Colloids and Surfaces B: Biointerfaces 119 (2014) 47–54
Contents lists available at ScienceDirect
Colloids and Surfaces B: Biointerfaces
j o ur nal ho me pa ge: www.elsevier.com/locate/colsurfb
Effect of pH and temperature upon self-assembling process between
poly(aspartic acid) and Pluronic F127
Loredana E. Nita
∗
, Aurica P. Chiriac, Maria Bercea
“Petru Poni” Institute of Macromolecular Chemistry, 41-A, Grigore Ghica Voda Alley, 700487 Iasi, Romania
a r t i c l e i n f o
Article history:
Received 21 February 2014
Received in revised form 3 April 2014
Accepted 23 April 2014
Available online 4 May 2014
Keywords:
Self-assembling
Poly(aspartic acid)
Pluronic F127
a b s t r a c t
The present investigation was made in order to evaluate the capability of self-assembling of the two
water soluble polymers, respectively, poly(aspartic acid) and Pluronic F127 into well interpenetrated
mixture, and to evidence the connection effects intervened during polymer complex formation to exhibit
good stability once formed, as well to understand and correlate the binding strength and the interval
between better association domains. The effect of pH and temperature on the interpolymeric complex
formation between poly(aspartic acid) and Pluronic F127 was studied by combining rheology with light
scattering technique. The solution mixtures between poly(aspartic acid) and Pluronic F127 are Newtonian
fluids for all ratios among them. Depending on the polymeric mixture composition and experimental
temperature, positive or negative deviations of the experimental values from the additive dependence
appear. An interesting behavior was registered around 1/1 wt. ratio between the two polymers, when
the hydrodynamic diameter of the interpenetrated polymeric particles decreased suddenly. This allows
us to conclude the formation of core–shell micelle structure with poly(aspartic acid) core and Pluronic
F127 as shell, performed through strong interactions between polymers. This behavior was sustained by
the increase of absolute value of zeta potential owing to the decrease of functional groups number at the
surface of micelles.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction
Self-assembling is a strategy for materials preparation which
can produce highly structured, compositionally defined, multi-
component and multifunctional materials from a discrete set of
molecular building blocks. Self-assembly has become very use-
ful in chemistry and materials science for diverse applications, in
fields ranging across electronic materials, synthetic biology, struc-
tural materials, chemical biology, and biomaterials. Thus, through
spontaneous self-assembly transitions of the initially disordered
molecules, acquired by specific noncovalent interactions, pre-
dictable supramolecular structures can be prepared. The forces that
direct contribute to molecular self-assembly are weak intermolec-
ular interactions between molecules in solution, which include
hydrogen bonding, hydrophobic interactions, Coulombic interac-
tions, -stacking, and van der Waals forces [1].
During preparation the self-assembling systems are highly
dependent on solution conditions such as pH, ionic strength, con-
centration, temperature, and solvent polarity. The self-assembling
∗
Corresponding author. Tel.: +40 232 217454; fax: +40 232 211299.
E-mail address: lnazarie@yahoo.co.uk (L.E. Nita).
processes enable the achievement of materials displaying complex
combinations of molecular features. Multifunctional materials can
be thus systematically assembled and optimized, even when multi-
ple co-assembling constituents are present, compounds which are
also able to be functionalized with ligands or chemical groups either
post-assembly or pre-assembly.
Soft condensed matters or biological systems are generally
self-associated through weak forces, which are acting together
being as well difficult to unravel their relative contributions. For
instance, the aggregates formed in water by association between
cationic and anionic polymers, or surfactants, become strongly
hydrophobic and precipitate in many cases. Also, hydrophobic-
ity results from the hydrogen bonds between a hydrogen donor
and a hydrogen acceptor, such as non-dissociated polyacids and
polyoxyethylene or polyethoxylated non-ionic surfactants. On the
other hand, the polyacid ionization at high pH reduces or even
destroys the ability to form hydrogen bonds [2]. Interpolymer com-
plexes are also prepared based on attractive interactions between
appropriate macromolecular chains dissolved in a common solvent.
These complexes are mainly stabilized via electrostatic interactions
in the case of a polyanion/polycation mixture, or through hydro-
gen bonds between a polyacid (H-bond donor) and a polybase
(H-bond acceptor). These complexes have long been known and
http://dx.doi.org/10.1016/j.colsurfb.2014.04.023
0927-7765/© 2014 Elsevier B.V. All rights reserved.