition,temperature is also a key factor In the formation process of nanoflowers:when the temperature is less than 4℃,the flower shape of nanoflowers is richer and the petals are larger,while when the temperature is more than 37℃,the petals tend to be compact[94]。

4.2 Application of Protein Hybrid Nanoflower Materials in Environmental Field

the three-dimensional protein hybrid nano-flower has unique shape and large specific surface area,and the structure contains a large number of active sites which can effectively chelate heavy metal ions.Moreover,the abundant charged amino acid residues can rapidly bind heavy metal ions in water through electrostatic interaction,so the protein hybrid nanoflowers can be used as an important metal adsorption material in the purification of polluted water.Zhang et al.Synthesized bovine serum albumin-Cu(Ⅱ)hybrid nanoflowers(BSA-Cu(Ⅱ)NFs)for solid phase extraction(SPE)of Cd(II)and Pb(II)in water,food,cigarette and hair samples[96]。 The limit of detection(LODs)of Cd(Ⅱ)and Pb(Ⅱ)were reduced to 0.37 mg/L and 8.8 mg/L,respectively,by optimizing the experimental conditions,and the risk of nebulizer clogging in the solid phase extraction process was also reduced by the nanoscale ultrafine particle size of bovine serum albumin-Cu(Ⅱ)hybrid nanoflowers.Cd(Ⅱ)and Pb(Ⅱ)in the solution can interact with amino acid residues in the nanoflower structure through electrostatic interaction,and can also be complexed with carboxyl groups and imidazole derivatives in proteins,thus greatly improving the adsorption performance.Koley et al.Synthesized three kinds of sericin hybrid nanoflowers in CuSO4-PBS solution with sericin as the organic component to remove Pb(Ⅱ)from water[97]。 Kinetic experiments show that the rapid adsorption process can be completed within 15 min,and the adsorption equilibrium can be reached within 1 H,with a removal rate of 99.8%(Figure 12).The high removal efficiency is closely related to the unique structure of the nanoflowers.Stacking of the nanoflower petals increases the surface porosity,and the dense and compact arrangement greatly increases the specific surface area.In addition,the electronegativity and ionic radius of Pb(Ⅱ)enhance the electrostatic interaction between the sericin-mediated hierarchical porous structure of copper phosphate,and the adsorption effect is greatly enhanced.Li et al.Synthesized red blood cell-like bovine serum albumin hybrid nanoflower BSA/Zn3(PO4)2by a simple coprecipitation method[98]。 The hybrid BSA/Zn3(PO4)2can adsorb Cu(Ⅱ)in solution repeatedly,and the removal rate of Cu(Ⅱ)can still reach 93.9%after 6 cycles of continuous adsorption,which has high reusability 。
enzymatic technology is often used to catalyze the degradation of organic pollutants in environmental water treatment processes,and the key of Enzymatic technology is to improve the activity of enzymes.Generally speaking,free enzymes have low toxicity and strong substrate specificity,but the molecular structure of free enzymes is not resistant to high temperature and difficult to separate,so the immobilization of free enzymes can make up for the shortcomings of poor stability and easy inactivation of free enzymes in solution[99,100]。 The three-dimensional nanoflower structure is often used for immobilizing a protease,and the enzyme exists in the nanoflower as an organic component and can still maintain high activity and stability,so that the enzyme catalytic performance can be improved by immobilizing the protease as a cofactor in the nanoflower structure,and efficient catalytic degradation[101~103]of organic pollutants can be realized.Li et al.Synthesized two kinds of enzyme-inorganic hybrid nanoflowers with lipase and papain as organic components and Cu3(PO4)2·3H2O as inorganic components to catalyze the degradation of p-nitrophenyl palmitate[104]。 After immobilization,the activity of the immobilized enzyme was significantly improved:the activity of lipase-inorganic nanoflowers for the catalysis of p-nitrophenyl palmitate was up to~878%,and that of papain-inorganic nanoflowers was even up to~7260%.Zhang et al.prepared lipase-Zn3(PO4)2hybrid nanoflowers in one step by classical co-precipitation method,as shown in fig.13[105]。 The hydrolysis of disodium p-nitrophenylphosphate(p-NPP)was used as a model reaction and the optimal reaction conditions were determined.The results showed that the hydrolysis activity of lipase-Zn3(PO4)2nanoflowers for p-NPP reached(855±13)U/G at pH=7.6 and 43℃,which was 147%of that of free enzyme.The lipase-Zn3(PO4)2nanoflowers have a larger surface area,which alleviates the mass transfer limitation,and the synergistic effect of the nanoscale three-dimensional structure and the metal Zn2+improves the activity of the immobilized lipase.He et al.Immobilized horseradish catalase(HRP)on the surface of copper phosphate crystals to obtain HRP-Cu3(PO4)2hybrid nanoflowers[106]。 The results of UV-Vis absorption spectrum showed that the HRP-Cu3(PO4)2hybrid nanoflowers had a good catalytic effect on tetramethylbenzidine(TMB),and the catalytic activity was increased by 30%compared with the free HRP enzyme,and the catalytic effect could still reach 85%after a week of storage 。
The protein-inorganic salt hybrid nanoflower with high bioactivity can also be used for detecting other bioactive substances in the environment.He et al.Constructed novel electrochemical nucleic acid aptamer sensors Co3(PO4)2@BSA and Co3(PO4)2@Apt aptamer sensors for the detection of platelet-derived growth factor PDGF-BB[107]。 Electrochemical impedance spectroscopy(Eis)results showed that the lowest detection limit of the sensor was 3.7 pg/mL,which was much lower than that of all previously reported aptamer sensors.Altinkaynak et al.Used LPO-Cu3(PO4)2hybrid nanoflowers prepared by lactocatalase(LPO)purified from milk and PBS solution as nanoprobes to detect dopamine and epinephrine[108]。 The results showed that the catalytic activity of the LPO-Cu3(PO4)2for DA and EP could be increased to 340%and 500%within 30 min,and the activity could still reach 60%or more of the initial activity after 6 cycles.In addition,Gutierrez et al used nanoflower structure to inactivate some pathogens[109]。 At room temperature,the brass sheet containing 87%of copper can kill 80%of Gram-negative Escherichia coli and Gram-positive Staphylococcus epidermidis,and when the copper content is increased to 91.7%,the biocidal effect is also increased by 10%to 15%,thereby providing an environment-friendly and non-toxic antibacterial method for production and life。
protein-inorganic hybrid nanoflowers are gorgeous,but they are not flashy.high porosity,high specific surface area and high bioactivity stability endow nanoflowers with potential practical application value.As an organic-inorganic hybrid material,it has both the activity of organic Protein component and the stability of inorganic nanoparticle component,and its excellent physical and chemical properties provide unlimited possibilities for the preparation and application of biomimetic multilayer structure materials。

5 Conclusion and prospect

The polydopamine, the amyloid fiber and the protein inorganic hybrid nano-flower are all composite functional protein composite materials formed by utilizing the self-assembly characteristic under certain conditions,Three types of functional protein materials make use of the characteristics of supramolecular structure, and realize the functional diversification of materials through metal coordination, chemical modification and synthesis of inorganic nanoparticles. In the field of water treatment, three kinds of functional protein materials improve the selectivity of pollutants by adjusting the interaction between themselves and pollutants, and show good removal performance for pollutants such as heavy metal ions and organic dyes.And the preparation process and the pollutant removal process do not cause secondary pollution to the environment, thereby providing a new way for the preparation and practical application of environment-friendly biomaterials in the future.
There are many examples to prove the superiority of functional protein materials in the field of environmental remediation, but there are still many limitations in the further application of functional protein composites: (1) Although a large number of studies have focused on the polymerization process of dopamine, the precise structure and intermediate products of PDA are still uncertain; The deposition process and mechanism of dopamine monomer with the help of oxidants under acidic conditions are still unclear. These aspects need to be further studied in order to promote the structural characteristics of dopamine at the molecular scale and provide theoretical support for more precise control of dopamine deposition and coating technology. (2) The formation mechanism of amyloid fibrils has been studied to a certain extent, but the formation process of amyloid fibrils is complex, and the composition, structure, size and interface properties of the products in each growth stage are still unclear; The amyloid protein is connected by a dense hydrogen bond network and is vertically arranged on the fiber axis, and the fiber structure can provide certain wet adhesion resistance, thereby providing reference for the development of a new generation of bioactive adhesives, the design of biomimetic materials and the improvement of performance; (3) The preparation of protein hybrid nanoflowers provides a general method to encapsulate bioactive organics in a protective inorganic framework, but the current synthesis of layered composite materials is mostly constructed by layering nanoscale components into microscale, and it is still a major challenge to accurately control the materials at the nanoscale; In addition, the synergistic interaction between protein molecules and metal phosphate crystals plays a key role in the functional properties of hybrid materials, but the mechanism of interaction between them still needs to be further explored.
In terms of practical application, three kinds of functional protein materials are facing the same problem to some extent, that is, whether they can be prepared on a large scale by simple, low-cost and environmentally friendly methods, which is a prerequisite for industrial production and application, and also a key issue in the field of environmental remediation. It is believed that through the continuous efforts of scientists to explore, in the near future, there will be more excellent materials with more powerful functions applied in many fields.

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Funding

the National Natural Science Foundation of China(21876145)

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