You are on page 1of 9

IEEE Transactions on Dielectrics and Electrical Insulation Vol. 13, No.

5; October 2006 1101

Layer-by-layer Films of Poly(o-ethoxyaniline), Chitosan and


Chitosan-poly(methacrylic acid) Nanoparticles and their
Application in an Electronic Tongue
Carlos E. Borato, Fábio L. Leite, Luiz H. C. Mattoso
Embrapa Instrumentação Agropecuária, CP 741, 13 560-970, São Carlos, SP, Brazil

Rejane C. Goy, Sergio P. Campana Filho


Instituto de Química de São Carlos USP, CP 780, 13 560-970 São Carlos, SP, Brazil

Cláudio L. de Vasconcelos, Cypriano G. da Trindade Neto, Márcia R. Pereira, José L. C.


Fonseca
Departamento de Química, Universidade Federal do Rio Grande do Norte, CP 1662, 59078-970 Natal, RN, Brazil

and Osvaldo N. Oliveira Jr.


Instituto de Física de São Carlos USP, CP 369, 13 560-970, São Carlos, SP, Brazil

ABSTRACT
Layer-by-layer (LbL) films have been produced with poly(o-ethoxyaniline) (POEA),
chitosan and chitosan-poly(methacrylic acid) (CS-PMAA) nanoparticles. Because the
adsorption of LbL films depends on ionic interactions and H-bonding, optimized
conditions had to be established for the growth of multilayer films. Unusually thick
films were obtained for POEA and CS-PMAA, thus demonstrating the importance of
using chitosan in the form of nanoparticles. These nanostructured films were deposited
on chromium electrodes to form a sensor array (electronic tongue) based on impedance
spectroscopy. This system was used to detect copper ions in aqueous solutions.
Index Terms – Electronic tongue, chromium electrodes, films, chitosan nanoparticles,
POEA, impedance spectroscopy.

1 INTRODUCTION chitosan nanoparticles in LbL films with alternated layers of


poly(o-ethoxyaniline) (POEA), a polyaniline derivative.
NANOSTRUCTURED films of chitosan, a POEA is highly stable, easily processed and may have its
polysaccharide obtained from the desacetylation of chitin, conductivity varied widely by doping and dedoping upon
have been fabricated in the last few years for a variety of protonation and deprotonation, respectively [12]. It has also
applications [1,2]. Chitosan is soluble in acidic media and can been used extensively in the fabrication of LbL films, where it
be used to produce layer-by-layer (LbL) films, which have normally functions as the polycation for adsorption via ionic
been employed as sensing units in taste sensors [3], and as interactions, or even through H-bonding [13]. With the
templates for immobilization of enzymes used for biosensing combination of distinct materials, one may envisage
[4]. The main interest in chitosan in the form of thin films is to biospecific recognition in LbL films, which opens up a
exploit its biocompatibility and ability to complex heavy metal number of novel possibilities. Of particular relevance for this
ions [2], in addition to its strong interaction with cholesterol work is the deposition of LbL films that may be used in taste
[5] and other biomolecules [6]. Nanoparticles of chitosan, on sensors. We use impedance spectroscopy [14] as the method
the other hand, have been used as bactericide and of detection with sensing units made of LbL films deposited
antimicrobial [7,8] and in the controlled release of drugs, onto metallic substrates and immersed in the liquid samples to
insulin and albumin [9-11]. In general, chitosan nanoparticles be analyzed. The aim is to exploit the high sensitivity provided
performed better in inhibiting growth of microorganisms than by the combination of nanostructured films with an ac
raw chitosan [8]. It is therefore important to verify whether electrical characterization method, which has given excellent
LbL films made of chitosan nanoparticles behave differently results in distinguishing complex liquids, e.g. wine, coffee,
from those of chitosan. juices and milk, and in detecting pollutants such as pesticides,
In this paper we compare the behavior of chitosan and heavy metals and humic substances in waters [15-19]. We also
compare the performance of these sensing units with an array
Manuscript received on 9 May 2006, in final form 9 August 2006. made of bare chrome electrodes.

1070-9878/06/$20.00 © 2006 IEEE


1102 C. E. Borato et al.: Layer-by-layer Films of Poly(o-ethoxyaniline), Chitosan and Chitosan-poly(methacrylic acid) Nanoparticles

2 EXPERIMENTAL DETAILS experiments with CuSO4 to check whether the electrodes had
been contaminated. Three measurements were taken for each
POEA was synthesized according to the procedures
concentration and, more importantly, the concentration was
described by Mattoso et al [20]. Chitin extracted from the
chosen randomly for each measurement. That is to say, we did
exoskeleton of crabs was submitted to desacetylation [21]
not obtain the measurements in a growing or decreasing
resulting in chitosan with viscosity average molecular weight
concentration of CuSO4 to minimize systematic errors. In the
(Mv) of 170,000 g/mol and average degree of acetylation
second set of experiments, the aim was to check
( DA ) of 10%. The dispersion of chitosan nanoparticles (CS- reproducibility of the measurements and attempt to determine
PMAA) was obtained from a 0.2% chitosan solution in whether even lower concentrations of copper could be
methacrylic acid (0.5%) using potassium persulfate as initiator detected. This was carried out by pouring 50mL of distilled
[22]. For the fabrication of LbL films of POEA (0.06%) and water into an acrylic trough constructed especially for
chitosan (0.15%) or chitosan nanoparticles (0.2%), the first coupling the sensor array. After stabilization, measurements
step was to determine an optimized immersion time for the were taken in pure water at each 20 min. For the 31st
substrate in the aqueous solutions, which were 3 minutes for measurement, pure water was added to the sample (i.e. copper
POEA and 8 minutes for chitosan and CS-PMAA, ions were deliberately introduced, but the sample suffered
respectively. The substrates were made of glass cleaned with a manipulation). In addition, in some other experiments aliquots
solution of 7:3 H2SO4/H2O2 (v/v) (during 60 min.) and then of varying concentrations of CuSO4 were added to pure water
with a solution of 5:1:1 H2O/NH4OH/H2O2 (v/v)) (during 40 to be compared with the cases where only pure water was
min.). Film growth on the substrate was monitored by added.
measuring the UV-VIS. absorption spectra of the substrate +
film, with absorption in the visible region being basically due 3 RESULTS AND DISCUSSION
to POEA. Before proceeding to film fabrication, the The first clear difference between chitosan and the
interaction in solution was investigated by measuring the UV- dispersion of chitosan nanoparticles (CS-PMAA) is observed
VIS. spectra of mixtures of POEA and chitosan or CS-PMAA. in the interaction with POEA in aqueous solutions, as
The materials used in the study were combined to generate 10 demonstrated in the spectra of Figure 1. The incorporation of
distinct films. LbL films with 10 bilayers were produced for CS-PMAA causes the absorption of POEA to shift
POEA alternated with chitosan or with CS-PMAA, where the considerably to lower wavelengths owing to dedoping of
POEA solutions had pH 3 or 5. Films were also produced POEA. Indeed, for a pH 3 POEA solution an absorption peak
from mixed solutions of 1:1 POEA/chitosan or POEA/CS- appears at ca. 780 nm, but as chitosan nanoparticles are added
PMAA, and from a single component, namely POEA, chitosan the peak shifts to ca. 530 nm, which is characteristic of
and CS-PMAA. The 10-layer films from a single component dedoped POEA. POEA dedoping can be associated with the
could be built, with no alternating layers, because secondary “competition” for its positive charges – as POEA was
interactions participated in the adsorption process, in addition protonated - with the nanoparticles. Further dedoping or
to the ionic interactions. All films were characterized with a changes in the oxidation state were also observed for a pH 5
Topometrix 2010 Discoverer atomic force microscopy (AFM), solution of POEA and CS-PMAA, which also shifted to lower
operating in the contact mode. LbL films of POEA and wavelengths. On the other hand, Figure 1b shows that addition
chitosan or CS-PMAA were also deposited onto chrome of chitosan solution (not in the form of nanoparticles) into a
electrodes for impedance spectroscopy measurements. The pH 3 solution of POEA does not cause any shift. The
latter were measured with a Solartron 1260 Impedance Gain absorbance merely decreases as a result of a smaller relative
Phase Analyser at 200 Hz and bias voltage of 50 mV. These quantity of POEA in the mixed solution due to a dilution
films were used as sensing units to detect copper ions in effect as the amount of chitosan is increased.
aqueous solution of CuSO4. The detection studies were made The adsorption of POEA in LbL films of chitosan and CS-
in two different steps, both using two arrangements referred to PMAA was also markedly different, as a much higher amount
as A and B. Each arrangement comprised five sensing units of POEA was adsorbed for CS-PMAA. This effect was
with double face (i.e. two back-to-back units), resulting in ten particularly strong for POEA at pH 5 and CS-PMAA at pH 3,
sensing units. Measurements using units with no deposited as indicated in Figure 2 and Table 2. For instance, a 10-bilayer
films, i. e. bare metal electrodes, were also carried out. Table 1 LbL film of POEA/CS-PMAA produced under the conditions
shows a list of films deposited in each arrangement. The just mentioned was ten times thicker than a similar film with
electrodes for the impedance measurements were either pH 3 for POEA. Even more surprising was the observation
interdigitated bare chrome electrodes or interdigitated chrome that LbL films of POEA/chitosan were much thinner, as also
electrodes coated with the films mentioned in Table 1. The indicated in Figure 2 and Table 2. A visual inspection of LbL
measurements were taken with the electrodes immersed in the films of POEA/CS-PMAA confirmed the fabrication of very
aqueous solutions. thick films, which is also consistent with AFM images in
Two sets of experiments were performed. In the first, higher Figure 3 where an unusually large scale appears for the Z-axis
concentrations of CuSO4 were used, viz. 1, 5, 10, 20 and (height). The LbL film for POEA/CS-PMAA is ca. 5 μm
50x10-3 mol/L. The sensing units were immersed in 50 mL of thick, which is atypical for a LbL film. In fact, films obtained
the solutions, with 20 min. elapsing for reaching equilibrium with CS-PMAA – with no alternating layers - are already
before the measurement was taken. Measurements with thick, which clearly points to the importance of the
distilled water were performed before and after the nanoparticles for a strong adsorption.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 13, No. 5; October 2006 1103

1.2 1.00
POEA POEA
1:0.2 1 : 0.2
λ = 684
1:0.5 1 : 0.5
1.0 λ = 778 nm 700
1:0.7 λ = 647 nm 1 : 0.7
1:1 1:1
1:2 0.75 1:2

Absorbance (u.a.)
Absorbance (u.a.)

0.8 1:4 701 1:4


1:8 1:8
nanoparticles 703

λ = 532 nm 703
0.6 0.50

0.4 703

0.25
703
0.2
705

0.0
0.00
400 500 600 700 800 900 300 400 500 600 700 800 900
Wavelength (nm) Wavelength (nm)

(a) (b)
Figure 1. UV-VIS. spectra of mixtures in different proportions of (a) POEA and CS-PMAA and (b) POEA and chitosan.

Table 1. Arrangements A and B and their corresponding deposited films.


Arrangement A Arrangement B
Sensing unit Film Sensing units Film
1 and 6 doped POEA 1 and 6 Chitosan
2 and 7 dedoped POEA 2 and 7 Chitosan nanoparticles (CS-PMMA)
doped POEA alternated with CS-
3 and 8 doped POEA alternated with chitosan 3 and 8
PMMA
dedoped POEA alternated with CS-
4 and 9 dedoped POEA alternated with chitosan 4 and 9
PMMA
5 and 10 Bare 5 and 10 Bare

1.2 1.2
POEA 0.06% pH 3 / nanoparticles 0.2% pH 3 POEA 0.06% pH=3
POEA 0.06% pH 5 / nanoparticles 0.2% pH 3 POEA 0.06% pH=5
1.0 1.0 POEA 0.06% pH=3/nanoparticles 0.2% pH=3
POEA 0.06% pH=5/nanoparticles 0.2% pH=3
Absorbance (u.a.)

0.8 0.8
Absorbance (u.a.)

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0

0 2 4 6 8 10 0 2 4 6 8 10
Number of layers Number of layers

(a) (b)
Figure 2. (a) Absorption at the peak vs. number of bilayers for LbL films of POEA and CS-PMAA for two pHs of POEA solution (3 and 5) (b) same as in a),
but including the growth of POEA films deposited onto POEA (no alternating layers).

The roughness is extremely high, almost two orders of which POEA layers have been deposited on top of already
magnitude larger than for a chitosan film (Table 2). The films formed POEA layers, with no alternating material. Such
with CS-PMAA are also thicker and rougher than POEA films deposition is possible because – in addition to ionic
alternated with any other polyanion reported in the literature. interactions – H-bonding plays an important role in the
Also presented in Table 2 are the values for POEA films in adsorption of polyanilines [23]. Thicker films are deposited
1104 C. E. Borato et al.: Layer-by-layer Films of Poly(o-ethoxyaniline), Chitosan and Chitosan-poly(methacrylic acid) Nanoparticles

for solutions of POEA pH 5 since there is little repulsion as of the system. Two sets of experiments were performed, the
POEA is dedoped. The latter film is also less rough than those first involving higher concentrations of CuSO4, namely (1, 5,
obtained with POEA pH 3. Interestingly, the film for POEA 10, 20 and 50x10-3mol/L). In a second set, to be discussed
pH 3 alternated with CS-PMMA is much thicker (30 times) later, we checked the reproducibility of the sensing units with
than the film obtained with the mixture between POEA and smaller concentrations of CuSO4. With the concentrations
CS-PMMA. It seems therefore that strong adsorption leading mentioned, each sensing unit could detect and distinguish
to thick films only takes place if CS-PMMA nanoparticles between these concentrations. By way of illustration, Figure 4
form a layer on their own, either in a film with a single shows the data for the sensing units of arrangements A and B,
component or alternated with POEA. The growth of a layer which were taken before and after the films were deposited.
containing CS-PMMA mixed with POEA is constrained, Therefore, sensing units 1 through 4 correspond to bare
which inevitably has to do with the interaction with POEA. chrome electrodes while the other sensing units are labeled
Since POEA forms much thinner layers, apparently the according to the material used in the LbL film. It is seen that
number of embedded CS-PMMA nanoparticles is limited by all sensing units are capable of detecting the presence of
the conformation of POEA. Nevertheless, a precise varied amounts of copper in the aqueous solutions. Moreover,
understanding of such interaction will require further studies. identical results were obtained in the measurements with pure
We also deposited 10-bilayer LbL films onto double-faced water, before and after a series of experiments, which
chrome electrodes to form sensor arrays as depicted in Table indicates that the sensing units can be reused if properly
1. Impedance measurements were taken at 200 Hz and bias washed, an important feature for an electronic tongue. Note
voltage of 50mV, and the data were treated with an equivalent also the lower capacitance values for the units with LbL films,
circuit analysis. The figure of merit used was the capacitance though the ability to detect copper was not affected.

Table 2. Average height (Z) and roughness for 10-bilayer LbL films.
Films Z (nm) Roughness (nm)
doped POEA 39.6 6.27
dedoped POEA 27.8 3.18
CS-PMAA 739.0 96.5
doped POEA alternated with CS-PMAA 412.0 61.3
dedoped POEA alternated with CS-PMAA 5200 645
Chitosan 10.6 1.20
doped POEA alternated with Chitosan 17.9 1.68
dedoped POEA alternated with Chitosan 22 3.01
Doped POEA mixed with Chitosan 22.6 2.53
doped POEA mixed with CS-PMMA 14.5 2.20

1.0µm 1.0µm

(a) (b)

(c) (d)
Figure 3. AFM images of the following films: (a) doped POEA alternated with CS-PMMA nanoparticles pH 3, (b) dedoped POEA alternated with CS-PMMA
nanoparticles pH 3, (c) doped POEA alternated with chitosan pH 3 and (d) dedoped POEA alternated with chitosan pH 3.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 13, No. 5; October 2006 1105

When the responses of the sensing units of a given array confirmed that the sensing units could easily detect copper
were combined in a Principal Component Analysis (PCA), ions in aqueous solutions at the mM level, we examined the
clusters are formed for the different copper concentrations, as possibility of going further down in concentration. It is known
shown in Figure 5. PCA is a statistical technique largely used that electrical properties are very sensitive to any impurities in
for feature extraction and is based on the reduction of input the water, especially when interfaces are analyzed [25], which
data dimension [24]. It works by processing data variance with is actually the reason for the high sensitivity of the electronic
a set of principal components, the first of which presents the tongues based on nanostructured films and using impedance
highest variance and provides most of the information to spectroscopy. However, this high sensitivity may lead to
discriminate the input data. Notably, the first component artifacts with nominally identical samples being distinguished
corresponds to more than 98% of the variance in three of the from each other by mere manipulation of the samples. With
plots, which not only denotes good reproducibility but also these concerns in mind, we conceived experiments with
indicates that this component could be taken on its own to copper ion concentrations down to the nM level, in addition to
distinguish between the various samples. Indeed, data points control experiments in which water was added into water.
for samples with higher concentrations are progressively Figure 6 illustrates some of these results for a bare chrome
located to the right hand side of the plot, which means that the sensing unit, from which one can see that for 1 μM of CuSO4
first principal component is highly correlated with the ion or higher the electrical response is distinguished from that of
concentration in the aqueous solutions. A comparison between water being added into pure water (control experiment). For
Figures 5a, 5c with 5b, 5d indicates that the distinguishing concentrations below 1 μM, an effect could also be seen if the
ability was practically the same for the arrays before and after scale for the capacitance was expanded, but then the changes
film deposition. We shall discuss this point later on. Having were within the range of changes in the control experiments.
sensor unit 1 sensor unit 2 sensor unit 3 sensor unit 4 POEA pH 3 POEA pH 5
POEA pH 3 alternated w ith chitosan POEA pH 5 alternated w ith chitosan
1.00E-06
50mM
5.00E-07
8.00E-07 50mM
20mM
4.00E-07
6.00E-07
10mM 10mM 20mM
3.00E-07
C (F )

5mM
C (F )

5mM
4.00E-07
2.00E-07
inicial final
2.00E-07 inicial 1.00E-07
1mM final water 1mM water
water water
0.00E+00 0.00E+00
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69
Measurement number Measurements number

(a) (b)

unit sensor 1 unit sensor 2 unit sensor 3 unit sensor 4


Chitosan CS-PMMA
50mM POEA pH 3 alternated w ith CS-PMMA POEA pH 5 alternated w ith CS-PMMA
8.00E-07
20mM
7.00E-07 7.00E-07 50mM
6.00E-07 6.00E-07
10mM
5.00E-07 5.00E-07
10mM 20mM
C (F )

4.00E-07 4.00E-07
C (F )

5mM 5mM
3.00E-07 3.00E-07
2.00E-07 2.00E-07
inicial 1mM final inicial 1mM final
1.00E-07 water 1.00E-07 water water
water
0.00E+00 0.00E+00
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69
Measurements number Measurements number

(c) (d)
Figure 4. Electric response, taking the film capacitance as figure of merit, for several sensing units immersed into solutions containing copper: (a) arrangement
A without films, (b) arrangement A with films, (c) arrangement B without films and (d) arrangement B with films.
1106 C. E. Borato et al.: Layer-by-layer Films of Poly(o-ethoxyaniline), Chitosan and Chitosan-poly(methacrylic acid) Nanoparticles

The ability to detect μM concentrations was demonstrated for response from nominally identical electrodes varied
sensing units with or without a film deposited, as shown in considerably, which was actually exploited in obtaining a sensor
Figure 7. Though these results again indicate that bare metal array with the same (nominally) electrode materials. In another
electrodes may be used for taste sensors, which reduces the cost paper [26], this has been shown to arise from the morphological
considerably, an optimized response may be obtained when differences among chrome electrodes that were produced by
interactions between analyte and film material are strong. This electrodeposition. The differences appear because the electrical
appears to be the case in Figure 7, for the sensitivity of the response basically depends on the interface phenomena. ii) by
electrode coated with a 10-bilayer LbL film of dedoped POEA the same token, with the interface with the liquid under study
and chitosan was higher than for the bare electrode. Figure 8 governing the response, the performance of a sensor array made
shows the distinguishing ability of the sensor arrangement A in of bare metal electrodes may equal that of an array produced
PCA plots, again before (bare electrodes) and after depositing with nanostructured films, as indicated here in Figures 4, 5 and
the LbL films. Similar results were obtained with arrangement 8. There are nevertheless cases in which strong interactions with
B, whose data are therefore omitted. Consistent with the the analyte become important, as illustrated in Figure 7 for LbL
conclusions drawn from the results for separate sensing units, films of dedoped POEA alternated with chitosan. Therefore, the
samples with 1 μM of CuSO4 concentrations or above could be challenge in searching for new materials for electronic tongues
distinguished in all cases, but those with lower concentrations is twofold: one has not only to seek various materials that
were lamped together with the data points for pure water. With respond differently to analytes but also identify materials with
regard to the surprising results for the sensing units made of some degree of specificity in their interaction with the analytes.
bare chrome electrodes, two points should be emphasized: i) the

(a) (b)

(c) (d)
Figure 5. PCA plots for the measurements using arrangements A and B with and without films, in detecting various amounts of copper in water. The copper
concentrations are indicated by differing symbols as given in the inset. PC1 and PC2 in the axes refer to the first and second principal components.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 13, No. 5; October 2006 1107

without film with film


water addition copper addition
0,1mM 6.50E-09
2.45E-09 0,1mM
6.00E-09
2.35E-09 5.50E-09
0,01mM
5.00E-09
2.25E-09
0,01mM 4.50E-09
C (F )

C (F )
0,001mM
2.15E-09 4.00E-09
0,001mM 0,1mM
2.05E-09 3.50E-09 0,01mM
3.00E-09 0,001mM
1.95E-09
2.50E-09
1.85E-09 2.00E-09
1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 86 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 86
Measurements number Measurements number

Figure 6. Monitoring of the electric response for a bare chrome sensing unit, Figure 7. Capacitance monitored as increasing amounts of copper solution
immersed in water and to which pure water and aqueous solutions containing were added to the water, for two sensing units: with no film and another with
copper were added. a 10-bilayer LbL film of dedoped POEA (pH 5) alternated with chitosan film

(c)

(a) (b)
Figure 8. PCAs plot for the measurements with arrangement A, including those taken with very small amounts of copper: (a) without film and (b) with
deposited films. The different symbols refer to various concentrations of CuSO4 employed and samples of water, as indicated in the insert. PC1 and PC2 in the
axes refer to the first and second principal components.
electrodes, which may have important implications in
4 CONCLUSIONS lowering the costs of such devices.
We have shown that entirely different LbL films are
obtained when chitosan is used in the form of nanoparticles ACKNOWLEDGMENTS
(CS-PMAA), for the films are much thicker than when raw This work was supported by FAPESP, CNPq, Capes,
chitosan is employed. In a particular case, where the POEA Nanobiotec, IMMP/MCT, Embrapa/Labex Program and CT-
solution had pH 5 and CS-PMAA had pH 3, a 10-bilayer film Hidro (Brazil).
reached ca. 5μm of thickness, which is unusual for an LbL
film. Interaction between the chitosan nanoparticles in the REFERENCES
dispersion and POEA was proven to be much stronger than for [1] G. A. F. Roberts, Chitin chemistry, London, UK, Macmillan Press, pp.
chitosan, being sufficient to alter the doping state of POEA. 349, 1992.
UV-VIS. absorption measurements with mixed solutions of [2] K. Kurita, Y. Koyama and A. Tanaguchi, “Studies on chitin. IX.
POEA and CS-PMAA indicated that the latter cause POEA to Crosslinking of water-soluble chitin and evaluation of the products as
adsorbents for cupric ion”, J. Appl. Polym. Sci., Vol. 31, pp. 1169-1176,
be dedoped. The LbL films could also be used in sensing units 1986.
to detect copper ions in solution down to the μM level. [3] R. A. A. Muzzarelli, “Human enzymatic activities related to the
Furthermore, we showed that high-performance electronic therapeutical administration of chitin derivatives”, Cell. Mol. Biol. Life
tongues could also be obtained with an array of bare chrome Sci., Vol. 53, pp. 131-140, 1997.
1108 C. E. Borato et al.: Layer-by-layer Films of Poly(o-ethoxyaniline), Chitosan and Chitosan-poly(methacrylic acid) Nanoparticles
[4] C.A. Constantine, S.V. Mello, A. Dupont, X. Cao, D. S. Dos Santos Jr., [26] C. E. Borato, F. L. Leite, O. N. Oliveira Jr. and L. H. C. Mattoso, “Efficient
O. N. Oliveira Jr., F. T. Strixino, E. C. Pereira, T. Cheng, J. J. Defrank taste sensors made of bare metal electrodes”, Sensor Letters, Vol. 4 , pp.
and R. M. Leblanc, “Layer-by-layer self-assembled 210-214, 2006.
chitosan/poly(thiophene-3-acetic acid) and organophosphorus hydrolase
multilayers”, J. Am. Chem. Soc., Vol. 125, pp. 1805-1809, 2003.
Carlos Eduardo Borato was born in São Carlos, Brazil,
[5] N. K. Mathura and C. K. Narang, “Chitin and chitosan: versatile
in 1975. He received the B. Sc. degree in physics in
polysaccharides from marine animals”, J. Chem. Education, Vol. 67, pp.
2000, and the M.Sc. degree in materials science and
938-942, 1990.
engineering, in 2002, both from the University of São
[6] M. N. V. R. Kumar, “A review of chitin and chitosan applications”,
Paulo. He is completing a Ph.D. Project at the University
Reactive and Functional Polym., Vol. 46, pp. 1-27, 2000.
of São Paulo on novel materials and electrode systems for
[7] S. A. Agnihotri, M. N. Mallikarjuna and T. M. Aminabhavi, “Recent
taste sensors.
advances on chitosan-based micro- and nanoparticles in drug delivery”,
J. Controlled Release, Vol. 100, pp. 5-28, 2004.
[8] L. Qi, Z. Xu, X. Q. Jiang and X Hu, “Preparation and antibacterial
activity of chitosan nanoparticles,” Carbohydrate Research, Vol. 339,
Rejane Celi Goy was born in Tupã, Brazil, in 1974. She
pp. 2693-2700, 2004.
received the B.Sc. degree in chemistry in 1999, and the
[9] T. Banerjee, S. Mitra, A. K. Singh, R. K. Sharma and A. Maitra.,
M.Sc. degree in materials science and engineering at the
“Preparation, characterization and biodistribution of ultrafine chitosan
University of São Paulo (USP), in 2002. She is currently
nanoparticles”, Intern. J. Pharmaceutics, Vol. 243, pp. 93-105, 2002.
completing her Ph.D. degree, also at USP, on studies
[10] T. López-León, E. L. S. Carvalho, B. Seijo, J. L. Ortega-Vinuesa and D.
involving chitosan-based materials (spheres,
Bastos-González, “Physicochemical characterization of chitosan
microspheres and thin films) for detection and removal
nanoparticles: eletrokinetic and stability behavior”, J. Coll. and Interface
of cooper ions from aqueous solutions.
Sci., Vol. 283, pp. 344-351, 2005.
[11] S. Schaffazick, “Caracterização e Estabilidade Físico-Química de
Sistemas Poliméricos Nanoparticulados para Administração de
Fármacos”, Química Nova, Vol. 26, pp. 726-737, 2003.
[12] P. N. Adams, P. J. Laughlin, A. P. Monkman and N. Bernhoeft, “A Fabio de Lima Leite was born in Itanhaém, Brazil, in
further step towards stable organic metals. Oriented films of polyaniline 1975. He obtained the B.Sc. degree in physics from the
with high electrical conductivity and anisotropy”, Solid State Comm., São Paulo State University (UNESP), in 2000 and the
Vol. 91, pp. 875-878, 1994. M.Sc. degree in materials science and engineering from
[13] L. G. Paterno, C. J. L. Constantino, O. N. Oliveira Jr. and L. H. C. the University of São Paulo, in 2002. Currently, he is a
Mattoso, “Self-assembled films of poly(o-ethoxyaniline) complexed Ph.D. student in the University of São Paulo, in São
with sulfonated lignin”, Coll. & Surf. B. Biointerfaces, 23, 257-262, Carlos, and doing research on conducting polymers and
2002. atomic force microscopy at the Agricultural Instrumentation Unit of Embrapa.
[14] S. das Neves, C. N. P. da Fonseca and M. A. De Paoli, “A.
Photoelectrochemical characterization of electrodeposited polyaniline”,
Synth. Metals, Vol. 89, pp. 167-169, 1997. Cláudio Lopes de Vasconcelos was born in São Paulo,
[15] A Riul Jr, R. R. Malmegrim, F. J. Fonseca and L. H. C. Mattoso, “An Brazil, in 1978. He received the B.Sc. degree in
artificial taste sensor based on conducting polymers,” Biosensors and pharmacy in 2000, and the M.Sc. degree in 2003, both at
Bioelectron, Vol. 18, pp. 1365-1369, 2003. the Federal University of Rio Grande do Norte. He has
[16] B. Lawton and R. Pethig, “Determining the fat-content of milk and been working in polymer chemistry and colloids. At the
cream using ac conductivity measurements”, Measurement Sci. Technol. moment, he is enrolled in a Ph.D. program at the Federal
Vol. 4, pp. 38-41, 1993. University of Rio Grande do Norte, with the research
[17] A. Riul Jr., H. C. Souza, R. R. Malmegrim, D. S. dos Santos Jr., A. C. P. focusing on the study of polyelectrolytes in solution,
L. F. Carvalho, F. J. Fonseca, O. N. Oliveira Jr. and L. H. C. Mattoso, stabilization of colloids and adsorption process of
“Wine classification by taste sensors made from ultra-thin films and biomacromolecules.
using neural networks”, Sens. & Actuators B, Vol. 98, pp. 77-82, 2004.
[18] C. E. Borato, A. Riul Jr., M. Ferreira, O. N. Oliveira Jr. and L. H. C.
Mattoso, “Exploiting the versatility of taste sensors based on impedance Cypriano Galvão da Trindade Neto was born in João
spectroscopy”, Instrum. Sci. Tech. Vol. 32, pp. 21-30, 2004. Pessoa, Brazil, in 1977. He received the B.Sc. degree in
[19] A. Legin, A. Rudnitskaya, Y. Vlasov, C. Di Natale, F. Davide and A. pharmacy in 2000, and the M.Sc. degree in chemistry in
D’Amico, “Tasting of beverages using an electronic tongue,” Sens. & 2004, both at the Federal University of Rio Grande do
Actuators, B, Vol. 44, pp. 291-296, 1997. Norte (UFRN). He is completing a Ph.D. project at the
[20] L. H. C. Mattoso, S. K. Manohar, A. G. Macdiarmid and A. J. Epstein, Chemistry Department of UFRN focused on the study of
“Studies of the chemical syntheses and on the characteristics of permeability and diffusion in membranes of chitosan and
polyaniline derivatives”, J. Polym. Sci. Part A: Polym. Chem., Vol. 33, its blends.
pp. 1227-1234, 1995.
[21] S. P. Campana-Filho and J. Desbrières, “Chitin, chitosan and
derivatives,” Natural Polymers and Agrofibers Composites, E. Frollini;
A. L Leão; L. H. C. Mattoso, eds. USP; UNESP; EMBRAPA, pp. 41-71,
2000. Sergio P. Campana-Filho was born in Jau, Brazil, in
[22] Y. Hu, X. Q. Jiang, Y. Ding, H. X. Ge, Y. Y. Yuan and C. Z. Yang, 1957. He obtained the B.Sc. and M.Sc. degrees in
“Synthesis and characterization of chitosan-poly(acrylic acid) chemistry from the University of São Paulo, in 1979 and
nanoparticles”, Biomaterials, Vol. 23, pp. 3193-3201, 2002. 1985, respectively, and the Ph.D. degree from the
[23] L. G. Paterno and L. H. C. Mattoso, “Influence of different dopants on University of São Paulo (USP) in 1990. He is a lecturer
the adsorption, morphology and properties of self-assembled films of at the Instituto de Química de São Carlos, USP, being an
poly(o-ethoxyaniline)”, J. Appl. Polym. Sci., Vol. 83, pp. 1309-1316, expert on the chemistry and physical chemistry of
2001. polysaccharides from microbial, vegetable and animal
[24] J. E. A. Jackson, A Users’ Guide to Principal Components; Wiley: sources. For the last 16 years, he has been working on
New York, 1991. bacterial polysaccharides, cellulose, chitin and chitosan.
[25] D. M. Taylor, O. N. Oliveira Jr. and H. Morgan, “The effect of water His work is focused on the extraction processes, chemical derivatization,
quality on the electrical characteristics of Langmuir monolayers”, Thin characterization and properties/applications of these polysaccharides and
Solid Films, Vol. 173, pp. L141-L147, 1989. derivatives.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 13, No. 5; October 2006 1109

Márcia Rodrigues Pereira was born in Rio de Osvaldo N. Oliveira Jr. was born in Barretos,
Janeiro, Brazil, in 1963. She graduated in chemical Brazil, in 1960. He obtained the B.Sc. and M.Sc.
engineering in 1986 at the State University of Rio de degrees in physics from the University of São Paulo,
Janeiro. She got the M.Sc. degree in polymer science in 1982 and 1984, respectively, and the Ph.D. degree
and technology at the Federal University of Rio de from the University of Wales, Bangor, in 1990.
Janeiro on the subject of reinforcing of polyurethane Currently he is an associate professor at the
elastomers (1991). In 1994 she obtained a PhD degree University of São Paulo, in São Carlos, Dr. Oliveira
in chemistry at Durham University (UK) on the has led research into the fabrication of novel materials in the form of ultrathin
subject of permeability of polymeric membranes. Since 1997 she has been a films obtained with the Langmuir-Blodgett and self-assembly techniques. Most of
lecturer at the Chemistry Department of the Federal University of Rio Grande do this work has been associated with fundamental properties of ultrathin films with
Norte and has been working with polymer membranes, solutions, colloids, and molecular control, but technological aspects have also been addressed in specific
polyelectrolyte complexes. projects. This is the case of an electronic tongue, whose response to a number of
tastants is considerably more sensitive than the human gustatory system. Prof.
Oliveira Jr. has helped establish the Núcleo Interinstitucional de Linguística
José Luís Cardozo Fonseca was born in Angra dos Computacional (NILC), which is a leading institute for natural language
Reis, Brazil, in 1961. He graduated in chemical processing of Portuguese. Research and development activities at NILC include
engineering in 1985 at the Federal University of Rio de the development of a grammar checker for Brazilian Portuguese, now available
Janeiro. At the same university he got the M.Sc. degree worldwide through Microsoft Word, and participation in the Universal
in polymer science and technology on the subject of Networking Language (UNL) Project, sponsored by the United Nations
viscoelastic behavior of polyurethanes (1990). In 1994 University.
he obtained the Ph.D. degree at Durham University (UK)
on the subject of glow-discharge plasma treatment of
polymer films. Since 1996 he has been a lecturer at the Luiz Henrique Capparelli Mattoso was born in São
Chemistry Department of the Federal University of Rio Grande do Norte and has Carlos, Brazil, in 1961. He obtained the B.Sc., M.Sc.
been working with polymer solutions, colloids, polyelectrolyte complexes, and and Ph.D. degrees in materials science from the Federal
membranes. University of São Carlos, São Paulo, in 1986, 1988 and
1993, respectively. Within this period he was a visiting
researcher at the Universitè des Sciences et Tecnologies
du Languedoc, Montpellier, and Domaine Universitaire
Saint Martin d´Hères, Grenoble, in France, and
University of Pennsylvania, USA. He was head of the
Research and Development Department of the Instrumentation Research Center
of the Brazilian Corporation for Research in Agriculture – Embrapa. He is
currently a lead scientist on nanotechnology and polymer science at Embrapa,
working in an international cooperation program between Brazil and the
Agricultural Research Service (ARS) of the USDA, in Albany, CA, USA. He
leads several R&D projects funded by government and companies on new uses of
agricultural products in plastics and composites, conducting polymers and taste
sensors, technological applications of natural rubber, the most recent being a
nanotechnology network involving several universities and research institutes in
Brazil in cooperation with USA, France and India.

You might also like