• 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:
    This sensor comprises at least one substrate comprising on at least one of its faces at least one electrode, said substrate and said electrode being covered with a layer of a molecular imprinted polymer.
    公开号:FR3024236A1
    申请号:FR1457204
    申请日:2014-07-25
    公开日:2016-01-29
    发明作者:Jerome Rossignol；Elias Bou-Maroun；Celine Lafarge；Didier Stuerga；Philippe Cayot
    申请人:INST NAT SUPERIEUR DES SCIENCES AGRONOMIQUES de l ALIMENTATION ET de l ENVIRONNEMENT；Universite de Bourgogne；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to a sensor with microwave transduction comprising as sensitive material a molecular imprinted polymer known as MIP according to the acronym "Molecularly Imprinted Polymer", and more particularly Molecular Imprinted Silica molecular cavity silicas known as MIS and a device for the detection of fungicides such as iprodione for example in a hydro-alcoholic medium such as wine for example.
    [0002] PRIOR ART In the field of analytical chemistry in particular, it is well known various means for analyzing liquids such as water or wine for example in order to determine in particular the chemical content of said liquids, and more particularly to determine the presence or no pollutants such as fungicides. Among the most commonly used systems are known test strips or chromatography.
    [0003] The test strips do not allow the detection of traces of fungicides of the order of a few ng / 1 and the chromatography has the disadvantage of being long and expensive.
    [0004] The most commonly used method for the determination of fungicides is high performance liquid chromatography known as HPLC. However, this analysis requires many preliminary operations consisting of extraction steps, purification, concentration and possibly drying. To avoid the sample treatment step (extraction, purification, concentration and drying), to reduce the analysis time and to reduce the large amounts of solvent used for the extraction, other means newer ones have been put in place.
    [0005] As an example, the SPME Solid Phase Micro Extraction fiber can be cited as "Solid Phase MicroExtraction". This method is based on the use of a silica fiber of 110 μm coated with an adsorbent with a thickness of 7 to 100 μm over a length of 1 cm and situated at the end of a syringe. For extraction of the compounds, the needle pierces the septum of the vial containing the sample and the fiber is immersed in the sample. After a given extraction time, the fiber is introduced into a gas chromatograph (Pichon V, 2012. Solid Phase Extraction for the Analysis of Organic Compounds [P 1420]) Engineer's Techniques, Document Database Chromatography and separatory techniques.) The SPME fiber requires the implementation of several steps before the determination of the fungicide: extraction of ten minutes followed by a chromatographic analysis which lasts at least 30 minutes.
    [0006] There are also known sensors comprising a molecular imprinted polymer known as MIP according to the acronym "Molecularly Imprinted Polymer". This is particularly the case for US patent applications US 2008/0144002, US 2012/0288944 and US 2004/0126814.
    [0007] US 2008/0288944 discloses a sensor having a molecular imprinted polymer for the detection of a specific target inorganic ion. Said sensor comprises one or more molecular imprinted polymer beads comprising a macroporous structure which has a plurality of so-called complexing cavities, said complexation cavities containing spatially oriented cationic ligands for selectively receiving and binding to a specific inorganic target ion in front of said complexing cavities. to be detected. The sensor, associated with a light source such as ultraviolet, infrared or visible light, provides luminescence of the molecular imprinted polymer beads upon which a specific inorganic target ion has been attached. US 2012/0288944 discloses a method for detecting a tracer molecular structure in a fluid using a sensor comprising a molecular imprinted polymer. The method comprises contacting a reticulated star-shaped molecular polymer with the fluid and then correlating the color change in the fluid with the amount of tracer molecular structure in the fluid. The device comprises polymeric arms attached to a core, and the core has molecular size cavities adapted to selectively receive and bind molecules having the tracer molecular structure, said core also having a colorimetric indicator. The displacement molecule is selectively removed from the molecular fingerprint cross-linked polymer by exposure to the tracer molecular structure in the fluid thereby indicating the presence of the tracer molecular structure in the fluid on the basis of a loss of color. US 2004/0126814 discloses a sensor for detecting a target analyte by means of a molecularly imprinted polymer (MIP) which has been printed with the target analyte. The MIP can be used as a working electrode in electrochemical impedance spectroscopy, either by coating a substrate or by being pressed onto a disk. The sensor may also use the molecularly imprinted polymer (MIP) to detect a target analyte by other electrochemical methods. All these methods have the disadvantage of being long and expensive to implement in particular. There is therefore a need for an analyte detecting device to reduce the steps of treating the sample prior to analysis, said steps being necessary to remove interferents present in the complex matrices, and providing a self-defeating measure the signal perturbation induced by said interferers. SUMMARY OF THE INVENTION One of the aims of the invention is thus to remedy these drawbacks by proposing a sensor for the rapid detection of an analyte such as a fungicide of simple and inexpensive design.
    [0008] For this purpose and in accordance with the invention, there is provided a sensor for detecting an analyte, such as a fungicide, a pesticide or the like, in a liquid, which consists of at least one substrate comprising on at least one of its faces, at least one electrode, said substrate and said electrode being coated with a layer of a molecular imprinted polymer. SUMMARY DESCRIPTION OF THE FIGURES Other advantages and features will become more apparent from the following description of a single variant embodiment, given by way of non-limiting example, of the device for detecting fungicides in a hydro-alcoholic medium in accordance with FIG. the invention, with reference to the accompanying drawings in which: - Figure 1 is a schematic representation of the device according to the invention, - Figure 2 is a top view of the sensor circuit comprising a molecular imprinting polymer of the device, FIG. 3 is a view from above of the sensor comprising a molecular imprinted polymer of the device according to the invention; FIG. 4 is a graphical representation of the response of the sensor comprising the MIS at the resonance frequency in the presence of the analyte, 25 - Figure 5 is a comparison of the response of the sensor comprising the MIS to that of the sensor comprising the NIS according to the invention in the presence of the analyte. DETAILED DESCRIPTION OF THE INVENTION In the following description of the device for detecting fungicides in a hydro-alcoholic medium according to the invention, the same reference numerals designate the same elements. The device according to the invention is particularly intended for the detection of fungicides, such as iprodione, in wine; however, it is obvious that the device according to the invention can find many applications such as the detection of fungicides in water without departing from the scope of the invention. With reference to FIG. 1, the device comprises a sensor (1), means 5 for transmitting (2) an electromagnetic wave at a frequency of between 1 and 300 GHz, more particularly between 1 and 10 GHz, and means for receiving (3) the wave reflected on the sensor (1) which is immersed in a hydro-alcoholic liquid comprising at least one analyte to be detected, said analyte consisting of a fungicide such as iprodione for example, and measuring means (4) of the ratio between the reflected wave and the incident wave as a function of frequency. Said emission means (3) of an electromagnetic wave and the reception means (4) of the reflected wave consist of a vector network analyzer. Furthermore, with reference to FIGS. 1 to 3, the sensor (1) consists of at least one substrate (10) comprising on at least one of its faces at least one electrode (11), said substrate (10) and said electrode (11) being coated with a layer (12) of a molecular imprinted polymer. The said molecular-imprinted polymer preferably consists of molecular-fingerprint silica called MIS according to the acronym "Molecularly Imprinted Silica". Said layer (12) of molecular imprinted polymer has a thickness of about one micrometer. In addition, the substrate (10) consists of a glass slide. In this particular embodiment, said blade has a substantially rectangular or square shape. It is obvious that the blade may have any shape without departing from the scope of the invention.
    [0009] In addition, said electrode (11) has an isosceles triangle shape, the length of each side of the triangle forming the electrode (11) being equal to k / 2, X being the wavelength. The electrode (11) further comprises two antennas (13) extending from two vertices of said triangle symmetrically with respect to the median passing through the free vertex of the electrode (11), each antenna (13) having an equal length at k / 2.
    [0010] It goes without saying that the electrode (11) may have any shape. In addition, it is obvious that the sensor (1) may comprise a plurality of electrodes (11) of any shape without departing from the scope of the invention. The method of manufacturing the sensor comprises a step of cutting the glass substrate in the form of a rectangular blade of about 1 cm by 2 cm before a mechanical polishing step. Then, said glass slide is covered with a layer of copper 5 with a thickness of 20 to 1.1.m. Said blade covered with copper then undergoes several polishing operations until a copper polymeric surface is obtained, then a resin that is sensitive to ultraviolet (UV) is deposited by a so-called "spin-coating" process well known to the skilled person. A mask representing the geometry of the sensor is then placed on the resin, then the blade is irradiated with ultraviolet (UV). After revelation of the resin, wet etching of the copper is performed and the remaining resin is removed by any suitable means well known to those skilled in the art. After rinsing with distilled water, the sensor may undergo another polishing and cleaning step to remove any imperfections. The sensor is, moreover, covered with a molecular imprinted silica layer which is elaborated with the presence of the target analyte, for example iprodione. Finally, the sensor is then equipped with an SMA connector (14) according to the acronym "Subminiature version A" which consists of a coaxial connector whose impedance is 50 Ohms and which is soldered to the electrode of the sensor.
    [0011] The synthesis of the MIS was carried out using the ratio chosen according to 1/4/59 (molar ratio of iprodione / monomers / crosslinking agent). The monomer used is APTMS (3-aminopropyltrimethoxysilane). The synthesis proceeded as follows: i) 16.8 mL of absolute ethanol was placed in a water bath at 40 ° C for 10 min. ii) 0.08 g of iprodione is added and then 2 mL of water. Iii) 0.18 mL of monomer (APTMS) was then added, and the samples were stirred for 5 minutes. iv) 3.1 mL of TEOS (Tetraethyl Orthosilicate) crosslinking agent was then added, and the samples were again stirred for 5 min. v) 1 mL of Inititator (Ammonium Hydroxide) was added, then the samples were stirred for 5 min. vi) The samples are then placed 24h in a water bath (40 ° C) with stirring. vii) The precipitate obtained is separated from the liquid phase by centrifugation at 7500 RPM (10000G) for 10 min at 20 ° C. Several successive washes were then performed with absolute ethanol, until there was no more iprodione in the washings when analyzed by HPLC. After the various washes, the polymer is placed in an oven at 60 ° C. for 24 hours. An unprinted polymer, NIS, according to the acronym "Non Imprinted Silica" 5 was synthesized following the same protocol as the MIS omitting the addition of iprodione in the synthesis medium. The MIS or NIS is deposited on the sensor in the form of a suspension. For this, PVC powder was added to a suspension of MIS in THF (tetrahydrofuran) at the following ratio: 25/8/4, MIS (mg) / PVC (mg) / THF (mL).
    [0012] The solution thus prepared was then deposited on the surface of the sensor by the spin-coating method using the following parameters: speed = 1000 rpm, acceleration = 4000 rpm, duration = 40 s.
    [0013] Thus, since the sensor is immersed in a liquid containing the target analyte, for example iprodione, the vector network analyzer emits an electromagnetic wave at an excitation frequency, in the microwave domain, and evaluates the wave. reflected at the entrance to it. The interaction of the liquid with the molecular fingerprint material of the sensor (1) induces variations in the dielectric properties of the sensitive material in the microwave range. The molecular fingerprint material participating in a microwave propagating structure sees its variation of dielectric properties exalted by the geometry of the sensor. In this way for each excitation frequency, the reflected wave / incident wave ratio is associated with the interaction of the molecular fingerprint material with the liquid. The network analyzer emits several frequencies of the order of one thousand in the range of 1 to 10 GHz providing a so-called microwave signature describing the interaction of the molecular fingerprint material with the liquid. With reference to FIG. 4, the response of the sensor according to the invention is represented, at the 2.3 GHz resonance frequency, in the presence of the determined pollutant. The signal represents the relative variation of the signal (real and imaginary part) with pollutant compared to the liquid without pollutant. Note that the measurement is made in about a minute. FIG. 5 is a graphical representation of the response of the sensor comprising an MIS in the presence of the determined pollutant compared to the response of a sensor comprising a NIS, the second NIS sensor being previously made from an unprinted NIS polymer (No 3024236 - 8 - imprinted silica) synthesized under the same conditions as MIS but in the absence of iprodione. Finally, it is obvious that the examples which have just been given are only particular illustrations and in no way limiting as to the field of application of the invention.
    权利要求:
    Claims (19)
    [0001]
    CLAIMS1 - Sensor for the detection of an analyte such as a fungicide, a pesticide or the like, in a liquid, characterized in that it consists of at least one substrate comprising on at least one of its faces at at least one electrode, said substrate and said electrode being coated with a layer of a molecular imprinted polymer.
    [0002]
    2 - sensor according to claim 1 characterized in that the molecularly imprinted polymer consists of silica molecular fingerprint.
    [0003]
    3 - Sensor according to any one of claims 1 or 2 characterized in that the molecular imprint polymer layer has a thickness between 50 and 950 nm.
    [0004]
    4 - Sensor according to any one of claims 1 to 3 characterized in that the substrate consists of a glass slide.
    [0005]
    5 - Sensor according to claim 4 characterized in that said glass plate has a substantially rectangular or square shape.
    [0006]
    6 - Sensor according to any one of claims 1 to 5 characterized in that said electrode has an isosceles triangle shape.
    [0007]
    7 - Sensor according to claim 6 characterized in that the length of each side of the triangle forming the electrode is equal to k / 2, X, being the wavelength.
    [0008]
    8 - sensor according to any one of claims 6 or 7 characterized in that the electrode comprises two antennas extending from two vertices of said triangle symmetrically with respect to the median through the free peak.
    [0009]
    9 - Sensor according to claim 8 characterized in that each antenna has a length equal to k / 2.
    [0010]
    10 - Device for detecting at least one analyte such as a fungicide, a pesticide or the like, in a liquid, characterized in that it comprises at least one sensor consisting of at least one substrate comprising at least one at least one of its faces at least one electrode, said substrate and said electrode being covered with a layer of a molecular imprinted polymer, means for emitting an electromagnetic wave at a frequency of between 1 and 300 GHz and means for receiving the wave reflected on the sensor which is immersed in the liquid and means for measuring the ratio of the reflected wave to the incident wave as a function of frequency.
    [0011]
    11 - Detection device according to claim 10 characterized in that the means for transmitting an electromagnetic wave and the means for receiving the reflected wave consist of a vector network analyzer.
    [0012]
    12 - Detection device according to any one of claims 10 or 11 characterized in that the molecularly imprinted polymer consists of silica molecular fingerprint.
    [0013]
    13 - Detection device according to any one of claims 10 to 12 characterized in that the molecular imprinted polymer layer has a thickness between 50 and 950 nm. 20
    [0014]
    14 - Detection device according to any one of claims 10 to 13 characterized in that the substrate consists of a glass slide.
    [0015]
    15 - Detection device according to claim 14 characterized in that said glass plate has a substantially rectangular or square shape.
    [0016]
    16 - Detection device according to any one of claims 10 to 15 characterized in that said electrode has an isosceles triangle shape. 30
    [0017]
    17 - Detection device according to claim 16 characterized in that the length of each side of the triangle forming the electrode is equal to k / 2, X, being the wavelength.
    [0018]
    18 - Detection device according to any one of claims 16 or 17 characterized in that the electrode comprises two antennas extending from two vertices of said triangle symmetrically with respect to the median passing through the free vertex.
    [0019]
    19 - Detection device according to claim 18 characterized in that each antenna has a length equal to k / 2.
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    同族专利:
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    WO2016012682A1|2016-01-28|
    FR3024236B1|2018-10-12|
    EP3172555A1|2017-05-31|
    US20170160254A1|2017-06-08|
    AU2015293757A1|2017-02-02|
    CL2017000083A1|2017-06-30|
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    引用文献:
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    US20130303868A1|2010-11-24|2013-11-14|Friedrich Alexander Universitaet Erlangen Nuernber|Detection device for the detection of a blood count parameter|
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    CN109799274B|2019-01-22|2021-03-30|西安工程大学|Preparation and test method of conductive polymer film material|
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    法律状态:
    2015-07-17| PLFP| Fee payment|Year of fee payment: 2 |
    2016-01-29| PLSC| Search report ready|Effective date: 20160129 |
    2016-08-01| PLFP| Fee payment|Year of fee payment: 3 |
    2017-07-21| PLFP| Fee payment|Year of fee payment: 4 |
    2018-07-28| PLFP| Fee payment|Year of fee payment: 5 |
    2019-07-23| PLFP| Fee payment|Year of fee payment: 6 |
    2020-07-27| PLFP| Fee payment|Year of fee payment: 7 |
    2021-07-29| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1457204|2014-07-25|
    FR1457204A|FR3024236B1|2014-07-25|2014-07-25|SENSOR AND DEVICE FOR THE DETECTION OF FUNGICIDES IN A HYDRO ALCOHOLIC ENVIRONMENT|FR1457204A| FR3024236B1|2014-07-25|2014-07-25|SENSOR AND DEVICE FOR THE DETECTION OF FUNGICIDES IN A HYDRO ALCOHOLIC ENVIRONMENT|
    CN201580038997.2A| CN106662539B|2014-07-25|2015-06-25|For detecting the sensor and equipment of the analyte in liquid|
    EP15753711.9A| EP3172555A1|2014-07-25|2015-06-25|Sensor and device for detecting an analyte in a liquid|
    US15/327,282| US10247715B2|2014-07-25|2015-06-25|Sensor and device for detecting an analyte in a liquid|
    PCT/FR2015/051717| WO2016012682A1|2014-07-25|2015-06-25|Sensor and device for detecting an analyte in a liquid|
    AU2015293757A| AU2015293757B2|2014-07-25|2015-06-25|Sensor and device for detecting an analyte in a liquid|
    CL2017000083A| CL2017000083A1|2014-07-25|2017-01-12|Sensor and device to detect an analyte in a liquid|
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