• 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:
    The object of the invention is a holographic sensor for detection of adulterants in essential oils. It consists of the use of a holographic recording technique and a photopolymer, in combination with the essential oil from which it is wanted to evaluate its possible adulteration. The sensor is able to detect different types of adulterants qualitatively. You can also make a quantitative measurement of the degree of adulteration of an essential oil by pre-calibrating the sensor for a particular adulterant. It can be miniaturized and manufactured at a low cost compared to traditional methods of analysis such as gas chromatography and high performance liquid chromatography. The sensor can be used by unqualified personnel. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2622336A1
    申请号:ES201730488
    申请日:2017-03-30
    公开日:2017-07-06
    发明作者:Manuel Francisco Ortuño Sánchez；Sandra FENOLL GAMBIN；Sergi Gallego Rico；Andrés MÁRQUEZ RUIZ；Augusto BELÉNDEZ VÁZQUEZ；María Inmaculada PASCUAL VILLALOBOS
    申请人:Universidad de Alicante；
    IPC主号:
    专利说明:

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    HOLOGRAPHIC SENSOR FOR DETECTION OF ADULTERANTS IN ESSENTIAL OILS AND METHOD OF OBTAINING SUCH SENSOR
    description
    Holographic sensor for detection of adulterants in essential oils and method of obtaining said sensor.
    field of the invention
    The present invention relates to a holographic sensor for detecting adulterants in essential oils and the method of obtaining said sensor. Essential oils are used in a large number of consumer products, from food and aromas for food, to cosmetics and perfumery.
    STATE OF THE PREVIOUS TECHNIQUE
    Essential oils are mixtures of intensely aromatic substances obtained from plants, flowers, fruits, wood, resins or roots by various physical processes such as distillation, solvent extraction or compression. They can reach a very high price in the market given the small percentage in which they are found in the plant species from which they come.
    To check its characteristics, different physical parameters such as density, viscosity, boiling point, color, etc. are used. However, these simple techniques do not provide conclusive data since essential oils show variations due to their natural origin and the fact that hydric, nutritional, climatological factors or the species of the plant can influence this variability. In addition, there are adulterant potentials that are not detectable by measurements of these parameters.
    To guarantee the purity of essential oils, sophisticated chemical analysis techniques such as gas chromatography or high-resolution Kquida chromatography are used. These techniques have the disadvantage of the high cost of the equipment, the large space required since it is very bulky machines, and the need for highly qualified technical personnel to perform the analysis and interpretation of the results.
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    At present, the development of low-cost, portable and easy-to-use sensors for the detection of substances and adulterants is subject to great inventive activity.
    The invention IN3624MU2015 (A) relates to a sensor for detecting adulterants in fish oil. Other patents cover a wide range of natural products or derivatives in which adulterations are detected. Thus, document CN103399091 (A) deals with the adulteration of milk proteins, the invention CN203224450 (U) refers to a kit for detection of adulteration in sesame oil, patent TWI261070 (B) refers to the detection of adulteration in juices from the processing of citrus. Patent CN104697954 (A) describes an apparatus for detecting adulterations in camellia oil by using electromagnetic radiation in the near infrared. None of the matrices mentioned in these studies are comparable to essential oils: neither milk, nor juice, nor sesame or camellia oils. These oils are vegetable oils that contain mainly fatty acids, unlike the essential oils referred to in the present invention. Therefore, none of the previous inventions solves the problem of detecting adulterants in essential oils.
    As for the detection methods, none of the previous inventions uses holographic techniques. If the patent DE10147447 (A1) does that it refers to a holographic sensor to recognize moisture on a glass of a motor vehicle. In recent years, a great research activity has been developed worldwide in relation to holographic sensors. Numerous publications show the application of holographic techniques for the development of temperature, humidity and different types of analyte sensors. Some examples are the works of Yetisen, AK (2014), Naydenova, I. (2009), Leite, E. (2010), Shi, J. (2007), Blyth, J. (1996) or Bianco, G. ( 2015). In the search carried out, no study has been found in which holographic techniques are used to detect adulterants in essential oils or to measure the quality of an essential oil. In addition, there are recent publications such as those by M. Moirangthem (2016) and D.J. Mulder (2014), which use polymers and liquid crystals in optical sensors and to detect metal ions, with techniques different from those used in the present invention, in addition to not being related to essential oils. Therefore, no study shows the application of holographic techniques to the determination of adulterants in essential oils.
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    Essential oils are used in a large number of consumer products, from food and aromas for food, to cosmetics and perfumery. The number of companies that use essential oils as raw material for their products is very high, however, most do not have the economic resources and qualified personnel necessary to perform analysis using high-resolution Kquida chromatography or gas chromatography. Therefore, a practical way is necessary to determine adulterations in essential oils without the need for specialized personnel or an expensive investment in analysis equipment. At the same time, it is required that analyzes can be performed quickly and at a low cost per analysis.
    EXPLANATION OF THE INVENTION
    It is necessary in the light of the above, to develop a new technology that can easily detect adulterations in high-cost products such as essential oils.
    Although the holographic techniques and photopolymers used in the cited studies are similar, the novelty introduced in the present invention consists in using the essential oil of which it is intended to measure its degree of adulteration as a component of the photopolymer used as a recording material in the art. holographic That is to say, a standard formulation of a photopolymer is chosen that is compatible with the essential oil from which its degree of adulteration is to be measured. The formulation of that photopolymer is then modified by adding the essential oil as an additional component thereof. The modification that introduces the essential oil in the photopolymer makes it possible to detect the degree of adulteration of the essential oil by means of the holographic technique used. The essential oil modifies the viscosity of the photopolymer and / or the size of the holes in the polymer network formed by using the holographic technique. The presence of adulterants in the essential oil affects the viscosity and / or size of the holes in the polymer network, allowing the holographic technique to detect if the essential oil is adulterated and to what degree.
    Therefore, in a first aspect, the present invention relates to a sensor that uses a holographic recording technique, to detect adulterations in essential oils. The sensor consists of at least two laser beams that emit electromagnetic radiation within the visible spectrum, with a wavelength within the range 380-780
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    nanometers The beams affect a point where the modified photopoimer is placed on a glass or plastic support, forming a solid or solid film. Radiometers or semiconductor light detectors are located on both sides of the point of incidence of the laser beams to detect the diffracted, transmitted and reflected light. The relationship between the diffracted light and the incident light makes it possible to determine if the essential oil incorporated in the photopoimer is adulterated, knowing previously the relationship obtained with the pure essential oil.
    Given the high sensitivity of holographic techniques, it is also possible to determine the degree of adulteration, that is, to perform a quantitative analysis, if the sensor is previously calibrated for a specific adulterant. Changes in the ratio of light beams are related to the percentage of adulterant in the essential oil.
    The modified photopolymer referred to above is a mixture of the following components:
    - Polyfunctional acrylic monomer, selectable from the following, but not limited: dipentaerythritol penta- / hexa acrylate, pentaerythritol tetra acrylate, trimethylpropane triacrylate, with a concentration of 10-90%.
    - Pneumatic liquid crystal with a concentration of 20-60%.
    - Sensitizing dye, selectable from the following, but not limited: ethyl eosin, eosin Y, eosin B, methylene blue, riboflavin, floxin B, erythrosine, rose flare, with a concentration of 0.01-10.00% .
    - Polymerization initiator, selectable from the following, but not limited: amino acids such as N-phenyl glycine, organic amines, with a concentration of 0.1-10.0%.
    - Essential oil on which you want to determine the degree of adulteration, with a concentration of 0.1-50.0%.
    In a particular embodiment, a solvent and / or a surfactant can be added to facilitate homogenization of the above components. The solvent is selectable from the following, but not limited: an organic linear chain acid with a number of carbon atoms between 5 and 12. The concentration may be between 0-30%. The surfactant is preferred among those that are non-ionic, although some ionic surfactants could be used. The concentration is 0-20%.
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    In a second aspect, the present invention also relates to the method for obtaining the holographic sensor for determination of adulterants in essential oils, which comprises the following steps:
    - Realization of a grid of threaded holes in the form of a grid, on a support plate with an area between 2 and 200 cm2, depending on the size and type of laser used
    - Fixing the following components on the grid-shaped mesh:
    - Registration laser
    - Reconstruction or reading laser
    - Two radiometers
    - Electronic data logger circuit
    - Connection interface to computer, mobile phone or tablet
    - Support of the photopolymer: two glass or plastic plates, one fixed and one mobile or the two mobile that are joined by a hinge mechanism, allowing to form a photopolymer film from a drop when applying a pressure using a micrometric screw system and spring or by a metal plate with adjustable curvature.
    - Anchoring of the photopolymer support: a piece of plastic or metal that is screwed to the support plate and allows the rapid coloration and extraction of the photopolymer support without removing screws.
    - Modified photopolymer
    - Union of the components to the support plate by means of plastic or metal parts screwed to the holes of the plate, which allow the positioning and adjustment of each component in the correct position.
    The present invention allows detecting the adulteration of an essential oil providing the following advantages:
    - the detection of adulterants is carried out quickly;
    - the sensor is capable of detecting adulterants with different physicochemical properties and not only a certain type of adulterant, that is, it can detect different types of adulterants without having to modify the sensor;
    - It can also be calibrated for a given adulterant so that a quantitative estimation of adulteration with an essential oil can be made;
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    - The sensor can work with essential oil samples of the order of microliters.
    Likewise, the determination of the present invention allows to overcome inconveniences in the aspects listed below:
    - It has a lower cost than the methods currently used for this task: gas chromatography and high resolution Kquida chromatography;
    - It can be miniaturized, with the advantage of having a portable sensor of small size;
    - It can be managed by personnel with a minimum training without the need to be a senior expert in chromatography.
    PREFERRED EMBODIMENT OF THE INVENTION
    Determination of adulterants in essential oils is carried out by holographic techniques in which laser beams emitting electromagnetic radiation within the visible spectrum are used, with a wavelength within the 380-780 nanometer range. The beams are filtered and adjust its diameter between 0.1-12.0 mm. The beams combine to form an angle between them between 10-350 degrees. The beams affect a point where the modified photopolymer is placed on a glass or plastic support, forming a liquid film with a thickness of 1-200 micrometers by applying a pressure of 0.01-100 millipascals.
    EXAMPLE 1: Sensor to detect adulterants in chamomile essential oil
    The sensor consists of a 532 nm laser whose beam is filtered and expanded to a diameter of 5 mm. This beam is divided into two forming an angle of 32 degrees. Additionally a 650 nm laser also filtered and with a diameter of 5 millimeters is combined with the previous ones forming an angle of 19.7 degrees with the bisector that form the other two beams.
    The beams affect a point where 16 microliters of the photopolymer are placed, which is described below on a glass plate, applying a pressure of 0.3 millipascals. Two radiometers located behind the point of incidence of the laser beams detect the light diffracted and transmitted by the photopolymer and the essential oil sample. The relationship between diffracted light intensity and the incident allows
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    Determine if the essential oil is adulterated. For this, the aforementioned relation for pure essential oil must be previously known.
    The photopoKmero is a mixture of the following components:
    Penta- / dipentaerythritol hexa acrylate 40%
    30% nematic liquid crystal
    0.05% ethyl eosin
    N-phenyl-glycine 0.50%
    Octanoic acid 9.45%
    20% chamomile essential oil
    EXAMPLE 2: Sensor for quantitative determination of adulterant triethyl citrate in peppermint essential oil
    The sensor consists of a 532 nm laser whose beam is filtered and expanded to a diameter of 6 mm. This beam is divided into two forming an angle of 32 degrees. Additionally a 632.8 nm laser also filtered and with a diameter of 6 millimeters is combined with the previous ones forming an angle of 19.1 degrees with the bisector formed by the other two beams.
    The beams affect a point where 20 microliters of the photopoimer is described on a glass described below, which includes a sample of 10 microliters containing varying amounts of essential oil of peppermint and triethyl citrate, by applying a pressure of 0 , 6 millipascals. Two radiometers located after the point of incidence of the laser beams detect the diffracted light transmitted by the photopoimer and the essential oil samples with triethyl citrate. Representing the relationship between the intensity of diffracted light and the incident against the concentration of triethyl citrate, a mathematical adjustment equation is obtained that allows to obtain the sensor calibration. The process is subsequently repeated with a sample of adulterated essential oil with an unknown amount of triethyl citrate. The comparison of the relationship between the intensity of diffracted light and the incident with the mathematical calibration equation obtained above allows to determine the percentage of triethyl citrate in the adulterated essential oil sample.
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    The photopoKmero is a mixture of the following components:
    Penta- / dipentaerythritol hexa acrylate 35.33%
    Crystal Knematics 24.00%
    0.03% ethyl eosin
    N-phenyl glycine 0.31%
    Octanoic acid 7.00%
    Peppermint essential oil with triethyl citrate in variable proportion 33.33%
    EXAMPLE 3: Sensor to detect adulterant triacetin in rose essential oil
    The sensor consists of a 532 nm laser whose beam is filtered and expanded to a diameter of 5 mm. This beam is divided into two forming an angle of 32 degrees. Additionally, a 650 nm laser also filtered and with a diameter of 5 miKmeters is combined with the previous ones forming an angle of 19.7 degrees with the bisector formed by the other two beams.
    The beams affect a point where 20 microliters of the modified photopoimer is described on a glass described below, applying a pressure of 0.4 millipascals. Two radiometers located after the point of incidence of the laser beams detect the light diffracted and transmitted by the photopoimer and the essential oil sample. Subsequently the process is repeated with a sample of essential oil of rose adulterated with triacetin and with a sample of which it is not known whether it is adulterated or not. The comparison of the relationship between the intensity of diffracted light and the incident obtained for each sample makes it possible to determine if the essential oil is adulterated.
    The photopolymer is a mixture of the following components:
    Penta- / dipentaerythritol hexa acrylate 40%
    35% nematic liquid crystal
    0.05% ethyl eosin
    N-Methyldiethanolamine 0.4%
    Octanoic acid 9.55%
    Rose essential oil 15%
    权利要求:
    Claims (20)
    [1]
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    1. Holographic sensor for determination of adulterants in essential oils formed by at least two laser beams that emit electromagnetic radiation within the visible spectrum with a wavelength within the 380780 nm range, a photopolymer located on a support where the laser beams and radiometers or semiconductor light detectors that are located on both sides of the point of incidence of the laser beams to detect the diffracted and reflected light, characterized in that the photopolymer used is a mixture of:
    - polyfunctional acrylic monomer,
    - nematic liquid crystal,
    - sensitizing dye,
    - polymerization initiator
    - and essential oil which wants to determine the degree of purity.
    [2]
    2. Holographic sensor for determination of adulterants in essential oils
    according to claim 1, wherein the polyfunctional acrylic monomer is selectable from the following, but not limited: dipentaerythritol penta- / hexa acrylate, pentaerythritol tetraacrylate or trimethylpropane triacrylate.
    [3]
    3. Holographic sensor for determination of adulterants in essential oils according to claim 2, wherein the polyfunctional acrylic monomer is dipentaerythritol penta- / hexa acrylate.
    [4]
    4. Holographic sensor for determination of adulterants in essential oils according to claim 1, wherein the concentration of the polyfunctional acrylic monomer is between 10-90%.
    [5]
    5. Holographic sensor for determination of adulterants in essential oils
    according to claim 1, where the concentration of the nematic liquid crystal is
    between 20-60%.
    [6]
    6. Holographic sensor for determination of adulterants in essential oils according to claim 1, wherein the sensitizing dye is selectable from the following, but not limited: ethyl eosin, Eosin Y, eosin B, methylene blue,
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    Riboflavin, Floxin B, Erythrosine or Rose Bengal.
    [7]
    7. Holographic sensor for determination of adulterants in essential oils according to claim 6, wherein the sensitizing dye is ethyl eosin.
    [8]
    8. Holographic sensor for determination of adulterants in essential oils according to claim 1, wherein the concentration of the sensitizing dye is between 0.01-10.00%.
    [9]
    9. Holographic sensor for determination of adulterants in essential oils according to claim 1, wherein the polymerization initiator is selectable from the following, but not limited: amino acids such as N-phenyl glycine or organic amines.
    [10]
    10. Holographic sensor for determination of adulterants in essential oils according to claim 9, wherein the polymerization initiator is N-phenyl glycine.
    [11]
    11. Holographic sensor for determination of adulterants in essential oils according to claim 1, wherein the concentration of the polymerization initiator is comprised between 0.1-10.0%.
    [12]
    12. Holographic sensor for determination of adulterants in essential oils according to claim 1, wherein the photopolymer formulation comprises a solvent and / or a surfactant.
    [13]
    13. Holographic sensor for determining adulterants in essential oils according to claim 12, wherein the solvent is a linear chain organic acid with a number of carbon atoms between 5 and 12.
    [14]
    14. Holographic sensor for determination of adulterants in essential oils according to claim 13, wherein the solvent is octanoic acid.
    [15]
    15. Holographic sensor for determination of adulterants in essential oils according to claim 12, wherein the solvent concentration is comprised between 0-30%.
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    [16]
    16. Holographic sensor for determination of adulterants in essential oils according to claim 12, wherein the surfactant can be ionic or non-ionic.
    [17]
    17. Holographic sensor for determination of adulterants in essential oils according to claim 16, wherein the surfactant is non-ionic type.
    [18]
    18. Holographic sensor for determination of adulterants in essential oils according to claim 12, wherein the concentration of the surfactant is between 0-20%.
    [19]
    19. Method for obtaining the holographic sensor for determination of adulterants in essential oils described in claim 1, comprising the following steps:
    - Realization of a grid of threaded holes in the form of a grid, on a support plate with an area between 2 and 200 cm2, depending on the size and type of laser used
    - Fixing the following components on the grid-shaped mesh:
    - Registration laser
    - Reconstruction or reading laser
    - Two radiometers
    - Electronic data logger circuit
    - Connection interface to computer, mobile phone or tablet
    - Support of the photopolymer: two glass or plastic plates, one fixed and one mobile or the two mobile that are joined by a hinge mechanism, allowing to form a photopolymer film from a drop when applying a pressure using a micrometric screw system and spring or by a metal plate with adjustable curvature.
    - Anchoring of the photopolymer support: a piece of plastic or metal that is screwed to the support plate and allows the rapid coloration and extraction of the photopolymer support without removing screws.
    - Modified photopolymer as described in claim 1.
    - Union of the components to the support plate by means of plastic or metal parts screwed to the holes of the plate, which allow the positioning and adjustment of each component in the correct position.
    [20]
    20. Use of the holographic sensor described according to claim 1 for determination of adulterants in essential oils.
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    同族专利:
    公开号 | 公开日
    WO2018178435A1|2018-10-04|
    ES2622336B2|2017-10-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2000028354A2|1998-10-16|2000-05-18|Digilens, Inc.|Light source locator using switchable holograms|
    CN204314215U|2014-12-24|2015-05-06|华东交通大学|A kind ofly judge based near infrared light line spectrum the pick-up unit that tea oil is adulterated|
    CN105424660A|2015-11-02|2016-03-23|天津商业大学|Method for quantitatively detecting vegetable oil adulteration|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201730488A|ES2622336B2|2017-03-30|2017-03-30|HOLOGRAPHIC SENSOR FOR DETECTION OF ADULTERANTS IN ESSENTIAL OILS AND METHOD OF OBTAINING SUCH SENSOR|ES201730488A| ES2622336B2|2017-03-30|2017-03-30|HOLOGRAPHIC SENSOR FOR DETECTION OF ADULTERANTS IN ESSENTIAL OILS AND METHOD OF OBTAINING SUCH SENSOR|
    PCT/ES2018/070153| WO2018178435A1|2017-03-30|2018-03-01|Holographic sensor for detection of adulterants in essential oils and method of obtaining such sensor|
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