Synthesis Of Aromatic Rotaxanes Based On Column[5] And Application Of Supramolecular Self-assembly Functional Materials

As the fifth generation macrocyclic main compound,the symmetric rigid electron rich cavity of column aromatic hydrocarbons is more conducive to the construction and development of various mechanical interlocking molecules and new nanomaterials based on host-guest properties.This kind of mechanical interlocking molecules and nanomaterials are widely used in molecular recognition and assembly,materials science and tumor biotherapy and other fields,and show a wide range of application prospects,and therefore get more rapid development.In this paper,several novel compounds of quasi-[1]rotaxane,[1]rotaxane and bi-[l]rotaxane based on column[5]aromatics were designed and synthesized,and their applications in molecular machines and sensors were explored.At the same time,two kinds of supramolecular nanomaterials were designed and synthesized based on the host-guest interaction of column aromatics and cations,and their applications in molecular recognition and tumor therapy were explored respectively.The main research contents are as follows:1.A series of amide quasi[1]rotaxane compounds were synthesized by amidation of mono-substituted column[5]aromatics with 1,8-diaminooctane and 1,10-diaminodecane.Then different groups were used to seal the formed quasi[1]rotaxane compounds and finally a series of[1]rotaxane compounds were synthesized.A series of quasi-[1]rotane and[1]rotane compounds were characterized by nuclear magnetic resonance(NMR),infrared spectrophotometer(IR),high resolution mass spectrometry(HRMS)and X-ray single crystal diffraction.It was found that diamino-octane and diamino-decane units could pass through the columnar aromatic cavity smoothly if they were long enough.And form stable quasi[1]rotane compounds,and at the same time with different groups can be stopped to form stable[1]rotane compounds.In addition,2D NOESY,NMR titration and other methods were used to explore the influence of different solvents on the series of rotaxane compounds[1],and it was found that the methylene branch chains in the column aromatics cavity can carry out a certain degree of expansion and movement in different solvents.This greatly enriches the diversity of mechanical interlocking molecules of column aromatics.2.A series of bis-[1]rotanes were synthesized by the reaction of[1]rotanes compound based on column[5]arene with Cu2+,Zn2+,Pd2+,Mn2+,Ni2+and other five metal ions.By means of nuclear magnetic resonance(NMR),infrared spectrophotometer(IR),solid state fluorescence and X-ray photoelectron spectroscopy(XPS),a series of synthesized metal complexes of di-[1]rotane were characterized.The results showed that these metal complexes could specifically recognize Zn2+,which greatly enhanced the fluorescence of di[1]rotane.We studied the fluorescence quantum yield,and the fluorescence quantum yield increased from 1.28%to 24.8%.In addition,the obtained bi-[1]rotane metal complexes were characterized by ultraviolet spectrophotometer(UV-vis)and fluorescence spectrophotometer.The results showed that the fluorescence intensity of the metal complexes was quenched-to different degrees when different proportions of water were added to the DMF solution.Thus,column[5]aromatics with controllable luminescence characteristics are obtained,which provides a new idea for the development of novel high performance supramolecular material sensors.3.Based on water-soluble column[5]aromatic hydrocarbon(WP5)and porphyrin guest cation(Por)host guest interaction to construct a water soluble column[5]aromatic hydrocarbon[3]rotanes with fluorescence enhancement properties for photodynamic(type I and type II)tumor therapy system.On the one hand,the nanomaterials can protect porphyrin guest molecules through the columnar aromatic cavity,inhibit π-π stacking between porphyrin molecules and enhance their fluorescence intensity,effectively improve the photostability of porphyrin guest molecules,which makes a breakthrough in near infrared fluorescence imaging.On the other hand,porphyrin guest molecules in the nanomaterial can produce reactive oxygen species and perform photodynamic therapy on tumors under the irradiation of 660nm laser due to its unique light capture ability.Studies have shown that WP5/Por can not only effectively improve the properties of poor photostability of porphyrins,but also combine targeted photodynamic therapy,greatly improve bioavailability,and show a good therapeutic effect in anti-tumor therapy.4.Based on column[5]arene(PeP5)and porphyrin object cation(PF6Por)subject role with sunlight(PTT)and optical power(PDT)collaborative treatment system of supramolecular nanoscale diagnosis and treatment.After the nanomaterials introduce porphyrin guest molecules into column aromatics,porphyrin molecules can effectively improve their photostability and other shortcomings due to the excellent host guest chemical properties and rigid hydrophobic cavities of column aromatics,which can release reactive oxygen species more effectively and greatly improve the bioavailability.At the same time,porphyrin guest molecules with PTT columnar aromatics and PDT effects were used to form vesicles through the host-guest interaction.Under the irradiation of 808nm laser,PeP5/PF6Por could convert light energy into heat energy and produce reactive oxygen species for photothermal and photodynamic treatment of tumor cells.Studies have shown that PeP5/PF6Por has good biotoxicity to human cervical cancer cells(HeLa cells),realizing the application of photothermal and photodynamic synergistic therapy in anti-tumor,and showing good therapeutic effect.