Colloids and Surfaces B: Biointerfaces 152 (2017) 12–17
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Colloids and Surfaces B: Biointerfaces
jo ur nal ho me p ag e: www.elsevier.com/locate/colsurfb
Protocols
Hybrid nano-composites made of ss-DNA/wrapped carbon nanotubes
and titania
Martina Romio, Camillo La Mesa
∗
Dept. of Chemistry, La Sapienza University, P.le A. Moro 5, 00185, Rome, Italy
a r t i c l e i n f o
Article history:
Received 15 July 2016
Received in revised form
25 November 2016
Accepted 8 December 2016
Available online 24 December 2016
Keywords:
Multi-walled carbon nanotubes
ss-DNA
DNA-MWCNT adducts
Titania nano-particles
Surfactant-assisted adsorption
Titania binding onto DNA-MWCNT adducts
a b s t r a c t
Multi-walled carbon nanotubes, MWCNTs, are stabilized thanks to the surface wrapping of single-strand
DNA, ss-DNA; the resulting adducts are kinetically and thermodynamically stable Such entities build up
nano-hybrids with titania, TiO
2
, nano-particles, in presence of surfactant as an adjuvant. The conditions
leading to TiO
2
adsorption onto ss-DNA/CNTs were investigated, by optimizing the concentration of
adducts, nano-particles (NPs), and of the cationic surfactant (CTAB). Controlling the working conditions
makes possible to get homogeneously organized hybrids.
Characterization by DLS, electro-phoretic mobility, SEM and AFM clarified the surfactant-assisted
association modes between adducts and CTAB-functionalized TiO
2
. Nano-particles’ clustering onto DNA-
wrapped adducts gives hybrids trough electrostatic interactions. Surface coverage by TiO
2
is significant
and homogeneous. It is expected that the reported hybrids can be useful for applications in heterogeneous
catalysis.
© 2016 Published by Elsevier B.V.
1. Introduction
Because of their outstanding physical and chemical proper-
ties carbon nanotubes, CNTs, play a key role in applied research
since over twenty years [1–3]. They are relevant in materials sci-
ences, surface coverage, heterogeneous catalysis, energy storage
and biomedical applications [4–7]. The above facts hold true despite
drawbacks met in the stabilization of their dispersions [8–10]. To
circumvent these disadvantages, hindering possible applications,
and to avoid the use of toxic solvents, efforts focus on the stabiliza-
tion in aqueous-based media. Accordingly, covalent, [11,12] or non
covalent [13–17], stabilization procedures were proposed. Among
stabilizers considered to date, single-stranded DNA received much
attention [18–21]. Dispersions of ss-DNA/CNTs are kinetically and
thermodynamically stable. It is possible, thus, to disperse sig-
nificant CNTs amounts (some wt%). Consider that the maximum
quantity effectively dispersible in the original form is orders of mag-
nitude lower. Many properties of such adducts were investigated
in detail, and the regions of existence of the different phases they
form were defined [22,23].
New research fields may take advantage from the behav-
ior of the above adducts. Along this line, the manuscript uses
∗
Corresponding author.
E-mail address: camillo.lamesa@uniroma1.it (C.L. Mesa).
ss-DNA/MWCNTs (Multi-Walled Carbon Nanotubes) as templates
for mono-dimensional nano-particles assembly [24]. The pro-
cedure deals with electrostatic interactions and replaces the
non-specific ones reported so far [25]. It is possible, for instance,
to get nano-hybrids, NHs, by mixing ss-DNA/MWCNTs and nano-
particles, NPs, in due ratios. We report on the preparation of NHs
made of ss-DNA/MWCNTs and titania, TiO
2
. NPs were functional-
ized and characterized before mixing them, to form the hybrids. The
preparation procedures and the control of intermediate adducts
formed accordingly are described. A physico-chemical and mor-
phological characterization of the hybrids were also performed and
the optimal working conditions leading to the desired products
were determined.
The manuscript gives information on the procedures and control
of forces leading to assembly. We described how TiO
2
adsorbs onto
ss-DNA/MWCNTs and controlled these processes by DLS, electro-
phoretic mobility, SEM and AFM in a step-by-step strategy. Data
analysis gives information on each stage, and on final NHs, as well.
We attempted to solve problems related with the self-assembly of
colloids differing in nature, size, shape, surface coverage and charge
density. The results showed that the formation of stable hybrids
is possible if binding of CTAB-covered TiO
2
is controlled by their
net charge. Binding requires a careful modulation of surface charge
density for effective interactions to occur.
Taking into account that CNTs are surface-functionalized by
DNA, the interactions are electrostatic in nature. Aqueous TiO
2
is
http://dx.doi.org/10.1016/j.colsurfb.2016.12.011
0927-7765/© 2016 Published by Elsevier B.V.