Adsorption of single chain Zwitterionic phosphocholine surfactants: Effects of length of alkyl chain and head group linker

The adsorption of a range of single chain zwitterionic phosphocholine surfactants (CnPmC) at the air/liquid interface has been studied by a combination of surface tension and neutron reflectivity. The critical micellar concentration (CMC) for CnPC (or CnP2C), where n varied from 12, 14 to 16, was found to be 0.91, 0.14, and 1.2 x 10(-2)mM[ respectively, and followed the same trend as observed for other zwitterionic and non-ionic surfactants. The area per molecule at the CMC, A(cmc), for CnPC was found to remain constant between 50 and 53 angstrom(2), indicating that the increase in the alkyl chain length had little effect on A,., at the interface. The neutron reflection measurement also showed an almost constant layer thickness (tau) of 20 +/- 2 angstrom from all the alkyl chain deuterated PC surfactants (dC(n)hPC) in null reflecting water (NRW), suggesting that the alkyl chains of the surfactant responded to changes in either chain length or solution concentration by varying their angle of tilt. In contrast, increasing the length of head group linker between P and N atoms in C12PmC, where m = 2, 4, to 6, resulted in a much slower decrease of CMC from 0.91, 0.7, to 0.5 mM, consistent with a different contribution to the free energy of micellization. A(cmc) for C12PmC did not vary when m was increased from 2 to 4, and this observation together with the thickness of the head group region indicated an almost perpendicular projection of the head group in C12P2C and C12P4C. A further increase in m to 6 resulted in an A(cmc) of 70 angstrom(2). This increase in A(cmc) however did not result in any change in either the total layer thickness or the fraction of the head group region submerged in the aqueous subphase, suggesting that the head group in C12P6C was bent away from the surface normal direction. Both increase in temperature from 25 to 40 degrees C and the addition of 0.1 M NaCl had little effect on the area per molecule or the thickness of C12PmC surfactant layer, showing that the C12PmC series behaved like CnP2C series. The main conclusion from this study is that for all the CnPmC surfactants studied, change in m or n has little effect on the total thickness, the thickness of the alkyl chain or that of the head group region. (c) 2005 Elsevier B.V. All rights reserved.