1318 Chem. Commun., 2013, 49, 1318--1320 This journal is c The Royal Society of Chemistry 2013
Cite this: Chem. Commun., 2013,
49, 1318
Protein-assisted 2D assembly of gold nanoparticles
on a polysaccharide surface†
Laura Taajamaa,
a
Orlando J. Rojas,*
ab
Janne Laine,
a
Kirsi Yliniemi
c
and
Eero Kontturi*
a
Site-specific assembly of gold nanoparticles on a polysaccharide
surface was accomplished via a straightforward method exploiting
interfacial polymer blends, selective protein adsorption and electro-
static interaction. The method could be useful in further applications
due to the universal nature of the utilized phenomena.
Site-specific assembly of molecular and supramolecular archi-
tectures on 2D systems is a fundamental challenge.
1
Potential
uses of such systems include biomedical applications, diagnos-
tics, data storage, nanoreactors and sensors.
1a,2
The 2D realm is
ever more intriguing when nanoparticles (NPs) are incorpo-
rated in these systems, and as a result numerous methods have
been published to explicitly decorate surfaces with various
NPs.
3
These techniques are often template-based, relying on
self-assembly and/or lithography.
3
In addition, organization at
a liquid–air interface (Langmuir film) has been extensively used
in the construction of 2D NP assemblies.
4
Although numerous accounts exist on arranging NPs on
polymer surfaces, we are not aware of any studies that present
site-specific NP assemblies on flat polysaccharide surfaces. On
the other hand, 2D oligo- and polysaccharide systems are an
active field of research
2b,5
with applications in, e.g., analytics,
2b,5,6
drug release
7
and cell encapsulation.
8
Moreover, macroscopic
chemical patterning of paper, which is essentially a network of
polysaccharide-based fibres, has recently gained attention.
9
Clearly, a facile method to immobilize NPs on flat poly-
saccharide surfaces with micro- and nanoscale lateral precision
is required. Here, we present the 2D assembly of gold NPs
(AuNPs) on specific, micro- and nano-sized sites on an ultrathin
polysaccharide film. The method is based on simple physico-
chemical phenomena: (i) interfacial phase separation of immis-
cible polymer blends, (ii) site-specific adsorption of bovine
serum albumin (BSA) protein on polystyrene (PS) on an ultra-
thin cellulose film, and (iii) electrostatically driven adsorption
of anionic AuNPs on BSA (Fig. 1). The NP textures range from
cellular networks to circular patches on cellulose. It is precisely
the well-established nature of all these three phenomena that
enables the effortlessness of their combination. The current
trend towards sustainable solutions promotes the use of renew-
able, biodegradable and non-toxic cellulose materials. Further-
more, cellulose has the potential for the construction of various
2D architectures.
10
Cellulose films were fabricated by spin
coating immiscible PS and trimethylsilyl cellulose (TMSC)
blends on silicon crystals followed by selective conversion of
the TMSC to cellulose (Fig. S1, ESI†), which does not affect the
PS domains in any way. Although hydrophilic, cellulose does
not dissolve in water and these films have been shown to be
stable in aqueous environments.
10b,c
Both protein and AuNP
(average diameter ca. 20 nm) adsorption was followed with a
Quartz-Crystal Microbalance with Dissipation monitoring
(QCM-D) instrument. Schematic of the adsorption process is
shown in Fig. 1. Further details of the experimental work
performed are described in ESI.†
Fig. 2 shows the course of the BSA and AuNP adsorption on
the cellulose films. In QCM-D, increasing adsorbed mass is
Fig. 1 Simple schematic representation of the protein-assisted 2D assembly of
AuNPs. The dimensions are not drawn to scale.
a
Department of Forest Products Technology, School of Chemical Technology,
Aalto University, P.O. Box 16300, FI-00076 Aalto, Finland.
E-mail: eero.kontturi@aalto.fi
b
Department of Forest Biomaterials, North Carolina State University, Box 8005,
Raleigh, North Carolina 27695-8005, USA. E-mail: ojrojas@nscu.edu
c
Department of Chemistry, School of Chemical Technology, Aalto University,
P.O. Box 16100, FI-00076 Aalto, Finland
† Electronic supplementary information (ESI) available: A detailed description of
the experimental work performed, qualitative and quantitative analysis of QCM-D,
AFM and XPS results. See DOI: 10.1039/c2cc37288f
Received 5th October 2012,
Accepted 22nd December 2012
DOI: 10.1039/c2cc37288f
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Taajamaa, L., Rojas, O. J., Laine, J., Yliniemi, K., Kontturi, E. (2013) Protein-assisted 2D assembly of gold nanoparticles on a polysaccharide
surface, Chem. Commun., 49 (13), 1318-1320. DOI: 10.1039/C2CC37288F. © 2013 Royal Society of Chemistry. Reproduced by permission of
The Royal Society of Chemistry.