Critical
micelle concentration (CMC) is the main chemical–physical
parameter to be determined for pure surfactants for their characterization
in terms of surface activity and self-assembled aggregation. The CMC
values can be calculated from different techniques (
e.g
., tensiometry, conductivity, fluorescence spectroscopy), able to
follow the variation of a physical property with surfactant concentrations.
Different mathematical approaches have been applied for the determination
of CMC values from the raw experimental data. Most of them are independent
of the operator, despite not all of the fitting procedures employed
so far can be applied in all techniques. In this experimental work,
the second derivative of the experimental data has been proposed as
a unique approach to determine the CMC values from different techniques
(tensiometry, conductimetry, densimetry, spectrofluorimetry, and high-resolution
ultrasound spectroscopy). To this end, the CMC values of five different
surfactants, specifically three anionic (sodium dodecyl sulfate, sodium
deoxycolate, and
N
-lauroyl sarcosinate) and two nonionic,
such as polyethylene glycol ester surfactants [polyethylenglicol (8) monostearate and polyethylenglicol
(8) monolaurate], have been determined by this approach. The “second-derivate”
approach provides a reliable determination of the CMC values among
all of the techniques investigated, which were comparable to those
calculated by the other operator-free routinely methods employed,
such as segmental linear regression or Boltzmann regression. This
study also highlighted the strengths and shortcomings of each technique
over the others, providing an overview of the CMC values of commonly
used anionic and nonionic surfactants in the pharmaceutical field,
determined by employing different experimental approaches.
In complexes with the uranyl dication salophen ligands are highly puckered. This implies that non-symmetrically substituted uranyl-salophen derivatives exist in principle as a pair of enantiomers. However, due to easy disrotations about the bonds connecting the phenoxide units to the imine carbons, the rate of interconversion between enantiomeric forms of simple, sterically unhindered compounds is extremely fast. Bulky substituents in appropriate positions decrease the interconversion rate and make this novel type of inherent chirality detectable by 1H and 13C NMR.
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