• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Sensor of the type consisting of three electrodes, each electrode including a contact, a conductive section and an active area, one of the electrodes being a working electrode, another of the electrodes an auxiliary electrode or counter electrode and the other electrode a reference electrode, all of them constituted by screen printing of an ink of conductive materials on a plastic sheet, where the conductive sections, the counter electrode and the working electrode are screen printed with a platinum conductive ink and the reference one with an Ag/AgCl ink in the area active Procedure for the determination of chloride ion comprising an activation stage of the working electrode, a calibration stage, and a measuring stage by adding the sample by covering the electrode system on the same electrode and recording the voltamperogram, transferring it to the calibration line to determine the concentration of chloride in the liquid sample. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2725248A1
    申请号:ES201830271
    申请日:2018-03-20
    公开日:2019-09-20
    发明作者:Martínez Julia Arcos；Silva Hugo Cunha
    申请人:Universidad de Burgos；
    IPC主号:
    专利说明:

    [0001]
    [0002]
    [0003]
    [0004] TECHNICAL FIELD OF THE INVENTION
    [0005]
    [0006] The present invention encompasses in the field of electrochemistry applied to chemical analysis, in particular in the analysis of chloride ion detection present in a liquid sample.
    [0007]
    [0008] The present invention relates to a sensor of the type consisting of three electrodes obtained by screen printing, to detect chloride ion in liquid samples, as well as to the method for carrying out the determination of chloride ion by said sensor.
    [0009]
    [0010] Thus, in one aspect, the present invention provides a sensor of the type consisting of three electrodes, each electrode including a contact, a conductive section and an active area, one of the electrodes being a working electrode, another of the electrodes an auxiliary electrode or counter electrode and the other electrode a reference electrode, all of them constituted by screen printing of an ink of conductive materials on a plastic sheet, where the conductive sections, the counter electrode and the working electrode are screen printed with a platinum conductive ink and the reference with an Ag / AgCl ink in the active area.
    [0011]
    [0012] According to a second aspect, the invention provides a method for the determination of the chloride ion in a liquid sample using said sensor.
    [0013]
    [0014] BACKGROUND OF THE INVENTION
    [0015]
    [0016] The concentration of chloride ions is an important parameter in various environmental applications, in the pharmaceutical and food industry (Hern, JA et al. Talanta 1983, 30 (9), 677-682; Morales, JA et al., J. Chromatogr. A 2000, 884 (1-2), 185-190, Galvis-Sánchez, AC et al. AOSS Food Control 2011, 22 (2), 277282, Pérez-Olmos, R. et al., MCBSM Food Chem. 1997, 59 (2), 305-311).
    [0017]
    [0018] This anion is also an essential electrolyte that maintains homeostasis within the body and its concentration can show the presence of various diseases.
    [0019]
    [0020] Thus, for example, the determination of chloride in sweat samples is the most useful diagnostic test in cystic fibrosis (Sosnay, PR et al., J. Pediatr. 2017, 181, S52-S57). Depending on age, the concentration of sweat chloride remains between 30 and 70 mmoll-1, while levels above 70 or 80 mmoll-1 are unequivocal evidence that the disease is suffered (Barrio Gómez de Agüero, MI et al. ., An. Spaniards Pediatr. 1999, 50 (6), 625-634; Farrell, PM et al., J. Pediatr. 2017, 181, S16-S26).
    [0021]
    [0022] In addition, the concentration of chloride chloride in sweat is a potential biomarker of electrolyte loss, since it is the most abundant ion in perspiration (Latzka, WA; J. Clin. Sports Med. 1999, 18 (3), 513- 524; Harvey, CJ; Int. J. Cosmet. Sci.
    [0023] 2010, 32 (5), 347-355; Stefaniak, AB, J. Toxicol. Vitr. 2006, 20 (8), 1265-1283). Equally important is the determination of its concentration in the blood plasma, whose range is between 96 and 106 mmoll-1. Minor or higher concentrations are indicative of hypo or hyperchloremia (Morrison, G., Clinical Methods: the history, physical, and laboratory Examinations .; Walker, HK, Hall, WD, Hurst, JW, Eds .; Boston: Butterworths, 1990; pp 890-894).
    [0024]
    [0025] Also the amount of chloride ion present in other biological fluids, such as urine, in which the chloride ion ranges in a concentration range of 110 to 250 mmoll-1, can provide information about a malfunction of the kidneys (Mutter, WP ; Korzelius, CA, Hosp. Med. Clin. 2012, 1 (3); Schrier, RW, J. Am. Soc. Nephrol. 2011, 22 (9), 1610-1613).
    [0026]
    [0027] It has also been observed that in patients suffering from amyotrophic lateral sclerosis the concentration of chloride in the cerebrospinal fluid has lower levels than usual (Watanabe, S. et al., HJ Neurol. Sci. 2009, 285 (1-2), 146-148).
    [0028]
    [0029] Therefore, the control of the chloride ion in these fields is of great importance.
    [0030] Among the methods commonly used for the determination of chloride are known volumetric methods, such as the Mohr method, in which a precipitation assessment of the chloride ion in the form of silver chloride is used, potentiometric methods using ion selective electrodes (Grubb , WT Chloride -selective electrode, US3740326, 1973), and more recently methods based on the use of ion chromatography (Pereira, JSF et al., J. Chromatogr. A 2008, 1213 (2), 249-252; Pimenta, AM et al., J. Pharm. Biomed. Anal. 2004, 36 (1), 49-55). Other optical techniques such as resonance light scattering or turbidimetric methods have also been used in the determination of chloride.
    [0031]
    [0032] Voltammetric methods using screen-printed electrode systems (SPE) have also been described in the state of the art. These types of disposable platforms have clear advantages due to their low cost, the possibility of use on site and their ease of modification (Renedo, OD et al., Talanta 2007, 73 (2), 202-219). Most of the works related to the determination of chloride with SPE are based on the formation of a stable compound between silver and chloride (Campos, I. et al., Sensors Actuators, B Chem. 2010, 149 (1), 71- 78; Chiu, MH et al., Biosens. Bioelectron. 2009, 24 (10), 3008-3013; Choi, DH et al., Sensors Actuators, B Chem. 2017, 250, 673-678). The Nernstian displacement of the voltammetric peak of a control species, which takes place in the presence of chloride when using pseudo reference electrodes SPE Ag / AgCl in the electrode system, has also been used for chloride analysis.
    [0033]
    [0034] For example from US10657760 an amperometric device is known that incorporates multiple sensors to obtain the analyte profile of a sample.
    [0035]
    [0036] In WO2007026152A1 an electrochemical sensor with an arrangement of electrodes printed on a support plate is described, the electrodes being isolated by a layer of insulating material provided with openings to expose the working area of each electrode arrangement.
    [0037]
    [0038] From ES201400313, a screen-printed sensor of the type described in the preamble of claim 1 is known, where a conductive carbon ink is used and where the presence of a ferrocenomethane or ferricyanide control is necessary, the chloride ion being determined indirectly from the oxidation of ferrocenomethanol or the reduction of ferricyanide.
    [0039]
    [0040] Although the existing sensors allow to obtain good results for some applications, they present several limitations and problems related mainly to the complexity in the preparation of the electrode systems and also allow very reduced ranges of use, so they lose applicability for the determination of chloride in biological media in general, its applications being useful in very limited fields.
    [0041]
    [0042] Thus, for example, sensors based on potentiometric methods are limited by the operability of the electrode membrane, which can accelerate its dysfunctionality when used in certain matrices. On the other hand, the measurement with these methods normally requires high reaction times, since longer times are necessary to reach the required equilibrium characterized by a stable reading of the potential. Reaching this balance requires more time when the sample is more complex, so the analysis as a whole takes more time. In addition, for example to measure chloride in any sample, for example in sweat, it is necessary to add an electrolyte (such as KNO3) to adjust the ionic strength of the medium, which requires more preparation in the analysis.
    [0043]
    [0044] As for the known screen-printed sensors, they generally imply the presence of another species in the system, a species that can interfere with certain matrices. In the particular case of the sensor described in ES201400313, the need for a control such as ferrocenomethanol or potassium ferricyanide directly influences the performance of the sensor. Since its use is essentially to determine chloride in aqueous samples, the presence of control substances can act as interfering agents in more complex matrices. Likewise, said presence limits the operating range and its detection limit. In tests conducted with the same using ferrocenomethanol, the detection capacity is 10 mM and the range of measurement concentrations is between 10 mM and 90 mM.
    [0045]
    [0046] The objective of the present invention is to provide a sensor of the type indicated above that solves the disadvantages of the known sensors, providing a very simple, easy-to-use and economical screen-printed sensor, in which a Pt-based ink has been used, compared to the carbon-based ones commonly used, for the construction of the working electrode (SPPtE). The sensitivity and versatility of the proposed sensor has significant advantages compared to the approaches described in the prior art for the detection of chloride ions in different types of food, environmental and pharmaceutical samples, being a very useful tool in the diagnosis of diseases related to low or high concentrations of chloride ion in the different biological fluids.
    [0047]
    [0048] The screen-printed sensor of the invention could be used for single use due to its low cost or it can be used in complex matrices more than 100 times without affecting its operation. On the other hand, the time necessary for the measurement is very short, obtaining results in only 20 seconds, very short time compared to that necessary to obtain response in the potentiometric method. In addition, the screen-printed sensor of the invention can directly measure chloride in sweat samples without the need to add any reagents, due to the absence of interference. This parameter is key to the diagnosis of cystic fibrosis, which increases the interest of its possible applications. It would also be useful in the analysis of food samples, pharmaceuticals, etc.
    [0049]
    [0050] The sensor provided by the invention, based on the electrochemical reaction that occurs on a Pt surface, catalyzes the electrochemical reaction of chloro-chloride oxidoreduction. Therefore, the observed signal originates directly from the electroactive species that is chloride. The material of the electrode for that reaction to occur is, therefore, the sensor key and, consequently, the detection limit reached is 0.76 mM, and the much wider range of use, from 0.76 a 150 mM
    [0051]
    [0052] BRIEF DESCRIPTION OF THE FIGURES
    [0053]
    [0054] The present specification is complemented with illustrative and non-limiting figures of embodiments of the invention.
    [0055]
    [0056] Figure 1 shows an example of a sensor of the invention showing a working electrode, an auxiliary electrode or counter electrode and a reference electrode, including the electrodes a contact, a conductive section and an active area, screen printed on a plastic sheet, as well as an insulating element that, although in the figure appears as an element Separated for clarity, it is a screen-printed insulator that covers the sensor except in the active areas of the electrodes and contacts.
    [0057]
    [0058] A diagram of the method of use of the sensor of the invention is shown in Figure 2.
    [0059]
    [0060] A linear scan voltampetogram obtained from known chloride ion concentration samples is shown in Figure 3A by using the procedure of Figure 2. Figure 3B shows the standard deviation associated with each curve.
    [0061]
    [0062] DESCRIPTION OF THE INVENTION
    [0063]
    [0064] The present invention is established and characterized in the independent claims, while the dependent claims describe other features thereof.
    [0065]
    [0066] As indicated above, in one aspect the invention aims to provide a chloride ion detection sensor present in a liquid sample, of the type consisting of a working electrode, an auxiliary or counter electrode and a reference electrode, including the electrodes a contact, a conductive section and an active area, all the electrodes screen printed with an ink of conductive materials on a plastic sheet, where the conductive sections, the counter electrode and the working electrode are screen printed with a platinum conductive ink and that of reference with an Ag / AgCl ink in the active area.
    [0067]
    [0068] Thus, as shown in Figure 1, the sensor of the invention consists essentially of a plastic sheet (4), usually porous of polyester or ePTFE, on which the contacts (1.3,2.3,3.3) are screen printed with platinum ink. and the sections (1.2,2.2,3.2) of a working electrode (2), a counter electrode (1) and an electrode of reference (3), as well as the active area (1.1) of the counter electrode (1) and the active area (2.1) of the working electrode (2), the active area (3.1) of the electrode being screen printed with an Ag / AgCl ink reference (3). The sensor of the invention also includes a screen-printed insulating material (5) that covers it except in the active areas of the electrodes (1.1,2.1,3.1) and the contacts (1.3,2.3,3.3).
    [0069]
    [0070] Although the figure shows concrete shapes for electrodes (1,2,3), active areas (1,1,2,1,3.1) and sections (1.2,2.2,3.2), in the illustrated example rectangular, arc or circular, said shapes are not limiting, these elements being able to have other suitable shapes and be sized in correspondence with the final shape desired for the sensor of the invention.
    [0071]
    [0072] Regarding conductive ink, platinum (Pt) is a noble metal with extensive applications in the electrochemical field. The properties of Pt electrodes are notoriously influenced by the presence of chloride. In fact, the interactions between chloride anions and Pt surfaces are described and several papers have been published studying these interactions. This metal proves to be especially susceptible to chloride when high anodic potentials are applied during the experiments (see for example Hall, SB et al., Electrochim. Acta, 2000, 45, 3573-3579). Also in the anodic limits, chloride ions are adsorbed specifically on platinum surfaces, blocking the adsorption of oxygen by the surface and causing the appearance of chlorine.
    [0073]
    [0074] Thus, the sensor of the invention efficiently detects the chloride ion considering the stable reaction between this anion and the surfaces screened with platinum ink:
    [0075]
    [0076] Pt H 2 O - e " ^ PtOH H + (R1)
    [0077] PtOH - e " ^ PtO H + (R2)
    [0078] PtO Cl " + H 2 O ^ PtCl 'ads + 2OH (R3)
    [0079] PtCl 'ads + Cl " + 2e " ^ PtCl 2 (R4)
    [0080] PtCl 2 + H 2 O ^ PtO OH 2Cl " + 2e " (R5)
    [0081]
    [0082] According to a second aspect, the invention provides a method for the determination of the chloride ion in a liquid sample using the sensor previously described, the procedure comprising:
    [0083]
    [0084] - an activation stage of the working electrode (2), adding 200 µl of a 0.1 M solution of KNO 3 to cover the electrode surface and subjecting it to 5 consecutive cyclical sweeps of potential between -0.2 and 1.5 V ; - a calibration step consisting of coating the electrode surface with a standard phosphate buffer solution pH = 6.2 containing chloride ion (approx. 200 pl) and applying an anodic deposition of 1.50 V for 15 seconds; record the linear voltamperogram by performing a cathodic scan; remove the solution, for example by adsorption with filter paper, washing with distilled water and drying by absorption and adding standard chloride ion solutions prepared in phosphate buffer (200 pl) in succession, repeating the same electrode washing and drying process after each measurement and construct the calibration line representing the voltammetric peak as a function of the chloride concentration; Y
    [0085] - a measurement step consisting of adding a small volume (200 pl) of a sample solution containing chloride ion to be tested by coating the electrode system on the same electrode once clean and dry and recording the voltamperogram, transferring it to the calibration line for Determine the concentration of chloride in liquid sample.
    [0086]
    [0087] The proposed mechanism for the operation of the sensor of the invention is as follows: the activation stage with 0.1 M KNO 3 favors the formation of platinum oxide according to reactions R1 and R2. Thus, the complexation of the chloride ion with the surface of the working electrode (2) occurs, as indicated in reaction R3. The anodic deposition step results in the formation of an oxidized state of the chlorine complexes (reaction R4), after which they are reduced in the linear scanning voltammetry (Linear Sweep Voltammetry, LSV), cathodic, recycling the oxide surface (reaction R5). Reactions R2 to R4 can occur at 1.5 V at the anode. The R5 reaction occurs due to the desorption of the chloride ions adsorbed to more negative potentials.
    [0088]
    [0089] As shown in Figure 2, the anodic potentials lead to the formation of oxidized Cl- - Pt complexes on the working electrode (2) screen-printed of the sensor the invention.
    [0090]
    [0091] Examples
    [0092]
    [0093] Manufacture of the sensor of the invention
    [0094]
    [0095] For the manufacture of the previously described sensor, polyester films (also could be made of ePTFE) of 0.5 mm thickness and Ag / AgCl and platinum inks supplied by Gwent Group (Mamhilad, United Kingdom). The sensor was manufactured by sequential deposition on the polyester film. Briefly, with the silver and silver / silver chloride inks hardened at 120 ° C for 20 minutes, the conductive sections (1.2,2.2,3.2) and the reference electrode (3) were printed respectively. To define the counter electrode (1) a carbon ink (supplied by Achenson Colloiden, Scheemda) was used and hardened at 60 ° C for 30 minutes. To define the working electrode (2), platinum ink was used, which hardened at 80 ° C for 30 minutes. Finally, a dielectric ink (supplied by Achenson Colloiden, Scheemda) was used to delimit the final geometry of the three electrodes (1,2,3), which hardened under the same conditions.
    [0096]
    [0097] Comparative analyzes were performed using a conventional sensor with a platinum electrode of 1.6 mm in diameter as a working electrode (2), a counter electrode (1) of platinum wire and a conventional silver / silver chloride electrode as an electrode. reference (3).
    [0098]
    [0099] Preparation of sample
    [0100]
    [0101] Samples obtained from whole-grain biscuits, from a chicken broth, both commercial, were prepared and human urine and sweat samples were collected from healthy volunteers, which were stored at -20 ° C until use. Briefly, the cookies were ground and calcined for 15 minutes at 400 ° C, the resulting product being dissolved in 500 ml of Milli-Q Water (Millipore, Bedford, USA). The suspension was filtered and centrifuged to remove suspended particles. The chicken broth was also centrifuged and the fat fractions and solids removed before analysis.
    [0102] Cyclic voltammetric measurements
    [0103]
    [0104] Before performing these measurements, each electrode (1,2,3) was activated with 200 pl of a 0.1 M solution of KNO3 and subjecting it to 5 consecutive cyclical sweeps of potential between -0.2 and 1.5 V, after which was calibrated with a standard solution of 0.31 mM phosphate buffer pH = 6.2 containing different concentrations of chloride ion from corresponding solutions of NaCl 5, 10, 20, 30, 60, 80 and 100 mM and applying a sweep of -0.70 V at 1.30 V (vs Ag / AgCl electrode) at 0.1 Vs-1, and 0.02 V potential steps.
    [0105]
    [0106] Voltammetric measurements were carried out using a PalmSens® electrochemical potentiostat with PS Trace 4.2 software (PalmSens® Instruments BV, Houten).
    [0107]
    [0108] Experiments with the conventional sensor were performed in a cell with 10 ml of reference electrolyte of a 3M NaCl solution.
    [0109]
    [0110] Linear scan voltammetry (LSV) for chloride determination
    [0111]
    [0112] Prior to the LSV, a deposition step of 1.50 V was applied for 15 seconds and the cathodic measurements were immediately carried out at a potential of 1.11 to 0.10 V, potential steps of 0.002 V and speed of scanning of 0.20 Vs-1, obtaining a reduction peak at 0.80 V. The measurements were obtained with 200 pl of the reference electrolyte containing different concentrations of NaCl (Figures 3A and 3B).
    [0113]
    [0114] Determination of chloride in samples containing chloride
    [0115]
    [0116] LSV tests were performed with 200 µl of synthetic sweat containing chloride concentrations in the range of 1 to 150 mM, and reduction peaks were used to construct the calibration curve. Different samples containing chloride were tested using the sensor and the method of the invention (A) and corroborated using a conventional chloride specific sensor by the potentiometric method (B). The results are shown in the following table:
    [0117]
    [0118]
    [0119]
    [0120] These results show that the sensor of the invention is applicable to all types of liquid samples, being useful in the food, biological, sanitary, environmental and pharmaceutical fields.
    权利要求:
    Claims (5)
    [1]
    1.-Chloride ion detection sensor present in a liquid sample, of the type constituted by a working electrode (2), an auxiliary electrode or counter electrode (1) and a reference electrode (3), including the electrodes a contact (1.3 , 2.3,3.3), a conductive section (1.2,2.2,3.2) and an active area (1.1,2.1,3.1), all electrodes screen printed with an ink of conductive materials on a plastic sheet (4), characterized by being screen printed the conductive sections (1.2,2.2,3.2), the counter electrode (1) and the working electrode (2) with a platinum conductive ink and the reference electrode (3) with an Ag / AgCl ink in the active area (3.1 ).
    [2]
    2. The chloride ion detection sensor according to claim 1, which further includes a screen-printed insulating material (5) that covers it except in the active areas (1.1,2.1,3.1) of the electrodes and contacts (1.3,2.3, 3.3).
    [3]
    3. Procedure for the determination of chloride ion in a liquid sample using the sensor according to claims 1 or 2, the procedure comprising:
    - a stage of activation of the working electrode (2), adding it to cover the electrode surface of a 0.1 M solution of KNO 3 and subjecting it to 5 consecutive cyclical sweeps of potential between -0.2 and 1.5 V; - a calibration step consisting of coating the electrode surface with a standard phosphate buffer solution pH = 6.2 containing chloride ion and applying an anodic deposition of 1.50 V for 15 seconds; record the linear voltamperogram by performing a cathodic scan; remove the solution, and add standard chloride ion solutions prepared in phosphate buffer successively, and construct the calibration line representing the voltammetric peak as a function of the chloride concentration; Y
    - a measurement step consisting of adding a small volume of a sample solution containing chloride ion to be tested by coating the electrode system on the same electrode and recording the voltamperogram, transferring it to the calibration line to determine the concentration of chloride in the liquid sample .
    [4]
    4. Procedure according to claim 3, characterized in that in the activation stage platinum oxide is formed according to reactions R1 and R2, the chloride ion complexing with the surface of the working electrode (2) screen printed with the conductive ink of platinum according to reaction R3.
    Pt H 2 O - e - ^ PtOH H + (R1)
    PtOH - e - ^ PtO H + (R2)
    PtO Cl - + H 2 O ^ PtCl -ads + 2OH (R3)
    [5]
    5. -Procedure according to claims 3 and 4, characterized in that in the anodic deposition of the calibration stage the chlorine complexes are oxidized according to reaction R4, after which they are reduced by means of cathode linear scanning voltammetry, recycling the oxide surface according to reaction R5.
    PtCl -ads + Cl - + 2e - ^ PtCl 2 (R4)
    PtCl 2 + H 2 O ^ PtO OH 2Cl - + 2e - (R5)
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    同族专利:
    公开号 | 公开日
    ES2725248B2|2020-03-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    IE980529A1|1998-06-30|2000-02-09|Univ Cork|The use of screen printed electrodes in the electrochemical analysis of electroactive species|
    WO2014188166A1|2013-05-20|2014-11-27|Isis Innovation Limited|Electrochemically determining the concentration of a halide or a pseudohalide|
    EP2980577A1|2014-07-31|2016-02-03|Electrochemical Sensor Technological Limited|Electrochemical sensor system and sensing method|
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