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WO2021102593A1 - Système et procédé pour la détermination et la quantification de la concentration d'un analyte, faisant intervenir un capteur à base de diamant optiquement actif, une chambre qui reçoit ledit capteur et des moyens d'entrée de l'échantillon, et utilisation dudit capteur - Google Patents

Système et procédé pour la détermination et la quantification de la concentration d'un analyte, faisant intervenir un capteur à base de diamant optiquement actif, une chambre qui reçoit ledit capteur et des moyens d'entrée de l'échantillon, et utilisation dudit capteur Download PDF

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Publication number
WO2021102593A1
WO2021102593A1 PCT/CL2019/050124 CL2019050124W WO2021102593A1 WO 2021102593 A1 WO2021102593 A1 WO 2021102593A1 CL 2019050124 W CL2019050124 W CL 2019050124W WO 2021102593 A1 WO2021102593 A1 WO 2021102593A1
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WO
WIPO (PCT)
Prior art keywords
sensor
sample
diamond
analyte
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CL2019/050124
Other languages
English (en)
Spanish (es)
Inventor
Enrique Javier MUÑOZ TAVERA
Ivan Alonso GONZALEZ PAVEZ
Jerónimo MAZE RIOS
Hossein TAVAKOLI DINANI
Vicente Andres SANTIBAÑEZ CISTERNAS
Raul Manuel GONZÁLEZ BROUWER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pontificia Universidad Catolica de Chile
Original Assignee
Pontificia Universidad Catolica de Chile
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pontificia Universidad Catolica de Chile filed Critical Pontificia Universidad Catolica de Chile
Priority to PCT/CL2019/050124 priority Critical patent/WO2021102593A1/fr
Publication of WO2021102593A1 publication Critical patent/WO2021102593A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/28—Details of apparatus provided for in groups G01R33/44 - G01R33/64
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/60—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using electron paramagnetic resonance

Definitions

  • the present invention relates to a system and method for determining and quantifying an analyte, wherein the measurement system comprises a diamond-based sensor having optically active color centers. Likewise, it refers to the use of said diamond-based sensor for the detection and quantification of an analyte that may correspond to an element, ion and / or chemical compound.
  • Highly sensitive chemical sensors that are capable of operating in extreme conditions and that also have the potential to be miniaturized are in high demand in the chemical, mining and gas extraction industries, where the high sensitivity of the sensors is crucial to detect small amounts of chemical elements that could alter the course of industrial processes or toxins that can be harmful to the environment or health.
  • the ability to miniaturize a sensor and work in conditions of high pressure, temperature or corrosive environments is highly desirable to access remote locations, mainly in industries that deal with the extraction of minerals, oil and gas, among others.
  • the present invention aims to solve this need through the development of a detection method that is based on recent scientific discoveries that show the ability of diamond to detect fluctuations in the electric field.
  • This method is highly sensitive since it is based on the monitoring of coherent properties of molecules inside the diamond that are in turn affected by fluctuations in the electric field produced by chemical reactions.
  • the sensor presents noble characteristics, such as high resistance to high pressures, high temperatures and chemical resistance to corrosive environments, which makes it ideal for working in a wide range of environmental conditions.
  • Nanodiamonds like diamonds, are made up of carbon atoms located in a crystal lattice. Nanodiamonds sometimes have impurities on their surface. This modification in the surface structure produces changes in the optical properties (absorption and emission of radiation).
  • Nanodiamonds with color centers or optically active molecules can detect the presence of reactants in a chemical reaction by measuring the electronic noise they generate.
  • the color centers are associated with an electronic spin whose dynamics at a very low magnetic field is affected exclusively by fluctuations in the electric field and which can be optically observed through the fluorescence associated with these color centers.
  • Nitrogen-Vacancy centers are point defects in diamonds composed of an impurity atom (nitrogen) and a vacancy in the carbon crystal lattice that is characteristic of diamonds. These defects are fluorescent, that is, they emit light at a very particular wavelength.
  • the inventors have generated stable NV centers at shallow depth (1-10 nm) below the diamond surface by the nitrogen ion beam implantation technique. These centers are sensitive to fields external to the diamond, and in turn, they are stable enough to be used as sensors.
  • Patent application WO2018155504 discloses a diamond magnetic sensor comprising a diamond having at least one nitrogen vacancy center (NV) close to the diamond surface, a microwave generator that irradiates the diamond with microwaves, a light generator of excitation that irradiates the NV center in the diamond with excitation light, and a fluorescence detector that receives fluorescent light generated by the NV center in the diamond.
  • the diamond magnetic sensor further comprises a pattern measurement device, which measures the patterns of time variation in the intensity of the magnetic field from changes in fluorescence intensity detected by the fluorescence detector.
  • nanoscale diamond color centers containing nitrogen-vacancy (NV) centers has also been established.
  • the present invention relates to a system and method for determining and quantifying an analyte (chemical compound, element or ion).
  • This system comprises a cell containing a diamond-based sensor that has optically active color centers close to the surface at a distance between 2-8 nanometers.
  • Figure 1 Confocal image of one of the NV implantation areas in the diamond.
  • Figure 2 Photographs of the camera that houses the diamond sensor.
  • Figure 3 Scheme of the system according to the present invention.
  • Figure 4 Scheme of the steps of the measurement method according to the present invention.
  • Figure 5 Illustration of the Flow Chamber housing the diamond-based sensor and sensor image.
  • Figure 6 Photograph of one embodiment of the system according to the present invention.
  • Figure 7 Photograph of an embodiment of the system according to the present invention.
  • Figure 8 Fluorescence signals associated with different magnetic resonances in the presence of magnetic fields.
  • Figure 9 Graph of the calibration curve obtained for the determination of copper.
  • Figure 10 Graph of the sample reading on the calibration curve.
  • Diamond with color centers close to the surface is prepared using the nitrogen ion beam implantation technique.
  • This implantation consists of accelerating nitrogen ions (isotope 15) with energies between 0.7 keV and 10 keV and doses between 10 and 10 ions per square centimeter, the latter allowing to control the number of color centers generated.
  • the NV centers generated are stable and lie at a depth between 1 and 10 nm relative to the diamond surface.
  • Figure 1 shows the image taken by confocal microscopy of one of the implantation areas.
  • the energies used between 0.7 keV and 10 keV produced color centers between 10 nm and 1 nm in depth with respect to the diamond surface.
  • the dose number of ions per square centimeter implanted was also varied to control the number of color centers.
  • the optical properties of the sensor are obtained by Ramsey resonance spectroscopy, which is similar to that used in clinical resonators, but in this case it is applied on the electronic spins of the diamond and not on the nuclear spins.
  • the experimental setup has a microwave generator with frequencies around 3 gigahertz and with a bandwidth of about 500 megahertz, to achieve resonance between the electronic spins and the microwave radiation.
  • the sample composed of electrical charges with Random movements, causes an electrical noise that is proportional to the concentration of charges in the solution that is detectable by the color centers.
  • the sensitivity of the sensor is controlled by a coil that generates an external magnetic field.
  • the sensor reaches its maximum sensitivity when the coil and power supply system cancels the magnetic field produced by the earth. Since this field (magnitude and direction) depends on the place where the measurement is taken. Calibration must be done during sensor power-up.
  • a microfluidic system was designed and developed that allows the entry of a solution to be measured and the application of microwave radiation to carry out the measurement protocol. In turn, this microfluidic system aims to keep the flow constant.
  • This system uses 50 mL motorized syringes. The flow can be varied between 0 and 50 mL / s.
  • the system consists of two inlets for the solution and one outlet that allows connection to the diamond-based sensor.
  • the chamber has a space that allows solutions to enter and mix, which in turn allows an electrode to be placed for pH detection for sensor calibration purposes.
  • Pieces of material resistant enough to prevent corrosion caused by the solutions that are added and the temperature differences that can be reached were designed and manufactured (see Figure 2).
  • the material used corresponds to a low fluorescence plastic material (Permanox®).
  • control software was developed in order to measure and manipulate different variables such as pH, internal diameter of an injection system based on motorized syringes (int. Diameter), added volume (volume), addition speed ( rate), among others.
  • Analyte measurement method The sample to be analyzed that comprises the analyte to be determined must be previously diluted depending on its initial concentration. Then a syringe is entered which is activated by the flow controller that allows the sample to circulate through the Flow Chamber where the diamond is found, as shown in Figure 3. The sample, when interacting with the diamond, changes its properties. optics that are measured by laser excitation and the recording of luminosity by means of a Fluorescence Detector. These optical properties are compared to a calibration curve that has been previously obtained. This comparison allows to know the concentration of the element to be measured in the sample.
  • the measurement of the analyte (chemical compound, element or ion) present in a sample is carried out through the following steps:
  • the diamond-based chemical reaction sensor consists of the reading of electronic noise that is associated with the presence of electrical charges present in a solution. To use the sensor, it must be calibrated for each analyte to be studied.
  • This first stage consists of determining the magnetic field associated with the longest coherence time of the optically active diamond.
  • the longest coherence time occurs when the applied magnetic field cancels the earth's magnetic field present in the place where the measurement is made, because the optically active diamond has an anisotropic response to the magnetic field. The value of this magnetic field must be obtained each time the Flow Chamber (and therefore the diamond) is used or moved.
  • This stage consists of calibrating the sensor with respect to a specific sample. For this, three measurements of the coherence time and / or Rabi frequency are taken: the first measurement is carried out in the presence of a solution at neutral pH (deionized water); the second and third measurements of the coherence time and / or frequency of Rabi are carried out with known standard samples with two different concentrations to associate each C1 and C2 concentration to the TI and T2 coherence times. In this way, a linear calibration curve is obtained that will be used in the next stage.
  • This stage consists of measuring the coherence time and / or frequency of Rab ⁇ with a solution containing the analyte to be quantified. This time and / or frequency is interpolated to the calibration curve and then the value of the analyte concentration in the solution is determined.
  • the system by which the above-described method can be carried out comprises a cell containing the described diamond-based sensor, in addition to a microwave generator to achieve resonance between the electronic spins and the microwave radiation.
  • the sample composed of charged species with random Brownian motion, causes a magnetic noise that is proportional to the concentration of these charges in the solution.
  • Figure 5 shows the Flow Chamber where the diamond that has been implanted with nitrogen atoms to make it optically active is housed.
  • the image shows a zone of implantation of 5 keV of energy that has been obtained by means of a confocal microscope.
  • the implantation size is only 25 Dm in diameter.
  • Figure 6 shows the objective lens and the flow chamber connected to a syringe containing the fluid to be analyzed.
  • Figure 7 shows the most relevant parts of the system according to the present invention: the excitation with a green laser of 532 nm and 1 Watt of power and the fluorescence detector capable of detecting individual photons. The counts of this detector reach several million photons detected per second.
  • the present invention is directed to a system for the determination and quantification of the concentration of an analyte in a sample that contains it, comprising:
  • optically active color centers correspond to nitrogen ion implantations.
  • the color centers are produced by the nitrogen ion beam implantation technique which consists of accelerating nitrogen ions with energies between 0.7 and 10 KeV.
  • the implants have a depth between 10 nm and 1 nm.
  • the implantations are carried out at doses between 10 9 and 10 12 ions / cm 2 .
  • the means that allow the entry and exit of the sample correspond to a microfluidic circuit that allows working with a minimum amount of sample.
  • the chamber has a space that allows the solutions to enter and mix.
  • the chamber allows an electrode to be placed for pH detection for sensor calibration purposes. Even more preferably, the chamber further allows to place an electrode for pH detection for sensor calibration purposes.
  • the chamber and means are made of a corrosion resistant material.
  • the present invention is also directed to a method for the determination and quantification of the concentration of an analyte present in a sample that contains it, which is carried out in the system described above, which comprises the following steps:
  • the first measurement is carried out in the presence of a solution at neutral pH.
  • the neutral pH solution is water.
  • stage II in stage II at least two remaining measurements are carried out with calibration standards of known concentration of the analyte to be determined in stage III, at which the coherence time and / or frequency of Rab ⁇ are measured. and the respective concentration is associated to them to obtain a calibration curve.
  • stage III the coherence time and / or Rab ⁇ frequency of the sample is measured, which is interpolated in the calibration curve and the sample concentration is obtained.
  • analyte corresponds to an element, ion and / or chemical compound.
  • the present invention refers to the use of the sensor described above for the determination and quantification of the concentration of an analyte by means of the fluorescence of a diamond with optically active color centers.
  • the analyte to be measured is selected from metals, pesticides, pH, fuels, pollutants, among others.
  • an optically active zone was selected that has been produced with an implantation energy of 5 keV and a dose of 10 14 ions per square centimeter. This generated in the confocal setup illustrated in Figure 5 a fluorescence intensity of approximately 4 million counts per second.
  • Ramsey spectroscopy was performed as a function of the applied magnetic field with a current generator that takes the values -10 and 0 mA.
  • a Rabi spectroscopy was performed as a function of the temporal width of the microwave disturbance.
  • Figure 8 shows the fluorescence signals associated with 7 magnetic resonances in the presence of magnetic fields generated by a coil system. Each curve is associated with the current of a current source used to power the coil system. As can be seen, the maximum sensitivity was obtained for -8 mA, which is where the maximum coherence time is observed. Therefore, to obtain the maximum sensitivity of the sensor, it is necessary to operate at this current in the power source.
  • a calibration curve was generated that measures the optical properties of the sensor for two known concentrations of copper. Specifically, the optical properties of the sensor are obtained by Ramsey resonance spectroscopy applied on the electronic spins of the diamond.
  • Table 1 Figure 9 shows a calibration curve obtained.
  • a control sample of copper was prepared with a concentration of 50 mg / L, which is within the prepared calibration curve, and the Rabi frequency was measured in duplicate.
  • the sensor gave a value of 13.81 MHz, which when interpolated in the calibration curve resulted in a copper concentration value of 48.96 mg / L, so the error with respect to the theoretical value was 2.1 % ( Figure 10).
  • the developed system and in particular the chemical sensor, allow the determination and quantification of the concentration of reactants by means of the fluorescence of a diamond.
  • the sensor allows monitoring the concentration of analytes (elements, ions or chemical compounds) by measuring the fluctuations in the electric field that these generate.
  • the proposed system allows its use in a multiplicity of industries.
  • the sensor in chemical measurements under extreme conditions, can be used in optimizing the extraction of fuels such as gas and oil.
  • fuels such as gas and oil.
  • environmental monitoring it will be useful in detecting heavy metals such as arsenic, lead and cadmium in lakes, seas and rivers and where conditions of high temperatures and pressures are present.
  • the developed system allows to generate measurements with greater accuracy and precision in the study of chemical reactions on a nano-metric scale in different environments such as: surface reactions, industrial catalysis, biocatalysis (food), pharmaceuticals and analytical chemistry.
  • the system and method of the present invention will make it possible to positively impact the increase in copper grade in concentrates and the recovery of elements of interest such as valuable metals (Cu, Mo, Re, U, Ge) , and in the control of impurities.

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

La présente invention concerne un système pour la détermination et la quantification de la concentration d'un analyte présent dans un échantillon, faisant intervenir un capteur à base de diamant qui comporte des centres de couleur optiquement actifs voisins de la surface, une chambre ou cellule qui reçoit le diamant et des moyens d'entrée de l'échantillon dans le système. En outre, la présente invention concerne un procédé de mesure d'un analyte présent dans un échantillon le contenant, lequel procédé est réalisé dans le système mis au point, ainsi que l'utilisation dudit capteur.
PCT/CL2019/050124 2019-11-29 2019-11-29 Système et procédé pour la détermination et la quantification de la concentration d'un analyte, faisant intervenir un capteur à base de diamant optiquement actif, une chambre qui reçoit ledit capteur et des moyens d'entrée de l'échantillon, et utilisation dudit capteur Ceased WO2021102593A1 (fr)

Priority Applications (1)

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PCT/CL2019/050124 WO2021102593A1 (fr) 2019-11-29 2019-11-29 Système et procédé pour la détermination et la quantification de la concentration d'un analyte, faisant intervenir un capteur à base de diamant optiquement actif, une chambre qui reçoit ledit capteur et des moyens d'entrée de l'échantillon, et utilisation dudit capteur

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PCT/CL2019/050124 WO2021102593A1 (fr) 2019-11-29 2019-11-29 Système et procédé pour la détermination et la quantification de la concentration d'un analyte, faisant intervenir un capteur à base de diamant optiquement actif, une chambre qui reçoit ledit capteur et des moyens d'entrée de l'échantillon, et utilisation dudit capteur

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120019242A1 (en) * 2008-11-04 2012-01-26 The University Of Melbourne Method and apparatus for monitoring a property of a sample
WO2012034924A1 (fr) * 2010-09-14 2012-03-22 Element Six Limited Cellule microfluidique et dispositif à résonance de spin destiné à être utilisé avec ladite cellule
WO2018128543A1 (fr) * 2017-01-06 2018-07-12 Rijksuniversiteit Groningen Spectroscopie par résonance magnétique instantanée d'un échantillon
WO2019145407A1 (fr) * 2018-01-26 2019-08-01 Element Six Technologies Limited Matériau en diamant synthétique
WO2019173743A1 (fr) * 2018-03-09 2019-09-12 Somalogic, Inc. Dosage protéomique utilisant des capteurs quantiques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120019242A1 (en) * 2008-11-04 2012-01-26 The University Of Melbourne Method and apparatus for monitoring a property of a sample
WO2012034924A1 (fr) * 2010-09-14 2012-03-22 Element Six Limited Cellule microfluidique et dispositif à résonance de spin destiné à être utilisé avec ladite cellule
WO2018128543A1 (fr) * 2017-01-06 2018-07-12 Rijksuniversiteit Groningen Spectroscopie par résonance magnétique instantanée d'un échantillon
WO2019145407A1 (fr) * 2018-01-26 2019-08-01 Element Six Technologies Limited Matériau en diamant synthétique
WO2019173743A1 (fr) * 2018-03-09 2019-09-12 Somalogic, Inc. Dosage protéomique utilisant des capteurs quantiques

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
KEHAYIAS, P. ET AL.: "Solution nuclear magnetic resonance spectroscopy on a nanostructured diamond chip", NATURE COMMUNICATIONS, vol. 8, no. 188, 2017, XP055829774, DOI: 10.1038/s41467-017-00266-4 *
SCHIRHAGL, R ET AL.: "Nitrogen-Vacancy Centers in Diamond: Nanoscale Sensors for Physics and Biology", ANNU. REV. PHYS. CHEM., vol. 65, 2014, pages 83 - 105, XP055758070, DOI: 10.1146/annurev-physchem-040513-103659 *
STEINERT, S. ET AL.: "Magnetic spin imaging under ambient conditions with sub-cellular resolution", NATURE COMMUNICATIONS, vol. 4, no. 1607, 2013, XP055501085, DOI: 10.1038/ncomms2588 *
WU, Y. ET AL.: "Nanodiamonds for Biological Applications", PHYSICAL SCIENCES REVIEWS, vol. 2017, 4 January 2016 (2016-01-04), XP055829773, DOI: 10.1515/psr-2016-0104 *

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