Colloids and Surfaces A: Physicochem. Eng. Aspects 412 (2012) 135–142
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Colloids and Surfaces A: Physicochemical and
Engineering Aspects
jo ur nal homep a ge: www.elsevier.com/locate/colsurfa
Reactivity of a lipophilic ingredient solubilized in anionic or cationic surfactant
micelles
Claire C. Berton-Carabin
a
, John N. Coupland
a
, Cheng Qian
b
, D. Julian McClements
b
, Ryan J. Elias
a,∗
a
Department of Food Science, The Pennsylvania State University, University Park, PA 16802, USA
b
Department of Food Science, University of Massachusetts, Amherst, MA 01003, USA
h i g h l i g h t s
◮ The location of a lipophilic spin probe
was measured in surfactant solu-
tions.
◮ The probe partitioned between
micelle and aqueous environments.
◮ The probe in anionic micelles
decreased its reactivity with the
anionic reactant.
◮ The probe in cationic micelles
increased its reactivity with the
anionic reactant.
g r a p h i c a l a b s t r a c t
a r t i c l e i n f o
Article history:
Received 13 June 2012
Received in revised form 16 July 2012
Accepted 18 July 2012
Available online 4 August 2012
Keywords:
Anionic surfactant
Cationic surfactant
Micelle
Electron paramagnetic resonance
Spin probe
a b s t r a c t
The aim of this work was to investigate the location and reactivity of a lipophilic spin probe, 4-phenyl-
2,2,5,5-tetramethyl-3-imidazoline-1-oxyl nitroxide (PTMIO) in anionic (sodium dodecyl sulfate, SDS) or
cationic (dodecyl trimethylammonium bromide, DTAB) surfactant micelles. The analysis of electron para-
magnetic resonance (EPR) spectra of PTMIO in micellar systems showed that probe molecules partitioned
between two populations: a more mobile fraction in the aqueous phase and a less mobile fraction in the
micelle. The fraction of PTMIO incorporated in surfactant micelles increased with surfactant concentra-
tion. The rate of the reduction of the nitroxide group of PTMIO by the negatively charged, water-soluble
ascorbate decreased when the probe was solubilized in anionic SDS micelles and increased when it was
solubilized in cationic DTAB micelles. Thus, both the surface charge as well as the solubilization capacity
of the micelles controlled the reactivity of the lipophilic molecule.
© 2012 Elsevier B.V. All rights reserved.
1. Introduction
A wide range of lipophilic ingredients (e.g., flavors, pigments,
vitamins, drugs, antimicrobials or phytochemicals) are added
to food, beverage, pharmaceutical and cosmetic products to
produce a desired functionality. Various formulation strategies
are used to disperse lipophilic ingredients into aqueous media
including emulsions, nanoemulsions and solid lipid nanopar-
ticles [1–4]. Emulsion-based delivery systems often contain
∗
Corresponding author at: Department of Food Science, The Pennsylvania State
University, University Park, PA 16802, USA. Fax: +1 814 863 6132.
E-mail address: elias@psu.edu (R.J. Elias).
appreciable amounts of non-adsorbed emulsifiers in the aqueous
phase surrounding the dispersed lipid particles. Non-adsorbed sur-
factant molecules form micelles when their concentration exceeds
a particular level know as the critical micelle concentration (CMC).
Surfactant micelles consist of a hydrophilic shell and a hydropho-
bic core that are capable of incorporating lipophilic molecules
[5–7]. Consequently, it is possible for any encapsulated lipophilic
component within an emulsion-based delivery system to partition
between the non-polar regions of the lipid droplets and the sur-
factant micelles [8–10]. Surfactant micelles may, therefore, play an
important role in the solubilization and localization of lipophilic
ingredients in multiphase systems. Accordingly, surfactant micelles
have been described as acting as a separate phase from water,
which constitutes the basis of the pseudophase model [11].
0927-7757/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2012.07.029