Study of Nanoparticle-Liquid Crystal Dispersions Using Optical Microscopy and Solid-State NMR.

摘要

This Thesis presents the synthesis of a new family of liquid crystal (LC)-capped gold nanoparticles (AuNPs) for a rationalized miscibility and assembly in liquid crystal matrices.;A new protocol based on the thiol-for-dimethylaminopyridine (DMAP) ligand exchange reaction was developed to prepare 4-5 nm AuNPs with mono and binary capping layers made of alkanethiol (CH3(CH2)mSH; m = 5, 11) and liquid crystal ligand 4'-(n-mercaptoalkoxy)biphenyl-4-carbonitriles (CBO(CH2)nSH; n = 8, 12, 16). AuNPs with a 1 : 1 CH 3(CH2)5SH/CBO(CH2)12SH ratio were found to have an unprecedented miscibility in isotropic 4-n-pentyl-4'-cyanobiphenyl (5CB) and 4-n-octyl-4'-cyanobiphenyl (8CB) liquid crystals exceeding 25 wt% Au.;While low NP concentrations are normally used to avoid aggregation, concentrated dispersions of these AuNPs form new structures at the LC phase transitions through coupling of the interparticle attractive forces with the LC elastic interactions. Upon cooling to TN-I, the AuNPs form a reversible, micron-scale network by concentrating at the nematic-isotropic liquid interfaces. The network topology and LC director field orientation are controlled by the cooling rate, surface alignment, film thickness, AuNP concentration and ligand shell composition. Completely different structures are formed at the nematic to smectic phase transition. AuNPs dispersed in homotropically aligned LC films reversibly form macroscopic domains of curved or linear arrays with micron scale periodicities. Based on the variation of the arrays with boundary conditions, AuNPs are proposed to concentrate at the edge dislocation defects in the smectic phase.;The molecular interactions that determine the miscibility and assembly of the AuNPs in LCs were studied using multinuclear solid-state NMR and isotopically labeled AuNPs and LCs. The interaction of the host LC with the AuNP surfaces is striking manifested by partial alignment of the ligands. The detection of an isotropic-nematic biphasic region of the host LC matrix below T N-I is an important finding that will be used to refine theoretical models of the network formation.;Finally another type of nanoparticle network, formed by aerosil in a Schiff-base-type of LC with a small dipole moment was studied by wideline 2H NMR to investigate the effect of different surface anchoring strengths on the memory effects displayed by these dispersions.;Keywords: nanostructure, microstructure, self-assembly, organic template, long-range order, liquid crystal, thermotropic, cyanobiphenyl, nematic, smectic, Schiff-base, phase transition, edge dislocation, dispersion, miscibility, nanoparticle, ligand exchange reaction, binary monolayer, gold, silica oxide, surface Plasmon resonance, filled nematic, memory effect, polarized optical microscopy, solid-state NMR.