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DOI: 10.1002/chem.

201304780 Full Paper

& Carbon Nanotubes

Supramolecular Assemblies of Nucleoside Functionalized Carbon


Nanotubes: Synthesis, Film Preparation, and Properties
Alessandra Micoli,[a] Antonio Turco,[a] Elsie Araujo-Palomo,[b] Armando Encinas,[b]
Mildred Quintana,*[b] and Maurizio Prato*[a]

Abstract: Nucleoside-functionalized multi-walled carbon ments confirmed the efficiency of the annealing process. Fi-
nanotubes (N-MWCNTs) were synthesized and characterized. nally, oxidative biodegradation of the films N-MWCNTs and
A self-organization process using hydrogen bonding interac- d-N-MWCNTs was performed by using horseradish perox-
tions was then used for the fabrication of self-assembled N- idase (HRP) and low concentrations of H2O2. Our results con-
MWCNTs films free of stabilizing agents, polymers, or surfac- firm that functional groups play an important role in the bio-
tants. Membranes were produced by using a simple water- degradation of CNT by HRP: N-MWCNTs films were com-
dispersion-based vacuum-filtration method. Hydrogen-bond pletely biodegraded, whereas for d-N-MWCNTs films no
recognition was confirmed by analysis with IR spectroscopy degradation was observed, showing that the pristine CNT
and TEM images. Restoration of the electronic conduction undergoes minimal enzyme-catalyzed oxidation This novel
properties in the N-MWCNTs membranes was performed by methodology offers a straightforward supramolecular strat-
removing the organic portion by thermal treatment under egy for the construction of conductive and biodegradable
an argon atmosphere to give d-N-MWCNTs. Electrical con- carbon nanotube films.
ductivity and thermal gravimetric analysis (TGA) measure-

Introduction strategies are usually employed, encompassing either a cova-


lent or a supramolecular approach. Whereas the first protocol
Carbon nanotube (CNT) processing is extremely important in exploits the chemical reactivity of the CNT graphitic wall by
the development of new advanced materials such as flexible grafting the nucleobase groups directly onto the tubular sur-
electrodes, electronic paper, antistatic coatings, protective face,[4] the second approach is based on noncovalent recogni-
clothing, high-performance composites for aircraft and auto- tion of the base-pairing motifs involving at least two hydro-
motive industry, and micro/nano-platforms for cell growth and gen-bond interactions as directional and predictable noncova-
differentiation.[1] To achieve this, it is well known that CNT han- lent attractive forces between complementary hydrogen donor
dling must be maximized to reach optimal material properties (D) and acceptor (A) moieties.[5]
such as strength, conductivity, and biocompatibility.[2] In this The molecular-recognition-driven assembly of CNT is mediat-
direction, a reliable and successful strategy for the construction ed by the quantity of functional groups covalently grafted to
of functional CNT-based architectures is the use of nucleo- the CNTs surface (cooperative effect). In particular, when the
baseCNT nanohybrids as building blocks in the self-assembly assembly is driven by thymine-derived CNTs, the self-organiza-
of multifunctional materials.[3] The presence of the nucleobase tion through the formation of double hydrogen bonded ho-
on the CNT surface improves the dispersibility of the nanohy- modimers results in compact 2 D or 3 D superstructures as the
brid in polar solvents and directs the recognition through hy- degree of covalent functionalization is increased.[6] Following
drogen bonding of complementary base pairs in nonpolar the same approach, herein, we demonstrate a versatile meth-
aprotic solvents. To achieve this goal, two functionalization odology for the construction of conductive CNT membranes
completely free of surfactants or polymers. This methodology
[a] Dr. A. Micoli, Dr. A. Turco, Prof. M. Prato is expected to improve the properties of conductive films[7]
Center of Excellence for Nanostructured Materials (CENMAT)
prepared from solutions containing stabilizing agents[8, 9] as
INSTM UdR di Trieste, Dipartimento di Scienze Chimiche e Farmaceutiche
University of Trieste strong interactions between the stabilizing molecules and
Piazzale Europa 1, 34127 Trieste (Italy) CNTs may significantly affect the electronic transitions,[10] re-
E-mail: prato@untis.it sulting in modification of the electronic properties of the com-
[b] E. Araujo-Palomo, Prof. A. Encinas, Prof. M. Quintana posite.[11] Furthermore, in some instances, the presence of sta-
Instituto de Fsica, Universidad Autnoma de San Luis Potos
bilizing molecules can also affect the biocompatibility of the
Manuel Nava 6, Zona Universitaria 78290, San Luis Potos, SLP (Mexico)
E-mail: mildred@ifisica.uaslp.mx CNT-based composite, in particular, the use of surfactants in bi-
Supporting information for this article is available on the WWW under oapplications.[12]
http://dx.doi.org/10.1002/chem.201304780.

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The procedure described here involves the covalent attach- of nucleoside molecules attached to the MWCNTs, calculated
ment of each of the four nucleosides moieties (Thymidine, T; by the Kaiser test[3] and TGA, is reported in Table 1.
Adenosine, A; Cytidine, C; Guanosine, G) to multi-walled CNTs Confirmation of the covalent attachment of nucleoside moi-
(MWCNTs) as supramolecular motifs, N-MWCNTs (N = A, T, G or eties to the CNTs surface was provided by TGA coupled with
C). The recognition between complementary base pair nanohy- online monitoring of the volatile products by mass spectrome-
brids, T/A-MWCNTs or G/C-MWCNTs systems dispersed in try. The peaks corresponding to the ionic fragments of the nu-
water, allows the fabrication of freestanding homogeneous cleoside moieties covalently bonded to MWCNTs evolved at
films by a simple vacuum-filtration method.[13] As depicted in higher temperatures compared with free nucleoside molecules
Scheme 1, the engineering design behind the formation and for all the N-MWCNTs nanohybrids (Figure S1 in the Support-
ing Information). IR spectra (Fig-
ure S2 in the Supporting Infor-
mation) also confirm the pres-
ence of the complementary rec-
ognition functions through the
characteristic peaks of the or-
ganic groups: stretching modes
of NH and OH (n = 38713408),
CH (n = 32752920), C=O (n =
17411736), C=N (n = 1739), and
C=C (n = 15881554).
Although all the nucleobases
have the ability to homodimer-
ize, the presence of complemen-
tary hydrogen-bond arrays, that
is, donor sites comprising the
NH amide and NH amine, and
acceptor sites comprising the O
and N functionalities, allow them
to oligomerize through hydro-
gen-bonding interactions.[16]
Thus, the influence of the inter-
action between nucleoside
Scheme 1. Representation of N-MWCNTs (N = Adenosine (A), Guanidine (G), Cytosine (C), and Thymidine (T)) and
groups on the dispersibility of N-
the recognition processes between complementary base pairs, A/T-MWCNTs and C/G-MWCNTs.
MWCNTs was compared in sol-
vents possessing different polari-
stabilization of the film is the establishment of hydrogen ty: DMF and H2O as polar solvents, and CH2Cl2 as a noncompe-
bonds between the complementary sites of the nucleotides A titive solvent unable to generate hydrogen-bond interactions.
T and GC (Ka = 102 m 1 and 103105 m 1 in CHCl3, respectively). After 5 min of sonication of 0.1 mg of each compound in 1 mL
The recognition event was monitored by IR spectroscopy and of the respective solvent, N-MWCNTs exhibited good dispersi-
TEM images. The restoration of the electronic conduction bility in DMF and H2O, whereas aggregates were always ob-
properties in the N-MWCNTs membranes was performed by served in CH2Cl2 (Figure S3 in the Supporting Information). The
removing the organic portion by thermal treatment under presence of the ribose or deoxyribose fragment in the nucleo-
argon, giving defunctionalized N-MWCNTs (d-N-MWCNTs), as side moiety covalently grafted to the CNT surface allowed the
demonstrated by electrical conductivity and thermal gravimet- complete dispersion of the different N-MWCNTs derivatives in
ric analysis (TGA) measurements. In addition, we demonstrate
that the new films become biodegradable, in contrast to films
formed by pristine CNTs, which are known to be potentially Table 1. TGA-determined weight loss and number of nucleoside groups
toxic.[14] covalently grafted onto the different N-MWCNTs.

Compound Nucleoside groups % wt loss (TGA)


[mmol g 1][a]
Results and Discussion
T-MWCNTs 584 11
The nanohybrids were prepared by using the diazonium salt- A-MWCNTs 602 13
based arylation reaction.[15] Firstly, MWCNTs with amino termi- C-MWCNTs 654 10
nal groups were synthesized, NH2-MWCNTs.[6] After this, each G-MWCNTs 506 10

of the four nucleoside moieties was easily introduced on NH2- [a] The amount of thymidine, adenosine, cytosine, and guanosine groups,
MWCNTs by nucleophilic substitution to obtain N-MWCNTs respectively, was calculated as the difference between the Kaiser test
before and after the covalent attachments of nucleoside groups.
(Scheme S5 in the Supporting Information). The final loading

Chem. Eur. J. 2014, 20, 5397 5402 www.chemeurj.org 5398  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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the polar solvents DMF and H2O in concentrations of MWCNTs the stretching mode of the C=O group shifts to
0.1 mg mL 1. lower frequencies, Figure 2 b, from 1644 cm 1 in DMF, to
To verify the selective molecular recognition by the comple- 1633 cm 1 in H2O, and to 1574 cm 1 in CH2Cl2. These results
mentary nucleobases TA and CG on N-MWCNTs, equimolar confirm that aggregation is guided by hydrogen-bond recogni-
amounts (in term of nucleoside functionalization) of T- tion in noncompetitive solvents.
MWCNTs (7.0 mg) and A-MWCNTs (6.8 mg) nanoybrids, and in There are different direct techniques for growing CNT films
a different set of experiments, C-MWCNTs (5.4 mg) and G- with high purity and relative absence of tube bundles.[1a] How-
MWCNTs (7.0 mg) nanohybrids were dispersed by sonication ever, films prepared from solutions are attractive as they can
in DMF, H2O or CH2Cl2 (70 mL). Each solution was stirred over- be cost-effectively scaled to large areas and are compatible
night at room temperature and the recognition between com- with a wide variety of substrates.[8, 9] Thus, after the complete
plementary N-MWCNTs in different solvents was analyzed by characterization of the nanohybrids and the verification of the
TEM. As expected, aggregation in CH2Cl2 was always observed, molecular recognition between complementary N-MWCNTs,
whereas good dispersibility in polar solvents like DMF and H2O we fabricated self-assembled freestanding membranes by
was obtained, as depicted in Figure 1. using a simple dispersion-based vacuum-filtration method. For
The formation of hydrogen bonds was assessed by means of this, equimolar amounts of T-MWCNTs and A-MWCNTs, and in
IR spectroscopy. More precisely, we observed a general shift of a different batch, C-MWCNTs and G-MWCNTs, were first dis-
frequencies towards lower values and the formation of wid- persed in water, and then the suspensions were filtered
ened and augmented intense bands. The IR spectra of the through a Millipore membrane (VSWP, 0.025 mm). Water was
three black solids, recovered by filtration from the three differ- chosen as a solvent to produce N-MWCNTs dispersions with
ent solvents, show a redshift of the C=O stretching frequency. concentration of 0.01 mg mL 1 to prevent aggregation, thereby
The characteristic peak at 1733 cm 1 in DMF, moves to favoring formation of homogeneous films. Then, the mem-
1638 cm 1 in H2O, and to 1558 cm 1 in CH2Cl2 for the T/A- brane filters were degraded in acetone to obtain the black
MWCNTs recognition system, Figure 2 a, whereas for the C/G- films of N-MWCNTs (Figure 3 a). The films were devoid of
traces of filter, as observed by SEM images (Figure 3 b) and cor-
roborated by Raman spectra (Figure S4 in the Supporting Infor-
mation). The membranes were allowed to dry under vacuum
overnight. It is important to note that the dispersion and filtra-
tion of pristine- (p-MWCNTs) or NH2-MWCNTs produces pow-
ders as they dry, whereas the filtration of only one type of N-
MWCNT results brittle films that break into pieces upon con-
tact.
Electrical conductivity measurements were performed at
room temperature on the samples by using a four-probe con-
figuration with a Jandel resistivity meter. The measurements
were repeated on three different places in each sample, and
current sweeps were performed with different ranges up to
100 mA. The N-MWCNTs annealing samples, d-N-MWCNTs,
were prepared following thermal treatment at 350 8C for
20 min in an inert atmosphere of argon to measure the trans-
port properties of a p-MWCNTs membrane. The successful de-
functionalization of the N-MWCNTs to give d-N-MWCNT mem-
branes was verified by TGA as shown in Figure 4.
Figures 5 a and b compare the measurements obtained in N-
MWCNTs and d-N-MWCNTs, along with the corresponding
linear fits, which provide the sample resistance. In all cases, the
samples show a linear IV curve consistent with ohmic behavior.
Moreover, these measurements show that for the d-N-MWCNT
films the removal of the functional groups reduces the electri-
cal resistance significantly, an observation that is consistent
with an enhancement of the conductivity. From the measured
values of the electrical resistance R, the bulk resistivity 1, sheet
resistance Rs, and electrical conductivity s, have been deter-
mined. Values are given in Figure 5. From these values it can
be seen that the removal of the organic portion increases the
conductivity of the d-N-MWCNTs membranes by an order of
Figure 1. TEM images of T/A-MWCNTs in a) DMF, b) H2O, and c) CH2Cl2 and
TEM images of C/G-MWCNTs in d) DMF, e) H2O, and f) CH2Cl2. Insets show magnitude. The conductivity values for A/T-MWCNTs and C/G-
the dispersibility of N/N-MWCNTs in the different solvents. MWCNTs membranes are 34.8 and 29.5 S m 1, respectively.

Chem. Eur. J. 2014, 20, 5397 5402 www.chemeurj.org 5399  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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ments of the membranes (ap-


proximately 2 mm per side) for
three days in Bovine Serum (Calf
Serum) at room temperature. A
clear difference was noticed in
the morphology of the films
after incubation. A strong inter-
action with the biological
medium was observed for N-
MWCNT membranes. An evident
swelling of the films was ob-
served, whereas d-N-MWCNTs
membranes remained stable as
a compact film, Figure 6. We
then performed the oxidative
degradation of the membranes
by using horseradish peroxidase
(HRP) and low concentrations of
H2O2.[17] TEM was used to exam-
ine aliquots taken from the sam-
ples after incubation at 3, 5, 7,
and 18 days. For d-N-MWCNTs,
the membrane remained un-
changed during the entire incu-
bation period, and TEM analysis
did not show any CNTs in the so-
lution at any time (Figure S6 in
the Supporting Information).
Conversely, a substantial degra-
dation of the N-MWCNTs film
was observed. The incubation
solution gradually changed to
a black dispersion. TEM analysis
at three days showed small
Figure 2. IR spectra of a) A/T-MWCNTs and b) C/G-MWCNTs recovered by filtration from DMF (upper), H2O membrane fragments, Figure 7 a.
(middle), and CH2Cl2 (bottom). Over the next few days, individu-
al CNTs were observed, Fig-
ure 7 b and c. At 18 days, debris
These values are considerably higher than those reported for was found on the TEM grid, Figure 7 d. Our results confirm pre-
MWCNT films prepared by using poly(p-phenylene sulfide) as vious studies, where it was demonstrated that functional
stabilizer, 0.01 S m 1,[9f] and MWNT films prepared in poly(vinyli- groups play an important role in the biodegradation of CNT by
dene fluoride), 2 S m 1.[9g]
Finally, we have compared the biodegradation of both N-
MWCNT and d-N-MWCNTs. First, we incubated small frag-

Figure 3. a) Image of freestanding A/T-MWCNTs membrane and b) SEM mi-


crograph of A/T-MWCNTs membrane. Figure 4. TGA of p-MWCNTs, A/T-MWCNTs, and d-A/T-MWCNTs.

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Figure 5. Comparison of the measured resistance of a) A/T-MWCNTs and d-


A/T-MWCNTs and b) C/G-MWCNTs and d-C/G-MWCNTs, along with the cor-
responding linear fits. c) The table shows the calculated values of the bulk
resistivity 1, sheet resistance Rs, and electrical conductivity s.

Figure 7. TEM images of N-MWCNTs at 3, 5, 7, and 18 days (a, b, c, and d, re-


spectively) during the degradation process by HRP/H2O2.

(D) and acceptor (A) moieties. The produced N-MWCNTs mem-


branes showed a linear IV curve consistent with ohmic behav-
ior. The thermal treatment in an inert atmosphere, affording d-
N-MWCNTs, significantly decreased the electrical resistance, an
observation consistent with the enhancement of the conduc-
tivity by an order of magnitude when compared with N-
MWCNTs. The covalent attachment of the nucleosides in N-
MWCNTs promotes their oxidative degradation by HRP/H2O2.
Importantly, d-N-MWCNTs remain as a stable film under the
same incubation conditions, demonstrating that functional
groups are essential for CNT biodegradation. By using a combi-
nation of covalent/noncovalent interactions, we were able to
tune CNTs properties such as biocompatibility, degradability,
Figure 6. Illustration of N-MWCNTs and d-N-MWCNTs membranes incubated and conductivity. Methodologies such as the one reported
in Bovine Serum for three days and ultrasonicated for 1 min. here are expected to impact the design of new advanced ma-
terials.

HRP and corroborate that pristine CNT suffers minimal enzyme-


catalyzed oxidation.[17] Experimental Section
Materials
Conclusion All reagents and solvents were obtained from commercial suppliers
(SigmaAldrich) and were used without further purification.
MWCNTs conductive films completely free of stabilizing agents,
MWCNTs 7000 series were purchased from Nanocyl (lot MWM
such as surfactants or polymers, were produced by a self-or- P031105, www.nanocyl.com).
ganization process using hydrogen-bond interactions. MWCNTs
were functionalized with one of the four nucleoside bases Characterization techniques
(Thymidine, T; Adenosine, A; Cytidine, C; Guanosine, G) as
supramolecular motifs. The functionalization of N-MWCNTs Thermogravimetric analyses were recorded on a TGA Q500 (TA In-
struments) using a flowing nitrogen atmosphere. The samples
and the directional recognition by hydrogen-bond interactions
were equilibrated (1 mg per sample) at 100 8C for 20 min and then
between complementary nucleoside pairs were followed by heated at a rate of 10 8C min 1 up to 1000 8C. Thermogravimetric
the Kaiser test, IR spectroscopy, TEM, and TGA, all of which analysismass spectrometry (TGA-MS) experiments were carried
confirmed the directional, reliable, and predictable noncova- out on a ThermoStar Mass Spectrometer (Pfeiffer Vacuum) coupled
lent attractive forces between complementary hydrogen donor to a Q500 thermogravimetric analyzer (TA Instruments) using

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a flowing He atmosphere by equilibrating the samples (approxi- elos, A. Bianco, Acc. Chem. Res. 2008, 41, 60; d) A. Bianco, K. Kostarelos,
mately 5 mg per sample) at 100 8C, and then heating at a rate of M. Prato, Chem. Commun. 2011, 47, 10182.
20 8C min 1 up to 800 8C. Infrared analyses were performed by [3] a) A. Micoli, M. Quintana, M. Prato, Supramol. Chem. 2013, 25, 567 573;
b) A. Micoli, M. L. Soriano, H. Traboulsi, M. Quintana, M. Prato, Eur. J.
using a Fourier-transform infrared (FT-IR) spectrometer (PerkinElmer
Org. Chem. 2013, 3685; c) M. Quintana, H. Traboulsi, A. Llanes-Pallas, R.
2000). The samples were prepared as KBr pellets. Transmission
Marega, D. Bonifazi, M. Prato, ACS Nano 2012, 6, 23; d) A. Prevoteau, C.
electron microscopy analyses were performed on a TEM Philips Souli-Ziakovic, L. Leibler, J. Am. Chem. Soc. 2012, 134, 19961; e) P.
EM208 using an accelerating voltage of 100 kV. The samples were Singh, C. Mnard-Moyon, J. Kumar, B. Fabre, S. Verma, A. Bianco, Carbon
prepared by dropping an aliquot of the dispersions in the specified 2012, 50, 3170; f) P. Singh, V. Venkatesh, N. Nagapradeep, S. Verma, A.
solvent on a TEM grid (200 mesh, Nichel, carbon only). For scan- Bianco, Nanoscale 2012, 4, 1972; g) P. Singh, M. F. Toma, J. Kumar, V.
ning electron microscopy measurements, the samples were sput- Venkatesh, J. Raya, M. Prato, S. Verma, A. Bianco, Chem. Eur. J. 2011, 17,
ter-coated with gold in an Edwards S150 A apparatus (Edwards 6772; h) P. Singh, G. Lamann, C. Menard-Moyon, F. M. Toma, E. Magna-
High Vacuum, Crawley, West Sussex, UK), and examined with no, F. Bondino, M. Prato, S. Verma, A. Bianco, Angew. Chem. 2011, 123,
10067; Angew. Chem. Int. Ed. 2011, 50, 9893; i) P. Singh, J. Kumar, M. F.
a Leica Stereoscan 430i scanning electron microscope (Leica Cam-
Toma, J. Raya, M. Prato, B. Fabre, A. Bianco, J. Am. Chem. Soc. 2009, 131,
bridge Ltd., Cambridge, United Kingdom). Raman spectra were re-
13555.
corded with an Invia Renishaw microspectrometer equipped with [4] D. Tasis, N. Tagmatarchis, A. Bianco, M. Prato, Chem. Rev. 2006, 106,
a HeNe laser at 633 nm using the 100 X objective. Samples were 1105.
prepared by drop casting of the dispersion on silicon oxide surfa- [5] a) W. H. Binder, Monatsh. Chem. 2005, 136, 1; b) E. A. Archer, H. Gong,
ces (Si-Mat silicon wafers, CZ) and the solvent was allowed to evap- M. J. Krische, Tetrahedron 2001, 57, 1139; c) A. Llanes-Pallas, K. Yoosaf,
orate. The thickness was obtained from three repeated measures H. Traboulsi, J. Mohanraj, T. Seldrum, J. Dumont, A. Minoia, R. Lazzaroni,
by using a high-accuracy digimatic micrometer (Mitutoyo, MD- N. Armaroli, D. Bonifazi, J. Am. Chem. Soc. 2011, 133, 15412.
H25). The sheet resistance and bulk resistivity values were recorded [6] M. Quintana, M. Prato, Chem. Commun. 2009, 6005.
[7] M. A. Correa-Duarte, N. Wagner, J. Rojas-Chapana, C. Morsczeck, M.
with a Jandel resistivity meter (RM3000) with a four-point probe
Thie, M. Giersig, Nano Lett. 2004, 4, 2233.
head (probe spacing of 0.635 mm, needles of tungsten carbide) by
[8] a) M. Zheng, A. Jagota, E. D. Semke, B. A. Diner, R. S. McLean, S. R.
repeating the measurements at three different points of the mem- Lustig, R. E. Richardson, N. G. Tassi, Nat. Mater. 2003, 2, 338; b) V. C.
branes. Moore, M. S. Strano, E. H. R. Haroz, H. Hauge, R. E. Smalley, J. Schmidt, Y.
Talmon, Nano Lett. 2003, 3, 1379; c) J. T. Han, S. Y. Kim, J. S. Woo, G. W.
Preparation of the N-MWCNTs Lee, Adv. Mater. 2008, 20, 3724; d) Q. Cao, H. Kim, N. Pimparkar, J. P. Kul-
karnim, C. Wang, M. Shim, K. Roy, M. A. Alam, J. A. Rogers, Nature 2008,
In a typical experiment, a solution of the nucleoside moiety 454, 495.
(46.7 mmol, see the Supporting Information) in anhydrous DMF [9] a) T. V. Sreekumar, T. Liu, S. Kumar, L. M. Ericson, R. H. Hauge, R. E. Small-
(1 mL) was added to a well-dispersed solution of NH2-MWCNTs ey, Chem. Mater. 2003, 15, 175; b) M. A. Meitl, Y. Zhou, A. Gaur, S. Jeon,
(30 mg) in anhydrous DMF (5 mL) and TEA (triethylamine; 4 mL, L. M. Usrey, M. S. Strano, J. A. Rogers, Nano Lett. 2004, 4, 1643; c) Z. C.
Wu, Z. H. Chen, X. Du, J. M. Logan, J. Sippel, M. Nikolou, K. Kamaras,
28.1 mmol). The resultant mixture was stirred at 90 8C for 48 h
J. R. Reynolds, D. B. Tanner, A. F. Hebard, A. G. Rinzler, Science 2004, 305,
under an argon atmosphere. The black suspension was filtered,
1273; d) D. Zhang, M. A. Kandadai, J. Cech, S. Roth, S. A. Curran, J. Phys.
washed with DMF, methanol, and dichloromethane and finally Chem. B 2006, 110, 12910; e) R. K. Jackson, A. Munro, K. Nebesny, N.
dried under vacuum. Armstrong, S. Graham, ACS Nano 2010, 4, 1377; f) J. M. Gonzlez-Dom-
nguez, P. Castell, S. Bespn-Gascn, A. M. Dez-Pascual, M. A. Gmez-
Fatou, A. M. Benito, W. K. Maser, M. T. Mrtnez, J. Mater. Chem. 2012,
Acknowledgements 22, 21285; g) A. Mandal, A. K. Nandi, J. Phys. Chem. C 2012, 116, 9360;
h) Q. Zhang, J. Q. Huang, W. Z. Quian, Y. Y. Zhang, F. Wei, Small 2013, 9,
This work was supported by the Italian Ministry of Education 1237.
[10] a) D. M. Guldi, G. M. A. Rahman, F. Zerbetto, M. Prato, Acc. Chem. Res.
MIUR (cofin Prot. 2010N3T9M4 and Firb RBAP11C58Y), the Eu- 2005, 38, 871; b) J. Zhaoa, X. Chenc, J. R. H. Xie, Anal. Chim. Acta 2006,
ropean Union through the ERC Advanced Grant Carbonano- 568, 161.
bridge. Thanks are given to CONACYT through the projects [11] S. Bose, R. A. Khare, P. Moldanaers, Polymer 2010, 51, 975.
CB-166014, CB-105568 and PROMEP/103.5/12/3953. E.A.P. [12] L. Dong, K. L. Joseph, C. M. Witkowski, M. N. Craig, Nanotechnology
2008, 19, 255702.
thanks CONACYT for the scholarship 328587. [13] L. Liu, W. Ma, Z. Zhang, Small 2011, 7, 1504.
[14] C. A. Poland, R. Duffin, I. Kinloch, A. Maynard, W. A. H. Wallace, A.
Seaton, V. Stone, S. Brown, W. MacNee, K. Donaldson, Nat. Nanotechnol.
Keywords: biodegradable carbon nanotubes conductive
2008, 3, 423.
films covalent functionalization nucleosides supramolecular [15] a) C. A. Dyke, M. P. Stewart, F. Maya, J. M. Tour, Synlett 2004, 1, 155;
assemblies b) J. L. Bahr, J. M. Tour, Chem. Mater. 2001, 13, 3823.
[16] S. Sivakova, S. J. Rowan, Chem. Soc. Rev. 2005, 34, 9.
[1] a) M. T. Byrne, Y. K. GuinKo, Adv. Mater. 2010, 22, 1672; b) C. Wang, J. [17] a) G. P. Kotchey, S. A. Hasan, A. A. Kapralov, S. H. Ha, K. Kim, A. A. Shve-
Zhang, K. Ryu, A. Badmaev, L. G. De Arco, C. Zhou, Nano Lett. 2009, 9, dova, V. E. Kagan, A. Star, Acc. Chem. Res. 2012, 45, 1770; b) B. L. Allen,
4285; c) M. Sangermano, S. Pegel, P. Ptschke, P. Voit, Macromol. Rapid P. D. Kichambare, P. Gou, I. I. Vlasova, A. A. Kapralov, N. Konduru, V. E.
Commun. 2008, 29, 396; d) S. H. Joo, S. C. Yoon, C. S. Lee, D. H. Nam, Kagan, Nano Lett. 2008, 8, 3899; c) J. Russier, C. Menard-Moyon, E. Ven-
S. H. Hong, H. S. Kim, J. Mater. Sci. 2010, 45, 4652; e) H. Presting, U. turelli, E. Gravel, G. Marcolongo, M. Meneghetti, E. Doris, A. Bianco,
Knig, Mater. Sci. Eng. C 2003, 23, 737; f) B. S. Shim, W. Chen, C. Doty, C. Nanoscale 2011, 3, 893.
Xu, N. A. Kotov, Nano Lett. 2008, 8, 4151; g) A. Fabbro, S. Bosi, L. Balleri-
ni, M. Prato, ACS Chem. Neurosci. 2012, 3, 611 618.
[2] a) A. A. Mamedov, N. A. Kotov, M. Prato, D. M. Guldi, J. P. Wicksted, A.
Hirsh, Nat. Mater. 2002, 1, 190; b) S. W. Kim, T. Kim, Y. S. Kim, H. S. Choi, Received: December 5, 2013
H. J. Lim, S. J. Yang, C. R. Park, Carbon 2012, 50, 3; c) M. Prato, K. Kostar- Published online on March 19, 2014

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