Biobased Chitosan Nanocomposite Films Containing Gold

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Biobased Chitosan Nanocomposite Films Containing Gold Nanoparticles: Obtainment, Characterization, and Catalytic Activity Assessment Oscar Ramirez, Sebastián Bonardd, Cesar Saldías, Deodato Radic, and Á ngel Leiva* Departamento de Química Física, Facultad de Química, Pontificia Universidad Católica de Chile, Vicuña Mackenna 4860, Macul, Santiago 7820436, Chile

ABSTRACT: A “green” two-step methodology to prepare biobased gold-chitosan nanocomposite films using chitosan and AuCl4− as a stabilizer and precursor, respectively, is reported. The biobased nanocomposites were prepared in situ by a wet chemical reduction method. Effects of hydrazine and L-ascorbic acid as different strength reducing agents on the characteristics of gold nanoparticles were observed. In addition, the performance of these nanocomposite films as catalytic materials was assessed. The relevance of this work underlies that the catalytic activity, conversion degree and order of the reaction of the 4-nitrophenolsodium borohydride (4NP-NaBH4) reduction system depend on the size distribution, content and mainly to the location of gold nanoparticles in the nanocomposite films. Finally, the potential recyclability of these nanocomposite films as catalytic materials was studied. KEYWORDS: chitosan, gold nanoparticles, nanocomposites, films, nanocomposite catalysts

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oxidation,14,18,19 Suzuki couplings,20 reduction of nitro derivatives21,22 and reduction of organic dyes.23,24 The catalytic activity of metal nanoparticles is highly dependent on their size, morphology, and synthesis method.25 One of the most reported methods for obtaining noble metal nanoparticles is the reduction of metal precursors in solution (i.e., a bottom-up method).26,27 This approach allows the tuning of the size, morphology and polydispersity of metal nanoparticles by controlling the experimental parameters (e.g., temperature, concentration, pH, reaction time and stabilizing agent).28−30 Considering this, polymeric materials have been widely used as stabilizing agents because of their broad chemical functionality and varied architectures. These materials can be absorbed on the surface of metal nanoparticles to control the growth and excessive agglomeration of nanosized metals. To date, many different types of polymeric materials have been used as stabilizing agents (e.g., block copolymers, graft copolymers, and dendrimers).31−37 Therefore, obtaining polymer-based nano-

INTRODUCTION Currently, the discovery, explanation, and understanding of new phenomena are highly devoted to the production and optimization of new technological materials useful in diverse applications. Additionally, the “green chemistry” concept is emerging as an attractive way to design and synthesize new materials having highly desirable properties such as biocompatibility, low toxicity, and biodegradability under determined environmental conditions.1−3 These properties should also be combined with good mechanical and thermal properties, as well as low cost of production. The rapid development of nanotechnology has also allowed the generation of a large number and variety of new materials for applications in the fields of optics, optoelectronics, medicine, waste industry and catalysis.4−8 Thus, the optimization and kinetic control of chemical reactions would minimize the generation of significant amounts of byproducts, avoiding excessive time consumption and cost overruns.9,10 A well-known example of nanomaterials with applications in catalysis is noble metal nanoparticles.11−17 These nanostructures have been demonstrated to have catalytic activity in diverse types of reactions, such as carbon monoxide © XXXX American Chemical Society

Received: March 29, 2017 Accepted: May 1, 2017 Published: May 1, 2017 A

DOI: 10.1021/acsami.7b04422 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

ACS Applied Materials & Interfaces

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composites could be achieved by removing the solvent. For example, the use of nanocomposites has been extensively addressed in current literature.38−42 However, some of these studies have shown experimental complications related to loss of the catalytic activity due to matrix degradation, nanoparticle desorption (attributed to weak nanoparticle−matrix interactions) and difficulty in recycling the material upon reaction.43 Thus, it is a worthy goal to design an organic−inorganic hybrid material wherein the polymer can act as a supporting matrix for the metal nanoparticles that would be responsible for the catalytic activity of the final nanocomposite.44−46 For these reasons, the use of polymeric matrices with good film forming ability, adequate mechanical properties, and numerous functional groups suitable for interaction with the nanoparticle surface are highly desirable features. Chitosan, a biodegradable, biocompatible, and nontoxic polymer obtained from the deacetylation of chitin, represents an outstanding alternative to forming nanocomposites with inorganic compounds for catalysis applications.47−50 In addition, this polyelectrolyte exhibits interesting mechanical properties and an excellent film forming ability.51−53 Moreover, chitosan can act as a strong chelating agent for different transition metal ions.54−56 More specifically, chitosan has been used as a reducing and stabilizing agent with gold, silver, and platinum metal nanoparticles.57−59 The reduction ability is attributed to −OH groups and the cleavage of glycosidic bonds.59,60 A significant contribution to the adsorption properties is also assigned to the presence of amine and amide groups along the chitosan backbone.55,61 Because of these features, chitosan appears to be an ideal matrix to host metal nanoparticles, having exploitable mechanical properties and environmentally friendly characteristics. Murugadoss et al.43 synthesized a “green” silver-chitosan nanocomposite that was successfully used in the catalytic reduction of a 4-nitrophenol-NaBH4 system. The synthesis of this nanocomposite was based on a two-step process: (i) the previous coordination and (ii) further reduction of metal ions by chitosan powder. Despite the nanocomposite exhibiting appropriate catalytic activity, the high temperatures needed for the formation of nanoparticles, as well as their poor distribution into the chitosan matrix and the low control of their sizes were relevant concerns that should be addressed by further studies. Therefore, the formation and study of chitosan nanocomposites requires further research aimed at improving their properties and performances, focused on technological applications. Considering the above challenges, we present a “green” twostep methodology, using nonhazardous and nontoxic reagents (e.g., water, acetic acid, L-ascorbic acid) to prepare biobased gold-chitosan nanocomposite films in order to assess their catalytic activity in the reduction of a 4-nitrophenol-NaBH4 system. Nanoparticle synthesis was performed by the reduction of previously adsorbed AuCl4− ions into the chitosan film using hydrazine (a strong reducing agent) and L-ascorbic acid (a soft reducing agent). As noted, external reducing agents are used to achieve more controlled reduction of metal ions. In consequence, better distribution of metal nanoparticles into the polymeric matrix, narrow polydispersity, specific morphology and controlled size of the nanoparticles should be expected.32,47,48,62 The effect of these two reducing agents on the polydispersity and size distribution of the nanoparticles obtained in the biobased films was studied. Additionally, the catalytic activity and the possible recyclability of these nanocomposite films in catalysis reactions were also analyzed.

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EXPERIMENTAL SECTION

Materials. Potassium gold(III) chloride (KAuCl4, 99.995%; SigmaAldrich), acetic acid (glacial 99.8%; Merck), chitosan (M̅ v = 70 000 g mol−1, with a degree of deacetylation of approximately 70%; SigmaAldrich), sodium borohydride (NaBH4, 98.0%, Sigma-Aldrich), sodium hydroxide (NaOH, 98.0%, Merck), hydrazine monohydrate (98%) and L-ascorbic acid (99.7%) were used without further purification. 4-Nitrophenol (Sigma-Aldrich) was recrystallized from water prior to use. Milli-Q water was used in all experiments. Preparation of Gold-Chitosan Nanocomposite Films. Five milliliters of a previously homogenized 1% (v/v) aqueous acetic acid chitosan solution was placed into a Petri dish and further dried under vacuum at 35 °C for 72 h. The films obtained were washed with 20 mL of 1.0 M NaOH and then rinsed with abundant Milli-Q water. To obtain films containing different amounts of gold ions, these films were immersed in KAuCl4 solutions at different concentrations (5, 10, and 20% w/v) for 24 h. Next, the films were washed with abundant water and dried under vacuum for 24 h at 35 °C. The kinetic adsorption of metal ions was monitored by UV−visible spectroscopy. The adsorbed gold ions were reduced using two different reducing agents. Briefly, the films were immersed in 20 mL of an aqueous solution of either L-ascorbic acid or hydrazine (both 1.5 mM) for 72 h. Then, the films were washed with abundant Milli-Q water and further dried under vacuum for 24 h. Assessment of the Catalytic Activity of Gold-Chitosan Nanocomposite Films. To assess the catalytic activity of nanocomposite films, the reduction of 4-nitrophenol (4NP) to 4aminophenol (4AP) was performed as a model reaction. In a typical experiment, 6 mL of 1.0 mM 4NP and 0.2 mL of 11 mg/mL NaBH4 were placed into a vial containing the gold-chitosan nanocomposite films. After addition of the catalyst, the bright yellow solution gradually faded as the reaction occurred. The reaction progress was monitored by UV−vis spectroscopy. The spectra were recorded at determined intervals to check the progress of the reaction. Characterization of Nanocomposite Films. The nanocomposite films were characterized by transmission electronic microscopy (TEM) using a TEM Phillips Tecnai 12. In brief, the samples were cut in the thickness direction to prepare ultrathin sections using a conventional microtome. Thermal degradation of the samples was performed using a TGA/SDTA851 Mettler-Toledo thermobalance, and the data were processed using the STARe version 8.1 program from Mettler. The thermograms were measured from 25 to 900 °C at a 10 °C min−1 heating rate under a nitrogen atmosphere. The crystalline morphologies of the nanocomposite films were observed using an Olympus BX60 microscope and a QImaging MP5CCD digital camera. Each film was placed between two parallel microscope slides. The optical images were recorded via QImaging QCapturePro software. The loading percentage of gold ions into chitosan films was analyzed using an inductively coupled plasma optical emission spectrometry (ICP-OES) instrument (Varian Liberty Series II Axial ICP-OES). The samples for ICP analyses were prepared using aqua regia as a digesting solution. In a typical stock solution preparation, a determined mass of gold-chitosan nanocomposite film was dissolved in an aliquot of aqua regia with sonication for 15 min. After the complete dissolution of catalyst into the aqua regia solution, the stock solution was filtered through syringe filters (0.22 μm) in order to remove possible insoluble impurities. The stock solution was further diluted with water to ppm level accordingly. For the catalytic activity studies, UV−vis spectra were recorded between 250 and 500 nm at 25 °C with an Agilent Cary 60 spectrophotometer.

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RESULTS AND DISCUSSION As described in the Experimental Section, the preparation of gold-chitosan nanocomposite films was carried out by the adsorption of gold ions into chitosan films. The process of adsorption was monitored by UV−vis spectroscopy and inductively coupled plasma spectrometry (ICP). To establish B


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Figure 2 shows TEM images for nanocomposite films obtained after reduction reactions by immersion into aqueous

the equilibration time needed to reach the maximum adsorption capacity and, in turn, obtain information on the adsorption kinetics, the metal ion adsorption into chitosan films was measured over time. Figure 1 shows a notable decrease in

Figure 1. Percentage of gold ions adsorbed into chitosan films (red) and the evolution of the maximum of the absorbance band at 305 nm for the AuCl4− complex over time (black).

the maximum of the absorption band centered at 305 nm. This decrease is attributed to the metal−ligand charge transfer corresponding to the AuCl4− complex.61 Therefore, the decrease in the absorption indicates a possible consumption of the complex due to its adsorption into chitosan films. The adsorbed amount increases as time passes, reaching equilibrium at approximately 360 min. The maximum adsorbed percentage of gold ions was approximately 89%, which would reflect an equilibrium situation. This result was corroborated by ICP measurements, from which an ∼86% value was obtained. These values are in the range of other previously reported nanocomposite films.55,56 As mentioned, the chitosan ability to adsorb different types of metals has generated many studies to generate technological applications;63−65 however, the mechanism by which these ions are coordinated remains undefined. Recently, Vo et al.61 proposed the participation of amino (−NH2) and hydroxyl (−OH) groups from chitosan in the coordinating process. This mechanism proposes that the Cl− ions from the AuCl4− complex are substituted by simultaneous coordination of amino and hydroxyl groups, releasing chloride anions. Considering this hypothesis, the presence of chloride ions in the supernatant solution obtained after gold ion adsorption was corroborated by the addition of silver nitrate. AgCl precipitation was observed, demonstrating the presence of free chloride ions. Although the maximum amount of gold ions adsorbed by films was approximately 86%, adsorbed amounts higher than 25% resulted in brittle samples. This brittleness could hinder the films’ processing, diminishing the number of potential applications. Thereby, chitosan films previously immersed in 5, 10, and 20% w/v KAuCl4 solutions were selected to carry out the studies presented here. These films were used for in situ synthesis of gold nanoparticles using two reducing agents, hydrazine (a strong reductant) and L-ascorbic acid (a soft reductant).

Figure 2. TEM images of gold-chitosan nanocomposite films obtained from immersion into (a, d) 5, (b, e) 10, and (c, f) 20% KAuCl4 solutions reduced with hydrazine (left side) and L-ascorbic acid (right side).

reductant solutions. As expected, the amount of gold nanoparticles formed was proportional to the concentration of the KAuCl4 solutions. An adequate distribution of nanoparticles was obtained for all films except for those immersed in the 20% w/v KAuCl4 solution and, subsequently, using hydrazine as the reducing agent (Figure 2c). In this case, significant increases in the size of nanoparticles and their polydispersity were detected. Additionally, nanoparticles having irregular shapes and forming aggregates were observed. A plausible explanation for this finding is the low kinetic control of the reduction reaction when a high concentration of gold ions and a stronger reducing agent are used. In general, the use of soft reductants, e.g., L-ascorbic acid, would allow the provision of a mild reducing environment desirable for kinetically controlled synthesis of gold nanoparticles. The reduction of gold ions adsorbed into chitosan films was also performed in the absence of external reducing agents. Under similar experimental conditions, agglomerated particles of approximately 200 nm (i.e., out of the nanosize range) were obtained (data not shown); in these cases, the chitosan films acted as the reducing agent. Per this result, external reductants would play a key role in the formation of this type of nanocomposite. Table 1 summarizes the size distribution of the obtained nanoparticles. Thermal decomposition profiles and differential thermogravimetric analysis curves (inset images) of chitosan films with gold ions adsorbed, formed nanocomposite films, and the plot C


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decomposition of chitosan. The onset decomposition temperatures, Tonset, and the gold content for each sample determined from analysis of the thermal degradation profiles are listed in Table 2. The percentage of gold nanoparticles compared with the gold ions adsorbed in the nanocomposite films was similar for loading contents up to 10% w/v KAuCl4 solutions. Above 10%, a remarkable difference between gold nanoparticles and gold ion adsorbed contents was observed. These results are consistent with the TEM images, which indicate a higher content of nanoparticles as the amount of gold ions adsorbed increases. Moreover, for reduction using hydrazine, the films tend to exhibit higher polydispersity for gold nanoparticle content above 10%. The presence of gold ions in chitosan films appears to contribute to a gradual decrease in the Tmd. This phenomenon can be explained in terms of two effects: (i) a possible weakening of chitosan covalent bonds due to interactions with gold ions, and (ii) a rupturing of intra- and intermolecular chitosan hydrogen bonds, also ascribed to interactions with

Table 1. Nanoparticle Size Distribution Calculated from TEM Image Analyses hydrazine sample gold-chitosan (5%) gold-chitosan (10%) gold-chitosan (20%)

nanoparticle size distributions (nm) 19.0 ± 1.8 20.8 ± 0.8 95.7 ± 5.7

L-ascorbic

sample gold-chitosan (5%) gold chitosan (10%) gold-chitosan (20%)

acid

nanoparticle size distributions (nm) 19.6 ± 1.7 25.0 ± 5.0 18.4 ± 1.2

of temperatures of maximum weight loss rate (Tmd) for all samples are shown in Figure 3. From the profiles of thermal degradation and the differential thermogravimetric curves, the water decomposition was detected, which exhibited a Tmd at approximately 100 °C. This value represents approximately 20% of the mass of the films. A second Tmd at approximately 200 °C was observed, which was attributed to the

Figure 3. (a−c) Degradation and differential thermogravimetric analysis (inset images) curves for gold-chitosan nanocomposite films at different contents of gold ions adsorbed and (d) plot of temperature of maximum weight loss rate (Tmd) for each film as a function of the content of gold ions. D


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ACS Applied Materials & Interfaces Table 2. Thermal degradation Onset, Tonset, Maximum Weight Loss Rate, Tmd, Temperatures (°C), and Gold Nanoparticle Content for All Samples Studied sample chitosan gold ions-chitosan 5% gold ions-chitosan 10% gold ions-chitosan 20% gold-chitosan 5% hydrazine gold-chitosan 10% hydrazine gold-chitosan 20% hydrazine gold-chitosan 5% L-ascorbic acid gold-chitosan 10% L-ascorbic acid gold-chitosan 20% L-ascorbic acid

Tonset (°C)

Tmd (°C)

gold nanoparticle content (%)

238 242 199 191 238 226 207 232

280 280 253 234 282 270 255 293

4.2 9.8 13 4.8

234

298

8

263

312

15

produces gold-chitosan nanocomposites having higher values of Tonset and Tmd than those obtained using hydrazine. Since the gold content in the films obtained with both reductants was quite similar (Table 2), the different size distribution and location of gold nanoparticles in the films could affect the thermal behavior of the nanocomposites. The reduction of gold ions with hydrazine occurs faster than with L-ascorbic acid. Thus, gold ions adsorbed on the film surface would be reduced before those occluded into the films. Therefore, the formation of nanoparticles using hydrazine would occur mostly on the film surfaces. In this fashion, the remaining gold ions occluded into chitosan films would produce the labilization of polymeric bonds. In contrast, L-ascorbic acid would act as a soft reducing agent allowing gold atoms to diffuse into the chitosan film. The generation of gold nanoparticles would thereby be performed both in the films and on their surface and would contribute to the decrease in the amount of gold ions available to interact with the chitosan functional groups along its backbone. The possible reduction processes for both reducing agents are depicted in Scheme 1. The optical reflectance and transmittance images for the obtained gold-chitosan 20% nanocomposite films using hydrazine and L-ascorbic acid are shown in Figure 4. The results demonstrated that reduction with hydrazine mainly occurred on the surface of the films. In this case, the image showed a metallic brightness on the nanocomposite film, while this brightness was not detected in the film obtained with Lascorbic acid. In addition, the transmittance image of this nanocomposite showed different colors. When using hydrazine and L-ascorbic acid for the reduction reaction, bluish and reddish colorations, respectively, were observed (Figure 4). The color of metal nanoparticle suspensions is due to the plasmon

gold ions. These effects help explain the obtained brittle chitosan films when they were immersed in aqueous solutions containing above 20% w/v of KAuCl4. Higher thermal stability was observed for films containing gold ions adsorbed up to 5%, which could be related to the decrease in the films flexibility (or increase of brittleness) at higher contents of gold ions. In previous studies, our group reported that the presence of gold nanoparticles increases the thermal stability of chitosan. This fact was attributed to the lower heat capacity and higher thermal conductivity of the metal nanoparticles compared with those of polymeric materials. Thus, in the first stage, significant heat flux would be trapped by the gold nanoparticles and then irradiated to the polymeric matrix. The use of L-ascorbic acid as a reducing agent

Scheme 1. Illustration of the Possible Interaction between Gold Ions and Chitosan Chains; Likely Effects of the Reducing Agents on Nanoparticle Distribution Are Also Represented

E


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Figure 4. Optical reflectance and transmittance images for the gold-chitosan 20% nanocomposite film using hydrazine and L-ascorbic acid as reducing agents.

Because an excess of NaBH4 was used in the kinetic studies, the obtained data were processed considering conditions of both pseudo-first order and pseudo-second order with respect to 4NP using eqs 1 and 2, respectively

resonance phenomenon which, in turn, is closely related to the size distribution and morphology of the nanoparticles.57,58 Therefore, gold nanoparticle suspensions having a bluish coloration would be composed of larger nanoparticles than those from reddish suspensions and helps confirm that hydrazine would yield a preferential reduction of gold ions on the film surface, triggering excessive growth and agglomeration of metal nanoparticles. These results would be supported by the size distributions listed in Table 1. Complementarily, the performance of nanocomposite films as heterogeneous catalytic materials in the 4-nitrophenolsodium borohydride reduction system was tested.66 Figure 5

ln[4NP]t = ln[4NP]0 − k′t

(1)

1 1 = + k′t [4NP]t [4NP]0

(2)

where k′ is the apparent rate constant and [4NP]t and [4NP]0 are the concentrations of 4-nitrophenol at time t and the initial time, respectively. Since the absorbance of 4NP is proportional to the concentration of 4NP in the reaction medium, it is possible to replace the concentration terms with the absorbance values, as shown in eqs 3 and 4 lnA t = lnA 0 − kt

(3)

1 1 = + k′t At A0

(4)

where At and A0 are the absorbance values at time t and the initial time, respectively. Thus, a plot of −Ln At vs t (pseudofirst order) or 1 vs t (pseudo-second order) yields the slope k′. At

Interestingly, the results showed that the reactions catalyzed by the nanocomposites obtained by reduction with hydrazine fit better with a pseudo-first order reaction, while those reduced with L-ascorbic acid fit better with a pseudo-second order reaction. The order of a reaction is usually related to the type of mechanism by which the reaction occurs. Therefore, different reaction orders would reflect the possible mechanisms for the reduction due to the different size distributions and locations of the gold nanoparticles in the films. The rate constant values for the first and second cycles and conversion percentages for the first cycle obtained from the 4NP-NaBH4 reduction system are summarized in Table 3. The results indicated that the higher the content of gold nanoparticles was, the larger the rate constant values and reaction conversion percentages obtained were (Figure 6a, b). This finding is in good agreement with previous studies demonstrating that the catalytic activity is proportional to the quantity of nanoparticles.67 In addition, higher rate constants and conversion rates were calculated for the gold-chitosan 5%

Figure 5. Time-dependent evolution of UV−vis spectra showing the catalytic reduction of 4-NP to 4-AP by gold-chitosan nanocomposite films. The complete reaction was reached at approximately 150 min.

shows the evolution of the reaction monitored by UV−visible spectroscopy. The initial UV−vis spectrum of 4NP exhibited an absorption band centered at 400 nm upon addition of NaBH4.43 Before the addition of nanocomposite films, the absorption band of 4NP remained stable over time. Upon the addition of nanocomposite films, a gradual decrease in the absorption band at 400 nm was monitored. Simultaneously, the appearance of another smaller band centered at 296 nm, corresponding to the 4-aminophenol (4AP) formation, was detected. F


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Table 3. Rate Constants of 4-NP Reduction for 1st and 2nd Cycles and the Respective Conversion Percentages for the 1st Cycle of Each Nanocomposite Film hydrazine

L-ascorbic

acid

rate constant and conversion

gold-chitosan 5%

gold-chitosan 10%

gold-chitosan 20%

gold-chitosan 5%

gold-chitosan 10%

gold-chitosan 20%

k′ (first cycle) k′ (second cycle) conversion (%)a

20.1 7.7 74

33.4 15.5 89

33.2 16.4 91

6.3 5.9 24

22.9 6.5 49

84.1 27.6 77

(1 − )100 (1 cycle)

a

At A0

st

Figure 6. (a, b) Recyclability tests and (c) plot of k′ as a function of gold composition for all gold-chitosan nanocomposite films.

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and gold-chitosan 10% nanocomposite films reduced with hydrazine compared with those formed with L-ascorbic acid (Figures 6c and 7). These results could be attributed to a preferential location on the surface of the films of the nanoparticles reduced with hydrazine. These nanoparticles would thereby be facing the reaction medium and would be more exposed to perform the catalysis. Astruc et al. demonstrated by using metal-dendrimer nanocomposites that the location of the nanoparticles is an important variable during the catalytic process.68 In the case of the gold-chitosan 20% nanocomposite reduced with L-ascorbic acid, the k′ is considerable higher than that calculated for the other samples. It is likely that two cooperative effects are present: (i) the higher amount of gold nanoparticles and (ii) the smaller size distribution of the nanoparticles offer many reactive sites and a high surface area for the catalytic reaction.

CONCLUSIONS

A “green” two-step synthetic method was developed to produce gold-chitosan nanocomposite films in situ, via reduction of the metal salt precursor by wet chemical methods. The size, polydispersity, location and agglomeration degree of the gold nanoparticles in the prepared gold-chitosan nanocomposite films proved to be strongly dependent on the type of reducing agent used. Apparently, these different features of the nanocomposite films are reflected in both their catalytic activity and the order of the catalyzed reaction for the reduction of 4NP. In general, the gold-chitosan nanocomposite films obtained with hydrazine as the reducing agent showed higher catalytic activity for gold content up to 10%, as well as recyclability, than seen for those obtained with L-ascorbic acid. Finally, the reported chitosan nanocomposite films are promising materials for technological applications, e.g., in heterogeneous catalysis of diverse chemical reactions. G


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Figure 7. Comparative catalytic conversions of 4-NP over gold-chitosan nanocomposite films. The faster kinetics for nitro reduction are clearly visible for nanocomposites reduced with hydrazine.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: +56226864392. Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. All authors contributed equally to this work. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This research was supported by FONDECYT, (grants 1120119 and 1161159). REFERENCES

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