Lyotropic liquid crystalline quaternary mixtures of potassium laurate (KL), potassium sulphate (K₂SO₄)/alcohol (n-OH)/water, with the alcohols having different numbers of carbon atoms in the alkyl chain ( ), from 1-octanol to 1-hexadecanol, were investigated by optical techniques (optical microscopy and laser conoscopy). The biaxial nematic phase domain is present in a window of values of , where is the number of carbon atoms in the alkyl chain of KL. The biaxial phase domain became smaller and the uniaxial-to-biaxial phase transition temperatures shifted to relatively higher temperatures upon going from 1-nonanol to 1-tridecanol. Moreover, compared with other lyotropic mixtures these new mixtures present high birefringence values, which we expect to be related to the micellar shape anisotropy. Our results are interpreted assuming that alcohol molecules tend to segregate in the micelles in a way that depends on the relative value of n with respect to . The larger the value of n, the more alcohol molecules tend to be located in the curved parts of the micelle, favoring the uniaxial nematic calamitic phase with respect to the biaxial and uniaxial discotic nematic phases.

The lyotropic mixture of potassium laurate/decanol/water presenting only the uniaxial nematic calamitic phase was doped with one strong (potassium chloride, KCl) and 11 weak electrolytes with phenyl-rings (DL-mandelic acid, benzoic acid, DL-phenyllactic acid, phenylacetic acid, phenol and phenylmethanol) and with cyclohexyl-ring (RS-hexahydromandelic acid, cyclohexanecarboxylic acid, cyclohexaneacetic acid, cyclohexanol and cyclohexylmethanol), separately. We also chose two nonpolar dopant molecules, benzene and cyclohexane, for the comparison of them with weak electrolytes, since they are located in the hydrocarbon core of the micelle. The nematic phase sequences, in particular the presence of the biaxial nematic phase, were investigated as a function of the dopant molar concentration and temperature. The laser conoscopy and small-angle X-ray scattering techniques were used to characterise the different nematic phases. Weak electrolytes having –COOH group as polar part were found to be very effective in stabilising the three nematic phases (two uniaxial and a biaxial). Guest molecules with only the –OH group did not show any effect on the stabilisation of other nematic phases. The experimental results are interpreted considering the screening effect of the hydrophilic parts of the dopants on the repulsion between the polar heads of the main amphiphilic molecules at micelle surfaces. This process favours the increase of the more flat micellar surfaces of micelles, which triggers the orientational fluctuations responsible for the biaxial and discotic nematic phases. Graphical Abstract

Lyotropic mixtures including different sodium salts of Hofmeister anions were studied in order to investigate the effect of these anions on the existence of biaxial nematic phase and on the uniaxial to biaxial phase transitions. For this purpose, these sodium salts were added singly into different mixtures of dodecyltrimethylammonium bromide (DDTMABr)/1-dodecanol/water, keeping the relative molar concentration of all the constituents constant. The uniaxial to biaxial phase transitions were determined from the temperature dependence of the birefringences by laser conoscopy. Micellar shape anisometry and average micellar volume were evaluated from small-angle X-ray scattering measurements. The results indicated that the Hofmeister anions were bounded to the head groups of DDTMABr molecules at the micelles’ surfaces, which significantly affect the different orientational fluctuations responsible for the formation of different nematic phases, biaxial phase domains and uniaxial to biaxial phase transition temperatures.