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Self-assembled biomolecular soft materials and their physical properties

Han Xu Xue Bin Cao Yi Wang Wei

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Self-assembled biomolecular soft materials and their physical properties

Han Xu, Xue Bin, Cao Yi, Wang Wei
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  • Self-assembling biomolecular soft materials are a novel type of soft matter formed through the self-assembly process by using biomolecules or biomolecular building blocks. The characteristics of bio-sourced origin and assembly driven by weak interactions endow these materials with advantages such as high biocompatibility, reversible assembly, dynamic responsiveness, and controllable microstructures. These properties offer immense potential for development in fields such as biomedicine, tissue engineering, and flexible sensing. This paper concisely reviews the fundamental construction principles of self-assembling biomolecular soft materials and discusses three categories, i.e. nanomaterials, gel materials, and composite materials, by using amino acids and peptides as examples of assembly units. The specific self-assembly molecular mechanisms, material construction strategies, and functional application scenarios of these materials are elucidated. We anticipate that the research on self-assembling soft matter biomolecular materials will evolve from exploring structural units and measuring properties to customizing multifunctional properties and integrating advanced applications. This will lead to the development of novel composite intelligent biomolecular soft matter materials, and further promoting their applications in biomedicine, organic semiconductors, and soft robotics.
      Corresponding author: Wang Wei, wangwei@nju.edu.cn
    • Funds: Project supported by the the National Natural Science Foundation of China (Grant Nos. 11934008, T2225016, T2322010) and the National Key Research and Development Program of China (Grant No. 2020YFA0908100).
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  • 图 1  基于氨基酸分子的自组织生物分子软物质纳米材料的力学性质受堆叠方式、氢键和手性影响 (a) 苯丙氨酸(L-Phenylalanine, L-Phe)、酪氨酸(L-Tyrosine, L-Tyr)和多巴(L-DOPE)的化学结构和晶体结构和堆叠方式[43]; (b) 缬氨酸(Valine, Val)、亮氨酸(Leucine, Leu)和甲硫氨酸(Leucine, Met)的化学结构、扫描电子显微镜(scanning electron microscope, SEM)照片(上), 原子力显微镜(atomic force microscope, AFM)测定的杨氏模量(中)以及Leu和Met分别的介电常数和压电常数(下)[46]; (c) 调控1, 2-二(4-吡啶基)乙烯(1, 2-bis(4-pyridyl)ethylene, BPE)和不同手性的乙酰化丙氨酸(acetylated alanine, AcA)的晶体组装模式以制备宏观物理性质可调的晶体材料示意图[47]

    Figure 1.  The physical and mechanical properties of self-assembling biomolecular soft matter nanomaterials based on amino acids are affected by stacking mode, hydrogen bonding and chirality: (a) Chemical structures, crystal structures and packing of phenylalanine (L-Phe), tyrosine (L-Tyr) and dopa (L-DOPE)[43]; (b) chemical structures, scanning electron microscope (SEM) images (top) and Young’s modulus (middle) measured by atomic force microscope (AFM) of valine (Val), leucine (Leu), and methionine (Met); the calculated dielectric constants and piezoelectric constants of Leu and Met (bottom)[46]; (c) schematic diagram of regulating the crystal assembling models of 1, 2-bis(4-pyridyl)ethylene (BPE) and different chirality of acetylated alanine (either L-AcA or D-AcA) to prepare crystal materials with macroscopic tunable physical properties[47].

    图 2  引入不同改性组件的自组织生物分子软物质纳米材料 (a) MCpP-FF纳米纤维在甲苯蒸发后聚集成的多空微球示意图及纳米微球的SEM照片[52]; (b) 二肽核酸自组装形成的超螺旋构象组成超分子框架的示意图和 SEM照片[53]; (c) 牛磺酸、ACES及CHES的化学结构(上)和超分子堆积示意图(下)[54]; (d) 含多苯环结构的短肽晶体的荧光照片(上), 热重分析和力学强度(下)[55]

    Figure 2.  Self-assembling biomolecular soft nanomaterials with different modified component: (a) Schematic diagram and SEM image of MCpP-FF nanofibers aggregated into porous microspheres after toluene evaporation[52]; (b) illustration and SEM image of supramolecular framework composed of the superhelix conformation formed by the self-assembly of dipeptide nucleic acid[53]; (c) chemical structures (top) and supramolecular packing diagram (bottom) of taurine, ACES and CHES[54]; (d) fluorescence images of short peptide crystals with polyphenyl structures (top), thermogravimetric analysis, and mechanical strength (bottom)[55].

    图 3  基于短肽及其衍生物的自组织生物分子软物质纳米材料应用开发 (a) 基于Fmoc-G-PNA缀合物的人工光合作用集成系统示意图[29]; (b) 含多巴的纳米纤维在pH调控下的细胞捕获和释放示意图(上)和光学照片(下)[59]; (c) 模仿抗冻蛋白结构的含苏氨酸的自组装多肽示意图(左上)、三种抑制肽的化学结构(左下)和随多肽浓度和过冷温度变化的冰晶生长速率(右)[60]

    Figure 3.  Applications of self-assembling biomolecular soft nanomaterials based on short peptides and their derivatives assemblies: (a) Schematic diagram of an integrated artificial photosynthesis system based on Fmoc-G-PNA conjugate[29]; (b) schematic diagram (top) and optical images (bottom) of cell capture and release of nanofibers containing Dopa under pH regulation[59]; (c) schematic diagram of threonine-containing self-assembling peptide mimicking the structure of antifreeze protein (upper left). Chemical structure of three peptides (lower left) and growth rate of ice crystals under different peptide concentration and supercooling temperature (right)[60].

    图 4  基于多肽及其衍生物的自组织生物分子水凝胶 (a) 钌络合物催化酪氨酸残基二聚的光交联方法增强凝胶机械稳定性示意图[64]; (b) 基于Dronpa145N的光响应水凝胶成胶原理示意图[66]; (c) 基于含多巴短肽可逆电氧化还原性质的超分子多肽水凝胶致动器设计(上)、电响应性质(中)和药物释放应用(下)[31]

    Figure 4.  Self-assembling biomolecular hydrogels based on peptides and their derivatives assemblies: (a) Schematic diagram of enhancing mechanical stability of hydrogel by photo-cross-linking strategy of tyrosine dimerization catalyzed by ruthenium complex[64]; (b) schematic diagram of photo-responsive hydrogels formation based on Dronpa145N[66]; (c) design (top), electro-response properties (middle), and drug release applications (bottom) of a supramolecular peptide hydrogel actuator based on the reversible electrochemical redox properties of dopa-containing short peptides[31].

    图 5  通过构建双网络或引入固体纳米材料构建自组织生物分子软物质复合材料 (a) 含自组装纳米纤维或纳米带的聚合物-超分子双网络水凝胶示意图[71]; (b) 石墨烯复合水凝胶的成胶原理示意图(上), 制备过程展示(左下)以及可注射性质展示(右下)[73]; (c) 传统“三明治”式凝胶和多肽包覆的石墨烯水凝胶的结构和等效电路示意图(上)、应变响应电容传感(中)和3D打印特性(下)[32]

    Figure 5.  Fabricating self-assembling biomolecular soft matter composite materials by constructing double networks or introducing solid nanomaterials: (a) Schematic diagram of polymer-supramolecular double network hydrogels containing self-assembled nanofibers or nanoribbons[71]; (b) schematic diagram of the gelation principle (top) and preparation process demonstration (lower left) of graphene hybrid hydrogel, as well as demonstration of its injectability (lower right)[73]; (c) structural and equivalent circuit diagram of traditional “sandwich” gel and peptide-coated graphene hydrogel (top), strain-responsive capacitance sensing (middle), and 3D printing characteristics (bottom)[32].

    图 6  通过生物分子离子螯合构建自组织生物分子软物质复合材料 (a) 单结合位点的单配体和多配体金属离子配位, 以及双结合位点的多配体金属离子配位的分子机制和状态模型示意图[76]; (b) 体内肿瘤或皮下注射(SC)水凝胶和钆离子溶液的随时间推移的磁共振成像照片[77]; (c) 具有分级结构的强韧水凝胶构建示意图. 与传统含物理交联点的双网络水凝胶(左上)相比, 该水凝胶自组装多肽-配位铜离子-隐藏柔性链聚合物的分级结构既耗散能量又提升机械强度[78]

    Figure 6.  Fabricating self-assembling biomolecular soft matter composite materials through biomolecular-ion chelation: (a) Schematic diagram of molecular mechanism and state model of single ligand and multiple-ligand metal ion coordination with single binding sites and tandem multiple-ligand coordination with double binding sites[76]; (b) magnetic resonance imaging images over time of intratumor or subcutaneous injection (SC) by hydrogels or gadolinium ion solutions[77]; (c) schematic diagram of strong, tough hydrogel with hierarchical structure. Compared with traditional double network hydrogel by physical crosslinking (upper left), this hydrogel’s hierarchical structure of self-assembling peptide-coordination copper ion-hidden flexible polymer both dissipates energy and improves mechanical strength[78].

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Publishing process
  • Received Date:  09 July 2024
  • Accepted Date:  01 August 2024
  • Available Online:  14 August 2024
  • Published Online:  05 September 2024

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