Diffusion of DSDMA Polyelectrolyte Solutions
J. Phys. Chem., Vol. 100, No. 23, 1996 9891
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coefficients (determined in the presence of D2O) will supply
us with basic information about solvation as about well as the
structure and dynamics of AOH solutions.33
Conclusions
A detailed analysis of the diffusivity of DSDMAX (X ) OH,
Cl, Br) has been conducted in the absence and presence of
sodium chloride (0.015 M) at three pH values [4.5, 5.5, and
7.5 (25 °C)] over a broad surfactant concentration range covering
concentrations below and above the CMC. By applying a
multicomponent analysis for the measured diffusivities, the large
coupled flow of NaCl in a pH dependent manner can be
explained on the basis of known diffusion coefficients and
concentrations of surfactant, counterions, and salt. The present
work also shows that the apparent diffusion coefficients for the
cationic micelles are higher than their true diffusivity due to
the presence of NaCl. The salt and pH dependent diffusivities
of DSDMAX, particularly for X ) OH, are of particular interest
because DSDMAOH undergoes a reversible transformation from
a vesicular state, through a threadlike state, to a micellar state.
This process is also concentration and salt dependent.
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National Meeting of the American Chemical Society, 1992, 32 (1), 907-
909.
Acknowledgment. M.T. and H.H.P. acknowledge the sup-
port of grants from Euram-Brite (No. 4088) and Project 28211
(No. Par 3). S.F.C. acknowledges F. Friedli, J. Fuller, and the
Witco Technical Center in Dublin, Ohio.
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(25) The pKa values were determined according to the equation:
References and Notes
ca - cs - [H+] 0.509
c
A
x
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pKa ) pH + log
+
cs + [H+]
1 +
c
x
A
where cA) na/(VA + x), cs ) xcb/(VA+ x), and [H+] ) 10-pH. nA is the
number of moles of DSDMAX, VA is the initial volume of the DSDMAX
solution, x is the volume of added base solution, cb is the initial normality
of base, cA is the concentration of acid, and cs is the concentration of base.
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(8) DSDMACl(OH) and ATP, ADP, GTP, and GMP form highly
organized columnar rods in solution at DSDMACl(OH) concentrations of
1-2 mM and 10-20 µM nucleotides at pH 7.0-7.5 (25 °C) in HEPES or
Na2HPO4 buffer. The DSDMA(Cl)OH‚ATP complexes, in the presence or
absence of NaCl, form columnar mesophases; the columns are composed
of a stacked array of ATP or ADP dimers held together by Coulomb
interactions between the cationic surfactants and stacking interactions
(Paradies, unpublished results, 1993). Moreover, there are strong interactions
between DSDMAX and exopolymers produced by environmental micro-
organisms, which we feel have gone unnoticed by many environmental
chemist (Paradies, H. H. In Physico-chemical Aspects of Metal-Biofilm
Interactions; Gaylarde, C., Videla, H., Eds.; Cambridge University Press:
Cambridge, UK, 1995; 196-269).
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JP960119N