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    • 专利摘要:
    Composite materials sonogel-carbon-conductive polymers and their variants: manufacturing process and its application in the constitution of electrochemical (bio) sensors. For the first time, a massive composite material based on sonogel, carbon and conductive polymer is synthesized by high energy ultrasound. The design of experiments allows to establish the most suitable parameters for the synthesis. The process is very versatile and generates multiple materials by varying the carbon source, the catalyst or the conductive polymer. These materials can be used to manufacture (bio) electrochemical sensors. Other advantages of the system are: - Speed and simplicity of the process and instruments used. - The polymer is a structural part of the material, increasing its conductivity (91% by weight) and stability with respect to other ceramic materials, influencing the efficiency of the sensor constituted. - The good mechanical and electrochemical renewal of the material allows a continuous use of these devices, solving the degradation problems of conductive polymer films in sensors.
    公开号:ES2670985A1
    申请号:ES201601037
    申请日:2016-12-02
    公开日:2018-06-04
    发明作者:David LÓPEZ IGLESIAS；Magdalena GARCIA ROMERO；Laura María CUBILLANA AGUILERA；José María PALACIOS SANTANDER；Ignacio NARANJO RODRÍGUEZ；Dolores BELLIDO MILLA
    申请人:Universidad de Cadiz；
    IPC主号:
    专利说明:

    SONOGEL-CARBON-POLLIMER COMPOUND MATERIALS DRIVERS AND THEIR VARIANTS: MANUFACTURING PROCEDURE AND ITS APPLICATION IN THE CONSTITUTION OF (BIO) ELECTRO-AIMICAL SENSORS_
    SECTOR OF THE TECHNIQUE
    The present invention describes, first of all, a method of manufacturing low instrumental complexity and low energy cost of sonogel-based materials (silicon and oxygen networks obtained by applying high-energy ultrasound), particulate or nanoparticulate carbon and conductive polymers , as well as
    its variants: Sonogel-Carbon-poly- (3,4-ethylenedioxythiophene) (SNG-C-PEDOT), Sonogel-Carbon-polyaniline (SNG-C-PANI), Sonogel-Carbon-polythiophene (SNG-C
    PT); Sonogel · Nanocarbon · PEDOT, Sonogel · Nanocarbon · PANI and Son0gel
    Nanocarbon-PT (SNG-NC-PEDOT, SNG-NC-PANI and SNG-NC-PT, respectively);
    Sonogel-Carbon Nanotubes-PEDOT, Sonogel-Carbon Nanotubes · PANI and
    Carbon Sonogel-PT Nanotubes (SNG-CNT-PEDOT, SNG-CNT-PANI and SNG-CNT
    PT, respectively); Sonogel · Carbon / Gold Nanoparticles-PEDOT, SonogelCarbon / Gold Nanoparticles · PANI, Sonogel-Carbon / Gold Nanoparticles-PT
    (SNG-C / AuNPs-PEDOT, SNG-C / AuNPs-PANI and SNG-C / AuNPs-PT, respectively); Sonogel-Nanocarbon / Gold Nanoparticles-PEDOT, SonogelNanocarbon / Gold Nanoparticles-PANI and Sonogel-Nanocarbon / Nanoparticles
    Gold-PT (SNG-NC / AuNPs-PEDOT, SNG-NC / AuNPS-PANI and SNG-NC / AuNPs-PT, respectively) and Carbonol Sonogel-Nanotubes Gold nanoparticles-PEDOT,
    Sonogel-Carbon Nanotubes / Gold nanoparticles-PANI and Sonogel-Nanotubes
    Carbonol Gold PT-nanoparticles (SNG-CNTlAuNPs-PEDOT, SNG-CNTIAuNPs
    PAN1 and SNG-CNTlAuNPs-PT, respectively). In all these materials, synthesized with the aid of design of experiments, the conductive polymer used, PEDOT, PANI or PT, constitutes the structural basis of the material, in addition to being one of the conductive components thereof. On the other hand, its application in the manufacture of (bio) sensors is described
    electrochemicals
    BACKGROUND OF THE INVENTION
    In recent years, the 501-gel process has undergone great development due to the possibility of generating ceramic materials without the need for a high temperature melting process. Numerous research groups have used this method to obtain various materials with applicability in multiple areas, including electroanalysis (Rezaei, B .; Khalili Borojeuni, M .; Ensafi, A. Electrochim Acta, 2014, 123. 332-339 ; Rameshkumar. P .; Viswanathan, P .; Ramaraj, R. Current Sensor. B-Chem., 2014, 202, 1070-1077; Rezaei, B .; Lofti-Foroushani, H.; Khalili Borojeuni, M .; Ensafi , A. Mal Sci. Eng. C, 2014, 37, 113-119) In general, the sol-gel method consists of the synthesis of compounds formed by inorganic oxide networks (Si, Al, etc.), constituting suitable matrices for the addition of modifiers used for electroanalytical purposes (Cordero-Randa, MM; Hidalgo-Hidalgo de Cisneros, JL; Blanco, E .; Naranjo-Rodriguez, 1. Anal. Chem., 2002, 74, 2423-2427; Zejli, H .; Hidalgo Hídalgo de Cisneros, JL; Naranjo-Rodríguez, l .; Liu, 8 .; Temsamaní, KR: Marty, JL Anal. Chim. Acla, 2008, 612, 198-203). Generally, the materials obtained by said method (Hench, L.L .; West, J. K. Chem. Rev., 1990, 90, 33-72) require the addition of an alcoholic solvent in order to homogenize the biphasic alkoxide-water mixture. The addition of this solvent generates low density matrices, which is undesirable in electroanalytical applications. The use of sonocatalysis, based on the insonation of the biphasic precursor mixture, normally alkoxide-water, homogenizes both phases, avoiding the addition of alcoholic solvents and generating
    high density matrices. This sonocatalytic method has been satisfactorily applied for the manufacture of materials called Sonogel (Blanco, E.; Esquivias, L .; Litrán, R.; Ramírez-del-Solar, M .; de la Rosa-Fax, N. Appl. Organomet Chem., 1999, 13, 399-418). The addition of a graphical modifier, necessary to provide electrical conductivity to the material, generates a material known as Sonogel-Carbon, whose manufacturing method is described in a previous patent (Hidalgo-Hidalgo de Cisneros, JL, Cordero-Randa, MM, Naranjo Rodriguez, l., Blanco, OE, Esquivias, FL, PatentES-2195715-B1, Spain, 2001) and in various articles included in the bibliography (Cordero-Rando, MM; Hidalgo-Hidalgo de Cisneros, JL; Blanco, E.; Naranjo-Rodriguez, 1. Anal. Chem., 2002, 74, 24232427; Cordero-Rando, MM; Naranjo-Rodriguez, l .; Palacios-Santander, JM; Cubillana-Aguilera, LM; Hidalgo-Hidalgo de Cisneros, JL Eleclroanal ., 2005, 17, 806-814; Cubillana-Aguilera, L .; Palacios-Santander, JM; Naranjo-Rodriguez, l .; Hidalgo-Hidalgo de Cisneros, JLJ Sol-Gel Sci. Roof., 2006, 40, 55 -64).
    The Sonogel-Carbon and its various modifications have been satisfactorily employed in the determination of various analytes of biological, agri-food and environmental interest (Bellido-Milla, D .; Cubillana-Aguilera, LM; El Kaoutit, M .; Hernandez-Artiga, MP ; Hidalgo-Hidalgo de Cisneros, JL; Naranjo-Rodriguez, l .; Palacios-Santander, JM Anal. Bioanal. Chem., 2013, 405, 3525-3539). The deposition of various nanoparticulate modifiers (metal nanoparticles or metal oxides) on the surface of the graphite transducer improves the electrochemical properties of the constituted device, obtaining good quality analytical parameters for an analyte of great interest in the agri-food sector such as ascorbic acid ( Ajaero, C .; Abdelrahim, MY; PalaciosSantander, JM; Almoraima Gil, ML; Naranjo-Rodríguez, l .; Hidalgo-Hidalgo de Cisne ros, JL; Cubillana-Aguilera, LM Sensor Acluat. B-Chem., 2012, 171 -172, 1244-1256; Abdelrahim, MY; Benjamin, S. R; Cubillana-Aguilera, LM; NaranjoRodriguez, l .; Hidalgo-Hidalgo de Cisneros, JL; Delgado, JJ; Palacios-Santander,
    J. M. Sensors, 2013, 13, 4979-5007). The electrochemical determination of this analyte by direct oxidation using base electrodes has certain drawbacks: the high overpotential and the adsorption of oxidized species on the electrode surface leads to a decrease in quality analytical parameters such as sensitivity and repeatability. The use of modified devices, such as those already mentioned, solve both drawbacks. However, the uses of these devices are limited due to the impossibility of renewing their surface mechanically. It should be noted that in all the Sonogel materials mentioned above, the carbon-based modifier used is graphite. However, the use of other carbon allotropes with better mechanical and electrical properties, such as Nanocarbon or carbon nanotubes, which also have some of their dimensions within the nanometric scale, make them very good candidates for synthesis of the sonogel material. On the other hand, conductive polymers, including those based on thiophene, have certain characteristics that make them suitable for the constitution of chemical sensors, such as their high stability and conductivity. For example, in the case of poly (3,4-ethylenedioxythiophene) (PEDOl), numerous synthetic methods are collected in the literature from its precursor monomer in two ways: chemical and electrochemical. The chemical pathway consists in the polymerization of the monomer by the addition of various oxidizing agents such as ferric chloride (Zhong, X; Fei, G; Xia, H.
    J. Appl. Polym Sci., 2010, 118, 2146-2152) And ferric sulfate (Jiang, C .; Chen, G .;
    Wang, X. Synth. Met., 2012, 162, 1968-1971). Said monomer is poorly soluble in
    aqueous media, which leads to a decrease in their conversion. The addition of surfactants, such as alkylnaphthalenesulfonate and naphthalene sulfonate (Kudoh, Y .; Akami, K .;
    Matsuya, Y. Synth. Me /., 1998, 98, 65-70; Lei, Y .; Dohata, H .; Kuroda, S .; Yamamoto,
    T. Synth. I/. , 2005, 149, 21 1-217) improve conversion, due to the generation of
    micellar structures that encapsulate the monomer. This route has other drawbacks, such as the high reaction time required and the complex instrumentation required. On the other hand, the electrochemical vla is based on obtaining the polymer by deposition on a support electrode, which can be carried out by three methods: galvanostatic, potentiostatic and potentiodynamic. The type of method used affects the morphology of the deposited film (Patra, S .;
    Barai, K .; Munichandraiah, N. Synth. Me /., 2008, 158, 430-435). With regard to its constitution as a sensor, in various articles of the literature it is stated that the cited polymer is obtained as a layer deposited on the surface of the electrode, being the electropolymerization of the monomer one of the methods used for such deposition (Senthil Kumar , S .; Mathiyarasu, J .; Phani,
    K. L J. Solid State Electrochem., 2005, la, 905-913: Sekli-Belaidi, F .; Temple-Boyer, P .; Gros, P. J. Electroanal. Chem., 2010, 647, 159-168; Bello, A; Giannetto, M .: Mori, G .; Seeber, R; Terzi, F .; Zanardi, C. Current Sensor. B-Chem., 2007, 121, 430-435; Pigani, L; Foca, G .; lonescu, K .; Martina, V .; Ulrici, A .; Vignali, M .; Zanardi, C .; Seeber, R Anal. Chim. Acta, 2008, 614, 213-222; Aranzazu Heras, M .; Lupu, S .; Pigani, L; PiNU, C .; Seeber, R; Terzi, F .; Zanardi, C. Electrochim. Minutes, 2005, 50, 1685-1691).
    The properties of the deposited polymeric film, as well as its conductivity and morphology, depend on the synthesis conditions used: type of support electrode, type of solvent and electropolymerization potential, among others. On the other hand, the incorporation of various modifiers in the polymeric film improves the electrochemical properties of the material and, therefore, enhances its applicability as a sensor. Some of the modifiers included in the literature are: carbon nanotubes (Lin, K. C .; Tsai, T. H .; Chen, S. M. Biosens. Bioelectron.,
    2010, 26, 608-614), gold nanoparticles (Zanardi, C .; Terzi, F .; Seeber, R Sensor Actuat. B-Chem., 2010, 148, 277-282; Kumar, SS; Mathiyarasu, J. ; Phani, K. L J.
    E / ectroana /. Chem., 2005, 578, 95-103), platinum nanoparticles (Lupu, S; Lakard,
    B .; Hihn, J .; Dejeu, J. Synth. Met., 201 2, 162, 193-198) And Prussian blue (Lupu, S. Synth. Me /., 201 1, 161, 384-390).
    However, devices consisting of PEDOr or other films
    conductive polymers (the PEDOT is specified as the one that is most commonly used in electroanalysis) usually has low stability, due to the degradation of the polymeric film after successive measures, which prevents its use continuously (Bello, A.; Gianneto, M .; Mari, G .; Seeber, R.; Terzi, F.; Zanardi, C. Current Sensor. BChern., 2007, 121, 430-435). On the contrary, the base material Sonogel-Carbon-conductive polymer could be the first one collected in the literature that uses these polymers in a massive way (and not in film), presenting a structural function, in addition to being conductive to form the body of the material. A high percentage of the material is made up of conductive species, around 91% by weight as opposed to the original 80nogel Carbon formulation, with a total of 45% by weight of conductive species. The high conductive percentage of the developed material increases the electronic transfer of the device, allowing some quality analytical parameters to be improved, such as sensitivity. As for its mechanical properties, it is worth noting a contraction of little appreciable volume and a little eroded surface after performing numerous electrochemical measurements, approximately 160, unlike other ceramic materials already mentioned, such as Sonogel-Carbon. Its greater stability, due to the renewability of its surface, allows its continued use for a longer time, as opposed to sensors based on deposited films. Therefore, the problems derived, both from devices based on conductive polymer films and on Sonogel-Carbon materials modified by deposition, seem to be solved with the developed sensor.
    EXPLANATION OF THE INVENTION
    The object of this new invention is a method of synthesis of a material that has the conductive polymer (PEDOT, PANI and PT) as a structural base, and whose conductive nature implies an increase in its conductivity with respect to other materials based on Sonogel-Carbon , in which the only conductive species is graphite. In addition, the reduction of the concentration of MTMOS, of an insulating nature, with respect to the original Sonogel-Carbon formulation, implies a greater increase in the conductivity of the material, around 46% by weight, and with a total of 91% in weight of conductive species in the electrode. This increase in conductivity is of vital importance, since it has a positive effect on quality analytical parameters such as sensitivity and the limit of detection, determining the constitution of electrochemical sensors in electroanalysis. On the other hand, the synthesis method used stands out for a low reaction time, 20 seconds, and a great experimental simplicity, only a high energy ultrasonic probe is required. In addition, the power used in the synthesis, between 6 and 12 W (120 and 240 J), indicates a low energy cost. To establish the most appropriate synthesis parameters, a series of experiment designs were carried out, whose approach requires defining the variables to be studied (factors) and the values that these variables take (levels). The study of the behavior of the system is carried out by determining a response variable, which is affected by the selected factors. The selection of said variable depends on the objective pursued in the design which, in this case, consists in establishing the best values for the variables involved in the synthesis process, with the idea of obtaining an electrode material as suitable as possible for its use. in electrochemical devices. In response to this purpose, the response variables for the proposed designs were the anodic (11) and cathodic (le) intensities due to the reversible redox process of potassium hexacyanoferrate (11):
    [Fe (CN), l3- + e - <=> [Fe (CN), l '
    Intensity values were recorded using cyclic voltammetry as an electroanalytical technique, at a scanning speed of 50 mV / s. The concentration of ana lito in the cell was 1 mM and the electrolytic medium used was a Brittan-Robinson pH 4 regulatory solution. A 2k factorial type design was proposed, which allows to know the effect of the different factors on the response without the need for Perform a multitude of experiments. In the cases considered, k equals 3, so 8 different experiments were carried out for each design proposed, with three different electrodes for each experiment. As an example, the design of experiments and the results obtained for the manufacture of a Sonogel-Carbon material with PEDOr as conductive polymer and its application for the construction of amperometric sensors are presented. In order to establish the conditions of the first design, previous studies were carried out, consisting of the manufacture of a set of SNG-C-PEDOT materials with variable EDOT volumes, between 100 and 300 ~ L, and with varying Hel concentrations, including between 0.2 MY 0.4 M. The other synthesis conditions remain constant in all cases: 100 ~ L of HCI / LiCIO "soundproofing time of 20 s, 11 W of power (220 J of energy) and 500 mg of graphite added to 50nosol Table 1 shows the established synthesis conditions.
    No.Synthesis 1 2 3 4 5 6 7 V ,, '/ uLI 100 150 200 250 300 100 150Hel MI 04 0.4 0.4 0.4 0.4 0.2 0.2
    Table 1. Parameters of sfntesls established for the previous studies
    After manufacturing, the determination of the double layer capacity for each sensor was carried out using cyclic voltammetry, as a technique
    10 electroanalytical, at different scanning speeds. Previous studies carried out concluded that materials with lower EDOT volume (100 ~ LY 150 ~ L) and higher concentration of HCI (OA M) had lower double layer capacity values, so that in these materials the load accumulation It was lower, indicating better electrochemical behavior.
    15 For manufacturing purposes, it was concluded that materials with lower volumes of EDOT had a better consistency for filling and compaction. At higher volume, the mixture becomes more liquid, which hinders its rise through the capillary and its subsequent compaction. On the other hand, the concentration of HCI did not have a noticeable effect on consistency.
    20 Based on these studies, the following factors are established for the first design: - Volume of EOOT added to the precursor mixture (VEDOT): This factor affects both the consistency and electrochemical behavior of the material. As concluded in previous studies, EDOT volumes greater than 150 IJL, when the volume of MTMOS is 500 ~ L, they generate materials with higher capacities of
    25 load, so that volume is set as the maximum value. The minimum value set is 75 ~ L. -Used ultrasonic power (P): It is proposed to reduce the energy cost of the synthesis by reducing the applied power. In the instrumentation used, the power is related to the amplitude. 11 W is established (220 J; amplitude at 40%)
    30 as maximum value and 8 W (160 J; amplitude at 30%) as minimum value.
    Experiment V'DOT (pL)P (W)C "I1If1to (mg)I.I ~ A) ± DE ·1, (~ A) ± DE '
    one 150eleven6001,42010,0121,35910,014
    2 150eleven5001,31410,0231,26610,015
    3 15086001,39010,0101,30210,008
    4 15085001,37410,0261,30610,026
    5 75eleven6001,42010,0351,34710,037
    6 75eleven5001,31910,0131,258 ± 0,012
    7 7586001,429 ± 0,0461,352 ± 0,046
    8 75 85001,315'0,0441,27710,056
    - Amount of graphite added to sonosol (Cgr • flto): It is postulated that a greater amount of graphite increases the conductivity of the material. The maximum value is set at 600 mg and the minimum value at 500 mg. The other synthesis conditions are kept constant: 500 ~ L of MTMOS, 100 ~ L of HCI / LiCIO, 004 / 0.05 M and soundproofing time of 20 s. The conditions and results obtained for each experiment are specified in Table 2.
    .
    Table 2. Parameters of slntesls established for dlsef'¡o 1. DE. Standard deviation .
    10 The results reflected in the previous table show little variability, which indicates a priori that the variation of the factors does not affect the intensity appreciably. On the other hand, in response to the experiments with a greater amount of graphite (experiments 1, 3, 5 and 7), greater inlensities are observed, indicating that this factor positively influences the response.
    15 The results obtained in the design of experiments were analyzed statistically, in order to elucidate which factors have a significant influence on the response. For this the Pareto diagram is used, defined as a representation that establishes a comparison between the factors according to their contribution in the response of the system studied (effect), and represented with a
    20 bar graph that shows the effect of the different established factors and their interactions. From this diagram, the factors that have a great influence on the response studied are quickly determined, compared to those that are not influential. The Pareto chart registered for this design (Figure 1A) determines that the
    The amount of graphite is the only significant factor in the response with a positive effect, which is expected due to its conductive character: a greater amount of graphite implies greater conductivity. On the other hand, the volume of EDOT is not significant in this design, which together with the low variability of the responses
    obtained by varying said factor, indicates that the polymer does not have a structural function in the material. In order that the structure of the material also depends on the conductive polymer and not only on the silane, the following design is focused on increasing the volume of EDOT added to the precursor mixture and decreasing the volume of MTMOS. The potency is set to the same values as the previous design and the amount of graphite added is set at 600 mg. It should be noted that, despite the increase in conductivity that would involve the addition of an amount of graphite greater than 600 mg (and, therefore, a greater intensity), the resulting material does not have a consistency suitable for its manufacture, so it is not get a
    10 electrode material useful for electroanalytical applications. In the new design proposed, the following synthesis parameters remain constant: insonation time in 20 s, amount of graphite in 600 mg, concentration of HCI in 0.4 M and LiCIO ", in 0.05 M. It should be noted that the volume of HCl / liCIO ", added to the precursor mixture is decreased from 1 00 ~ L to 40 IJL, in
    15 cases in which the volume of MTMOS decreases from 500 ~ L to 200 ~ L, in order to keep the alkoxide volumetric volume in 5: 1. The conditions of this new design, together with the results obtained for each experiment, are outlined in Table 3.
    Experiment V, oo, (~ l)P (W)VMTMOS (", l)1, (~ A) tDE '1, (~ A) tDE '
    , 360'one5001,447tO, 1271,299tO, 085
    2 360eleven2001,786tO, 0281,635'0,038
    3 36085001,416tO, 0671,258tO, 083
    4 36082001,801> 0,0811,606'0,069
    5 150eleven5001,419tO, 0351,347 <0.037
    6 150eleven2001,284tO, 0191,102tO, 025
    7 15085001,390'0,0101,302tO, 008
    8 150 82001,398tO, 0531,180tO, 089
    Table 3. Synthesis parameters established for design 2. · DE; Standard deviation
    In view of the results presented in the previous table, it is observed that in the cases in which the volume of EDOT added is greater (experiments 1, 2, 3 and 4), the responses obtained are superior to the remaining cases (experiments 5, 6, 7 and 8), indicating a priori that the volume of EDOT significantly affects the intensity.
    25 The Pareto chart registered for this design (Figure 1 B) establishes as significant factors the volume of EDOT, with a positive effect on the response and the volume of MTMOS, with a negative effect. This implies that the intensity is maximized at maximum EDOT volumes and minimum EDOT volumes. For another
    On the other hand, the power does not present a great relevance, being able to use the lowest value
    established in order to reduce the energy cost of the synthesis. In addition, this design establishes that the increase in conductivity implies greater intensity. For this reason, in the third design carried out, the
    5 volume of MTMOS (insulating nature) and increase the volume of EOOT (conductive nature). The power is also decreased in order to reduce the energy cost of the synthesis even further. It should be noted that, as in the previous case, the volume of HCI / LiCIO ~ added to the precursor mixture is decreased from 30 IJL to 20 IJl in cases, in which the volume of MTMOS decreases from 150 IJL to
    10 100 IJL, in order to keep the alkoxide / water volumetric ratio at 5: 1. The other parameters of synthesis, time of insonation and amount of graphite, remain constant for all experiments in 20 s and 600 mg, respectively. The experiments proposed for this design are shown in Table 4, as well as the
    15 anodic and cathodic intensities obtained.
    Experiment 1 2 3 4 5 6 7 8 V'DOrl ~ L) 380 380 380 380 360 360 360 360P (W) 8 8 6 6 8 8 6 6VMTMOS (pL) 150 100 150 100 150 100 150 100l. (~ A) iDE '1,774iO, 062 2,004'0,003 1,797> 0.106 1,926iO, 115 1,920,0,057 1,722iO, 094 1,973iO, 058 1,783'0,0651, (~ A) iDE '1,657> 0, 079 1,839iO, 056 1, 632iO, 110 1,79 "0,129 1,653iO, 034 1,566iO, 089 1,850iO, 056 1,595'0,079
    Table 4. Synthesis parameters established for design 3. -DE: Standard deviation
    Based on the previous results, it is observed that in cases in which the volume of EDOT is greater and that of MTMOS is lower (experiments 2 and 4), the
    20 answers obtained are superior. This indicates, a priori, that the response is maximized by the inverse relationship between both factors in the established range. The Pareto diagram shown in Figure 1 e confirms what has been observed, establishing the interaction Volume EDOTNolumen MTMOS as the only significant interaction, with a negative effect on the response. In this way, as in the
    25 previous design, the response is maximized to maximum EDOT volumes and minimum MTMOS volumes.
    From the realization of the designs, it has been possible to reduce the amount of silane added in the precursor mixture and increase the volume of EDOT, which implies an increase in the conductivity of the material (in total 91% by weight of the material is driver), and therefore, an increase in the response in volume to 40% compared to that obtained in the first design (table 5).
    Design 1 (Experiment 7) 2 (Exoeriment 4) 3 (Experiment 2) V'DOT (~ LJ 75 360 380V100 40 20L)VOTES (~ L) 500 200 100I. (~ AJ 1,429 1,801 2, 004I, (~ AJ 1,352 1,606 1,839
    Table 5. Anodic and cathodic intensities obtained for the selected experiments of
    Each design The insonation time in the selected experiments was 20 s, the
    applied power was 8 W and the amount of graphite added to sonosol was 600 mg.
    10 Figure 1 D shows a comparison of the results for the response variables by selecting the configurations of each design that presented the greatest value for them. This diagram shows an improvement in the response in the different designs to maximize it in the third, indicative of greater sensitivity. On the other hand, the recorded voltamperograms have narrow and defined peaks
    15 in all the cases studied, which indicates a good functioning of these materials as sensors. However, the signal corresponding to the material synthesized with Design 3 is significantly higher than for the other designs, thus offering these sensors a better electrochemical response. To illustrate these facts, recorded voltamperograms are shown in Figure 1 E
    20 for the configurations of each design that presented greater intensity. Due to the conductive nature of the polymer and the insulating nature of the silane, it is postulated that an increase in EDOT volumes and a decrease in established MTMOS volumes would lead to greater conductivity. However, when trying to increase and decrease these volumes, respectively, the
    25 drying times of the resulting material are greatly increased, as well as its fragility, which prevents its correct polishing. Therefore, volumes of EDOT greater than 380 ~ L and volumes of MTMOS below 100 ~ L generate materials with inadequate mechanical properties for later use as sensors.
    30 In accordance with the above, the following synthesis parameters: 380 ~ L of EDOT, 8 W of power (160 J of energy), 100 ~ L of MTMOS, 20 ~ L of HCI / LiCIO. 0.4 / 0.05 M, 600 mg of graphite and a soundproofing time of 20 s, are the most suitable for the generation of a material with electroanalytical applicability.
    5 This material also stands out for its mechanical and electrochemical properties. As for its mechanical properties, it is worth noting a zero volume contraction and a slightly eroded surface once the electrochemical measurements have been carried out. To illustrate these facts, the micrographs recorded for an unused and used electrode (approximately) are shown in Figures 2A and 28
    10 160 measurements), in which there is an insignificant separation between the material and the capillary. Also shown in Figures 2C and 20 are the micrographs recorded for the Sonogel-Carbon material, where the effects of erosion are evidenced, both in the high number of cracks and gaps, and in the material / capillary separation. With this comparison it is intended to corroborate the best
    15 mechanical properties of the developed sensor. With regard to the electrochemical properties of said sensor, the load capacity is lower than other Sonogel-Carbon materials modified and included in the literature (table 6): Sonogel-Carbon modified with sono-particles of gold, Sonogel-Carbon modified with nanoparticles of cerium oxide and Sonogel-Carbon
    20 modified with cerium oxide nanoparticles which, in turn, are decorated with sononano gold particles (Ajaero, C .; Abdelrahim, MY; Palacios-Santander, JM; Almoraima Gil, ML; Naranjo-Rodríguez, l .; Hidalgo- Hidalgo de Cisneros, J. l .; Cubillana-Aguilera, LM Sensor Ac / ua /. B-Chem., 2012, 171-172, 1244-1256; Abdelrahim, MY; Benjamin, SR; Cubillana-Aguilera, LM; Naranjo -Rodriguez, l .;
    25 Hidalgo-Hidalgo de Cisneros, J. l .; Delgado, J. J .; Palacios-Santander, J. M. Sensors, 2013, 13, 4979-5007).
    Material Layer observed (~ F / cm2)Double layer capacity (IlF / cm2)
    SNG-C 28.0024.00
    SNG-C-AuSNPs 55.0049.00
    SNG-C-CeO, 46.8246.08
    SNG-C-AuSNPs / CeO, 44.9743.96
    SNG-C-PEDOT 42.6137.76
    Table 6. Comparison of load capacities of different materials based on Sonogel Carbon. E / ectropholic medium: phosphate regulatory solution (PBS) pH 6.9
    The lower capacity implies a lower accumulation of charge on the electrode and, therefore, a greater availability of said charge for oxidation / reduction of the analyte to be determined. Studies using cyclic voltammetry in the presence of hexacyanoferrate
    (11) Potassium allowed to evaluate the electrochemical behavior of the developed sensor. Measurements were made at different scanning speeds (10-200 rnV / s) in the presence of 5 mM potassium hexacyanoferrate (11), in a 0.5 M potassium nitrate solution. In the presence of the anaphyte, two narrow peaks were observed. and defined: a peak over 0.200 V associated with the reduction and another over 0.288 V associated with the oxidation. The relationship between the anodic and cathodic peak intensities is similar to 1, which together with the small variability of potentials when increasing the scanning speed is indicative of a typically reversible redox process (F. Scholtz (Ed.), Electronalytical Melhods. Guide experimenls and Application, 2nd Ed .; Springer Verlag: Hildelberg, 2010). With respect to the mechanism that takes place on the surface of the electrode, the representation of the anodic and cathodic peak intensities against the square root of the scanning speed has a high linearity, with adjustment coefficients greater than 0.999, which indicates a process controlled by dissemination (F. Scholtz (Ed.), Eleclronalytical Melhods. Guide lo experimenls and Application, 2nd Ed .; Springer Verlag: Hildelberg, 2010). As an example, the anodic intensity adjustment equation obtained for an electrode of the developed material is presented.
    ¡. (IlA) = 0.619 + 1.211 vl / 2 (mVs-l)
    Regarding its application as a sensor, it should be noted that the peaks associated with the oxidation of ascorbic acid, test analyte, are narrow and defined. Figures 3A and 3B show the recorded voltamperograms using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), respectively. On the other hand, the quality analytical parameters for ascorbic acid are comparable to other sensors included in the literature (table 7), all of them modified: carbon nanotubes and PEDOl, Ni / Si and PEDOl, Unmodified Sonogel-Carbon, Sonogel -Carbon modified with sononano gold particles, Son0gelCarbon modified with cerium oxide nanoparticles and Sonogel-Carbon modified with cerioque oxide nanoparticles, in turn, are decorated with
    Sononano gold particles (Lin, K. C .; Tsal, T. H .; Chen, S. M. Biosens. Bioelectron.,
    2010, 26, 608-614; Yu, S .; Luo, C .; Wang, L .; Peng, H; Zhu, Z. Analyst, 2013, 138,
    1149-1155; Ajaero, C .; Abdelrahim, M. Y .; Palacios-Santander, J. M .; AJmoraima Gil,
    M. L.; Naranjo-Rodrlguez, l .; Hidalgo-Hidalgo de Cisneros, J. L .; Cubillana-Aguilera, L.
    M. Sensors Actuat. B-Chem., 2012, 171-172, 1244-1256), among others.
    R '
    Material
    linear
    Table 7. Comparison of quality parameters of different materials for the determination of AA. Measurements made using differential pulse voltammetry (OPV) as an electroanaltic technique and a pH close to 7.
    10 The high sensitivity obtained for the synthesized material indicates that PEOOT facilitates load transfer due to its conductive nature. On the other hand, the modifications made to most of the materials shown in the table above enhance sensitivity and load transfer. However, the material
    15 Sonogel-Carbon-PEDOT developed is not modified yet, it constitutes a base material, without any addition, so it is expected that subsequent modifications of the same, with nanomaterials, for example, generate even better results than those already obtained. Repeatability and reproducibility studies were carried out. In the case of
    20 reproducibility, three calibration curves were recorded for each electrode, using three different electrodes. The results expressed as average sensitivity (mean of the slopes of the calibration curves) and the respective coefficients of variation are shown in Table 8.
    Table 8. Results obtained in the repeatability studies, using the same electrode, and reproducibility, using three different electrodes (recording three calibration curves for each electrode in both cases) and the best limits of detection and quantification (LD and
    5 LQ, respectively) for the sensor developed using two electroanalytical techniques. Electrolytic medium: PBS pH 6.8. eDE = Standard deviation.
    The repeatability obtained in the determinations is high, indicative that the surface erosion caused by electrochemical measurements is not appreciable and does not affect the electrochemical behavior of the material. Reproducibility is also quite satisfactory, which indicates that the manufacturing process generates sensors with similar electrochemical behaviors. The limits of detection and quantification, analytical parameters of quality used for the electrochemical characterization of the sensor, correspond to three and ten times the standard deviation of the target,
    15 respectively (Miller, JN; Miller, JC Statistics and Chemomelrfa for Analytical Chemistry, 4 Ed., Prentice Hall, Madrid, 2002) .The limits obtained are lower using the OPV, which is expected according to the greater sensitivity achieved by this technique. Likewise, sensor validation was carried out by acid determination
    20 ascorbic in a commercial pharmaceutical sample (Redoxón '', also obtaining very satisfactory results. Two calibration methods were used: standard addition method (table 9) and calibration curve (table 1 O).
    Technique Reference valueDetermined valueAccuracy ('lo)
    electroanalytical (~ M)(~ M) 'DE'n = 3
    CV 45.4242, 07 <2.885.41
    DPV 45.4245, 27'1, 420.24
    Table 9. Experimental results for the AA content in RedoxónfJ using the standard addition method, Measured for three electrodes and two determinations for 25 e / ec / rodo. Medium e / ec / ralltico PBS pH 6.8. 'FROM; Deviation is / walking
    Technique Reference valueDetermined valueAccuracy (%)
    electroanalytic (mM)(mM) tOE '0-3
    CV 1,5241,559tO, 0441.63
    DPV 1,5241,372'0,0127.43
    Table 10. Experimental results for the AA content in Redox using the calibration curve method. Measured for three electrodes and two electrode determinations. PBS pH 6.8 e-electrolytic medium. DE = Standard deviation
    The mechanical renovability of the sensor surface constructed with the developed material was also studied by registering different cyclic voltamperograms, at 50 mVls, in the presence of 2 mM ascorbic acid. After each renewal, three determinations were made.
    10 The results shown in Table 11 and the graph shown in Figure 4 indicate that the sensor response (4.006 ± 0.49 ~ A) is quite stable after subsequent mechanical renovations, with a variability between measurements of less than 4%. Therefore, the mechanical renewal of the sensor surface allows its continued use, which is an important advantage over the use of PEDOT as a surface coating,
    15 which is how it has been used, generally, so far.
    No. of mechanical renovations 1, (~ A) tOE '
    one 4,207tO, 045
    2 4,187tO, 074
    3 4,077tO, 050
    4 4,033'0,072
    5 3, 840tO, 017
    6 4,097tO, 015
    7 3, 807tO, 021
    8 4,153tO, 006
    9 3, 840tO, 044
    10 3,930,0,030
    eleven 3,900'0,030
    Table 11. Experimental results for the anodic peak intensities (1,) of 2 mM AA before successive electrode renewals. Afeetrol / Lico medium: PBS pH 6.8. "Standard deviation.
    Once the electrochemical validation of the sensor was carried out, a structural characterization of the material developed using Raman spectroscopy and nitrogen fisisorption was carried out. Raman spectroscopy is used as a first approach to structural elucidation. In the Raman spectrum recorded for the material (figure 5A) a band about 1430 cm "associated with the symmetric vibration Co = CIl of the thiogenic rings of the polymer (Yu, S .; luo, C .; Wang, L .; Peng, H .; Zhu, Z. Analyst, 2013, 138, 1149-1155) The other polymer bands do not appear in the recorded spectrum, mainly due to fluorescence phenomena, on the other hand, nitrogen fisisorption is used to pore size determination The pore size distribution obtained from the analysis of the recorded isotherm (figure 58) concludes that the characterized material predominantly has a pore size between 2 and 10 nm (average diameter of 5 , 09 ± 2,03nm.) This size is indicative of a mesoporous material (Kim, M .; Oh, l .; Kim, JJ PowerSources, 2015, 282, 277-285). This application also proposes the manufacture of other materials based on Sonogel, particulate or nanoparticulate carbon, others conductive polymers other than PEDOT, such as PANI and PT, and two types of acid catalysts, using the synthesis parameters at the same intervals as those defined for the SNG-C-PEDOT material (see Figure 6). The modifications made are set out below:
    · Sonogel-Carbon-Polyaniline and Sonogel-Carbon-Polythiophene (SNG-C-PANI and SNG-C-PT, respectively): Addition of 75-380) lL of aniline or thiophene to the precursor mixture. The generated materials, with a powdery appearance similar to Sonogel-Carbon-PEOOT, presented a consistency suitable for the construction of electrodes. In this case, the precursor monomer used in the SNG-CPEDOT material is replaced by aniline or thiophene, so that the obtained polymer (PANI or PT) forms the structural basis of the material.
    -Sonogel-Nanocarbon-PEOOT, Sonogel-Nanocarbon-PANI and SonogetNanocarbon-PT (SNG-NC-PEDOT, SNG-NC-PANt and SNG-NC-PT, respectively): Addition of 350-400 mg of nanocarbon to sonosol. By increasing the amount of nanocarbon, solids were obtained with better consistency for the manufacture of electrodes. This material is synthesized in equal conditions to the SNG-C-PEDOT, SNG-C-PANI and SNG-CPT materials, but replacing the particulate graphite with Nanocarbon or nanoparticulate carbon.
    MSonogel-Carbon Nanotubes-PEDOT, Sonogel-Carbon NanotubesPANI and Sonogel-Carbon Nanotubes-PT (SNG-CNT-PEDOT, SNG-CNTPANI and SNG-CNT-PT, respectively): Addition of 30.0-32.5 mg of multiple-wall carbon nanotubes (MWCNT) to son0501. The addition of more carbon nanotubes led to the generation of more granulated solids, making filling difficult. The synthesized materials presented greater fragility than the materials based on graphite and nanocarbon. In this case, the particulate graphite has been replaced by MWCNT, which generates an even more sensitive material than the original.
    -Sonogel-Carbon / Gold Nanoparticles-PEDOT, 5000gelCarbon / Gold Nanoparticles-PANI, Sonogel-CarbonolGold Gold Particles-PT, Sonogel-Nanocarbon / Gold Nanoparticles-PEDOT, SonogelNanocarbon / Gold Nanoparticles-PANI, Gold Sonogel -PT, Sonogel-Carbonot Nanotubes Gold nanoparticles-PEDOT, Sonogel-Carbon Nanotubes / Gold Nanoparticles-PANI and Sonogel-Carbonot Nanotubes Gold-nanoparticles-PT (SNG-CIAuNPs-PEDOT, SNG-CIAuNPsPANI, SNG-CPNI-SNG , SNG-NCIAuNPs-PEDOT, SNG-NCIAuNPs-PANI, SNGNCIAuNPs-PT, SNG-CNTIAuNPs-PEDOT, SNG-CNTIAuNPs-PANI and SNGCNT / AuNPs-PT, respectively): Addition of 20-100 IJL of AuNPs / LiCI0 dissolution to the pre-insonation precursor mixture (depending on the volume of MTMOS added, in order to maintain the MTMOS / AuNPs volumetric ratio at 5: 1) The generated material presented an adequate consistency for filling and subsequent compaction. In this case, the acid catalyst used in the sonogel synthesis process (0.4 M Hel solution) is replaced by a very acidic pH solution (around 2.20) resulting from the synthesis of nanoparticles of gold from geranium leaf extract (Pelargonium zone / e) (Franco-Romano, M .; Gil, M. L A .; Palacios-Santander, JM; Delgado-Jaén, JJ; Naranjo-Rodriguez, l .; Hidalgo-Hidalgo de Cisneros, JL; Cubillana-Aguilera, L M. Ultrason. Sonochem., 2014, 21, 1570-1577). 80% of the nanoparticles measured by dynamic light scattering (DDL) had a diameter between 10 nm and 18 nm (mean value of 14.2t3.1 nm, presenting a maximum plasma absorbance of surface resonance of the nanoparticles at 534 nm, measured by UV-Vis spectrophotometry.
    In conclusion, the novelties of the sensor or sensors developed can be summarized
    as follows: - A 50n0gel carbon-based material for electroanalysis with a conductivity close to 91% by weight of its components is obtained, thanks to the presence of a conductive pOlimer: poIH3,4-ethylenedioxythiophene), pOlianilina and polythiophene. -The synthesis process is carried out in a short time and at a low energy cost, using a simple instrumental system. Only one high energy ultrasonic probe is necessary. -The conductive polymer has a double function: structural and conductive. -With this material, electrochemical sensor devices with a mechanical and electrochemical renewable surface can be easily manufactured, which implies a great advantage over polymer films generally used in current electroanalysis research. To the best of our knowledge, these electrodes constitute the first massive and monolithic conductive polymer electrode manufactured to date, since they are generally used in the form of deposited or electrodeposited films. -Good mechanical properties of the material: zero volume contraction and super-erosion erosion practically negligible after multiple electrochemical measurements in sensor devices (more than 150 electrochemical measurements with the material in an electrode). -Good electrochemical behavior: low observed capacity and double layer, comparable to other electrode materials. -Front a test analyte such as ascorbic acid, the quality parameters of the sensor as a base material, without modification, are quite good, comparable to those of other nanomaterial modified sensors, mainly, collected in the literature. In addition, it can be used in real samples.
    ~ The synthesis process is very versatile, since it allows multiple variants of the material to be obtained, including carbon-based nanomaterials or
    Gold nanoparticles as base material: SNG-C-PEDOT, SNG-C-PANI, SNG-CPT, SNG-CNT-PEDOT, SNG-CNT-PANI, SNG-CNT-PT, SNG-NC-PEDOT, SNGNC-PANI , SNG-NC-PT, SNG-C / AuNPs-PEDOT, SNG-C / AuNPs-PANI, SNGC / AuNPs-PT, SNG-NC / AuNPs-PEDOT, SNG-NC / AuNPs-PANI, SNG-NC / AuNPsPT , SNG-CNTlAuNPs-PEDOT, SNG-CNT / AuNPs-PANI and SNG-CNT / AuNPs-PT.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Figure 1. Results obtained for the designs of experiments performed for the
    Synthesis of the Sonogel-Carbon-PEDOT material. Figures lA, lB and lC
    correspond to standardized Pareto diagrams for the anodic intensity corresponding to designs 1, 2 and 3, respectively. The gray bars correspond to the negative effects in the response, while the white bars correspond to the positive effects. Figure 10 corresponds to the bar chart in which a comparison of the anodic and cathodic intensities obtained for the configurations of each design that presented greater intensity is shown,
    whose conditions are: design 1, experiment 7 (75 ~ L of EDOT, 500 ~ L of MTMOS, 100 ~ L of HCILLICE,), design 2, experiment 4 (360 ~ L of EDOT, 200 ~ L of MTMOS, 40 ~ L of HCI / LiCIO,) and design 3, experiment 2 (380 ~ L of EDOT, 1 00 ~ L of MTMOS, 20 ~ L of HCI / LiCI04). The other conditions are constant: 8 W of power (160 J of energy), 600 mg of graphite and 20 s of sounding time. The white bars correspond to the anodic intensity, while the black bars correspond to the cathodic intensity. For each experiment the error bar is represented, corresponding to the standard deviation taking into account three different electrodes. Figure 1 E corresponds to a comparison between the voltamperograms obtained for the configurations of each design that presented higher values for the response variables. These voltamperograms were recorded using cyclic vtammetry as an electroanalytical technique at a scanning speed of 50 mV / s. The electrolytic medium used was BrittonRobinson pH 4 and the concentration of potassium hexacyanoferrate (11) was 1 mM. The conditions for each configuration are: design 1, experiment 7 (75 ~ L of EDOT, 500 ~ L of MTMOS, 1 00 ~ L of HCI / LiCIO,); design 2, experiment 4 (360 ~ L of EDOT, 200 ~ L of MTMOS, 40 ~ L of HCI / LiCIO.) and design 3, experiment 2 (380 ~ L of EDOT,
    100 ~ L of MTMOS, 20 ~ L of HCI / LiCIO.). The other conditions are constant: 8 W of power (160 J of energy), 600 mg of graphite and 20 s of insonation time.
    Figure 2. SEM micrographs recorded for material based electrodes
    5 Sonogel-Carbon-PEDOT and Sonogel-Carbon. Figures 2A and 2B correspond to the unused and used electrode (approximately 160 measured in electrolytic media of pH 4 and 6.8) of the Sonogel-Carbon-PEDOT and the figures. 2C and 20 correspond to the unused and used Sonogel-Carbon electrode (under the same conditions as before). All micrographs were obtained using an electron microscope
    10 Quanta 200 scan coupled to an EDAX system. In the case of Sonogel-CarbonPEDOT (Figure 2A and 2B), the acceleration potential was 20 kV. In the case of Sonogel-Carbon (Figure 2C and 20), the acceleration potential was 30 kV.
    Figure 3. Voltamperograms corresponding to the electrochemical sensor based on the developed Sonogel-Carbon-PEDOT material, using 0.02M PBS as an electrolytic medium (pH = 6.8), in the presence of different concentrations of ascorbic acid:
    (a) 0.01 mM; (b) 0.05 mM; (e) 0.10 mM; (d) 0.499 mM; (e) 0.996 mM: (1) 1.49 mM; (g) 1.96 mM; (h) 2.49 mM; (i) 2.97 mM; (j) 3.45 mM. Figure 3A corresponds to the cyclic voltamperogram, recorded at 50 mV / s, and Figure 3B to the voltamperogram
    20 obtained from DPV, registered with the following experimental conditions: 0.4 s of interval time, 100 mV of modulation amplitude and 16 mV of step potential.
    Figure 4. Representation of the evolution of the corresponding response to the sensor
    25 developed after successive mechanical renovations. For each intensity value obtained, the error bar is represented, corresponding to the standard deviation taking into account three measurements made after each renewal. The concentration of ascorbic acid in the cell was 2 mM and the electrolytic medium used was a phosphate regulatory solution (PBS) 0.02 M pH 6.8. As electroanalphic measurement technique
    30 cyclic voltammetry was used at a scanning speed of 50 mV / s.
    Figure 5. Results obtained for the structural characterization of the SNG · C · PEDOT. Figure 5A corresponds to the Raman spectrum of the material, recorded on an 8Wtek i-Raman spectrometer. The laser, with a wavelength of 785 nm, has been focused for 4 s with a 20x microscope objective. Figure 58
    corresponds to the pore size distribution of the material, obtained from a registered adsorption isotherm using a Quanta Chrome AutoadsorbiQ analyzer.
    Figure 6. Scheme of the manufacturing process for SNG-C-PEDOT materials and their variants. The monomers used in the syntheses are: 3,4- (ethylenedioxythiophene)
    (EDOT), aniline (ANI) and thiophene (T). The catalyst used is a 0.4 M hydrochloric solution in the case of SNG-C-PEDOT, SNG-CNT-PEDOT, SNGNC-PEDOT and its variants with PANI and PT. In the case of SNG-C / AuNPs-PEDOT, SNG-NC / AuNPs-PEDOT, SNG-CNTlAuNPs-PEDOT and its variants with PANI and PT, the
    Catalyst was replaced by the solution resulting from the synthesis of gold nanoparticles from geranium leaf extract (Pe / argonium zone / e). In the case of particulate or nanoparticulate carbon added to sonosol, the species used were: spectroscopic grade graphite powder, carbon nanotubes and nanocarbon.
    MODE OF INVENTION
    This section details the manufacturing method of the SNG-CPEDOT, SNG-NC-PEDOT, SNG-CNT-PEDOT, SNG-C / AuNPs-PEDOT, SNGNC / AuNPs-PEDOT, SNG-CNT / AuNPs-PEDOT and its variants with other polymers
    conductors (PANI and PT), as well as the experimental conditions established for conducting electrochemical studies.
    a) Preparation of the precursor mixture: Place the following volume ranges of MTMOS, HCIlLiCIO .. and EDOT on a 16 mL pesafilter (in this
    order):
    • MTMOS: 100-500 ~ L.
    • HCI / UCIO .: 20-1 00 ~ L. It should be noted that the added volume of
    This solution is established in order to keep the ratio at 5: 1
    volumetric MTMOS / H, O.
    • EDOT: 75-380 ~ L. In the case of SNG-C / AuNPs-PEDOT, SNG-C / AuNPs-PANI, SNG-C / AuNPs-PT, SNG-NC / AuNPs-PEDOT, SNG-NC / AuNPs-PANI, SNGNC / AuNPs- PT, SNG-CNT / AuNPs-PEDOT, SNG-CNT / AuNPs-PANI and SNG
    CNT / AuNPs-PT add to the precursor mixture 20-100 ~ L of AuNPs / LiCIO ..,
    instead of the HCI / LiCI04 solution. To obtain the solution, dissolve
    the corresponding amount of LiCI04 in 1 mL of AuNPs, synthesized
    following the methodology included in the following article of the bibliography
    (Franco-Romano, M .; Gil, M. L. A.; Palacios-Santander, J. M .; Delgado-Jaén, J.
    5 J .; Naranjo-Rodríguez, l. ; Hidalgo-Hidalgo de Cisneros, J. L.; Cubillana
    Aguilera, L. M. Ultrason. Sonochem., 2014, 21, 1570-1577), so that the
    Dopant concentration is 0.05 M.
    In the case of SNG-C-PANI, SNG-NC-PANI and SNG-CNT-PANI add aniline
    (ANI) to the precursor mixture and in the case of SNG-C-PT, SNG-NC-PT and SNG
    10 CNT-PT add thiophene (T), replacing EDOT.
    b) Coat the pesafilter with a water jacket in order to avoid
    overheating Dip the probe tip into the precursor mixture and
    apply high energy ultrasound for 20 s, setting a value of
    power lower than the maximum output power (600 W) in all cases: 8
    fifteen W (in the case of adding EDOT to the precursor mixture) and 12 W (in the case
    of adding ANI or T to the precursor mixture); when the solution is used
    of AuNPs as an acid catalyst, the potency is also 12 W.
    Soundproofing was carried out using a MISONIX ultrasonic generator
    4000 equipped with 13mm diameter replaceable titanium tip.
    twenty After the soundproofing time, add the corresponding amount of
    Particulate carbon or nanoparticulate to sonosol: 350-400 mg of nanocarbon
    in the case of SNG-NC-PEDOT, SNG-NC-PANI, SNG-NC-PT, SNG
    NC / AuNPs-PEDOT, SNG-NC / AuNPs-PANI and SNG-NC / AuNPs-PT; 30-32.5 mg
    MWCNT in the case of SNG-CNT-PEDOT, SNG-CNT-PANI, SNG-CNT-PT,
    25 SNG-CNT / AuNPs-PEDOT, SNG-CNT / AuNPs-PANI and SNG-CNT / AuNPs-PT; Y
    500-600 mg of graphite powder in the case of SNG-C-PEDOT, SNG-C-PANI,
    SNG-C-PT, SNG-C / AuNPs-PEDOT, SNG-C / AuNPs-PANI, SNG-C / AuNPs-PT.
    Once the corresponding amount has been added, homogenize with the help of
    a spatula for about 1 minute, generating a solid
    30 granulated with a certain viscosity.
    and) For the construction of electroqufmlcos sensors with materials
    above, insert the glass capillary (external diameter of 1.55 ± 0, 05 mm and
    internal diameter of 1.15 ± 0, 05 mm) inside the solid once brought to
    out the homogenization, rotating around its vertical axis in both directions
    in order to favor the rise of the mixture by capillarity. Avoid
    formation of holes in the electrode during filling.
    d) Compact the mixture by inserting a cable in the capillary with the filling, previously supporting said capillary in a watch glass. Once the compaction is done, remove the watch glass and press the material in order to leave a portion of the filling out of the capillary. Ensure that the height of the material inside is approximately 5 mm.
    e) Arrange the capillaries at 45 ° on a support for about 24-48 hours.
    f) After the drying time has elapsed, polish the excess material with a Struers P1200 silicon carbide sandpaper (10.6 ~ m grain size) and then with a white satin paper (placed on a smooth surface) until a smooth and shiny surface is obtained.
    g) Electrochemical sensors manufactured in this way are used as working electrodes in a three electrode cell consisting of a platinum auxiliary electrode and an Ag / AgCI reference electrode, 3 M KCI. The connection of the working electrode to the measuring equipment is made through a copper wire, in contact with the filling material.
    For electrochemical characterization of electrochemical sensors based on the Sonogel-Carbon-PEDOT material, 25 rnL of a Britton-Robinson (BR) pH 4 regulatory solution or a phosphate regulatory solution (PBS) pH 6.8 were used as electrolytes, depending on the pH at which the determination is desired.
    • The capacity determination was carried out using cyclic vltamperometry in the absence of anallto, at different scanning speeds: 10, 25, 50, 75, 100, 125, 150, 175 and 200 mV / s. The measuring range was -0.4 V to 0.7 V, using two regulatory solutions, BR pH 4 and PBS pH 6.8.
    • The determination of the sensitivity and the limit of detection was carried out by adding AA of a 0.25 M stock solution to a cell containing 25 mL of a regulatory solution. The resulting cell ascorbic acid concentrations after each addition are indicated below: 0.01; 0.05; 0.10; 0.499; 0.996; 1.49; 1.98; 2.48; 2.97 and 3.45 mM. The range of potentials for the measurement is established between -0.1 V and 0.7 V. The electroanalytical techniques used were cyclic voltammetry, with a scanning speed of 50 mVls and differential pulse voltammetry,
    selecting the conditions attending prel / ios studies with Sonogel-Carbon materials (Ajaero, C .; Abdelrahim, MY; Palacios-Santander, JM; Almoraima Gil, ML; Naranjo-Rodríguez, l .; Hidalgo-Hidalgo de Cisneros, J. L; Cubillana-Aguilera, LM Sensors Actual. B-Chem., 2012, 171-172, 12441256): 16 mV step potential, 100 mV modulation amplitude and 0.4 s pulse interval time. Taking the peak intensities for each concentration value, the calibration curves were obtained, whose slopes correspond to the sensitivity.
    • The determination of ascorbic acid in a commercial capsule is carried out using two calibrations: Calibration curve and standard additions. For the calibration curve method, the tablet was dissolved in 50 mL of water previously soundproofed for 15 minutes in a Selecta brand ultrasonic bath, with a maximum output power of 200 W. Subsequently, 340 J..IL of said solution to a cell containing 25 mL of PBS, registering the corresponding potential intensity curve. The peak intensity obtained was correlated with the corresponding calibration curve in order to determine the concentration of ascorbic acid in the cell. For the standard addition method, the tablet was dissolved in 100 mL of water previously soundproofed in the same ultrasonic bath and for the same time as in the previous case. Subsequently, the addition of 20 J..IL of said solution to a cell containing 25 mL of PBS was carried out, registering the corresponding intensity-potential curve. After this measurement, six additions of 100 J..IL of a 9 mM ascorbic acid solution were carried out, recording the intensity-potential curve in each case. The peak intensities obtained were represented against the concentration, obtaining the concentration of ascorbic acid in the cell by extrapolation. For both methods, cyclic voltammetry and differential pulse voltammetry were used as electroanalytical measurement techniques.
    INDUSTRIAL APPLICATION
    The synthesized material is susceptible of industrial application, since it can be used as an electrochemical sensor coupled to any commercial portable measurement system in the on-site determination of electroactive analytes of interest in multiple areas: agri-food, biomedicine and environment. The massive use of a conductive polymer, together with the renewability of the surface of the electrodes based on these materials, allows to solve the degradation problems suffered by the conductive polymer films (PEDOr, PANI or PT), commonly used, in
    5 general, in electrochemical devices. Surface renewal stands out for its speed and ease, allowing the use of the sensor repeatedly, with a variability in response, after subsequent renovations, less than 5%. Such renovation can be mechanical, using a fine-grained sandpaper P1200, and electrochemical , using sulfuric acid as a medium
    10 electrolytic, in the range of concentrations 0.05 M and 0.1 M, and cyclic vOltamperometry as an electroanalytical technique. Likewise, its low response time allows a multitude of analyzes to be performed in a short time, which is a great advantage in electroanalytical applications. Finally, the synthesis process used allows to greatly expand the range
    15 of materials based on Sonogel, carbon and conductive polymers, which can be used to manufacture sensor devices with good mechanical and electrochemical properties, and whose applicability for the detection of analytes or chemical species of environmental, biomedical and / or agri-food interest, among others, it is very high.
    权利要求:
    Claims (23)
    [1]
    one. A process for the preparation of 50n0gel composites, particulate or nanoparticulate carbon, and conductive polymers, using an acid catalyst, which can include gold nanoparticles, by high energy ultrasound.
    [2]
    2. A process for manufacturing materials according to claim 1, comprising the following steps:
    • Preparation of the precursor mixture, containing: methyltrimethoxysilane (MTMOS), precursor monomer of the conductive polymer and a catalyst solution + dopant .: liCIO. 0.05 M.
    • Application of high power ultrasound to the precursor mixture for 20 seconds: obtaining the sun.
    • Addition to 50n0501 of a carbon allotrope. and homogenization.
    • Filling the mold or capillary (in the case of sensors).
    • Drying for a minimum of twenty four hours and obtaining the sonogel material.
    [3]
    3. A process for the manufacture of materials according to claims 1 and 2, wherein the conductive pOlimer is: PEDOT, PANI or PT, obtained from their respective monomers: 3,4 ~ ethylenedioxythiophene, aniline or liophen.
    [4]
    Four. A process for the manufacture of materials according to claims 1 and 2, wherein the carbon allotrope can consist of: particulate carbon in the form of high quality and spectroscopic grade graphite powder, multiple wall carbon nanotubes, nanocarbon or carbon nanoparticulate or any other graphite based material.
    [5]
    5. A process for the manufacture of materials according to claims 1 and 2, characterized by the use of a catalyst solution composed of He l 0.4 M
    or the solution resulting from the synthesis of gold nanoparticles from plant extracts, preferably from geranium leaves (Pe / argonium zone / e).
    [6]
    6. Composite material Sonogel-Carbon-Conductive Polymer (SNG-C-PEDOT), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic sitano: methyltrimethoxysilane, in the range 100-500 IJL of the commercial reagent.
    • Precursor monomer of the conductive polymer: 3,4-ethylenedioxythiophene, in the range 75-380 JL of the commercial reagent.
    • Conductive polymer dopant: LiCIO ~ 0.05 M.
    • Acid catalyst: Aqueous solution of Hel 0.4 M, in the range 20-100 IJL.
    • Carbon allotrope: particulate carbon in the form of spectroscopic grade graphite powder, in the 500-600 mg range of the commercial reagent.
    [7]
    7. Composite material Sonogel-Carbon-Conductive polymer (SNG-C-PANI), obtained according to claims 1 to 5, comprising:
    • Non-hydrophobic precursor site: methyltrimethoxysilane, in the range 1 00-500 ~ L of the commercial reagent.
    • Precursor monomer of the conductive polymer: aniline, in the range 75-380 ... tL of the commercial reagent.
    • Dopant of the conductive polymer: licio .. 0,05 M.
    • Acid catalyst: Aqueous solution of 0.4 M HCl, in the range 20-100 ¡..tL
    • Carbon allotrope: particulate carbon in the form of spectroscopic grade graphite powder, in the 500-600 mg range of the commercial reagent.
    [8]
    8. Composite material Sonogel-Carbon-Conductive Polymer (SNG-C-PT), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 100-500 ... tL of the commercial reagent.
    • Precursor monomer of the conductive polymer: thiophene, in the range 75-380 IJ.L of the commercial reagent.
    • Dopante of the conductive polymer: liCIO .. 0,05 M.
    • Acid Catalyst: Aqueous solution of 0.4 M HCI in the range 20-100 ¡..tL
    • Carbon allotrope: particulate carbon in the form of spectroscopic grade graphite powder in the 500-600 mg range of the commercial reagent.
    [9]
    9. Composite material Sonogel-Carbon-Conductive polymer (SNG-NC-PEDOT),
    obtained according to claims 1 to 5, comprising:
    • Hydrophobic 8ilane precursor: methyltrimethoxysilane, in the range 100-500 ~ L of the commercial reagent.
    • Precursor monomer of the conductive polymer: 3,4-ethylenedioxythiophene, in the range 75-360¡LL of the commercial reagent.
    • Conductive polymer dopant: LiCI04 0.05 M.
    • Acid catalyst: Aqueous solution of Hel 0.4 M, in the range 20-100 1lL.
    • Carbon allotrope: nanoparticulate carbon in the form of nanocarbon, in the range 350-400 mg of the commercial reagent.
    [10]
    10. Composite material Sonogel-Carbon-Conductive polymer (SNG-NC-PANI), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 100-500 IJL of the commercial reagent.
    • Precursor monomer of the conductive polymer: aniline, in the range 75-380 ~ L of the commercial reagent.
    • Conductive polymer dopant: liCIO .. 0.05 M.
    • Acid catalyst: Aqueous solution of HC1 0.4 M, in the range 20-100 IJL.
    • Carbon allotrope: nanoparticulate carbon in the form of nanocarbon, in the range 350-400 mg of the commercial reagent.
    [11 ]
    eleven . Composite material Sonogel-Carbon-Conductive polymer (SNG-NC-PT), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 100-500 IJL of the commercial reagent.
    • Precursor monomer of the conductive polymer: thiophene, in the range 75-380 ~ L of the commercial reagent.
    • Conductive polymer dopant: liCIO .. 0.05 M.
    • Acid catalyst: Aqueous solution of HCl 0.4 M, in the range 20-100 ~ l.
    • Carbon allotrope: nanoparticulate carbon in the form of nanocarbon, in the range 350-400 mg of the commercial reagent.
    [12]
    12. Composite material Sonogel-Carbon-Conductive polymer (SNG-CNT-PEDOT),
    obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 1 00-500 ~ L of the commercial reagent.
    • Precursor monomer of the conductive polymer: 3,4-ethylenedioxythiophene, in the range 75-380 ~ L of the commercial reagent.
    • Conductive polymer dopant: LiCIO ~ 0.05 M.
    • Acid catalyst: Aqueous solution of Hel 0.4 M, in the range 20-100 IlL.
    • Carbon allotrope: particulate carbon in the form of multi-walled carbon nanotubes, in the range 30-32.5 mg of the commercial reagent.
    [13]
    13. Composite material Sonogel-Carbon-Conductive Polymer (SNG-CNT-PANI), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 1 00-500 ~ L of the commercial reagent.
    • Precursor monomer of the conductive polymer: aniline, in the range 75-380 ... tL of the commercial reagent.
    • Conductive polymer dopant: LiCI04 0.05 M.
    • Acid catalyst: Aqueous solution of HCl 0.4 M, in the range 20-100¡tL.
    • Carbon allotrope: particulate carbon in the form of multi-walled carbon nanotubes, in the range 30-32.5 mg of the commercial reagent.
    [14]
    14. Composite material Sonogel-Carbon-Conductive Polymer (SNG-CNT-PT), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 100-500 ~ L of the commercial reagent.
    • Precursor monomer of the conductive polymer: thiophene, in the range 75-380 µl of the commercial reagent.
    • Conductive polymer dopant: liCIO .. 0.05 M.
    • Acid catalyst: Aqueous solution of 0.4 M HCI, in the range 20-100 ~ L.
    • Carbon allotrope: particulate carbon in the form of multi-walled carbon nanotubes, in the range 30-32.5 mg of the commercial reagent.
    [15]
    15. Composite material Sonogel-Carbon / Gold nanoparticles-Conductive polymer (SNG-C / AuNPs-PEDOT), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 1 00-500 ~ L of the commercial reagent.
    5 • Precursor monomer of the conductive polymer: 3,4-ethylenedioxythiophene, in the75-380 ~ L range of commercial reagent.
    • Conductive polymer dopant: liCIO .. 0.05 M.
    • Acid catalyst: Solution resulting from the synthesis of gold nanoparticles from the extract of geranium leaves (Pe / argonium zonale), in the interval
    10 20-100 ~ L.
    • Carbon allotrope: particulate carbon in the form of spectroscopic grade graphite powder, in the 500-600 mg range of the commercial reagent.
    [16]
    16. Composite material Sonogel-CarbonJ Gold nanoparticles-Conductive polymer 15 (SNG-C / AuNPs-PANI), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 1 00-500 ~ L of the commercial reagent.
    • Precursor monomer of the conducting polymer: aniline, in the range 75-380 ~ L
    of the commercial reagent. 20 • Conductive polymer dopant: 0.05 M.
    • Acid catalyst: Solution resulting from the synthesis of gold nanoparticles from the extract of geranium leaves (Pe / argonium zone / e), in the interval
    20-100 ~ L.
    • Carbon allotrope: particulate carbon in the form of spectroscopic grade 25 graphite powder, in the 500-600 mg range of the commercial reagent.
    [17]
    17. Composite material Sonogel-Carbon / Gold nanoparticles-Conductive polymer (SNG-C / AuNPs-PT), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 100-500 ~ L of the commercial reagent.
    • Precursor monomer of the conductive polymer: thiophene, in the range 75-380 IJL of the commercial reagent.
    • Dopant of the conductive polymer: licio "0,05 M.
    • Acid catalyst: Solution resulting from the synthesis of gold nanoparticles from the extract of geranium leaves (Pe / argonium zone / e), in the range 20-100 ~ L.
    • Carbon allotrope: particulate carbon in the form of spectroscopic grade graphite powder, in the 500-600 mg range of the commercial reagent.
    [18]
    18. Composite material Sonogel-Carbon / Gold nanoparticles-Conductive polymer (SNG-NC / AuNPs-PEDOT). obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 1 00-500 ~ L of the commercial reagent.
    • Precursor monomer of the conductive polymer: 3,4-ethylenedioxythiophene, in the range 75-380 IlL of the commercial reagent.
    • Conductive polymer dopant: liCIO. 0.05 M.
    • Acid catalyst: Solution resulting from the synthesis of gold nano particles from the extract of geranium leaves (Pe / argonium zonale), in the range 20-100
    ~ L.
    • Carbon allotrope: nanoparticulate carbon in the form of nanocarbon, in the range 350-400 mg of the commercial reagent.
    [19]
    19. Composite material Sonogel-Carbon / Gold nanoparticles-Conductive polymer (SNG-NC / AuNPs-PANI), obtained according to claims 1 to 5, comprising:
    • Hydrophobic 8ilane precursor: methyltrimethoxysilane, in the range 1 00-500 ~ L of the commercial reagent.
    • Precursor monomer of the conductive pOmer: aniline, in the range 75-380 IlL of the commercial reagent.
    • Dopant of the conductive polymer: licio. 0.05 M.
    • Acid catalyst: Solution resulting from the synthesis of gold nano particles from the extract of geranium leaves (Pe / argonium zone / e), in the range 20-100
    ~ L.
    • Carbon allotrope: nanoparticulate carbon in the form of nanocarbon, in the range 350-400 mg of the commercial reagent.
    [20]
    20. Composite material Sonogel-Carbon / Gold nanoparticles-Conductive polymer (SNG-NC / AuNPs · PT), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 100-500 IlL of the commercial reagent.
    • Precursor monomer of the conductive pOmer: thiophene, in the range 75-380 ... tL of the commercial reagent.
    • Conductive poly dopant: UCI04 0.05 M.
    • Acid catalyst: Solution resulting from the synthesis of gold nanoparticles from the extract of geranium leaves (Pelargonium zona / e). in the range 20-100 ~ L.
    • Carbon allotrope: nanoparticulate carbon in the form of nanocarbon, in the range 350-400 mg of the commercial reagent.
    [21 ]
    twenty-one . Composite material Sonogel-Carbon / Gold nanoparticles-Conductive polymer (SNG-CNT / AuNPs-PEDOT), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 100-500 IJ.L of the commercial reagent.
    • Precursor monomer of the conductive pOmer: 3,4-ethylenedioxythiophene, in the range 75-380 ~ L of the commercial reagent.
    • Dopant of the conductive polymer: LiCI04 0.05 M.
    • Acid catalyst: Solution resulting from the synthesis of gold nanoparticles from the extract of geranium leaves (Pe / argonium zone / e), in the range 20-100
    ~ L.
    • Carbon allotrope: particulate carbon in the form of multi-walled carbon nanotubes, in the range 30-32.5 mg of the commercial reagent.
    [22]
    22. Composite material Sonogel-Carbon / Gold nanoparticles-Conductive polymer (SNG-CNT / AuNPs-PANI), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 100-500 IlL of the commercial reagent.
    • Precursor monomer of the conductive polymer: aniline, in the range 75-380 IlL of the commercial reagent.
    • Conductive polymer dopant: LiCI04 0.05 M.
    • Acid catalyst: Solution resulting from the synthesis of gold nanoparticles from the extract of geranium leaves (Pelargonium zone / e), in the range 20 · 100
    ~ L.
    • AI6 carbon trope: particulate carbon in the form of carbon nanotubes of multiple wall, in the range 30-32.5 mg of the commercial reagent.
    [23]
    23. Composite material Sonogel-Carbon / Gold nanoparticles-Conductive polymer (SNG-CNT / AuNPs-PT), obtained according to claims 1 to 5, comprising:
    • Precursor hydrophobic silane: methyltrimethoxysilane, in the range 100-500 ~ L of the commercial reagent.
    • Precursor monomer of the mere polymer: thiophene, in the range 75-380 ~ L of the commercial reagent.
    • Dopant of the conductive polymer: licio "0,05 M.
    • Acid Catalyst: Solution resulting from the synthesis of gold nanoparticles at
    15 from the extract of geranium leaves (Pelargonium zonale), in the range 20-100 "L.
    • AI6 carbon trope: particulate carbon in the form of multi-walled carbon nanolubes, in the range 30-32.5 mg of the commercial reagent.
    Use of the materials obtained according to claims 1 to 5 and described in claims 6 to 23, for the construction of modified amperometric sensors and biosensors.
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