| Fullerene(C60)shows many attractive application prospects in the fields of antifriction and anti-wear,organic photoelectric materials,biomedicine,skin care due to its excellent properties such as perfect spherical structure,electron acceptance,photogenic singlet oxygen,quenching free radicals,etc.However,the poor solubility in most solvents especially in water greatly limits its further application.Therefore,it is particularly important to improve the solubility of fullereneC60 in water and even in various solvents.Two strategies were proposed to improve the solubility of C60 in water,that is,covalent synthesis and noncovalent doping.Moreover,as a ringid unit,it is also of significant importance to study the structure of fullerene C60 itself and its derivatives on the properties of the system.In this paper,utilizing covalent modification,starting from the rigid C60,we synthesized a series of fullerene C60 amphiphiles,containing oligo(poly(ethylene oxide))chains(o-PEO)alone and oligo(poly(ethylene oxide))chains(o-PEO)together with quaternization co-functionalized C60 amphiphiles,and systematically studied the influences of number or substitution position of the o-PEO on their self-assembly and properties;constructed two functional systems using C60 and C60 amphiphiles through non-covalent interactions,and investigated their application in friction lubrication and photocatalytic degradation of dyes separately.There are totally six chapters in this paper,as follow:Chapter ? is the introduction,in this part,we briefly describe the discovery,structure,properties,and applications of fullerene C60.The types of fullerene C60 amphiphiles are summarized in detail,and the deficiencies in the field of fullerene C60 amphiphiles are pointed out.The knowledge of surfactants and self-assembly was briefly introduced,and the relationship between surfactants and fullerenes C60 in system design was pointed out.Finally,the basis for the selection of the topic and the research content of this paper are pointed out.In Chapter ?,we designed and synthesized a series of N-methylfullerene pyrrolidine molecules(4a-f)modified oligo(poly(ethylene oxide))chains(o-PEO).The effects of the number and position of o-PEO on the solubility,self-assembly behavior and electrochemical properties of 4a-f were systematically studied.The aggregation behavior of two water-soluble amphiphilic fullerenes C60 with substitution pattern of 3,4,5(4d)and 2,3,4(4e)in aqueous solution was studied,and the aggregates morphology was confirmed to be vesicles for 4d and irregular flake aggregates for 4e.In Chapter ?,the self-assembly behavior of the synthesized fullerene C60 amphiphiles in Chapter II at the air/water interface and on a glass slide were investigated,and well-ordered honey-comb structures(HCSs)with the highest C60 content(>60 wt%)reported so far was prepared.The influence of the number and position of o-PEO on the formation of the HCSs was systematically studied,and the amphiphiles with two o-PEO chains were found to be having the outstanding advantage.Wrinkles were found in between the pores for the HCSs formed at the air/water interface,while hierarchically organized pores were observed for those formed on glass slides.In addition,the introduction of linear or branched can not only optimize the surface morphology and/or the internal structure of the HCSs,but also bring in photoluminescence to the HCSs.In Chapter ?,we transferred the neutral C60 derivatives(la-f)synthesized in Chapter II to ionic ones(2a-f)through a facile one-step quaternization,which was found to be effective in improving water solubility.The aggregation behavior and hydroxyl radicals scavenging ability of 2a-f in aqueous solution were systematically studied.The corresponding relationships among molecular structure,assembly structure and free radicals scavenging ability were discussed combined with the theory of critical packing parameter(P),and provided the first example of comprehensive analysis of aggregation behavior and biological activity of water-soluble C60 derivatives with specific structure,which offers a favorable guidance for the design of new type of water-soluble C60 derivatives.In Chapter ?,we developed a new salt-free zero-charged catanionic surfactant system(TTAO)which can form La phases in water within a wide concentration range(0.2-95 wt%),and prepared a series of C60/LLCs hybrid materials by doping C60 into the lamellar liquid crystals(LLCs)formed by TTAO through non-covalent interaction.C60 can not only be well solubilized in the LLCs,without their destroying the layer structure,but also can effectively enhance the mechanical properties of the LLCs.When applied to tribology,a small amount of C60 into the LLC phase can effectively lower the friction coefficient and wear volume,which provides a new methodology to prepare C60-based lubricants for practical applications.In Chapter ?,we synthesized flower-like copper phosphate crystals(FLCs-Cu)templated by three synthetic water soluble C60 derivatives for the first time.The influences of the concentration of amphiphiles and PBS and the types of metal ions,counter anions,and amphiphiles on the formation of the FLCs-Cu were systemically discussed.As the C60 derivative mainly acted as a template during the preparation of FLCs-Cu,the same aqueous solution of the C60 derivative can be used repeatedly,making this strategy suitable to produce massive FLCs-Cu at a low cost.The FLCs-Cu showed good performance in the photocatalytic degradation of dyes at the presence of H2O2,which can still maintain high activity after recycled for multiple times.This work proved that water soluble C60 derivatives have a high potential to be applied in the synthesis of inorganic materials with diverse morphologies. |
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