| Hierarchial self-assembly is the basic strategy of constructing life,and the development of artificial multi-level self-assembly strategies is important for in-depth understanding and accurate simulation of biological functions and biological processes,but also provides reliable ways to build advanced functional materials.Hierarchical self-assembling of polymers is an important method of being equipped into primary micelles in a primary micelle,as well as complex and highly accurate hierarchial assemblies.The surface chemical nature of the anisotropic patch micelle is an important primary micelle that can be embodied in ordered hierarchial assemblies.During hierarchial self-assembly,the last level of sub-process leads the next level of self-assembly;therefore,the preparation structure is clear and the native patch micelle is a key to obtain an orderly hierarchial assembly.The block sequence controllable copolymer provides a solution in the self-assembly of the solution to construct the patch micelle.In recent years,a large number of studies have been devoted to the preparation of"valence"multi-compartment micelles through hierarchial self-assembly of block copolymers,but the polymer system focuses on triblock copolymers with certain block ratio,and the preparation process is mostly based on complex hierarchial assembly process.The dependence on complex polymer structural parameters and assembly process is not conducive to the continuous regulation of structural parameters and large-scale preparation of"valence"multi-compartment micelles and their hierarchial assemblies.This paper starts from a single-two-two block copolymer polymethyl methacrylate-b-polyethylene naphthalene(PAA-b-PVN,referred to as PAV),simple mixed precursor micelle and modified molecule,Through the synergistic action of multiple non covalent interactions such as non covalent complexation between modified molecules and polymers andπ-πinteraction between modified molecules,the structural transformation of precursor micelles is driven to prepare"Hamburg"patch micelles(HCM)with two symmetrically distributed patches;Based on this,the formation of patch micelles is clarified;hierarchial self-assembly of patch micelles and reversible transformation to precursor micelles are implemented,which is based on simple polymer complications.The controllable construction of the room is provided with direct and efficient new strategies and provides a basis for commercial production of multi-compartment micelles.The main research includes the following three aspects:1.Microbes induced by non-covalent complexation andπ-πaction synergistic micelles reversible dilation and hierarchial self-assemblyThe isotropic micelles assembled by PAV in DMF/Et OH mixed solution were used as precursor micelles and small molecule naphthyl methylamine(NMA)was used as post modification molecule.The grafting of NMA in micelles was realized by the hydrogen bond interaction between modification molecule and PAA;Then,through the directionalπ-πinteraction between modified molecules,the phase separation of modified and unmodified polymer chains was induced,and the"one-to-one"transformation from precursor micelles to"Hamburg"patch micelles(HCM)was successfully realized to obtain monodisperse patch micelles with uniform particle size,morphology and patch distribution.By simply adjusting the proportion of solvent and the proportion of modified molecule NMA,the structure,size and patch size of HCM can be controlled,and the controllable preparation of different HCM by a single polymer can be realized.By introducing carbon dioxide into monodisperse HCM solution,the ordered one-dimensional hierarchial assembly of HCM can be realized,and one-dimensional linear multi-compartment micelles(LCM)with a length of micron level was prepared.More interestingly,both HCM and LCM can be transformed into precursor micelles at high temperature,and can be reversed into corresponding HCM after the temperature returns to normal temperature,which provides a basis for the regeneration of micelles.2.uniformity of micelle piping based on multi-non-covalent synergyFrom the precursor micelle based on the block copolymer PAV,the modified molecule of different chemical structures,by changing the number of rhythmary hydrocarbons in the modified molecules,the length of the modified molecularπ-πstacking effect is adjusted;Change the type of complexable groups in the modified molecules,adjust the complexation between the modified molecules and polymers,study the synergistic effect of non covalent interaction on the structural transformation of precursor micelles,and explore the necessary conditions for the formation of HCM.When there is no aromatic ring providingπ-πaction in the modified molecular structure,and there are multiple or no groups that can complex with PAA in the precursor micelles,the modified molecules can not guide the micelles to form HCM.When the monocomposite aromatic compound contains a monochromormia,the length of the spacer group between the amino group and the conjugated aromatic ring and the aromatic ring substitution have an effect on the dicing of the micelle.By simply adjusting the proportion of solvent and modified molecule,the degree of micellar phase separation guided by modified molecule and the patching of micelles can be adjusted,and finally the controllable preparation from single diblock copolymer to HCM with different chemical composition can be realized.3.In situ characterization of micelle piping based on multi-non-covalent synergyTaking pyrene derivative(pyrene methylamine(PA))with different emission wavelengths in free ground state(I_m～395 nm)and aggregation excited state(I_e～475 nm)as modified molecules,the aggregation state of PA in micellar solution was determined by two emission peak intensity ratios I_m/I_e,the relationship between the formation of micellar patching structure and spectral data was clarified,and the quantitative relationship between the morphological transformation of assembly and the luminescence of PA was established.On this basis,the synergistic effect of multiple non covalent interactions on the evolution of micellar patching structure was determined by the luminescence of pyrene;The reversible characteristics of temperature responsive micellar patching process were characterized in situ by fluorescence spectroscopy,which provided a new idea for the development of fluorescent detection materials with application value. |
