1. Introduction
Biogenic amines or polyamines, such as putrescine, spermidine
and spermine, are important in a range of biochemical functions
[1–3]. Polyamines are small flexible polycations, and are involved
in a variety of physiological roles associated with cell growth and
proliferation. Their interaction with different charged species in
bio-macromolecules such as DNA and in the cell membrane is of
central importance. As such they are associated with DNA compaction and precipitation [4–6], protein folding and unfolding [7] and
have been exploited in the formation of polyplexes for potential
gene delivery vehicles associated with gene therapy [8–10].
The focus of this paper is on the surface interaction between the
biogenic amines and the anionic surfactant sodium dodecyl sulphate, SDS. Although this focus is rather specific, how the surface
interaction is affected by the structure and molecular weight,
MW, of the polyamine has much broader biological and technological significance and implications. In this broader context the
poly(ethyleneimine), PEI, based polymers and the polyamines are
important polyelectrolytes because of their widespread applications, and so have been extensively studied [11]. Hence the surface
adsorption behaviour of polyelectrolyte/surfactant mixtures has
also been extensively studied [12,13]. Depending upon the nature
of the polyelectrolyte–surfactant interaction enhanced absorption
in the form of a monolayer occurs down to relatively low surfactant concentrations due to polyelectrolyte–surfactant surface complexation. In many cases, close to charge neutralisation where the
solutions are cloudy and precipitation/coacervation occurs, the
surface structure is more complex and ordered layered structures
from a trilayer to multiple bilayer structures are formed or adsorb
at the interface. Recent studies attributed the surface multilayer
formation to a wetting of the surface by a more surface active concentrated precipitated/coacervated phase which is highly surface
active and has a lower surface tension than the coexisting dilute
phase [14]. This surface ordering phenomenon and the systems
where only monolayer adsorption accompanied by the partial
desorption that occurs in the region of charge neutralisation are
now described by a full thermodynamic treatment [15].
PEI is a particularly important polyelectrolyte, in which the nature of its interaction with surfactant varies with pH, MW, and polymer architecture (branched or linear) [16–18]. In combination with
SDS PEI exhibits the full range of surface properties summarised in
the previous paragraph. However, a notable feature is that the PEI–
http://dx.doi.org/10.1016/j.jcis.2014.11.011
0021-9797/ 2014 Elsevier Inc. All rights reserved.
⇑ Corresponding author at: ISIS Facility, STFC, Rutherford Appleton Laboratory,
Chilton, Didcot, OXON, UK.
E-mail address: Jeff.penfold@stfc.ac.uk (J. Penfold).
1. IntroductionBiogenic amines or polyamines, such as putrescine, spermidineand spermine, are important in a range of biochemical functions[1–3]. Polyamines are small flexible polycations, and are involvedin a variety of physiological roles associated with cell growth andproliferation. Their interaction with different charged species inbio-macromolecules such as DNA and in the cell membrane is ofcentral importance. As such they are associated with DNA compaction and precipitation [4–6], protein folding and unfolding [7] andhave been exploited in the formation of polyplexes for potentialgene delivery vehicles associated with gene therapy [8–10].The focus of this paper is on the surface interaction between thebiogenic amines and the anionic surfactant sodium dodecyl sulphate, SDS. Although this focus is rather specific, how the surfaceinteraction is affected by the structure and molecular weight,MW, of the polyamine has much broader biological and technological significance and implications. In this broader context thepoly(ethyleneimine), PEI, based polymers and the polyamines areimportant polyelectrolytes because of their widespread applications, and so have been extensively studied [11]. Hence the surfaceadsorption behaviour of polyelectrolyte/surfactant mixtures hasalso been extensively studied [12,13]. Depending upon the natureof the polyelectrolyte–surfactant interaction enhanced absorptionin the form of a monolayer occurs down to relatively low surfactant concentrations due to polyelectrolyte–surfactant surface complexation. In many cases, close to charge neutralisation where thesolutions are cloudy and precipitation/coacervation occurs, thesurface structure is more complex and ordered layered structuresfrom a trilayer to multiple bilayer structures are formed or adsorbat the interface. Recent studies attributed the surface multilayerformation to a wetting of the surface by a more surface active concentrated precipitated/coacervated phase which is highly surfaceactive and has a lower surface tension than the coexisting dilutephase [14]. This surface ordering phenomenon and the systemswhere only monolayer adsorption accompanied by the partialdesorption that occurs in the region of charge neutralisation arenow described by a full thermodynamic treatment [15].PEI is a particularly important polyelectrolyte, in which the nature of its interaction with surfactant varies with pH, MW, and polymer architecture (branched or linear) [16–18]. In combination withSDS PEI exhibits the full range of surface properties summarised inthe previous paragraph. However, a notable feature is that the PEI–http://dx.doi.org/10.1016/j.jcis.2014.11.0110021-9797/ 2014 Elsevier Inc. All rights reserved.⇑ Corresponding author at: ISIS Facility, STFC, Rutherford Appleton Laboratory,Chilton, Didcot, OXON, UK.E-mail address: Jeff.penfold@stfc.ac.uk (J. Penfold).
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