Reading Notes Macromolecules: Deshmukh and Kasi Introduction Interest in self-assembled synthetic materials with hierarchical order Multifunctional

al properties associated with hierarchical structures are attained by organization w. precision at discrete length scales from molecular (nanometer) to macroscopic (micrometer) Hierarchical structures can be created through several molecular interactions/phenomena o Hydrophilic/hydrophobic interactions, ionic interactions, hydrogen bonding, microphase segregation of block copolymers (BCPs), and liquid crystalline order In synthetic polymers, BCPs w. 2 incompatible polymer blocks can undergo microphase segregation b/c of unfavorable mixing enthalpy (heat taken up or given off when mixing two different things) and weak mixing entropy (total increase in entropy when mixing) o This allows for various morphologies, such as: lamella, cylindrical, bicontinuous, and spherical But the domain sizes are limited to 10-100nm To introduce another level of order, the BCPs are made with other interactions and anisotropic moieties (directional groups), such as: hydrogen bonding, pi-pi interactions (aromatic molecules interacting with each other), polyelectrolyte-surfactant, and liquid crystal mesophase formation o Liquid crystalline block copolymers (LCBCPs): ability to form hierarchal structures due to orientation ordering by LC mesogens and microphase separation Display order on 3-10nm length scales for LC ordering and 10-100nm for microphase separation of the blocks o But, LCBCPs with helical mesophases w. periodicities comparable to the wavelength of visible light (cholesteric or chiral semetic mesophases) with microphase segregated domains have not been attained LCBCPs w. chiral mesogens have very high surface-volume ratio of the microphase-separated LCBCP structure inhibits helical mesophase formation o The ability to produce cholesteric helical mesophases in conjunction w. microphase segregated domains will enable the design of visible light reflecting cholesteric mesophase and thermal, mechanical, and morphological attributes of the macromolecular superstructure. This is promising for the creation of new photonic materials, sensors, lasers, and actuators In this work: combination of LC order and microphase segregation of brushlike PEG side chains create a new scaffold architecture that self-assembles into hierarchical structure presenting photonic properties. o Ring-opening metathesis polymerization (ROMP) is used to synthesize liquid crystalline random brush copolymers (LCRBC) made of cholesteryl mesogens and PEG side chains LCRBS architecture allows for multiple self-assembled length scales 1. LC order 3-7 nm

2. Microphase segregation of PEG side chain 10-12nm 3. Periodicity in cholerestic mesophase at scales greater than 100nm Key to the observed hierarchical assembly lies in the interplay of LC order, PEG side chain microphase segregation and their supramolecular cooperative motion all allow for a controlled structure formation on each discrete length scale