Accepted Manuscript

Phenanthroline-functionalized MWCNTs as versatile platform for lanthanides

complexation
Laura Maggini, Jennifer Ahrens-Jensen, Giada Lo Re, Jean-Marie Raquez,
Philippe Dubois, Davide Bonifazi
PII:
DOI:
Reference:

S0008-6223(13)01182-2
http://dx.doi.org/10.1016/j.carbon.2013.12.040
CARBON 8621

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Carbon

Please cite this article as: Maggini, L., Ahrens-Jensen, J., Re, G.L., Raquez, J-M., Dubois, P., Bonifazi, D.,
Phenanthroline-functionalized MWCNTs as versatile platform for lanthanides complexation, Carbon (2013), doi:
http://dx.doi.org/10.1016/j.carbon.2013.12.040

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Phenanthroline-functionalized MWCNTs as versatile platform for lanthanides

complexation
Laura Maggini,a Jennifer Ahrens-Jensen,a Giada Lo Re,b Jean-Marie Raquez,b Philippe Duboisb
and Davide Bonifazi* a,c

Namur Research College (NARC) and Department of Chemistry, University of Namur (UNamur),
Rue de Bruxelles 61, 5000 Namur Belgium
E-mail: davide.bonifazi@unamur.be
b

Centre dInnovation et de Recherche en Matriaux Polymres CIRMAP, Service des Matriaux

Polymres et Composites, Universit de Mons, Place du Parc 23, B-7000 Mons, Belgium

Department of Chemical and Pharmaceutical Sciences, INSTM UdR Trieste, University of Trieste,
Piazzale Europa 1, 34127 Trieste Italy

Abstract

A multiwalled carbon nanotube (MWCNT) scaffold was covalently functionalized with

phenanthroline moieties capable to chelate tris Eu(III) complexes, such as Eu(III) tris-(2-theonyl)trifluoroacetonate ([EuL3]), yielding a brightly luminescent hybrid (MWCNTs-Phen[EuL3]). The
material was thoroughly characterized by means of TGA, XPS, TEM and steady-state UV-Vis
absorption and emission investigations. These studies demonstrated both the integrity of the
luminescent Eu(III)-based complex in the hybrid, as well as its high loading. The versatility of the
coordinating properties of phenanthroline allowed the anchoring of other lanthanides like Gd(III),
producing functional hybrids with potential applicability as magnetic resonance agents. Finally, the
developed hybrid revealed to be highly dispersible in biodegradable polymer matrices such as
Poly(L-lactide) (PLLA), making it a promising luminophore for applications in biomaterial science.

1. Introduction
The unique chemical and physical properties of carbon nanotubes (CNTs),[1-2] including but not
limited to their electrical conductance, high mechanical stiffness, light weight, transistor behavior,
piezo-resistance, thermal conductivity, luminescence, electrochemical bond expansion, and
versatile chemistry, make of them superb materials for a broad spectrum of applications.[3-7] Indeed,
also in the field of nano-medicine CNTs are currently the subject of intense investigations as
innovative nano-carriers for theranostic devices.[8-10] In fact, the possibility of functionalizing CNTs
both exo- and endohedrally[11] with biologically-active molecules, together with their ability to
penetrate into cells,[12-13] makes these carbon structures extremely attractive for the development of
novel therapeutic approaches.[14-16] In addition, the intrinsic optical characteristics of single-walled
CNTs (SWCNTs) resulted extremely functional in the field of biomedicine, where their NIR
emission properties[17-18] are exploited for engineering contrast agents for imaging applications both
in in-vitro and in-vivo.[19] Moreover, the strong NIR-centered absorbance of SWCNTs,[17] has been
also used for hyperthermia inside cancer cells, selectively activating or triggering cell death.[14]
Multi-walled CNTs (MWCNTs) are also starting to attract attention for their possible exploitation
in biomedical applications, as shown by Burlaka et al.[20] Recently, we have gone a step further,
demonstrating the efficiency of MWCNTs-based nano-therapeutic tools in cancer treatment by
preparing iron-filled MWCNTs (Fe@MWCNTs) exohedrally functionalized with a monoclonal
antibody (mAb) known to bind a plasma membrane receptor (epidermal growth factor receptor,
EGFR) over-expressed in several cancer cells (EGFR+).[21] In-vitro cytotoxicity evaluations by
classic cell staining procedures after application of an electromagnetic radiation inducing magnetic
fluid hyperthermia (MFH), showed a selective suppression of the EGFR+ cell line.
Nevertheless, tagging MWCNTs with chromophores emitting in the visible or the NIR
region could dramatically improve their theranostic potential. Among the possible choices, trivalent
lanthanide ions complexes (LnCs) represent an alternative system to organic luminescent stains in
view of their very fine emission profile, enabling easy spectral and time discrimination of their

emission bands.[22-23] In bio-imaging, the first staining of biological cells with lanthanides dates
back to 1969, when a sample of Escherichia coli was treated with an aqueous ethanolic solution of
an Eu(III)-thenoyltrifluoroacetonate complex.[24] Since then Soini et al. applied Eu(III), Sm(III),
Tb(III), and Dy(III) polyaminocarboxylates and -diketonates as luminescent sensors in timeresolved luminescent (TRL) immunoassays,[25] fostering a vigorous development in homogeneous
TRL assays,[26] bio-conjugation methods for lanthanide luminescent chelates,[27] and time-resolved
luminescence microscopy (TRLM) applications.[28] Very recently, Reddy and co-workers also
reported on the use of lanthanide- -diketonates complexes as bio-probes for cellular imagining.[2930]

In an earlier collaborative work with Armarolis group, we have first reported a simple method to

prepare LnC-CNTs composites by the direct adsorption of a neutral Eu(III)-based LnC onto
oxidized single-wall CNTs (ox-SWCNTs) through hydrophobic interactions,[31] an approach
successfully employed also for graphene sheets,[32] as demonstration of its wide-ranging
applicability. Indeed, the blending of the two materials led to a strongly emitting composite in
which the structural and electronic properties of both constituents resulted preserved.[33-34] Different
approaches to blend CNTs and LnCs have thereafter been reported such as i) the in-situ preparation
of LnCs directly onto the external walls of carbon nanotubes through a layer-by-layer approach,[3536]

ii) covalent CNT functionalization with pendant alkyl chains terminating with diketonate or

bipyridyl ligands, both able to effectively chelate Ln(III) ions,[37-39] iii) adsorption of dendrimers
chelating Ln(III) ions,[40] and iv) the in-situ sol-gel condensation of silane-derivatized complexes
onto silane-derivatized CNTs.[41] Although it remains the only example, Sitharaman et al. reported
on the synthesis of luminescent SWCNTs from Eu(III)-based catalysts, providing encapsulation of
the luminescent ions directly during the growth process.[42]
Following the exohedral supramolecular approach, we have been able to exploit electrostatic
interactions to decorate with negatively charged Eu(III) complexes MWCNTs previously
functionalized with positively charged imidazolium-based ionic liquids,[43] ammonium-terminating
dendrons,[44] and pyridinium-based polymers.[45] The latter were also magnetically aligned,

demonstrating exploitable anisotropic emission properties in hydrogels.[45] Recently, we have also

attempted the endohedral functionalization of MWCNTs with a neutral and hydrophobic trishexafluoro acetylacetonate Eu(III) complex, via a nano-extraction methodology[46] and by
exploiting the fullerene-CNT affinity employing a C60-based nano-carrier for LnCs.[47] Among the
prepared materials, the latter could have represented a perfect solution for the preparation of biocompatible luminescent materials, as the encapsulated luminophores would have been isolated by
the external environment, avoiding toxicological side effects of the lanthanide ions. Yet, these
materials still suffer lower luminescence efficiencies compared to the exohedral derivatives, making
them at the moment less appealing candidates in bio-imaging applications.
Since the exohedral functionalization is still the most promising methodology to prepare
highly loaded luminescent CNT/LnC hybrids, we have decided to investigate another non-covalent
route to prepare hybrid luminescent systems. Specifically, inspired by the works of Mirochnik et
al.,[48] Zhang et al.[49] and Binnemans et al.,[50] who have independently reported on the formation of
complexes between lanthanide derivatives and 1,10-phenanthroline (Phen) grafted to polyacrylic
acid, mesoporous silica and sol gel glass respectively, we decided to undertake the synthesis of a
phenanthroline-bearing CNT hybrid (MWCNTs-Phen). Indeed, being Phen an optimum ligand for
LnCs,[51] such hybrid material is in principle capable of exohedrally confining Eu(III) complexes
through coordination interactions. The preparation of the luminescent hybrid was hence performed
in two stages: i) first the synthesis of MWCNTs-Phen, via the thiol-ene click-type reaction
between cysteine-derivatized MWCNTs and a 5-maleimido-1,10-phenanthroline (1); and
subsequently through the ii) coordination of an Eu(III) complex, namely Eu(III)-tris-(2-theonyl)trifluoroacetonate ([EuL3]). The obtained luminescent material was hence thoroughly characterized
by means of thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS),
transmission electron microscopy (TEM), and photoluminescence studies (PL), before employing it
in the preparation of bio-based composites with bio-sourced polylactide (PLLA).

2. Results and discussion

2.1 Synthesis of the luminescent hybrid

Figure 1. a) Synthetic pathway for the preparation of MWCNTs-Phen; b) synthesis of the maleimido-derivatized
phenanthroline 1.

To ease the preparation of the envisioned phenanthroline-functionalized MWCNT hybrid,

we foresaw to exploit the highly efficient addition reaction of thiols to electron deficient carbon
carbon double bonds[52] to graft the Phen moieties onto the carbon scaffold. Therefore, we foresaw

equipping the phenanthroline moiety with a highly reactive double bond, namely a maleimido
substituent (1, Figure 1), and MWCNTs with thiol-terminating appendages (MWCNTs-SH, Figure
1). Among the many possibilities, we decided to use cysteine.
The synthesis of 1 was accomplished following the protocol previously reported by Reetz et
al.[53] Specifically, maleic anhydride was first reacted with 5-amino-1,10-phenanthroline in a
Michael addition type reaction affording an intermediate, 5-maleimido-1,10-phenanthroline, which
was subsequently allowed to intramolecularly cyclize in presence of NaOAc and Ac2O, affording
desired product 1 (Figure 1b). Similarly to a previously reported procedure,[44] the first
functionalization step for preparing MWCNTs-Phen involved a diazotization reaction[54] with 4[(N-Boc)aminomethyl]aniline to obtain NH2-derivatized carbonaceous scaffold MWCNTs-NH2.
Peptidic bond formation with a Boc-S-trityl-L-cysteine in DMF, and subsequent removal of the
trityl S-protecting group via acidic treatment afforded the carbon frameworks terminating with free
thiol groups, MWCNTs-SH.
To

confirm

deprotection,

and

the

efficient

consequently

the

presence of free thiol groups on the

MWCNTs
test[55]

was

exo-surface,
firstly

the

Ellman

conducted

on

MWCNTs-SH (Fig. 2). To a dispersion

of MWCNTs-SH in the mixed solvent
water/DMF (1:4) and in presence of
TRIS buffer (pH = 8), the Ellmans
reagent,
acid)

5,5-dithio-bis-(2-nitrobenzoic

(DTNB) was added.

In the

presence of free thiols, DTNB is

Figure 2. UV-vis spectra recorded at r.t. of a sample

containing MWCNTs-SH (7.610-3 mg/mL) dispersed in
DMF/H2O (4:1) solution in absence (black line) and in
presence (red line) of the Ellmans reagent (DTNB, 4.010-4
M). In the inset: a suspension of MWCNTs-SH in DMF/H2O
(4:1) before (a) and after (b) the addition of DTNB.

involved in a thiol-disulfide exchange reaction,[56] affording a new thiolate product characterized by

a peculiar absorption feature at 450 nm. Indeed, as displayed in Figure 2, upon introduction of
DTNB in the suspension, the absorption profile of MWCNTs-SH changes, displaying the
envisaged spectroscopic fingerprint of the indicator at 450 nm. Once assessed the success of the
grafting of cysteine onto MWCNTs-NH2 and ensuing the deprotection step, preparation of
MWCNTs-Phen was pursued by reacting MWCNTs-SH with phenanthroline derivative 1 in a
heat-activated thiol-ene click-type reaction.[57] To qualitatively prove the efficient grafting of the
Phen moiety a simple metal-induced precipitation test was performed. In particular, addition of a
transition metal ion to the solution, such as Ag+, should induce a precipitation as a consequence of
the supramolecular aggregation of the CNTs due to the occurrence of coordinative interactions
between the metal center and the phenanthroline (MWCNTs-PhenAg).[58-59] Indeed, upon
introduction of AgBF4 into a suspension of MWCNTs-Phen in a 2:1 mixture of CHCl3/toluene, the
occurrence of an extensive precipitation was observed, as displayed in Figure 3. The formation of
insoluble bundles is hence a first indirect proof of the presence of active Phen moieties onto the
MWCNTs-hybrid.

Figure 3. Comparison of the stable suspension of MWCNTs-Phen before (left) and upon addition of AgBF4 (right).

Finally, to construct the luminescent hybrid MWCNTs-Phen[EuL3], MWCNTs-Phen was

first dispersed by ultra-sonication in the mixed solvent CHCl3/cyclohexane (CHX) (3:1) before
adding Eu(III) tris-(2-theonyl)-trifluoroacetonate ([EuL3]) to the suspension (10-fold excess, Fig. 4).
The mixture was stirred at r.t. for 14 hours and then filtered, followed by copious washings with
toluene and CHCl3. Re-dispersion and filtration of the material with CHCl3 was also undertaken to
remove the non-coordinated [EuL3] complex. The final hybrid MWCNTs-Phen[EuL3] was
finally dried under vacuum and used as recovered.

Figure 4. Graphical representation of the complexation reaction affording luminescent MWCNTs-Phen[EuL3]

hybrids.

2.2 Characterization of the hybrid

Photophysical characterization of the hybrid,
performed upon excitation at 360 nm, is
displayed in Figure 5. As it is evident from
the

emission

Phen[EuL3],

profile
the

of

MWCNTs-

characteristic

Eu(III)

emission is centered at 612 nm, indicating an

efficient emission from the [EuL3] complex
upon excitation of the antenna ligands. These
data not only confirm the presence of the

Figure 5. Emission spectrum of MWCNTs-Phen[EuL3]

(0.3 mg/mL in CHCl3) excited at = 360 nm. Inset: the
dispersion of MWCNTs-Phen[EuL3] a) daylight and b)
upon exposure to UV light, showing the typical Eu(III)
red emission.

intact complex, but also demonstrate once more[43-45] the limited electronic interaction between
[EuL3] and the MWCNTs framework, which act as a silent scaffold with exohedrally bonded LnCs.

Table 1. XPS atomic percentage values obtained for p-MWCNTs and the hybrids MWCNTs-NH2, MWCNTs-SH,
MWCNTs-Phen and MWCNTs-Phen[EuL3 ].*
C[%]

O[%]

N[%]

S[%]

F[%]

Eu[%]

MWCNTs

97.5 1.0

2.5 1.0

MWCNTs-NH2

89.9 3.1

8.7 2.9

1.4 0.4

MWCNTs-SH

93.9 2.0

4.9 1.7

0.8 0.3

0.4 0.1

MWCNTs-Phen

94.1 0.6

4.6 0.5

1.0 0.2

0.3 0.1

MWCNTs-Phen[EuL3]

70.9 0.2

11.9 0.6

1.1 0.4

4.8 0.2

10.3 0.6

1.0 0.1

*Each value is the average of three measurements on the sample.

Qualitative determination of the elemental composition of the materials was firstly assessed
via XPS analysis (Table 1; Fig. S2, S.I.). By mean of this technique, confirmation of the presence of
the grafted organic appendages could be pursued through the detection of their elemental
fingerprints. Specifically, as depicted in Table 1, besides the C (1s) and the O (1s) signals mainly
deriving from the carbonaceous scaffold, MWCNT hybrids MWCNTs-NH2 and MWCNTs-SH
also presented the signals of N (1s) and S (2p), centered at 401 and 164 eV, respectively. The signal
of N in MWCNTs-NH2 originates from the aniline moiety grafted onto the MWCNTs, whilst for
hybrid MWCNTs-SH, the signal of the S atom is evidence of the presence of the cysteine residue.
The same atomic species observed in the samples of MWCNTs-SH were also found in MWCNTsPhen, whilst specimens containing luminescent hybrid MWCNTs-Phen[EuL3] also featured the
characteristic peaks fingerprinting the presence of the complex, namely Eu (3d) and F (1s) centered
at 1134 and 686 eV, respectively.
The collected XPS data found confirmation in the TGA results reported in Table 2 (Fig. S3,
S.I.). From the analyses performed, it resulted that whilst MWCNTs resulted stable until 650 C, all
the hybrids presented combustion events in the temperature range before the decomposition of the
pristine CNTs. Specifically, as it can be seen from the reported data, all the materials feature intense
single weight loss episodes starting from 300 C, whose extent increased from 21.7 to 62.9 passing

Table 2. TGA analysis results for the MWCNTs-based hybrids.

MW*

TGA % Loss**

mol/mg

MWCNTs-NH2

106

21.7

2.0 0.5

MWCNTs-SH

210

25.4

1.2 0.1

MWCNTs-Phen

484

32.6

0.7 0.1

MWCNTs-Phen[EuL3]

1299

62.9

0.6 0.1

*The molecular weight refers to the aryl functionalisation of the CNTs and the structure of the complex, as
depicted in Scheme 1. **Each value resulted from the average of the data collected in three different analyses
of the same sample. The TGA loss was calculated at 680 C, temperature at which CNTs start to degrade. All
the experiments were carried out in (80 % N2 / 20%) air atmosphere with a temperature ramp of 10 C /min.

from MWCNTs-NH2 to MWCNTs-Phen[EuL3]. Notably, for MWCNTs-Phen[EuL3] the

single well-defined weight-loss indicates that the newly formed CNT-based complex acts as a unite
entity (Fig. S3, S.I.).
Morphological characterization of MWCNTs-Phen[EuL3] was accomplished by TEM (Fig.
6). Besides evidencing a good dispersibility of the hybrid material, which retained the original
tubular structure even upon functionalization, the analysis clearly confirmed the presence of the
Eu(III) complex as little aggregates homogeneously dispersed along the sidewall of the tubes (Figs.
6a-b). To better determine the presence of the Eu(III) complex in the hybrid material, dark-field
(DF) TEM observations have been undertaken. In fact, DF-TEM images are obtained from the
electrons scattered from the specimen, which are, contrarily to the transmitted ones, the electrons
interacting with the sample. Since heavy atoms such as Eu(III) present higher electronic density, a
more intense scattering of electrons should be observed, giving rise to brighter signals if compared
to lighter elements such as carbon. Indeed, as shown in Figures 6c-d (see also Fig. S4, S.I.), Eu(III)
is well visible as bright white spots homogeneously distributed along the whole length of the tube
profile.

Figure 6. (a-b) Bright and (c-d) dark-field TEM images of MWCNTs-Phen[EuL3].

2.3 Hybrid composite in polymeric matrix (PLLA)

Among the different studies on CNTs/polymer nano-composites, those involving biodegradable
materials arose special interest due to their great potential for biomedical applications. Especially
Poly(L-lactide) (PLLA) has attracted much attention as it is biodegradable, biocompatible,
producible from renewable resources, and nontoxic to the human body and the environment.[60]
Recent innovation on the production process has lowered significantly the production costs, which
further stimulates the studies on its properties and potential applications.[61] However, its relatively
poor mechanical features, slow crystallization rate, and slow degradation rate have limited its wide
practical application. To overcome the aforementioned problems, the preparation of nanocomposites with CNTs resulted a suitable and convenient way.[62-63] CNTs are in fact considered
perfect reinforcing agents for the production of high-strength and conductive polymer composites,
because of their mechanical response and high electrical conductivity.[64] Especially the electrical
conductivity at micro- and nanoscale are making the CNTs outstanding candidates, as this property
is considered extremely promising for the rational modulation of the communication between cells
and polymer nanocomposites.[65] Because of the growing interest, we show here how easily

homogeneous luminescent composites of MWCNTs-Phen[EuL3] and PLLA polymer can be

obtained. By doing so, we would endow the PLLA-CNT composite of luminescent properties, thus
paving the way for the preparation of a novel generation bio-materials in which luminescence could
be used to control the integrity or the proper functioning of the composite within the final
application. The preparation of the composite was performed by solvent-casting technique. A
sample of MWCNTs-Phen[EuL3] (1 mg) was dispersed in a solution of the polymer (100 mg) in
toluene (25 mL), and finally poured into shaped containers to allow the solvent to evaporate
affording the desired luminescent composite material displayed in Figure 7. Indeed, even at very
low loading of CNT-based hybrid, a highly and homogeneously luminescent composite was
obtained.

3. Conclusions
In

this

paper

we

have

reported

the

straightforward preparation of a novel carbonbased luminescent material in which a MWCNT

scaffold decorated with phenanthroline moieties
could be used as versatile scaffold to form
complexes with tris Eu(III) complexes ([EuL3]),
affording

brightly red-emitting

(MWCNTs-Phen[EuL3]).

Thanks

material
to

its

luminescent properties and its dispersibility in

Figure 7. Solid-state PL spectrum of the PLLA

composite containing MWCNTs-Phen[EuL3] (1%
w/w). In the two insets, the composite material
shown under daylight (top) and upon exposure to
UV light (bottom image), displaying the typical
Eu(III) red emission.

biodegradable polymeric matrices such as PLLA, MWCNTs-Phen[EuL3] holds great promise for
the preparation of luminescent substrates to be incorporated in real-life biomedical devices.
Moreover, thanks to the versatility in the chelating action of the Phen ligand toward other
lanthanides or transition metal ions, the as-constructed MWCNTs-Phen hybrid could be considered
as a versatile multifunctional scaffold, the properties of which could in principle be triggered by the

presence of different metal ions. As an example, we also tested the complexation of a Gd(III)
complex, Gd(III) tris-acetylacetonate ([GdL3]), possibly exploitable as magnetic resonance imaging
(MRI) contrast agent. Indeed, both a Gd(III) and a mixed Eu(III)/Gd(III) hybrid were successfully
prepared (Fig. 8; see also Table S1; Fig. S5-6, S.I.), clearly displaying the possibility of designing
unique MRI agents featuring multifunctional activity.

Figure 8. Picture of a CHCl3 dispersion under light excitation of MWCNTs-Phen decorated with (from left to right):
an Eu(III) complex, a Gd(III) complex and Eu(III)/Gd(III) (1:1) mixture of complexes.

Acknowledgments
D.B. gratefully acknowledges the EU through the ERC Starting Grant COLORLANDS project
and the FP7-NMP-2012-SMALL-6 SACS network (contract n GA-310651), the FRS-FNRS
(FRFC contracts n 2.4.550.09), the TINTIN ARC project (09/14-023), the MIUR through the
FIRB Futuro in Ricerca (SUPRACARBON, contract n RBFR10DAK6). The Namur Mons
collaboration has been supported by the Science Policy Office of the Belgian Federal Government
(project PAI-6/27). JMR is a Research Associate by the FRS-FNRS.

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