Photo-switchable liquid crystalline brush as an aligning surface for liquid crystals: modelling via mesoscopic computer simulations

Abstract

We consider the mesoscopic model for the liquid crystalline brush that might serve as a photoswitchable aligning surface for preorientation of low molecular weight liquid crystals in a bulk. The brush is built by grafting the polymer chains of a side-chain molecular architecture, with the side chains terminated by a chromophore unit mimicking the azobenzene unit, to a substrate. When irradiated with ultraviolet light, the chromophores photoisomerize into a non-mesogenic cis state and the whole system turns into an ordinary polymer brush with no orientational order and two states: the collapsed and straightened one, depending on the grafting density. When irradiated with visible light, the chromophores photoisomerize into a mesogenic trans state, resulting in formation of a transient network between chains because of a strong attraction between chromophores. Spontaneous self-assembly of the brush in these conditions results in an orientationally isotropic polydomain structure. The desired uniaxial planar ordering of chromophores within a brush can be achieved at certain temperature and grafting density intervals, as the result of a two-stage preparation protocol. An external stimulus orients chromophores uniaxially at the first stage. The system is equilibrated at the second stage at a given temperature and with the external stimulus switched off. The preoriented chromophores either keep or loose their orientations depending on the strength of the memory effect inherent to a transient network of chains that are formed during the first stage, similarly to the case of the liquid crystalline elastomers, where such effects are caused by the covalent crosslinks.

Adsorption of Low Density Lipoproteins on an Azobenzene-Containing Polymer Brush: Modelling by Coarse-Grained Molecular Dynamics

“…Strong repulsion, with the energy parameter U = 2U in Equation (3), is introduced for the interaction of both trans-azobenzene and polymer beads with solvent, reflecting their poor solubility in water. Such type of modelling of azobenzenes has been already used in a number of previous studies [40][41][42][43][44].…”

“…In doing this, we follow our previous studies on modelling photo-sensitive polymers using coarse-grained simulations [40][41][42][43][44]. The modelling approach is covered in detail in Section 2.…”