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    • 专利摘要:
    Chromogenic sensors for amines. A polymeric material comprising a polymer with functional groups of formula (I), wherein r is selected from -nh- and -o-, functional groups of formula (II), or a combination of both groups. Preferably, the polymeric material is in the form of a membrane, film, film or fiber. Process for obtaining this material and its application as a chromogenic amine sensor, especially biogenic amine, both in solution and in the gas phase. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2557332A1
    申请号:ES201400595
    申请日:2014-07-23
    公开日:2016-01-25
    发明作者:Saúl Vallejos Calzada；Pablo MARTÍNEZ ANAYA；Jesús Luis PABLOS LAGARTOS；María Asunción MUÑOZ SANTAMARÍA；María José ROJO CÁMARA；Félix Clemente GARCÍA GARCÍA；Aranzazu MENDÍA JALÓN；José Miguel GARCÍA PÉREZ；Miriam TRIGO LÓPEZ；Felipe Serna Arenas
    申请人:Universidad de Burgos；
    IPC主号:
    专利说明:

    CHROMOGENIC SENSORS FOR AMINAS
    TECHNICAL SECTOR
    The present invention is within the field of polymeric materials. In particular, it refers to a polymeric material with trinitrobenzene groups that can be used as a chromogenic sensor of amines, that is, in the analysis of compounds with amino groups by visual observation of the color change. The polymeric material of the present invention can be used, among others, in the food industry, environmental control and chemical industry. BACKGROUND OF THE INVENTION
    The development of methods of analysis for the determination and quantification of the presence of amines is of the utmost interest, especially of biogenic and food-bearing amines, both in aqueous media and in the gas phase. Among the new analysis procedures are those related to chemical sensors, which give rise to a detectable signal when they interact with the target molecules for whose detection they were designed.
    In this sense, with the objective of facilitating the detection of analytes, the development of systems with chemical substructures that act as chromogenic or fluorogenic sensors is a topic of great scientific and technological relevance (R. Martinez-Mañez, F. Sancenon, Chem. Rev. 2003, 4419-4476; J. Janata, Chem. Rev. 2008, 108, 327-328). Its design, synthesis, and tuning as sensor systems gives rise to new analyte detection technologies characterized by being cheap, for having high sensitivity, and for its simple use that allows its use by non-specialized personnel. Moreover, its preparation or transformation in the form of membrane, film, film, coating or printing as sensing materials is another step in the development of this field (J.
    M. García, F. C. García, F. Serna, J. L. de la Peña, Polym. Rev. 2011, 51,341-390). Thus, the provision of solid films that can be easily handled, both dry and wet, opens up new perspectives for this technology, which are clearly expanded with the development of intelligent fibers with the same objective (JL Pablos, M Trigo-Lopez , F Serna, FC Garcia, JM Garcia, Chem. Comm. 2014, 50, 2484-2487).
    Especially interesting are the chromogenic sensors, since the detectable signal is a color change that, in addition to allowing quantification by a cheap and sensitive technique such as visible ultraviolet spectroscopy, enables the qualitative or semi-quantitative determination of the species of interest to the naked eye , and by non-specialized personnel (J.
    M. García, F. C. García, F. Serna, J. L. de la Peña, Polym. Rev. 2011,51,341-390).
    As a characteristic example of utility, the consumer's assessment of the freshness of a food through the color of an intelligent label can be noted. In addition to this advantage, the evaluation of the evolution in the organoleptic and sanitary quality of food without destruction of the sample, in the packaging itself, stands out. In contrast, the usual complexity of this type of analysis can be indicated, which requires destruction of the sample, treatment of the sample, and use of equipment and specialized personnel (M. Yoshinobu, E. Makoto, JPH0450756, 1992).
    Likewise, the use of intelligent fibers for occupational safety and health and for industrial and environmental control of basic species (amines) in an atmosphere and aqueous media, as well as labels or integrated into the fabrics themselves in clothing (L.) Van Langenhove, C. Hertleer, A. Schwarz, Smart Textiles: An Overview, in Intelligent Textiles and Clothing for Ballistic and NBC Protection, NATO Science for Peace and Security Series
    B: Physics and Biophysics, P. Kiekens, S. Jayaraman (eds.), Springer: Dordrecht, 2012, Ch 6, pp 119-136).
    As examples of related background, sensor polymers for the detection of biogenic amines using complex chromogenic subunits derived from lanthanides (H.-W. Lam, C.-F. Chow, US 2011/0306140, 2011) or aromatic rings have been described condensed with various substituents (L. Zang, Y. Che, US2013 / 0302902, 2013), which were claimed, among other aspects, as films, membranes and fibers or nanofibers. Similarly, intelligent tissues sensitive to amine colorimetrically have been prepared by dispersing pyrimidinium chloride derivatives in commercial viscose fabrics (D. Staneva, R. Betcheva, J.-M. Chovelon, J. Appl. Polym. Sci. 2007, 106, 1950-1956), polymers with diestyrylbenzenes supported on silica gel (J. Kumpf, J.
    Freudenberg, S. T. Schwaebel, U. H. F. Bunz, Macromolecules 2014, 47, 2569-2573), as well as epoxy resins with azo groups for the colorimetric detection of dissolved amines
    (S. Ghosh, e, K. Dey, Supramol. Ehem. 2009, 21, 591-596). As for the detection of vapors, phthalocyanides have been dispersed in various polymers, such as polysiloxanes and vinyl polyalcohol, which have been transformed into amines sensor films (L. Sutarlie, K.-L. Yang, Sens. Actuators B 2008, 134 , 1000-1004), as well as dispersed azoderivatives in nanoparticles of polymers and polymers with riboflavin derivatives for printing on volatile amine sensor paper (T. Soga, Y. Jimbo, K. Suzuki, D. eitterio, Anal. Ehem . 2013, 85, 8973-8978; H. lida, M. Miki, S. Iwahana, E. Yashima, ehem. Eur. J. 2014, 20, 4257-4262).
    In general, the use of polymeric sensor materials offers a series of advantages over low molecular weight organic and inorganic molecular probes, among which we can mention: polymers can be transformed into materials with structural function, that is, in addition to the Sensor behavior can be transformed into a solid usable physical form; polymers have a chemical resistance superior to discrete molecules; a hydrophilic polymeric environment allows the exploitation of hydrophobic sensor groups, therefore not soluble in water, in aqueous media; the chemical anchoring to the polymers prevents the migration of the sensor groups; the sensitivity of the sensor groups is generally increased in solid environments as well as in conjugated polymers; etc.
    DESCRIPTION OF THE INVENTION
    Brief Description of the Invention
    The present invention relates to a polymeric material comprising a polymer with trinitrobenzene groups, as well as to its use as a colorimetric or chromogenic sensor for animals. In this patent application it should be understood that the terms colorimetric and chromogenic are equivalent.
    Additionally, the invention relates to the preparation of the polymeric material by chemical modification of aromatic groups present in starting polymers containing aromatic moieties, in particular phenyl groups. The sensor material of the present invention can be obtained or transformed into different formats, such as membranes, films, fibers or coatings. Likewise, the polymeric material described changes color before chemical compounds containing amino groups, both primary and secondary or tertiary, both in solution and in the gas phase; this color change being clearly visible to the naked eye.
    Additionally, the present invention relates to various applications of the polymeric material described, among which, without limitation, the monitoring of the concentration of compounds with amino groups at the environmental, clinical or industrial level, preferably in the monitoring of aging of foods that in their degradation and decomposition give off compounds with amine groups, even more preferably they give off biogenic amines.
    In especially preferred embodiments, the present invention relates to the development of smart labels that by color scale inform the consumer of the freshness of some foods, preferably fish. It also relates to labels that can be made in the form of fabric, by coating fibers, films or films, coating other types of polymeric and non-polymeric materials by conventional methods, by printing, or other procedures known in the art. Detailed description of the invention
    The invention refers to a new polymeric material with trinitrobenzene subgroups, as well as a process for obtaining it by chemical modification of polymers that can be prepared from acrylic co-monomers, both acrylates and methacrylates, derived from aniline or phenol.
    In a first aspect, the present invention relates to a polymeric material comprising a polymer characterized in that it comprises functional groups of formula (1), where R is selected from -NH-and -0-, functional groups of formula (11) , or a combination of these groups:
    5 In the present invention, "polymeric material" is understood as meaning a material that may consist solely of a polymer with functional groups of formulas (1) and / or (11) in its structure or, in addition to this polymer, may also comprise one or more additional compounds such as additives to modify the properties and / or ease of handling the material.
    1O Preferably the molar ratio of functional groups (1) and / or (11) in the polymer will vary between 1 and 50%, more preferably between 1 and 10%, and even more preferably 1%.
    fifteen Additionally, the term copolymer polymer.bereferinisinventionso muchtoovenhowto
    twenty In a preferred embodiment, the polymeric material of the present invention comprises a polymer that is a crosslinked copolymer. Preferably this copolymer comprises polymerized units of trinitrophenyl (meth) acrylate, trinitrophenyl (meth) acrylamide or trinitrophenylstyrene, together with polymerized units of vinyl monomers, and is crosslinked by a difunctional monomer such as ethylene glycol dimethacrylate, ethylene glycol diacrylate 2 - (acryloylamino) ethyl] acrylamide.
    25 In an even more preferred embodiment, the crosslinked copolymer comprises polymerized units of N-trinitrophenylmethacrylamide (TNFMA), 1-vinyl-2-pyrrolidone (VP) and 2-hydroxyethyl acrylate (2HEA), and the chains are crosslinked by ethylene glycol dimethacrylate (EGDMMA). Even more preferably, the molar ratio between VP: 2HEA: TNFMA: EGDMMA is 75: 24: 1: 10, or alternatively this molar ratio is 67: 23: 10: 10.
    In another preferred embodiment, the polymeric material comprises a linear polymer. In particular, the polymer is linear both in solution and in solid state. Linear polymers, unlike crosslinked ones, can be dissolved in various solvents, as well as used in solution and transformed into films and coatings. Preferably, the polymeric material comprising a linear polymer is soluble in water and / or in an organic solvent such as tetrahydrofuran, acetone, ethyl acetate, dioxane, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, etc. Even more preferably, the polymeric material is a linear water soluble polymer.
    In another preferred embodiment, the linear polymer described in this patent application comprises polymerized units of trinitrophenyl (meth) acrylate, trinitrophenyl (meth) acrylamide, or trinitrophenylstyrene, together with polymerized units of vinyl monomers.
    In an even more preferred embodiment, the linear polymer is a copolymer comprising polymerized units of N-trinitrophenylmethacrylamide (TNFMA), 1-vinyl-2-pyrrolidone (VP) and 2-hydroxyethyl acrylate (2HEA). Even more preferably, the molar ratio between VP: 2HEATNFMA is 75: 24: 1, or alternatively this molar ratio is 67:23:10.
    The polymeric material object of this invention changes color when amines are present in the same medium, either in solution or in the atmosphere, that is, in the gas phase. Preferably it changes color in the presence of biogenic amines. This behavior allows its use in the detection of amines, preferably biogenic, by color changes, that is, in the visible spectrum. So that in addition to a spectrophotometer, the preferred object of the invention can be assessed with the naked eye. Thus, sensors based on these techniques can be developed for the qualitative, semi-quantitative or quantitative detection of amines, preferably biogenic amines, in solution and in the gas phase. The color change due to the presence of biogenic amines can be observed in the different media without any previous treatment of the sample.
    With regard to the present invention, biogenic amines are biologically active amines that are present or naturally generated in food products.
    Additionally, the invention also relates to a solid state polymeric material, preferably in the form of a membrane, film, film or fiber.
    In particular, the polymeric material comprising a solid state crosslinked copolymer, such as membrane, film or coating, is characterized by an ideal combination of mechanical properties, both dry and swollen, that is, with water within the polymeric network. . Specifically, the crosslinked copolymer prepared with 1-vinyl-2-pyrrolidone (66.3 mol%), 2-hydroxyethyl acrylate (22.7 mol%), N-phenylacrylamide (1.0 mol%) Ethylene glycol dimethylmethacrylate (10.0 mol% ) has a Young's modulus and a tensile strength of 830 and 22 MPA, respectively.
    Thus, in another preferred embodiment, the polymeric material of the present invention has a Young's modulus greater than 200 MPA and / or a tensile strength greater than 10 MPA. This makes them especially advantageous materials for the production of solid sensors that can be used, among other areas, in the detection of biogenic amines in all types of samples.
    In another preferred embodiment, the polymeric material described in this patent application is a coating. In particular a coating of fibers or other surfaces.
    The present invention also relates to a process for obtaining the polymeric material comprising a polymer with functional groups (1) and / or (11) described in this patent application. This process is characterized in that it comprises the chemical modification step of a starting polymer with phenyl groups.
    In a preferred embodiment, the process of the invention comprises the nitration of phenyl groups present in the starting polymer, in particular a polymer comprising polymerized units of phenyl (meth) acrylamide, phenyl (meth) acrylate or phenylstyrene. Additionally, these starting polymers can be obtained, as the case may be, by polymerization of (meth) acrylamides derived from aniline or (meth) acrylates derived from phenol,
    or by polymerization of phenylstyrene. Nitration is a common process in organic chemistry. However, it is not known that this reaction has been carried out successfully on a solid material, such as a polymeric membrane.
    In an even more preferred embodiment, the process of the invention comprises the nitration of phenyl groups present in a crosslinked copolymer comprising polymerized units of phenyl (meth) acrylamide, phenyl (meth) acrylate or phenylstyrene, by reaction of the polymer with a sulfonometric solution for at least 2 hours, at a maximum temperature of 2 oC.
    Scheme 1 illustrates the non-limiting process that can be followed to obtain the (meth) acrylic polymer according to especially preferred embodiments of the invention.
    R IVVV ~ -; '
    === <Po
    Various vinyl comonomers H N
    H2S04 / HN03, CH2CI2
    HN •
    AIBN, 60 oC aOC, 12h
    b b
    R = H, CH3
    10 Scheme 1
    The synthesis of the polymers, in particular copolymers with one or more additional vinyl monomers, can be carried out by direct reaction of the vinyl bond with an initiator
    Thermal, both in solution and in block, as shown as an example in Scheme 1. In general the copolymerization of the monomers, as well as copolymerizations with commercial or non-commercial vinyl monomers, can be carried out by any of the procedures described in the literature for the polymerization of multiple bonds.
    In Scheme 1 the structure of two of the preferred co-monomers is shown: N-phenylmethacrylamide (CAS No. 1611-83-2) and N-phenylacrylamide (CAS No. 2210-24-4), which in this example provide the aromatic ring which will be transformed into the sensor subgroup by nitration, although the aromatic moiety can come from any other nitrable monomer.
    25 A preferred example of nitration is shown in Scheme 2. Nitration can be carried out on the polymer in any of its finishes, crosslinked or not. The nitration reaction is exemplified with the model compound N-phenylmethacrylamide (CAS No: 1611-83-2) to obtain the ideal conditions for the finished materials following scheme 2.
    Scheme 2
    As described in the state of the art, the obtaining of polymers with trinitrotoluene subgroups is not carried out by polymerization of vinyl monomers with trinitrotoluene substructures because the presence of these substructures prevents the polymerization process by conventional methods (CF Bjork, WA Gey, JH RObson, R.
    W. Van Dolah, J. Am. Chem. Soco 1953, 75, 1988-1989; R. H. Wiley, L. C. Behr, J. Am. Chem. Soco 1950,72,1822-1824).
    However, the present invention also provides a new process for the preparation of polymeric polymer materials with three nitro groups in a single aromatic ring by an alternative method to unsuccessful attempts carried out so far. According to this procedure, for the polymerization of monomers with the aforementioned trinitrobenzene groups to take place, that is, trinitrophenyl (meth) acrylate, trinitrophenyl (meth) acrylamide, or trinitrophenylstyrene, optionally together with one or more additional vinyl comonomers and / or agents crosslinking agents, the use of unconventional methods is necessary, in particular in the presence of an initiator, for example thermal, such as AIBN, at a temperature above 80 ° C, preferably above 100 ° C, and more preferably at 150 ° C
    The present invention also relates to the use of the polymeric material described in this patent application as a chromogenic sensor of amines, preferably of biogenic amines such as putrescine, spermidine, spermine, cadaverine, tyramine, [3-ethylphenylamine, histamine, tryptamine or trimethylamine.
    As mentioned above, the polymeric material of the present invention changes color in the presence of an amine, whether primary, secondary or tertiary. Therefore, it is very useful in the qualitative, semi-quantitative or quantitative analysis of substances with amino groups by means of spectroscopic techniques, preferably in the visible spectrum, around 550 nm, as well as by direct visual observation.
    The mechanism of recognition of amines is the formation of the Mesisenheimer complex
    (J. Meisenheimer, Justus Liebigs Ann. Chem. 1902, 323, 205-246; F. Terrier, Chem. Rev. 1982,82,77-152).
    In a preferred embodiment, the present invention relates to the use of the polymeric material as intelligent chromogenic labels in the evaluation of food freshness. Thus, as food degradation occurs, especially in fish, partially volatile amino acids are generated that interact with the polymeric material, or smart label, resulting in a visible color change to the naked eye.
    In another preferred embodiment, the present invention also relates to the use of the polymeric material as a sensor for the control of amines in controlled atmospheres and in the environment. Thus, the color change of the polymers in the presence of amine in the atmosphere allows both visual detection of the presence of amino acids and the approximate determination of their concentration, that is, their semiquantification, as well as the exact determination of their concentration. by analytical techniques, such as ultraviolet / visible spectroscopy, that is, its quantification.
    In another preferred embodiment, the present invention also relates to the use of the polymeric material as a sensor for the industrial control of animals in the food industry. Thus, the color change of the polymers in the presence of amine in food allows both the visual detection of the presence of amines and their visual quantification and by spectroscopic techniques such as UV / vis. In this sense, there are amines of biogenic origin and others that are used as additives.
    In another preferred embodiment, the present invention also relates to the use of the polymeric material as a sensor for the industrial control of amines in the chemical industry. The chemical compounds with amino groups are widely used in the chemical industry, to a greater extent than in the food industry, so the sensors that change color in their presence are of maximum interest for their detection and, where appropriate, quantification and concentration control.
    Additionally, a method of analysis of amines, in solution or gas phase, is also described, where the method comprises: a) contacting a sample to be analyzed with the polymeric material described in this patent application, and b) determining the change of color produced by the amine-polymer interaction. This change allows the semiquantitative determination of the concentration visually, as well as the quantitative determination using an analytical technique such as visible ultraviolet spectroscopy.
    The method of the present invention allows to analyze the presence of an amine by direct visual observation, without the need for prior treatment of the sample to be analyzed. Therefore, the method of analysis described is especially advantageous because of its simplicity.
    In preferred embodiments, the present invention also relates to the method of analysis described for the applications specifically mentioned in this patent application. BRIEF DESCRIPTION OF THE FIGURES
    Figure 1. Characterization of N- (2,4,6-trinitrophenyl) methacrylamide. Fig. 1 a: chemical structure; Fig. 1b: infrared spectrum; Fig. 1c: proton magnetic resonance (1H NMR); And Fig. 1d: 13 carbon magnetic resonance (13C NMR).
    Figure 2. Characterization of the membrane (M1) with 10 mol% of N- (2,4,6trinitrophenyl) methacrylamide. Fig. 2a: chemical structure of M1, where the molar ratio is
    X: Y: Z: V = 67: 23: 10: 10; Fig. 2b: infrared spectrum.
    Figure 3. Characterization of the sensor membrane (M1 sen) from the nitration of M1. Fig. 3a: chemical structure of M1 sen, where the molar ratio is X: Y: Z: V =
    67:23: 1O: 1O; Fig. 3b: infrared spectrum.
    Figure 4. Color band formed in the ultraviolet-visible spectrum by adding an equivalent of trimethylamine to a solution of N- (2,4,6-trinitrophenyl) methacrylamide in a 50:50 mixture of dimethylacetamide and buffered water at pH 10.
    Figure 5. Detection of biogenic amines (trimethylamine (TMA) in gas phase by M1sen. Fig. 5a: photograph of samples M1 to M13; Fig. 5b data of the color definition (RGB) of the photograph (digital color definition in terms of intensity of red (R), green
    (G) and blue (B). Values range between O and 255); Fig. 5c: titration curve (moles TMA vs main components); and Fig. 5d: titration curve (Iog (Moles) TMA vs main components).
    Figure 6. Detection of biogenic amines (Cadaverine) in the gas phase by M1 sen. Fig. 6a: photograph of samples M1 to M11; Fig. 6b: color definition data (RGB) of the photograph (digital color definition in terms of intensity of red (R), green (G) and blue (B). Values range from 0 to 255); Fig. 6c: titration curve (cadaverine moles vs. main components); and Fig. 6d: titration curve (Iog (Moles) cadaverine vs. main components).
    Figure 7. M1sen behavior as smart tag. Evolution of food degradation in a real fish sample (Oceanic Bonito, Sardinian Sardinian). Fig. 7a: fresh fish; Fig. 7b: detail of the internal (right) and external (left) sensor with fresh fish; Fig. 7c: degraded fish; Fig. 7d: detail of the internal (right) and external (left) sensor with degraded fish. EXAMPLES
    The following illustrative examples are not intended to be limiting and describe: a) the nitration reaction of the model compound N-phenylmethacrylamide to give rise to N- (2,4,6-trinitrophenyl) methacrylamide; b) the preparation of sensor membranes by polymerization of the N-phenylmethacrylamide monomer with other co-monomers and subsequent nitration; e) the behavior as a colorimetric sensor of these materials in the presence of biogenic amines in the gas phase; d) the behavior as a colorimetric sensor of the membrane against the presence of biogenic amines produced in the decomposition of fish.
    Example 1. Modeling of the nitration reaction in finished materials.
    Transformed polymeric materials containing aromatic rings are transformed into sensor materials by trinitating these rings. Nitration reactions are adjusted to optimal conditions with model compounds, since the work with the materials is complex from the point of view of chemical characterization since most are insoluble, because they are crosslinked, and especially because the molar ratio of Structural or co-structural units capable of being trinitrated is small, preferably 10% or less.
    This example illustrates the preparation of the trinitrated model according to Scheme 2: 1.1 Synthesis of N- (2,4,6-trinitrophenyl) methacrylamide.
    In a three-neck, round bottom flask, 6.2 mmol of N-phenylmethacrylamide (1 g) are dissolved in 25 ml of dichloromethane. The flask is immersed in an ice bath, and 4.75 ml of sulfuric acid (100%) is added dropwise. Next, 1.56 ml of smoking nitric acid is added, ensuring that the temperature of the solution does not exceed 2 ° C. The reaction is stirred at room temperature for 12 hours, and then both phases are separated. The aqueous phase is precipitated over ice water and stirred until a yellow solid forms. The yield was 50%. Characterization: see Figures 1a-1d.
    Example 2. Preparation of M1sen sensor membrane. 2.1. M1 membrane preparation
    A membrane with the composition indicated below was prepared by block copolymerization. Monomers: 1-vinyl-2-pyrrolidone (VP), 2-hydroxyethyl acrylate (2HEA) and N-phenylmethacrylamide, with a 67.23 and 10 molar ratio, respectively. Crosslinker: ethylene glycol dimethacrylate (EGDMMA), with a weight percentage of the rest of the monomers of 10%. AIBN thermal initiator with a weight percentage of 1%. The resulting solution was injected into a mold of silanized crystals, 200 µm thick, in the absence of oxygen, and conditioned in an oven at 60 ° C overnight.
    Characterization: Figures 2a and 2b. Mechanical properties: Young's modulus = 900 MPA; tensile strength = 30 MPA. 2.2. M1sen membrane preparation
    The M1 membrane was cut into 10 mm diameter discs, and these in turn were immersed in an Erlenmeyer flask containing sulfontric solution (3 parts of 100% sulfuric acid and one part of smoking nitric acid) for 2 hours at 20 ° C. The discs were then washed first with dichloromethane, and then with acetone until the acid residues were completely removed. Finally they were immersed in water overnight and then air dried. Characterization: Figures 3a and 3b.
    Example 3. Preparation of M2sen sensor membrane. 3.1. M2 membrane preparation
    A membrane with the composition indicated below was prepared by block copolymerization. Monomers: VP, 2HEA and N-phenylmethacrylamide, with a 74, 25 and 1 molar ratio, respectively. Crosslinker: EGDMMA, with a weight percentage of the rest of the 10% monomers. AIBN thermal initiator with a weight percentage of 1%. The resulting solution was injected into a mold of silanized crystals, 200 IJm thick, in the absence of oxygen, and conditioned in an oven at 60 ° C overnight. 3.2. M2sen membrane preparation
    The M2 membrane was cut into 10 mm diameter discs, and these in turn were immersed in an Erlenmeyer flask containing sulfontric solution (3 parts of 100% sulfuric acid and one part of smoking nitric acid) for 2 hours at 20 ° C. They were then washed first with dichloromethane, and then with acetone until the acid residues were completely removed. Finally they were immersed in water overnight and then air dried.
    Example 4. Colorimetric detection of biogenic amines in gas phase using the M1sen membrane.
    This example illustrates the behavior as colorimetric sensor materials, the synthesis of which is illustrated in Example 2, towards biogenic amines in the gas phase.
    The addition of increasing amounts of biogenic amines (putrescine, spermidine, spermine, cadaverine, tyramine, 3-ethylphenylamine, histamine, tryptamine and trimethylamine) to hermetically sealed containers and containing M1sen membrane discs cause color changes in the material, which corresponds to an absorption in Uv / vis in the environment of 550 nm as shown in Figure 4. As an example, two gas phase titrations were carried out with trimethylamine and cadaverine as illustrated in Figures 5 and 6 respectively. For the cadaverine the detection limit reached was 1.45 ppm, and the quantification limit of 4.4 ppm, and for trimethylamine these limits were 9.2 and 28.0 ppm, respectively. In this calculation ppm expresses mg / L (milligrams of amine per liter of air).
    Example 5. Behavior of M1sen as an intelligent label in the face of aging of a real sample of fish (oceanic beautiful, Sardinian Sardinian).
    250 grams of the sample of fresh fish (Bonito oceanic, Sarda sarda; purchased at the local Burgos Market) were placed in a food tray (polyethylene tray, ethylene vinyl alcohol and polystyrene brand "Sanviplast"). A sensor disc of M1 sen, prepared according to Example 2, was adhered to one of the internal walls of the tray and sealed under vacuum (34% vacuum) within a food film (cast polyamide film / brand polyethylene "Vacioplast Salamanca"). Another sample of the M1 sen membrane was placed as a reference in the outer wrap. The sample was kept at 25 ° C for one week, during which time digital photographs were taken to see the evolution of the color of the M1 sen membrane, related to the presence of amines that are generated in the fish decomposition processes , and as shown in Figure 7.
    权利要求:
    Claims (14)
    [1]
    1. A polymeric material comprising a polymer characterized in that it comprises
    5 functional groups of formula (1), where R is selected from -NH-and -0-, functional groups of formula (11) or a combination of these groups:
    2. Polymeric material according to claim 1, wherein the polymer is a crosslinked copolymer.
    [3]
    3. Polymeric material according to claim 2, comprising polymerized units of
    trinitrophenyl (meth) acrylate, trinitrophenyl (meth) acrylamide or trinitrophenylstyrene, together with polymerized units of vinyl monomers, and is crosslinked by a difunctional monomer.
    [4]
    4. Polymeric material according to claim 3, comprising polymerized units of N-trinitrophenylmethacrylamide (TNFMA), 1-vinyl-2-pyrrolidone (VP) and 2-hydroxyethyl acrylate (2HEA), and the chains are crosslinked by ethylene glycol dimethacrylate (EGDMMA).
    [5]
    5. Polymeric material according to claim 1, wherein the polymer is linear and the material is water soluble.
    [6]
    6. Polymeric material according to claim 5, comprising polymerized units of
    Trinitrophenyl (meth) acrylate, trinitrophenyl (meth) acrylamide or trinitrophenylstyrene, together with polymerized units of vinyl monomers.
    [7]
    7. Polymeric material according to claim 6, comprising polymerized units of
    N-trinitrophenylmethacrylamide (TNFMA), 1-vinyl-2-pyrrolidone (VP) and 2-hydroxyethyl acrylate 30 (2HEA).
    [8]
    8. Polymeric material according to any one of claims 1 to 7, in the form of a membrane, film, film or fiber.
    [9]
    9. Process for obtaining the polymeric material as described in any one of claims 1 to 8, characterized in that it comprises the chemical modification of a starting polymer comprising phenyl groups.
    [10]
    10. Process for obtaining the polymeric material according to claim 9, wherein the chemical modification is the nitration of phenyl groups present in the starting polymer.
    [11]
    eleven. Process for obtaining the polymeric material as described in any one of claims 3, 4, 6, 7 or 8, characterized in that it comprises the polymerization of trinitrophenyl (meth) acrylate, trinitrophenyl (meth) acrylamide or trinitrophenylstyrene monomers, in the presence of a thermal initiator, at a temperature above 80oe.
    [12]
    12. Use of the polymeric material described in claims 1 to 8, as a chromogenic amines sensor.
    [13]
    13. Use according to claim 12, wherein the amine is a biogenic amine.
    [14]
    14. Use according to any one of claims 12 or 13, as a chromogenic sensor in the evaluation of food freshness, as a sensor for the control of amines in controlled atmospheres and in the environment, sensor for the industrial control of amines in the food industry, or sensor for the industrial control of amines in the chemical industry.
    [15]
    fifteen. Amines analysis method characterized in that it comprises:a) contact a sample to be analyzed with the polymeric material described inany one of claims 1 to 8, andb) determine the color change produced by the amine-polymer interaction.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20040072359A1|2002-09-19|2004-04-15|Southard Glen E.|Sensor for monitoring an analyte|ES2692432A1|2017-06-02|2018-12-03|Universidad De Burgos|Amine fluorometric and colorimetric sensors |
    TWI714821B|2018-01-24|2021-01-01|國立高雄大學|Method and device for detecting biogenic amine of food materials|
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