Chirally orientated fiber

Kimura, Shirai and coworkers used two chiral dimeric porphyrins 95 and 96 to investigate their self-assembling behavior [162,163]. While incorporation into fibers made of the alkylamide derivatives of (fl,fl)-DACH, 95 formed stable well-resolved fibrous assemblies as visualized by transmission electron microscopy, the fluorescence of which was not quenched by external electron acceptors [162]. However, the induced CD was not detected indicating an inability of 95 to form chirally orientated aggregates under the applied conditions. In contrast, 96 was able to produce optically active inter molecular self-assemblies with an enhanced chiroptical response through the //-oxo bridging in an alkali solution, while intramolecular //-oxo dimer formation was excluded on the basis of steric reasons [163]. 

The synthesis and gelation properties of compounds 52-55, containing aromatic chromophores, were reported (Scheme 21). The central unit A of gela-tor 52 is based on two azobenzene chromophores that are connected by a central flexible diamino chain [76]. This compound was observed to gelate various organic solvents, such as 1-hexanol, 1-octanol, toluene, m-xylene, and p-xylene, under 1.0-5.0wt%. As observed in the case of ALS systems, CD spectroscopy pointed to the chiral orientation of 52 molecules within the gel aggregate and TEM photographs showed the occurrence of helical fibers. 

The observed structures were explained by a chiral bilayer effect mechanism proposing that only the enantiomerically pure compounds can lead to the formation of helical fibers which in turn slowly rearrange to enantiopolar crystal layers (Scheme 7.1). Within the micellar fibers, the polar head groups are oriented toward the aqueous environment and must therefore go through an energetically unfavourable -slow- dehydration followed by a 180 ° to form the enantiopolar crystals. 

Cellulose is the most abundant biopolymer on earth. It can be used in different applications, namely in the form of fibers, and cellulose can be converted into numerous cellulose derivatives. Cellulose micro- and nanofibers have been the subject of intense research in the field of composites. Cellulose derivatives can show liquid crystalline chiral nematic phases, which can be used for the production of diverse composite systems. All-cellulosic composites based on liquid crystalline cellulosic matrices reinforced by cellulose micro- and nanofibers can show enhanced mechanical properties due to fiber orientation induced by the liquid crystalline matrix. Cellulose-based fibers electrospun from liquid crystalline phases can develop different structures, which are able to mimic the shape of plant tendrils on the nano- and microscale, opening new horizons for ceDulosic membrane applications. 

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