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    • 专利摘要:
    Sonogel-Carbon nanotubes and Sonogel-Nanocarbon composite materials: manufacturing process and its application for the construction of electrodes and (bio) electrochemical sensors. For the first time, a massive composite material based on sonogel and carbon nanotubes or nanocarbon is synthesized by high energy ultrasound. The synthesis parameters are optimized for both cases and the properties of carbon in the form of nanomaterial are exploited to generate materials that can be used to manufacture (bio) electrochemical sensors. The presence of a carbon nanomaterial increases the electronic transfer of the electrode devices and their analytical parameters of quality. Other advantages of the system are: - Speed, simplicity and low cost of the process and instruments used. - Significant reduction of the amount of carbon to make the material conductor. - The good mechanical and electrochemical renewal of the material allows a continuous use of these devices. - The manufacturing process is quite reproducible. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2683026A1
    申请号:ES201700270
    申请日:2017-03-22
    公开日:2018-09-24
    发明作者:José María PALACIOS SANTANDER；Jesús CABEZA SAUCEDO；Magdalena GARCIA ROMERO；Joaquín Rafael CRESPO ROSA；David LÓPEZ IGLESIAS；Laura María CUBILLANA AGUILERA；Ignacio NARANJO RODRÍGUEZ；Dolores BELLIDO MILLA；José Luis HIDALGO HIDALGO DE CISNEROS
    申请人:Universidad de Cadiz；
    IPC主号:
    专利说明:

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    Table 2: Average values of observed capacity and capacity of the double layer together with the standard deviations and the respective coefficients of variation (%), calculated for several SNG-CNT electrodes optimized in a Britton-Robinson medium at different pH values.
    As can be seen, the capacity values are now much lower for the optimized material with respect to the non-optimized material and the graphite-based sonogel material, giving quite acceptable coefficients of variation, in general. On the other hand, if we change the regulatory medium, the trend of improvement is maintained, obtaining similar capacities at similar pH values (see Table 3), except for the NH3 / NH4 + medium at pH 9, where they are slightly higher.
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    Table 3: Average values of observed capacity and capacity of the double layer together with the standard deviations and the respective coefficients of variation (%), calculated for several SNG-CNT electrodes optimized in different pH regulating means.
    In general, the lower the value of the capacity, the better the electrochemical performance of the electrodes, since there is less accumulation of charge on the electrode and, therefore, there is a greater availability of said charge for oxidation. analyte reduction to be determined. Therefore, it can be considered that the optimized SNG-CNT material can be very useful for the analysis of substances of environmental, biological and / or agri-food interest. In addition, by obtaining capacity values an order of magnitude lower than those of the sonogel material based on graphite, it is expected to improve the results of the analyzes as far as quality analytical parameters are concerned.
    Studies using cyclic voltammetry in the presence of potassium hexacyanoferrate (II) (K4Fe (CN) 6) and hexaaminrutenium chloride (III) ([Ru (NH3) 6] Cl3), typically reversible redox species, allowed to evaluate the behavior Electrochemical sensor developed with the optimized SNG-CNT material. Measurements were made, with three electrodes in each case, at different scanning speeds (10-200 mV / s), in the presence of each of the above species with a concentration of 1 mM and in 0.2 M phosphate regulating medium (pH 6.9).
    In the case of K4Fe (CN) 6, voltamperograms have a pair of well-defined peaks and are attributed to the oxidation and reduction of iron (Fe) present in the analyte. The anodic peak is associated with the oxidation of Fe (ll) to Fe (lll) while the cathodic peak corresponds to the reduction of Fe (llI) to Fe (ll), as the following reaction shows:
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    In all cases, a difference was obtained between the anodic and cathodic peak potentials (AEP) that increases slightly with the scanning speed, the AEP at low speeds of 110 mV and AEP at high speeds of 180 mV. As can be seen from these data, the values are higher than 0.059 / n volts, where n is the number of electrons involved in the redox process (1 in our case), and dependent on the scanning speed,
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    Zhang, L .; Tian, Y .; J. Electroanal. Chem. 15 781 (2016) 278-283; Inoue, Y .; Okazaki, Y .; Muguruma, H .; Inoue, H .; Ohsawa, T .; Anal. Sci. 32 (2016) 797-799; Deng, K .; Li, X .; Huang, H .; Microchim. Acta, 183 (2016) 2139-2145; Tsierkezos, N.G .; Othman, S.H .; Ritter, U .; Hafermann, L .; Knauer, A .; Kohler, J.M .; Downing, C .; McCarthy, E.K .; Sensors Actuat. B-Chem., 231 (2016) 218-229; Yan, S .; Li, X .; Xiong, Y .; Wang, M .; Yang, L .; Liu, X .; Li, X .; Alshahrani, L. Abdullah M .; Liu, P .; Zhang, C .; Microchim. Acta, 183 (2016) 1401-1408; da Silva, L.V .; Silva, F.A.S .; Kubota, L.T .; Lopes, C.B .; Lima, P.R .; Costa, E.O .; Pinho Junior, W .; Goulart, M.O.F .; J. Solid State Electrochem., 20 (2016) 2389-2393), among others.
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    Table 4. Comparison of quality parameters of different materials for the determination of AA. Measurements made using differential pulse voltammetry (DPV) as an electroanalytical technique and a pH close to 7.
    The limits of detection and quantification, analytical quality parameters used for electrochemical characterization of the sensor, were calculated as three and ten times the standard deviation of the target divided by the slope of the calibration curve, respectively (Miller,
    20 J. N .; Miller, J. C. Statistics and Chemometrics for Analytical Chemistry, 4 Ed., Prentice Hall, Madrid, 2002).
    As can be seen, the sensitivity of the SNG-CNT electrode against ascorbic acid is quite good, comparable and, in some cases, better than other more complex electrochemical devices that include more modifiers. In addition, the main advantage of electrodes manufactured with SNG-CNT is that its surface can be renewed, as already mentioned previously, mechanically and / or electrochemically, giving rise to a new electrode that maintains its electrochemical behavior. To this we add the good sensitivity due to the
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    Of the six NC configurations tested and described above for the preparation of electrodes, the 250 mg was discarded due to the impossibility of constructing the electrodes. Therefore, the studies collected below refer exclusively to electrodes containing in their composition the amounts of 300, 325, 350, 375 and 400 mg of NC. It is also necessary to comment that the capillaries with the material are arranged for drying at an angle of 45 ° with respect to the vertical; subsequently, and once dry, they undergo the mechanical polishing process to obtain the electrodes.
    Next, the devices obtained were evaluated by means of the calculation of the capacitive currents, considering as optimal that formulation used for the manufacture of electrodes that offered lower values of the capacities. Again, the main idea is to have an electrode material with the lowest values of the response variable, which, in principle, would make them more suitable for use in electrochemical (bio) sensor devices.
    Figure 5 shows the cyclic voltamperograms corresponding to electrodes constructed with SNG-NC material using different amounts of NC (300-400 mg), in different pH regulating media: Britton-Robinson pH 4 (Figure 5A) and buffer phosphate (PBS) pH 6.9 (Figure 5B), using a scanning speed of 100 mV / s. As can be seen from the figure, the SNG-NC material manufactured with 350 mg of NC has a distance between anodic and cathodic curves much smaller than the rest, indicative of a lower accumulation of charge on the electrode and, therefore, of more values Small for capacitive current. Therefore and from the point of view of capacity, devices with this configuration should, in general, have a better electrochemical behavior.
    Table 7 shows the values of Cobs, obtained at 100 mV / s, and CDC for the different Sonogel-Nanocarbon configurations, in two different regulatory media: Britton-Robinson pH 4 and PBS pH 6.9.
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    Table 7: Values of observed capacity and double layer capacity calculated in different pH regulating means for electrodes made of SNG-NC material, with different amounts of NC.
    As can be seen in the table, SNG-NC materials with amounts greater than and less than 350 mg generate electrodes with higher Cobs and CDC values, thereby corroborating the results obtained in the CV voltamperograms shown in Figure 5. The capacity values for the material with 350 mg of NC are very similar to those of the Sonogel-Carbon electrode (sonogel with 500 mg of tornado pulverized graphite as a reference: Cobs = 28.08 and CDC = 24.47 pF / cm2, see Table 1) (Ajaero, C .; Abdelrahim, MY; Palacios-Santander, JM; Almoraima Gil, ML; Naranjo-Rodríguez, I .; Hidalgo-Hidalgo de Cisneros, JL; Cubillana-Aguilera, LM Sensors Actuat. B- Chem., 2012, 171-172, 1244-1256; Abdelrahim, MY; Benjamin, SR; Cubillana-Aguilera, LM; Naranjo-Rodríguez, I .; Hidalgo-Hidalgo de Cisneros,
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    After performing the enzymatic deposition on the Sonogel-Nanocarbon electrodes, the biosensor device tests were performed using the electroanalytic chronoamperometry technique against 3 different analytes: caffeic acid (ACF), catechol (CAT) and hydroquinone (HDQ), with the purpose of calculating its analytical parameters of quality and comparing these biosensors with those that appear in the literature and that are formed by a sonogel material with 500 mg of graphite powder (Attar, A .; Cubillana-Aguilera, L .; Naranjo-Rodríguez , I .; Hidalgo-Hidalgo de Cisneros, JL; Palacios-Santander, JM; Amine, A .; Bioelectrochem., 101 (2015) 84-91). The concentration ranges studied for the analytes were: 1-60 µM for ACF and HDQ and 10-600 µM for CAT.
    Figure 8 shows, as an example, the chronoamperometric signals corresponding to the determination of caffeic acid for biosensors constructed with SNG-NC material with different amounts of NC and, as a reference, the biosensor based on the 500 mg sonogel material of graphite powder, without AuNPs. As can be seen, the serial corresponding to the HRP / SNG-NC biosensors with different amounts of NC are similar and with much larger current density jumps (especially for the biosensor with 350 mg of NC) than those corresponding to the biosensor based on graphite powder. This indicates that the sensitivity of the electrochemical device is increased by the presence of nanopulverized carbon in the sonogel material, mainly due to the improvement of the current transfer made by the nanomaterial.
    Table 8 shows the best quality parameters for these biosensors considering the three analytes:
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    Table 8: Quality analytical parameters for the three analytes (caffeic acid, hydroquinone and catechol): sensitivity (slope of the calibration curve) and detection limit for HRP biosensors, using the SNG-NC material as a transducer with different quantities of NC, and taking as reference the sonogel material with 500 mg of graphite powder. The electrolytic medium is acetic / sodium acetate at pH 5 and with H202 at the concentration of 10 mM; applied potential = -0.15 V. 1 Attar, A; Cubillana-Aguilera, L; Naranjo-Rodríguez, I .; Hidalgo-Hidalgo de Cisneros, J.L .; Palacios-Santander, J.M .; Amine, A; Bioelectrochem., 101 (2015) 84
    91.
    As can be seen from the table, for all SNG-NC materials, the sensitivity values are higher than those of the biosensor based on the sonogel and powdered graphite material. In addition, the detection limits are lower in some order of magnitude. This demonstrates that the presence of nanocarbon in the electrode material facilitates and increases the electronic transfer, thanks to its peculiar properties as nanomaterial, against graphite powder.
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    In Table 9, the kinetic and analytical parameters of quality for the biosensor (HRP + AuNPs) / SNG-NC 350 mg are collected and compared with those described in the literature for a biosensor with AuNPs based on sonogel and 500 mg of powder Graphite Clearly, in all cases, it is observed that the sensitivity and detection limit values are better for the biosensor based on the new SNGNC material.
    On the other hand, in terms of kinetic parameters, Jmax represents the maximum current density, which should be as high as possible, as is the case for SNG-NC material with 375 mg of NC. Regarding the KM parameter, defined as the minimum substrate concentration (analyte) at which the biocatalysis rate of the enzyme is equal to half of the maximum current density, the higher this value, the better the catalysis process will lead to carried out by the enzyme, a fact that is quite evident when the SNG-NC material is used.
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    Table 9: Kinetic parameters: Jmax and KM, and quality analytics for the three analytes (caffeic acid, hydroquinone and catechol): sensitivity and limit of detection for HRP biosensors with AuNPs, using the SNG-NC material as a transducer with different quantities of NC, and taking as reference the sonogel material with 500 mg of graphite powder. The electrolytic medium is acetic / sodium acetate at pH 5 and contains 10 mM of H202; applied potential = -0.15 V. 1 Attar, A; Cubillana-Aguilera, L; Naranjo-Rodrlguez, I .; Hidalgo-Hidalgo de Cisneros, J.L; Palacios-Santander, J.M .; Amine, A .; Bioelectrochem., 101 (2015) 84-91.
    These results serve to reaffirm that the presence of the Nanocarbon, as a massive modifying nanomaterial of the electrode transducer, increases the electronic transfer and greatly increases the sensitivity. Therefore, it is concluded that the SNG-NC material is viable for use as an electrochemical biosensor, improving the kinetic and quality parameters with respect to the sonogel material based on 500 mg of graphite powder.
    On the other hand, as regards the structural characterization of the electrodes manufactured with the SNG-NC material, the surface of the materials with 350 and 375 mg was characterized by atomic force microscopy (AFM) in tapping mode. The size of the sampling area was 1.5x1.5 or 2.5x2.5 pm. According to the data obtained from the AFM, in both cases, the surface roughness is within the manometric scale (<100 nm): 31.43 nm for electrodes with 350 mg of NC and between 11.6 and 14.0 nm for the electrode with 375 mg (see profiles in Figure 7). In addition, in most cases, valleys predominate on the surface of the material, indicative of the presence of pores. Along the same lines, the presence of fairly sharp peaks also emerges from the data.
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    -  Good mechanical and structural properties of the materials: very little volume contraction and practically negligible surface erosion after multiple electrochemical measurements in (bio) sensor devices.
    -  Good electrochemical behavior: low observed capacity and double layer, comparable to that of other electrode materials or even smaller up to an order of magnitude.
    -  As base materials that are and without modifications, compared to a test analyte such as ascorbic acid, the quality parameters of the (bio) sensors obtained with said materials are quite good, comparable or even better than those of other sensors modified in a way more or less complex according to the bibliography. In addition, it allows its use in real samples. In the case of its use as biosensors, the kinetic parameters are also improved with respect to the literature.
    -  Finally, it should be noted that, thanks to the peculiar properties of nanomaterials (CNT and NC) present massively in electrode devices, electronic transfer is greatly increased during the electrochemical measurement process. This also implies an increase in sensitivity and, therefore, an improvement in the kinetic and analytical parameters of the quality of the (bio) sensors.
    Brief description of the drawings
    Figure 1. Cyclic voltamperograms corresponding to an electrode made of Sonogel-Nanotubes Carbon material with 32.5 mg of MWCNT and 100 µL of 0.2M HCI as catalyst and submerged for several days (0, 3, 7, 10, 14 and 17 days) in a Britton-Robinson pH 4 regulatory solution. The scan rate is 50 mV / s.
    Figure 2. Cyclic voltamperograms corresponding to two Sonogel-Nanotubes Carbon electrodes synthesized with 32.5 mg MWCNT and different volume and concentration of the acid catalyst solution: (red) 35 µL of 0.6 M HCI solution and (blue ) 100 µL of 0.2 M HCI. The electrolytic medium corresponds to a Britton-Robinson pH 4 regulator and the scanning speed is 50 mV / s.
    Figure 3. Voltamperograms obtained from DPV corresponding to the electrochemical sensor based on the optimized Carbon Sonogel-Nanotubes material (32.5mg of MWCNT and 35 µL of 0.6M HCI solution, under the appropriate drying conditions), using as 0.2 M PBS electrolytic medium (pH = 6.9), in the presence of different concentrations of ascorbic acid: (a) baseline; (b) 1.14 µM (≈1.14x10-6 M); (c) 3.43 µM; (d) 8.00 µM; (e) 12.56 µM; (f) 23.94 µM; (g) 35.27 µM; (h) 46.55 µM; (i) 80.13 µM; (j) 0.1133 mM;
    (k)  0.1785 mM; (I) 0.2839 mM; (m) 0.3854 mM; (n) 0.5063 mM; (o) 0.7020 mM; (p) 0.8907 mM;
    (q)  1,272 mM; (r) 1,996 mM; (s) 3.307 mM (= 3.31x1 O'3 M). Voltamperograms were recorded under the following experimental conditions: 0.4 s interval time, 100 mV modulation amplitude and 16 mV step potential. The inner graph represents the current intensity versus the corresponding analyte concentration with the calibration curve obtained from the previous voltamperograms. The adjustment curve and the coefficient of determination R2 are also represented.
    Figure 4. SEM micrographs recorded for electrodes based on optimized Carbon Sonogel-Nanotube materials (32.5 mg MWCNT and 35 µL of 0.6 M HCI solution, under the proper drying conditions) and Sonogel-Carbon (sonogel based Graphite powder: 500 mg). Figures 4A and 4B correspond to the unused and used electrode (more than 150 measurements in various electrolytic media of different pH) of the Sonogel-Carbon and Figures 4C and 4D correspond to the unused and used electrode of the Carbon Sonogel-Nanotubes (in the
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    of the SNG-NC material as biosensor, 10 mL of acetic acid regulator and sodium acetate pH 5 were used as electrolyte.
    • The determination of capacities was carried out using cyclic voltammetry in the absence of analyte, at different scanning speeds: 10, 25, 50, 75, 100, 125, 150, 175 and 200 mV / s. The measuring range was -0.5 V to 1.0 V, using different regulatory solutions, at different pH values.
    • The study of the electrochemical mechanism against (K4Fe (CN) 6) for both materials, and of hexaaminrutenium chloride (III) ([Ru (NH3) 6] CI3), only for SNGCNT was carried out in CV, in the presence of 1 mM of the chemical species in question. Measurements were made at different scanning speeds: 10, 25, 50, 75, 100, 125, 150, 175 and 200 mV / s, the range of potentials being from -0.5 V to 1.0 V The electrolytes used were Britton-Robinson ( BR) pH 4 or a phosphate regulatory solution (PBS) pH 6.9, as appropriate.
    • SNG-NC biosensors based on peroxidase enzyme and with or without AuNPs, HRP / SNG-NC and (HRP + AuNPs) / SNG-NC, respectively, were constructed following the chemical cross-linking method according to the literature (Attar, A .; Cubillana-Aguilera, L .; Naranjo-Rodríguez, I .; Hidalgo-Hidalgo de Cisneros, JL; Palacios-Santander, JM; Amine, A .; Bioelectrochem., 101 (2015) 84-91):
    o HRP / SNG-NC: 1 mg of HRP enzyme is weighed in a round bottom eppendorf and dissolved in 1 mL of Milli-Q water. They take 17 µL of said solution and transfer to another eppendorf. 3 µL of BSA (0.5% in Milli-Q water), 25 µL of Milli-Q water and 5 µL of glutaraldehyde (0.5% in Milli-Q water) are added in the new container. Said mixture is removed with the help of a vortex shaker. For the deposition of the enzymatic mixture, the electrodes are placed vertically and, with the help of a micropipette, 4.1 µL of the mixture (equivalent to 2 AU / biosensor) is deposited on the surface of the electrodes. Finally, they are allowed to dry for 1 to 2 hours, at room temperature, and kept immersed in a regulatory solution of AcH / AcNa pH 5, while not being used, and stored in the refrigerator.
    or (HRP + AuNPs) / SNG-NC: 1 mg of HRP enzyme is weighed in a round bottom eppendorf and dissolved in 0.32 mL of Milli-Q water and 0.68 mL of AuSNPs, prepared according to (Cubillana- Aguilera, LM; Franco-Romano, M .; Gil, MLA; Naranjo-Rodríguez, I .; Hidalgo-Hidalgo de Cisneros, JL; Palacios-Santander, JM; Ultrason. Sonochem., 18 (2011) 789-794). From that solution 17 µL are taken and transferred to another eppendorf, in which 3 µL of BSA (0.5% in Milli-Q water), 25 µL of the solution of synthesized AuSNPs and 5 µL of glutaraldehyde (0 , 5% in Milli-Q water). Said mixture is removed with the help of a vortex shaker. Once the enzymatic mixture of HRP + AuSNPs has been prepared, the deposition and preservation of the biosensors is carried out in the same way as previously mentioned.
    • The determination of the analytical parameters of quality: sensitivity, limit of detection, reproducibility and repeatability was carried out by adding AA of a 0.25 M stock solution to a cell containing 25 mL of 0.2 M PBS regulatory solution ( pH = 6.9). The resulting cell ascorbic acid concentrations after each addition are indicated below: 0.01 (≈1.00x10-5 M); 0.05; 0.10; 0.50; 1.00; 1.50; 2.00; 2.50; 2.85; and 3.20 mM (≈ 3.20x10-3 M) for SNG-CNT, and 1.14 (≈ 1.14x10-6 M); 3.43; 8.00; 12.56; 23.94; 35.27; 46.55; 80.13; 113.3; 178.5; 283.9; 385.4; 506.3; 702.0; 890.7; 1272; nineteen ninety six; 3307 µM (≈3.31x10-3 M) for SNG-NC. For the calculation of
    Kinetic parameters of the HRP / SNG-NC biosensors: Jmax and KM, the analyte concentration range was: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 and 60 µM for caffeic acid and hydroquinone, and 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350 , 400, 450, 500, 550 and 600 µM for catechol. In the case of ascorbic acid, the electroanalytic technique used was differential pulse voltamperometna, selecting the conditions according to previous studies with sonogel materials with 500 mg of graphite powder (Ajaero, C .; Abdelrahim, MY; Palacios-Santander, JM ; Almoraima Gil, ML; Naranjo-Rodrlguez, I .; Hidalgo-Hidalgo de Cisneros, JL; Cubillana-Aguilera, LM Sensors Actuat. BChem., 2012, 171-172, 1244-1256): 16 mV step potential, 100 mV modulation amplitude and pulse interval time of 0.4 s. Taking the peak intensities for each concentration value, the calibration curves were obtained, whose slopes correspond to the sensitivity. For caffeic acid, hydroquinone and catechol, the technique used was chronoamperometry, with a fixed potential of -0.15 V and a maximum measurement time of 3000 s. In this case, the differences in current density between the serial without analyte and the serial with analyte were calculated and plotted against the concentration of the analyte to obtain the calibration curve, whose slope corresponds to the sensitivity.
    • For the determination of ascorbic acid in apple juice for babies, 24 ml of 0.2 M phosphate buffer solution at pH 6.9 (PBS) was started, to which 1 ml of apple juice (approximate concentration of ascorbic acid of the label = 25 mg / l; reference value obtained by high performance liquid chromatography (HPLC): 21.8 mg / l). The voltammetric technique used was the DPV and the determination of the analyte in the sample was carried out using the standard addition method.
    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 nanomaterials, such as the CNTs or the NC, together with the renewal of the surface of the electrodes based on said materials, allows to solve the problems of contamination or poisoning of the surfaces of the electrochemical devices manufactured with these materials. Surface renewal stands out for its speed and ease, allowing the use of the sensor repeatedly. Said renewal can be mechanical, using a fine-grained sandpaper P1200, and / or electrochemical, using sulfuric acid as an electrolytic medium, in the range of concentrations 0.05 M and 0.1 M, and cyclic voltammetry 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 presence of nanomaterials increases the electronic transfer through the (bio) electrochemical sensors which, in turn, allows to improve the analytical parameters of quality of said devices: sensitivity, limit of detection, limit of quantification, repeatability, reproducibility, stability, etc., and increase its applicability for the detection of analytes or chemical species of environmental, biomedical and / or agri-food interest, among others.
    权利要求:
    Claims (1)
    [1]
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