Amino Acid/Short Peptide Based Self-assembly System

In this work,based on amino acid and short peptide derivatives,the new self-assembling molecules were designed and synthesized:ferrocene-amino acids/short peptide derivatives,and porphyrin-amino acids,and then designed the self-assembly and co-assembly system.Inspired by nature,we proposed photo-induced polymerization and self-assembly,achieving the reconfigurable assembly.Moreover,based on the structure and functions of molecules,the assembled nanostructures were applied in biomineralization,mimic enzyme,chiral catalysis and chiral resolution.(1)A new self-assembling animo acid derivative was synthesized.Under UV light irradiation,the ferrocene-tyrosine(Fc-Y)molecules could be oxidized,and crosslinked into the polymers.The change of molecular structure induced the reconfigurable self-assembly.Under UV light irradiation,the Fc-Y nanospheres would transform into hollow nanovesicles with a nanopieces folded surface.On account of the reducibility of Fc-Y,the AuNPs could be biomineralized on the surface of nanovesicles,achieving the AuNPs@Fc-W nanostructures,and exhibiting the mimic enzyme property.What's more,the Fc-Y self-assembled nanostructures could be used in energy storage to prepare biocapacitor.(2)The co-assembled mimic enzyme system was constructed based on Fc-Y molecules.The GOx/AuNPs and hemin were introduced into the co-assembly system.Under different light conditions,the components could co-assemble into nanospheres,surface folded nanoparticles,AuNPs@nanospheres,and AuNPs@truncated polyhedrons.The diverse nanostructures could be used to catalyze cascade reaction,exhibitng the high stability and catalytic activity.(3)A new self-assembling animo acid derivative was synthesized.Ferrocene-tryptophan(Fc-W)molecules can self-assemble into 3D microflowers with multi-layers stacked structures.Then the AuNPs can biomineralize on the surface of microflowers,achieving the AuNPs@Fc-W superstructure.The Au-amino acid superstructures exhibited the photothermal effect and catalytic activity,with a great potential to apply in phtothermal therapy.(4)A new self-assembling animo acid derivative was synthesized.The Fc-CO-NH-P molecules could self-assemble into different nanostructures,such as nanospheres,sheets,nanoflowers,and pieces.The self-assembled nanoflowers had a large specific surface area,and the catalytic active sites could be fully exposed.Moreover,the catalytic active sites could align as a chiral configuration.These merits made the Fc-CO-NH-P nanoflowers were efficient in the chiral aldo reaction catalysis,exhibiting the high yield(>99%)and ee%(>99%).What's more,the nanoflowers were a kind of universal supramolecular catalyst,showing a superior catalytic performance towards aromatic aldehydes.(5)A kind of self-assembling amphiphilic tripeptides were synthesized.At the aqueous/organic interface,the ferrocene-tripeptides could self-assemble into uniform and stable nanospheres.By tailoring the aqueous/organic volume ratio,temperature,and the sequence of amino acid,the size distribution and phase of emulsion could be precisely manipulated.Below the room temperature,the entropy-induced phase transition was occurred in Fc-FFH nanoemulsions,and the nanoemulsions could transform into hydrogels.What's more,the Fc-FFH nanoemulsions can exhibite the redox-active and mimic enzyme properties.(6)Self-assembling animo acid derivatives,TCCP-F₄ and TCPP-W₄ were synthesized.TCCP-_L-F₄and TCCP-_D-F₄could self-assemble into nanohelix with left and right handedness,respectively.Through regulating solvent,solvent volume ratio,p H,and temperature,the diameter and pitch of nanohelix could be precisely controlled.Moreover,by changing the sequence of amino acid,the handedness of nanohelix could be reversed.TCCP-_L-W₄and TCCP-_D-W₄can self-assemble into nanohelix with right and left handedness,respectively.What's more,the TCCP-F₄nanohelix can be used in the chiral resolution of racemix compounds.