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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-
Chem. Eur. J. 2014, 20, 5397 5402 5397 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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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.
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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Chem. Eur. J. 2014, 20, 5397 5402 www.chemeurj.org 5400 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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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,
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