Liquid crystals freeze fractured

An alternative method is the freeze-etching technique [24, 25], which consists of producing platinum shadowed replicas of fractures created in rapidly frozen biological systems or lyotropic liquid crystals. The fracture orientation is somewhat haphazard, but occurs preferentially within the paraffinic level of the bilayers. These methods offer the possibility of viewing bilayers directly and preparing stereoviews. Beautiful pictures of liquid crystalline DNA, both cholesteric and hexagonal, have been obtained, but individual molecules are not easily resolved. However, the director distribution can be deduced from the images [26],... 

Structured laundry liquids are currently available in Europe and were recently introduced in the United States [50,51]. These products typically contain high levels of surfactants and builder salts, as well as enzymes and other additives. In the presence of high ionic strength, the combination of certain anionic and nonionic surfactants form lamellar liquid crystals. Under the microscope (electron microscope, freeze fracturing) these appear as round droplets with an onion-like, multilayered structure. Formation of these droplets or sperulites permits the incorporation of high levels of surfactants and builders in a pourable liquid form. Stability of the dispersion is enhanced by the addition of polymers that absorb onto the droplet surface to reduce aggregation. 

Figures 9a-c represent transmission electron micrographs of different lyotropic liquid crystals after freeze fracture without etching. The layer structure of the lamellar mesophase including confocal domains, hexagonal arrangement of rodlike micelles within the hexagonal mesophase, as well as close-packed spherical micelles within the cubic liquid crystal can be clearly seen.

FIG. 11. Transmission electron micrographs of freeze fractured oily droplets dispersed (a) in a hexagonal and (b) in a cubic liquid crystalline phase, bar 100 nm. From Mueller-Goymann, C., Liquid crystals in emulsions, creams and gels, containing ethoxylated sterols as surfactant, Pharm. Res. 1 154-158 (1984). 

Fig. 9 Transmission electron micrographs of freeze fractured liquid crystals. (A) lamellar with confocal defects, bar 100 nm (B) hexagonal, bar lOOnm (C) cubic of type I, bar lOOnm (D) multilamellar vesicle consisting of dodecyl-PEG-23-ether, cholesterol and water, bar 200 nm (E) multivesicular vesicle, bar 1 pm. (A and B Adapted from Ref C Adapted from Ref. ° D Adapted from Refs. l)...

The final evidence for the formation of an Abrikosov flux lattice of screw dislocations in liquid crystals was achieved by Zasadzinski et al. [39] via the visualization of the screw dislocations of (R)- and (S-)l-methylheptyl 4 -(4-n-tetradecyloxyphenylpropioloyloxy)-biphenyl-4-carboxylates using freeze-fracture transmission electron microscopy. Freeze-fracture transmission microscopy (TEM) is an essential tool for visualizing the TGBA phase at sufficient resolution in order to resolve the molecular organization. 

Fig. 3.11 Polarized light Microscopy images of graphene oxide liquid crystals (a) and freeze fracture SEM image of nematic phase (b). Reproduced with permission from [115]. Copy right 2011 Wiley-VCH...

An alternative to the above preparation methods, albeit a rather involved one, is the freeze-fracture technique, in which the dispersion is shock frozen by being poured into liquid nitrogen. The freezing process has to be fast enough to avoid crystallization of the water phase. The sample is then cryo-transferred to the electron microscope where it is fractured. The fracture surfaces can then be imaged using, for example, replica techniques. 

Infiltration of the permeable concrete with molten sulfur yields a matrix which is almost impermeable to water. The freeze-thaw durability tests have indicated this is so, and immersion tests showed that fully infiltrated specimens absorbed less than 0.3% water by volume over several months, although methanol immersion and vacuum poro-simeter measurements revealed that a pososity of over 5% was available for filling. A total shrinkage of about 13% (Table I) occurs when liquid sulfur crystallizes to the stable low-temperature S< form, but much of the volume change appears to be accommodated in closed pores and intercrystal inversion fractures which affect the permeability little. 

---