US20200191740A1 - Nano- and/or micro-structured printed electrodes - Google Patents

Nano- and/or micro-structured printed electrodes Download PDF

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US20200191740A1
US20200191740A1 US16/609,306 US201816609306A US2020191740A1 US 20200191740 A1 US20200191740 A1 US 20200191740A1 US 201816609306 A US201816609306 A US 201816609306A US 2020191740 A1 US2020191740 A1 US 2020191740A1
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electrode
group
chlorine
nano
sensor
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Fabiana Arduini
Daniela Neagu
Maria Rita Tomei
Antonio Boccella
Danila Moscone
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Tecnosens Srl
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Assigned to TECNOSENS SRL reassignment TECNOSENS SRL ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MOSCONE, DANILA, TOMEI, Maria Rita, ARDUINI, Fabiana, BOCCELLA, Antonio, NEAGU, Daniela
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/307—Disposable laminated or multilayered electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/182—Specific anions in water
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/301—Reference electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Definitions

  • the present invention relates to new electrochemical sensors and probes comprising one or more of said sensors, useful for the measure in a fluid of an analyte selected from the group consisting of: free chlorine, chlorine dioxide, total chlorine and peracetic acid; characterized in that said sensor includes at least a printed electrode nano- or micro-structured with a nano- or micromaterial selected from the group consisting of: nano- or microparticles of carbon black and/or nano- or microparticles of a metal selected from the group consisting of gold, silver, platinum, copper and combinations or alloys thereof; useful for monitoring water pollution and/or compounds useful for disinfecting water for domestic or industrial use, or water for swimming pools.
  • the present invention also relates a kit of an integrated system for the management of the sensors of the invention, and the use of such integrated system or kit for monitoring water pollution and/or compounds useful for the disinfection of domestic, industrial and swimming pool water.
  • the drinking water biological pollutants represent still today the compounds responsible for acute infectious diseases.
  • Chlorine dioxide was initially used as whitener in paper industry; since the 1950s it has also been employed as disinfectant and algaecide. The disinfectant properties of chlorine dioxide remain unaltered over a wide pH range and this product does not significantly alter the organoleptic characteristics of the water in which it is added.
  • Free chlorine is defined as the sum of the concentrations of the hypochlorite ion and of the hypochlorous acid, which both are produced by the reaction of hydrolysis of sodium hypochlorite, gaseous chlorine, calcium hypochlorite and isocyanuric acid derivatives (sodium dichloroisocyanurate and trichloroisocyanuric acid).
  • Total chlorine is defined as the sum of inorganic free chlorine and organic/inorganic combined chlorine. When nitrates of organic origin and/or ammonia compounds are present in water, inorganic chlorine reacts forming chloramines and its presence constitutes the combined chlorine. Combined chlorine can be classified in combined inorganic chlorine, derived from the reaction with ammonia, and in combined organic chlorine, obtained from the reaction between chlorine and nitrogen compounds, such as amino acids.
  • Peracetic acid is a liquid organic compound with a characteristic pungent odor, mainly employed as disinfectant in food, cosmetics and pharmaceuticals industries.
  • peracetic acid also presents negative aspects concerning its instability, though it definitely remains one of the most used disinfection products on industrial scale. Actually, peracetic acid solution is available on market with different concentrations; those at 5% and 15% w/w are the most used.
  • Electrochemistry Communications 47 (2014) 63-66 describes an electrode for measuring hydrogen peroxide, in which the printed electrode is functionalised with carbon black and nanoparticles of Prussian blue.
  • U.S. Pat. No. 6,627,058 refers to an electrode for measuring glucose, in which the printed electrode is functionalised with carbon black and nanoparticles of Prussian blue.
  • Microchim Acta (2016); Vol 183; #10; 2799-2806 reports an electrode for measuring hydrogen peroxide in which on the printed electrode are present silver nanoparticles, and said electrode is functionalized by using reduced graphene and cerium IV.
  • DE 4319002 describes a sensor for the measurement of peracetic acid, in which on the printed electrode platinum microparticles may be present.
  • an electrochemical sensor comprising at least one printed electrode as defined before.
  • such sensor comprises
  • the reference electrode and the counter electrode may be located on the other side of the printed electrode, i.e. exposed to the reservoir (in other words, different electrode in different side of the printed electrode).
  • said printed electrodes group comprising at least an “printed electrodes group” containing at least a working electrode; at least a reference electrode; and at least an auxiliary electrode; preferably said printed electrodes group is further characterized in that it comprises at least one hole ( 21 ) that allow the gel contained in the reservoir ( 12 ) to pass through and to act as contacting electrolyte (see FIG. 1 d ).
  • the working electrode is activated/prepared with metal microparticles selected from the group consisting of gold, silver, platinum, copper and combinations or alloys thereof, having an average diameter of from 20 to 0.05 ⁇ m; preferably from 10 to 0.3 ⁇ m; more preferably (about) 1 ⁇ m;
  • the amount of nano- or microparticles of carbon black, or metallic particles deposed on the working electrode is from 0.1 to 50 ⁇ l; preferably from 1 to 20 ⁇ l; more preferably from 2 to 14 ⁇ l;
  • the printed electrodes obtained by drop-casting, with the process above described are further characterized in that:
  • It is a further object of the present invention is a method for preparing an electrochemical sensor nano- and/or micro-structured; comprising:
  • said printed electrodes group containing at least a working electrode; at least a reference electrode; and at least an auxiliary electrode; in which, preferably. said printed electrodes group is characterized in that it comprises at least one hole ( 21 ) that allow the gel contained in the reservoir ( 12 ) to pass through and to act as contacting electrolyte (see FIG. 1 d ).
  • the working electrode and the reference electrode are prepared, during the process of printing, using an ink containing a metal microparticles selected from the group consisting of gold, silver, platinum, copper and combinations or alloys thereof, having an average diameter of from 20 to 0.05 ⁇ m;
  • the amount of nano- or microparticles of carbon black, or metallic particles deposed on the working electrode is from 0.1 to 50 ⁇ l; preferably from 1 to 20 ⁇ l; more preferably from 2 to 14 ⁇ l;
  • the printed electrodes obtained by drop-casting, with the process above described are further characterized in that:
  • Another object of the invention is a kit comprising at least an electrochemical probe as described before and further comprising:
  • the senor comprises a printed electrode, as defined before, and preferably it consists of a working electrode, a reference electrode, a counter electrode and an electronic device that has the task to configure the electrodes group and to acquire and decode the current signal coming from the electrode group, in which the output signal can be a signal in voltage and/or current and/or digital and/or LAN and/or radio frequency connection.
  • the sensor according to the invention is suitable for being used for single analytical determinations (see FIG. 1 a ) or to be inserted in line for continuous monitoring of the analytes (see FIGS. 1 b and 1 c ).
  • FIG. 1 a it is shown the probe according to the present invention, useful for a single detection of tan analyte, comprising:
  • FIG. 1 b the probe according to the invention is presented, for a continuous detection of the analyte under examination.
  • FIG. 1 c shows a sectional detail of the probe according to the invention, for a continuous detection of the analyte under examination, comprising:
  • FIG. 1 d shows the printed sensor (working electrode/reference electrode/auxiliary electrode) ( 10 ), in which some holes ( 21 ) are present, that allow the gel contained in the reservoir ( 12 ) to pass through and to act as contacting electrolyte.
  • FIG. 1 e shows an example of a probe holder useful to contain at least one probe object of the present invention, in which:
  • ( 17 ) represents a flow meter (for the control of flow parameters);
  • ( 18 ) represents the pH probe or electrode known in the art.
  • ( 19 ) represents the probe or electrode according to the present invention.
  • a probe holder may consist of a single module ( 19 ), if a flow parameter control is carried out upstream; otherwise it may consist of module ( 17 ) and ( 19 ); or of module ( 17 ), ( 19 ) and at least a further module in which to insert one or more probes for further measurement of analyte.
  • FIGS. 2 a and 2 b show the printed electrodes group ( 1 ), both disassembled ( FIG. 2 a ) and assembled ( FIG. 2 b ) comprising:
  • FIGS. 3 a and 3 b Figures obtained by electron microscopy of the printed electrodes, before ( FIGS. 3 a and 3 b ) and after ( FIGS. 3 c and 3 d ) the modification by drop-casting with the dispersion of Carbon Black (CB), are shown.
  • FIGS. 3 c and 3 d the deposition of CB nanoparticles that completely cover the working electrode surface is clearly evidenced.
  • FIG. 4 shows the control and/or actuation unit (known in art) which has the function of collecting data detected by the various peripheral probes and to activate the dosing pumps for modifying this data, if any.
  • the control of these parameters can be made manually or automatically, locally or using a remote control of the parameters.
  • FIGS. 5 a , 5 b , 5 c and 5 d report:
  • FIGS. 6 a and 6 b show the data obtained (amperometric curve with relative equation and calibration curve-insert) related to the inter-electrode ( FIG. 6 a ) and intra-electrode ( FIG. 6 b ) repeatability.
  • FIG. 7 shows the results obtained in the interference study by evaluating possible interfering ionic species (NO 3 ⁇ , SO 4 2 ⁇ , CO 3 2 ⁇ , HCO 3 ⁇ and Cl ⁇ ions). These ions may be present in swimming pool water during maintenance treatments. The results obtained show that the presence of the ions did not modify the sensor response compared to the analyte and, above all, the sensor(s) did not show an electrochemistry response against them.
  • interfering ionic species NO 3 ⁇ , SO 4 2 ⁇ , CO 3 2 ⁇ , HCO 3 ⁇ and Cl ⁇ ions
  • FIG. 8 b reports the results obtained from the amperometric study carried out by applying a potential of 0 V vs AgCl and using a sensor modified with various amounts of CB ( FIG. 8 b ).
  • FIGS. 9 a and 9 b data obtained from the study of dioxide chlorine concentration as a function of pH in buffer B.R 0.02 M+KCl 0.02 M by spectrophotometric analysis (black bars, instant concentration, gray bars, after 24 h) ( FIG. 9 a ) are showed.
  • FIGS. 11 a , 11 b , 11 c and 11 d results obtained from amperometric studies by the sensor for the measurement of peracetic acid, conducted for the choice of operating parameters, are reported:
  • FIG. 12 shows a block diagram of the system in which the sensor was optimized and integrated with a potentiostat, developed to allow an automatic measurement of free chlorine. Inside the probe, a block that provided for conditioning, processing and transmitting data coming from the electrodes using electrical diagrams and software well known in the art was present.
  • FIG. 13 shows the communication system between the sensor and the operational amplifier.
  • the signal conditioning system provided the use of operational amplifiers to keep the voltage constant and to measure the current.
  • the operational amplifier was able to decouple the control system of the microcontroller from the measurement system.
  • FIG. 14 shows the communication system between microcontroller and operational amplifier.
  • the processing system provides a continuous data exchange between the microcontroller and the operational amplifiers through ADC and 12 bit DAC.
  • the microcontroller using the DAC, continuously provides the working voltage to be applied to the electrodes.
  • the operational amplifier is used to transform the current coming from the electrodes. This current is changed into voltage and measured through the ADC present on the micro.
  • a signal is generated at the output of the electronic system, which in turn is sent to the control and/or to the implementation control unit. This signal is proportional to the measured analyte concentration.
  • the potentiostat circuit and the microcontroller that acquires the signal in current coming from the electrode assembly constitute a system that allows the measurement of particular analyte concentrations; the device that manages the system logic is a microcontroller well known in the art.
  • FIG. 15 the operational algorithm of the program, easily written by a technician skilled in the art, is reported.
  • the main program (see also FIG. 12 ) provides, after the Pin assignment, the variables declaration used within it, including the working voltage variable to which the electrodes are subjected. After setting the working voltage variable, the program will start measuring the current between the electrodes providing an input voltage to the microcontroller. The program also allows choosing the type of output signal.
  • the functionalized sensor for free chlorine measurement As “starting product”, a not functionalized sensor or electrode was used; the functionalization was carried out by depositing on the surface of the working electrode 10 ⁇ l (5 depositions of 2 ⁇ l each) of a dispersion of CB (Carbon Black N 220 from Cabot Ravenna Italy); the dispersion was prepared by placing 1 mg of CB in 1 ml of a water and dimethylformamide solution (1: 1); before use, this dispersion was sonicated for an hour at 59 KHz; with obtaining a functionalized electrode for the detection of free chlorine.
  • CB Carbon Black N 220 from Cabot Ravenna Italy
  • the liquid to be analyzed (for the detection of free chlorine), before reading, was placed in a working solution, consisting of a Britton-Robinson buffer+KCl at pH 5, with an ionic strength of 0.02 M Britton- Robinson and 0.02 M for the KCl.
  • a potential of ⁇ 0.1 V vs Ag/AgCl was applied.
  • the free chlorine electrode according to the invention was characterized by the analytical point of view to determine the linear range, sensitivity and inter- and intra-electrode repeatability.
  • the results obtained show an excellent inter- ( FIG. 6 a ) and intra-electrode repeatability ( FIG. 6 b ); the sensor according to the invention was able to detect a free chlorine concentration range between 0.05 and 200 ppm.
  • the non-functionalized sensor or electrode was used as “starting product”, for which an ink based on gold microparticles was used for working electrode.
  • an electrolyte solution consisting of a buffer system, preferably phosphate, borate, acetate, citrate, or mixtures thereof, was used, based on the field of application of the sensor, more preferably a buffer which maintains the pH value in a range from 2 to 12 is used, a supporting electrolyte preferably a halogenated salt in relation to the type of reference electrode of the sensor and to the analyte to be determined at a variable concentration more preferably between 1% and 15%; and if necessary.
  • a buffer system preferably phosphate, borate, acetate, citrate, or mixtures thereof
  • starting product a non-functionalized the sensor was used; the functionalization was carried out using 2 ⁇ l of carbon black nanoparticles (prepared as described in Example 1) ( FIG. 8 ).
  • the chlorine dioxide standard solution was prepared using the reagent h, chlorine dioxide release mixture,
  • the chlorine dioxide electrode was characterized by the analytical point of view to determine the linear range, sensitivity and inter- and intra-electrode repeatability.
  • the senor according to the invention also proved its validity in pool water. Because pool water is a complex matrix, it was necessary to dilute the sample and the dilution factor chosen, as a compromise between sensitivity and low matrix effect, it was equal to 1:5 v/v in buffer solution. The sensitivity obtained was 5.4 ⁇ 0.4 nA/ppm. The accuracy of the sensor was evaluated using the recovery method, obtaining a percentage recovery of 78 ⁇ 8%.
  • the functionalized electrode useful for the determination of chlorine dioxide, showed an improved sensitivity equal to 278 ⁇ 65 nA/ppm.
  • the non-functionalized sensor or electrode was used, as “starting product”, for whose working electrode an ink based on gold microparticles was used.
  • an electrolyte solution consisting of a buffer system, preferably phosphate, borate, acetate, citrate, or mixtures thereof, was used, based on the field of application of the sensor, more preferably a buffer is used which maintains the pH value in a range from 2 to 12, a supporting electrolyte preferably a halogenated salt in relation to the type of reference electrode of the sensor and to the analyte to be determined at a variable concentration more preferably between 1% and 15%; and if necessary.
  • a buffer system preferably phosphate, borate, acetate, citrate, or mixtures thereof
  • the non-functionalized sensor was used; the functionalization was carried out using 6 ⁇ l of gold nanoparticles (reagent g).
  • an electrolyte solution consisting of a buffer system, preferably phosphate, borate, acetate, citrate, or mixtures thereof, was used, based on the field of application of the sensor, more preferably a buffer is used which maintains the pH value in a range between 2 and 8), a supporting electrolyte preferably a halogenated salt in relation to the type of reference electrode of the sensor and to the analyte to be determined at a variable concentration more preferably between 1% and 15%; and if necessary.
  • a buffer system preferably phosphate, borate, acetate, citrate, or mixtures thereof
  • the screen-printed electrode for the sensor useful for the measurement of total chlorine was functionalized during the printing process using ink based on gold microparticles with an average diameter of 1 ⁇ m (reagent c).
  • an electrolytic solution or gel consisting of a buffer system, preferably phosphate, borate, acetate, citrate and mixture of them was used, chosen in accordance with the scope of the sensor, more preferably a buffer that can maintains the pH value in an inclusive range between 2 and 12, a supporting electrolyte preferably a halogenated salt in relation whit the type of reference electrode of the sensor and to the analyte to be determined at a variable concentration, more preferably between 1% and 15%; and if necessary, in accordance with the type of membrane used, a gelling agent chosen from the family of organic compounds of natural origin, miscible in water in percentage ranging from 85% to 100%.
  • a buffer system preferably phosphate, borate, acetate, citrate and mixture of them was used, chosen in accordance with the scope of the sensor, more preferably a buffer that can maintains the pH value in an inclusive range between 2 and 12, a supporting electrolyte preferably a halogenated salt in relation whit the type of reference
  • the functionalized sensor for measuring the acid peracetic, as “starting product”, the not functionalized sensor was used; the functionalization was carried out using 6 ⁇ l of a dispersion of gold nanoparticles ( FIG. 11 a ) with a diameter of 5 nm commercially available, purchased from Strem Chemicals, n. of catalog 79-0180 (reagent g), and applying a potential of ⁇ 0.1 V vs Ag/AgCl ( FIG. 11 b ).
  • FIG. 11 c a working solution consisting from an acetate buffer 0.1 M at pH 5.4 was used ( FIG. 11 c ), and an ionic strength of 0.1M ( FIG. 11 d ); applying to the electrodes a potential of ⁇ 0.1 V vs Ag/AgCl.
  • the peracetic acid electrode according to the invention was characterized by the analytical point of view to determine the linear range, sensitivity and inter- and intra-electrode repeatability.
  • the sensor according to the invention, was able to detect a concentration range of peracetic acid between 20 and 1000 ⁇ M (from 1.5 to 76 ppm).
  • the limit of detection (LOD) and LOQ of the sensor, according to the invention were calculated and they resulted to be 1 and 3 ⁇ M, respectively.
  • the senor according to the invention also proved its suitability in pool water. Because pool water is a complex matrix, it was necessary to dilute the sample and the dilution factor chosen, as a compromise between sensitivity and low matrix effect, was equal to 1:4 v/v in buffer solution.
  • the sensitivity obtained was 6.06 ⁇ 0.03 nA/ ⁇ M up to 1000 ⁇ M.
  • the accuracy of the sensor was evaluated with the recovery method, obtaining a percentage recovery of 96.4 ⁇ 0.6%, demonstrating the accuracy of the sensor, according to the invention tested.
  • the non-functionalized sensor or electrode was used as “starting product”, for whose working electrode an ink based on gold microparticles was used.
  • a working solution consisting of 0.05 M acetate buffer or Britton-Robinson buffer at pH 5.4 and an ionic strength of 0.05 M was used; applying to the electrodes a potential of ⁇ 0.2 V vs Ag/AgCl.
  • the LOD and LOQ were calculated and they resulted to be 0.8 and 2.5 ⁇ M, respectively.
  • the probes obtained shown in FIGS. 1 b - e were connected to the electronic part to carry out in line measurements.
  • the probe was inserted into a suitable probe holder equipped with a flow meter, through which it was possible to check the liquid flow parameters, such as pressure, flow, temperature, etc., see FIGS. 1 b , 1 c and 1 d.

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US11536685B2 (en) 2020-02-06 2022-12-27 Trustees Of Boston University High throughput assay for identifying microbial redox enzymes
EP4180805A1 (en) * 2021-11-12 2023-05-17 Consejo Superior de Investigaciones Cientificas Screen-printed electrode, manufacturing method thereof, electrochemical sensor comprising said electrode for detecting water pollutants, and operating method of said sensor

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WO2022232670A1 (en) 2021-04-30 2022-11-03 Trustees Of Boston University Hormone electrochemical biosensor

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CN107202823B (zh) * 2017-06-20 2019-10-29 龚雨 一种喷墨印刷制备微电极阵列传感器的方法及其应用

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US11331020B2 (en) 2020-02-06 2022-05-17 Trustees Of Boston University Enzyme-based electrochemical nicotine biosensor
US11536685B2 (en) 2020-02-06 2022-12-27 Trustees Of Boston University High throughput assay for identifying microbial redox enzymes
EP4180805A1 (en) * 2021-11-12 2023-05-17 Consejo Superior de Investigaciones Cientificas Screen-printed electrode, manufacturing method thereof, electrochemical sensor comprising said electrode for detecting water pollutants, and operating method of said sensor
WO2023084031A1 (en) * 2021-11-12 2023-05-19 Consejo Superior De Investigaciones Científicas Screen-printed electrode and manufacturing method thereof

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US20230194458A1 (en) 2023-06-22
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EP3619528A2 (en) 2020-03-11
JP2020518804A (ja) 2020-06-25
WO2018202793A2 (en) 2018-11-08
IT201700046831A1 (it) 2018-11-03
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RU2019138625A3 (it) 2021-09-28
RU2019138625A (ru) 2021-06-03

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