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    • 专利摘要:
    Amine fluorometric and colorimetric sensors. Copolymers of formula (I) are described, {IMAGE-01} and also fibers, or fabrics, coated therewith. Said copolymers and materials comprising them are applicable as colorimetric sensors of amines in gas phase, and in particular of biogenic amines. Said applications include their use, for example, as an intelligent freshness label in food containers with a controlled atmosphere such as packaged fish. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2692432A1
    申请号:ES201730765
    申请日:2017-06-02
    公开日:2018-12-03
    发明作者:Saúl Vallejos Calzada；José Miguel GARCÍA PÉREZ；Félix GARCÍA GARCÍA；Miriam TRIGO LÓPEZ；Ana SANJUAN CORTÁZAR；Blanca Sol PASCUAL PORTAL；Felipe Serna Arenas
    申请人:Universidad de Burgos；
    IPC主号:
    专利说明:

    Fluorimetric and calorimetric sensors of amines.
    OBJECT OF THE INVENTION:
    The present invention relates to the preparation of new copolymers that act as fluorometric and calorimetric sensors in the gas phase, of amino acids, and in particular of biogenic amines, such as putrescine or cadaverine. The copolymers described are polyamides obtained by polycondensation of two or more monomers, among which one of said is a monomer capable of detecting said amines. Such copolymers can be presented in the form of membranes and can also be used as a coating for textiles.
    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 amines, in the food sector.
    In particular, biogenic amines are amines formed by the degradation of amino compounds, such as amino acids, found in food or other organic matter, by the action of enzymes generated by microorganisms.
    In recent years, the use of smart tags in various products and services has become increasingly frequent, with the aim of providing the end user and / or consumer with certain information on that product that is registered on the label in the form of a color change, fluorescence, or any other physical and / or chemical property that is visible to the naked eye. For example, the control of the freshness of the fish through an intelligent label present on the package, which changes color and fluorescence as the food deteriorates.
    Until now, the expiration date (or preferred consumption date) is the only information available to the consumer to know the useful life of a food, with all the risks assumed with this methodology, given that, on the one hand, a food may have been damaged by external reasons (such as the breakage of the cold chain) and yet not exceeded the preferred consumption date. On the other hand, it could also be the opposite case, in which the food was in a correct state for its intake, but it would have exceeded its preferred consumption date. For all this, with the use of an intelligent label of freshness in the container, food poisoning could be avoided
    in poor condition, but it could also extend the shelf life of a food that, although it has exceeded its expiration date, is still suitable for consumption.
    The most recognized and proven method for the determination of biogenic amines in fish is high performance liquid chromatography (HPLC). This method requires a digestion of the fish sample, several chemical reagents that make the analysis possible and, above all, an analytical equipment that requires a very high initial investment, as well as very high maintenance costs.
    Thus, the development of sensors such as those described above is a topic of great scientific and technological news. In general, the use of polymeric sensing materials offers a number of advantages over low molecular weight organic and inorganic molecular probes. Among these advantages can be mentioned: polymers can be transformed into materials with structural function, that is, in addition to the sensor behavior they can be transformed into a usable solid 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.
    In particular, J. L. Pablos, S. Vallejos, A. Muñoz, M. J. Rojo, F. Serna, F. C. García, J. M. Garda, ehem. Eur. J. 2015, 21, 8733-8736, and patent P201400595 describe polymers that detect amines by calorimetric methods. However, these polymers have certain drawbacks, given the difficulty of obtaining synthetic fibers from them and therefore have disadvantages when including them or manufacturing materials for use in industrial applications, such as the manufacture of smart tags.
    Therefore, it is of interest to find alternative amines sensing materials to those already known that can also be handled easily, can be used in coatings that can be applied to different textiles, or even in the manufacture of sensor fibers.
    BRIEF DESCRIPTION OF THE INVENTION
    The present invention relates to a copolymer of formula (1) comprising at least one unit X:
    x (1)
    where
    Ra is a group independently selected from alkyl, aryl or heteroaryl; Rb is a group independently selected from alkyl, aryl or heteroaryl; Zl and Z2 are each and independently H or halogen, and where Zl and Z2 cannot be both H.
    Another aspect of the invention relates to a textile fiber coated with at least one copolymer of the present invention.
    The invention also relates to the use of a copolymer of the present invention, or of the textile fibers described above, for the detection of amines in the gas phase.
    Another embodiment of the present invention relates to a method of determining the level of deterioration of a food comprising:
    (to) introducing a copolymer of the present invention, or a material comprising it, into a container containing said food and where said copolymer, or the support comprising it, is not in direct contact with the food,
    (b) detecting and / or quantifying in said copolymer, or in the material comprising it, at least one gas phase biogenic amine produced by said food, by at least one method independently selected from:
    the use of a chromatic scale comprising at least two different color shades, where each of said shades defines a concentration range of said amines; the use of the RGB parameters of a digital photograph; or the use of spectroscopic techniques.
    The present invention also relates to a compound of formula (VIII):
    (VIII) where Rb is independently selected from alkyl, aryl or heteroaryl; Zl and Z2 are each independently and H or halogen, and where Zl and Z2 cannot both be H. Another embodiment of the invention relates to a method of obtaining a copolymer of formula (1) of the present invention , wherein said method comprises performing a polycondensation of the compound of formula (VIII) described above, with at least one other monomer comprising two amino groups of formula H2N-R ...- NH2, where Ra is independently selected from an alkyl group, aryl or heleroaryl. Additionally, the present invention also relates to the use of the compound of formula (VIII), for the detection of amines in the gas phase. Another embodiment of the invention relates to the use of the compound of formula (VIII) for the manufacture of polymers for the detection of amines in the gas phase. 15 DESCRIPTION
    The present description thus refers to a copolymer of formula (1) comprising at least one unit X:
    H H O O
    ,, -. lL
    -j-N-R, -N Rb-1L - t ~
    I
    ~
    Z1 Z2
    X (1)
    where Ra is a group independently selected from alkyl, aryl or heteroaryl; Rb is a group selected from alkyl, aryl or heteroaryl;
    Z1 and Z2 are each and independently H or halogen, and where Z, and Z2 cannot both be H.
    In a preferred embodiment Z1 is H and Z2 is Br.
    5 In a preferred embodiment Ra is an aryl group.
    In a more preferred embodiment Ra is an aryl group that is independently selected from:
    or
    F3C CF3 f) C'Q
    V ~ yy
    Noel
    In a more preferred embodiment Ra is phenyl.
    For the purposes of the present invention the term "alkyl" refers to a linear or branched hydrocarbon aliphatic chain of 1 to 20 carbons which may or may not have different substitutions.
    For the purposes of the present invention the term "aryl" refers to a group that may comprise one or more hydrocarbon aromatic rings substituted or unsubstituted with
    15 other functional groups. Such substitutions with other functional groups comprise, but are not limited to alkyl, haloalkyl, arylalkyl, sulfone, nitro, halogen, ether, carbonyl, alcohol, ester, amine, thiol, cornflower groups.
    For the purposes of the present invention the term "heteroaryl" refers to a group that may comprise one or more aromatic rings comprising one or more heteroatoms.
    Said copolymers comprise, covalently linked to the main chain, structures or groups of formula (IX) derived from 1,8-naphthalimide substituted with at least one halogen group,
    5 (IX)
    and where groups (IX) act as amines sensors, and in particular biogenic amines. Also, the present invention refers to the applications that are obtained from these copolymers in different fields.
    The copolymers of formula (1) of the present invention are polyamides, that is, they are
    10 polymers comprising amide groups as a link between the different monomers they comprise. Since the polyamides described in the present invention are copolymers, for the purpose of the present invention they are called copolyamides.
    The term "polymer" refers to a molecule that comprises one or more structural units that are repeated successively. These units are called monomers. The
    Polymers are obtained by repetitive binding of said monomers by reacting reactive groups (or polymerizable groups) present in each of the monomers, in a process called polymerization.
    The term "copolymer" refers to a polymer comprising at least two different monomers.
    For the purposes of the present invention the term "comprises" includes the term "consists".
    The present invention also relates to the preparation of said copolymers of formula (1), both in the form of a dense or porous membrane, and a coating. The copolymers of formula (1) described in the present invention are in the form of films or solid membranes (which can be dense or porous), and can also be used as a coating
    25 of fibers (such as a cotton fabric). The present invention therefore relates to the copolymers of formula (1), their membranes, and fibers coated by said copolymers.
    The copolymers of formula (1) of the present invention act as chromogenic and / or fluorogenic sensors, that is, they are materials that change color and / or fluorescence in the presence of certain substances. These changes occur when exposing the sensors to amines in the gas phase. The copolymers of formula (1) of the present invention are therefore useful in the detection of amines in the gas phase, and in particular of biogenic amines.
    For the purposes of the present invention, and as indicated above, those amines resulting from the degradation of amino compounds, such as amino acids, found in food or other organic matter, are called biogenic amines by the action of enzymes generated by microorganisms. Non-limiting examples of biogenic amines are B-ethylenediamine, spermine, spermidine, cadaverine, histamine, trimethylamine, morpholine, piperazine, tryptamine, tyramine, B-phenylenediamine or putrescine. In a preferred embodiment, the color change occurs when there are Betylenediamine, cadaverine, trimethylamine, morpholine and / or putrescine present in the medium. In another embodiment, a fluorescence change occurs in the presence of B-ethylenediamine, cadaverine, morpholine and / or putrescine.
    This specific detection capacity, or sensing capacity, allows the detection of amines, such as putrescine, cadaverine or B-ethylenediamine by color changes and / or fluorescence, so that the amount of said amino acids can be quantified through, a color scale, or by digitally defining the color (RGB) of a photograph taken to the material. The change in color and / or fluorescence is observed by generating putrescine vapors, for example, and exposing the membranes or textile materials and fibers coated with copolymers of formula (1) of the present invention, without any prior treatment of the sample, to those vapors. Therefore, the copolymers of the invention can be used as sensors for the qualitative or quantitative detection of said amines.
    In one of the embodiments of the invention said copolymers are used in methods of determining the level of deterioration of a food by detecting and / or quantifying said biogenic amines with the copolymers of formula (1), of materials comprising them, such as textile fibers coated by said copolymers. These methods allow the manufacture of products such as smart labels that can indicate the level of freshness of food products.
    For the purposes of the present invention, the term copolymer is used in an equivalent manner to the term copolyamide, because said copolymers of formula (1) are polyamides. In addition, the copolymers of formula (1) are physically presented in membrane form and, therefore, for the purposes of the present invention the terms membrane and copolymer are used in an equivalent manner. Likewise, the copolymers of formula (1) described in the present invention are referred to interchangeably as sensor membranes or sensors, due to the properties they present, described herein.
    The copolymers of formula (1) of the present invention thus comprise halogenated groups of 1,8-naphthalimide which are covalently linked to the polymer chain through the nitrogen atom of said group:
    ~
    ~ Z, Z,
    (IX)
    10 These groups are referred to interchangeably, for the purposes of the present description, receiver group, sensor group, receiver unit or sensor unit, since said group is responsible for the union or reaction process with the different amines.
    One embodiment relates to the use of polymers comprising said sensor group (IX) for the detection of gas phase amines, preferably biogenic amines.
    A particular embodiment relates to copotimers in which said halogenated 1,8-naphthalimide groups comprise a 4-position bromine of the 1,8-naphthalimide group, and their use for the detection of amines in the gas phase:
    The amines detection process can be described according to the following Scheme
    1, using as a non-limiting example a polymer of formula (1) comprising a Sr in position 4 of the 1,8-naphthalimide group:
    H H o o
    ,, N-Ra-N-C- "Rb-C" I '"'"
    CQ
    I '"'"
    Br
    R, NHR2
    X
    Scheme 1
    H H o o
    ,, N-Ra-N-C- "Rb-C" I I '"'"
    CQ ~ '"
    R {N'R,
    X
    Said Scheme 1 graphically represents the detection process that occurs when
    A molecule of amine R, -NH-R2 reacts with the "Bromo" substituent of the sensor group, giving rise to a nucleophilic substitution reaction on aromatic ring spontaneously and in the gas phase, being R1 and R2: H or a alkyl, hydroxyalkyl, aminoalkyl, alkoxyalkyl, alkenyl, alkynyl, aryl group, or a mono or polyaromatic group containing or not heteroatoms.
    An embodiment of the present invention is the method of obtaining a copolymer of formula (1):
    by polycondensation of a halogenated monomer derived from 1,8-naphthalimide, or compound of formula (VIII), also called sensor monomer:
    or or CI) lR (lCI
    I
    ~ z, z,
    15 (VII I)
    where Rb is a group selected from alkyl, aryl or heteroaryl, Z1 and Z2 are each independently H or halogen, and where Z1 and Z2 cannot both be H; with at least one other monomer comprising two amino groups of formula H2N-Ra-NH2 where Ra
    5 is a group independently selected from alkyl, aryl or heteroaryl.
    Said monomer of formula (VIII) is also referred to for the purpose of the present invention,sensor monomer, since it is the monomer responsible for the detection of amino acidsby nucleophilic substitution reaction with the halogen groups.The monomers of formula (VIII) therefore comprise sensor groups (IX) which are the
    10 halogenated derivatives of 1, B-naphthalimide, described above.
    An embodiment of the present invention relates to the use of said compound of formula (VIII) for the detection and / or quantification of amines in the gas phase, preferably the detection and / or quantification of biogenic amino acids.
    Another embodiment of the invention relates to the use of a compound of formula (VIII) for the
    15 manufacture of polymers for the detection and / or quantification of amines in the gas phase. Preferably said polymers are used for the detection and / or quantification of biogenic amino acids.
    In a preferred embodiment the Rb group is a phenyl group and said compound of formula
    (VIII) is a compound of formula (VIII) b:
    In another embodiment of the invention the Rb group is a phenyl group, Z1 is H, Z2 is a Br in
    4-position of group 1, B-naphthalimide, and said compound of formula (VIII) is a compound
    of formula (VIII):
    o o Cly CI
    0CQ
    No
    I '"'"
    or or
    Br (VIII),
    For the purposes of the present invention, a polycondensation is a polymerization process where a condensation reaction occurs between monomers having two groups
    5 functional, leading to the formation of a polymer also called polycondensate. For the purposes of the present invention a condensation reaction is a reaction in which two molecules react resulting in the loss of a small molecule such as a water molecule.
    In an embodiment of the present invention the condensation reaction occurs, by
    Thus, between a monomer that is an H2N-Ra-NH2 diamine with a monomer of formula (VIII) that is an acid dichloride, and in which one molecule of hydrochloric acid is generated for each new amine-acid chloride bond It is generated.
    In a preferred embodiment of the invention, the polymerization is carried out in solution.
    For the purposes of the present invention, the polymerization technique is referred to as the polymerization technique in which in addition to the monomers and initiator, a solvent is used.
    In general, the polymerization of the present invention, whether it comprises commercial monomers or not, can be carried out by any of the procedures described in the literature for polycondensations (see for example "Encyclopedia of Polymer Science and Technology" Vol. 3, Chapter: Polyamides, aromatic, p. 558-584).
    The compounds of formula (VIIII), or sensor monomers of formula (VIII) are obtained by halogenating acenaphthene as schematized in Scheme 2.
    ((9. ~ - ~ - ~ o o o o ~ o HOOCA) lCOOH
    Scheme 2
    M
    xx:
    OR NOT
    Jr o ~ eA) le ~ o
    the el
    In said scheme 2 the synthesis of 5- (6-bromo-1, 3-dioxo-1 H5 benzo (de] isoquinolin-2 (3H) -yl) isophthaloyl dichloride, which is a monomer of formula (VIII), is represented a in which Z1 is H and Zz is Sr in 4-position of the 1,8-naphthalimide group.
    The synthesis of the sensor monomer can also be carried out by other conventional routes in organic chemistry.
    The reagents used to obtain the compound of formula (VIII) described in the present invention can be both commercial reagents and synthesis reagents.
    In a preferred embodiment of the invention, the method of obtaining the copolymers of formula (1) further comprises the monomers of formula (VIII) and H2N-RaNH2 diamines, a third monomer selected from a CI-C acid dichloride ( Q) -Re-C (O) -CI or a carboxylic diacid HO (CO) -Rc (CO) OH, where Re is independently selected from
    Alkyl, aryl or heteroaryl. In a preferred embodiment Re is a group selected from
    F3C CF3 -DC'Q
    Therefore, in a particular embodiment, the copolymer of formula (1)
    It is a copolymer of formula (111) further comprising Y units:
    1 1 11 11 i H H ° 0+
    N-Ra-N-C-Rc-C and
    where said X and Y units are in a molar ratio of 0.01: 99.99 to 100: 0, and where Ra, Rb and Re are each independently a group selected from alkyl, aryl or heteroaryl. More preferably Ra Rb and Re are each independently selected from:
    In a preferred embodiment of the invention, the CI-C (Q) -Rc C (Q) -CI acid dichloride is independently selected from isophthaloyl chloride, terephthaloyl chloride or any aromatic acid dichloride.
    In a preferred embodiment of the invention, the H2N-Ra-NH2 diamine is independently selected from meta-phenylenediamine, para-phenylenediamine, ortho-phenylenediamine, or any aromatic diamine.
    In a preferred embodiment of the copolymers of formula (1) the compound of formula (VIII) is the compound of formula (VIII) to:
    or or ClyCI
    0CQ
    NO I "" ""
    ~ ~
    Br (VII I),
    In a preferred embodiment, the CI-C (O) -Rc-C (O) -CI dichloride is isophthaloyl chloride.
    In another preferred embodiment Ra is a phenyl group, and the H2N-Ra-NH2 diamine is
    10 melaphenylenediamine.
    In another preferred embodiment the compound of formula (VIII) is the compound of formula (VIII) "CI-C (O) -R, -C (O) -CI acid dichloride is isophthaloyl chloride, and diamine H, NR, NH2 in methenylenediamine.
    A preferred embodiment of the method of obtaining the copolymers of formula (1) comprises polycondensation of monomers of formula (VIII)
    O o CI) lR ((CI
    I
    %
    z, z, (VIII)
    with H2 N-Ra-NH2 diamines and a CI-C (Q) -Rc-C (Q) -CI acid dichloride.
    In a more preferred embodiment the monomer of formula (VIII) is a compound of formula (VIII) "5- (6-bromo-l, 3-dioxo-l H-benzo [de] isoquinolin-2 (3H)) - il) isophthaloyl,
    Cly ° ° CI
    0CQ
    N °
    I '"'" "" '"
    Br (VIII), where Z, is H, Z2 is a 4-position Br of the 1, 8-naphthalimide group and Rb is a phenyl group; said CI-C (O) -Rc-C (O) -CI is isophthaloyl chloride where Re is a phenyl group; and said diamine H2N-Ra-NH2 is methanylenediamine, where Ra is a phenyl group; and the copolymer of formula
    (1) obtained is a copolymer of formula (IV). Therefore, in said particular embodiment of the invention, the copolymer of formula (11) is a copolymer of formula (IV), wherein the X units are groups
    or
    - +- ~ -o- ~ -OLL .., é
    0CQ
    NO
    I '"'" '"'"
    Br
    x
    10 And where Y units are groups:
    Y
    In another preferred embodiment of the invention the X and Y units are in a molar ratio of 0.5: 9: 5 to 1.5: 8.5.
    A non-limiting schematic representation of a copolymer of formula (IV) would be: H H or o
    H H o o N I: N
    NI: N '" '-OR-'
    '-O-' ""
    Y
    os (IV)I '"'""" ""
    Br
    X
    where X units and Y units are repeated on both sides consecutively, repeatedly or alternately.
    In an embodiment of the method of obtaining the copolymers of formula (1), the third monomer is a CI-C (Q) -Rc C (Q) -CI acid dichloride, and the molar ratio between H2N-Ra diamine -NH2 and of the total acid dichloride CI-C (O) -Rc C (O) -CI together with the compound of formula (VIII), is 1 to 1, and the molar ratio between the acid dichloride CI- C (O) -Rc-C (Q) -CI and compound of formula (VIII) is between 1.1: 9.9 to 9.9: 1.1.
    The copolymers of structures of formula (1) described in the present invention, and the solid state membranes, films, coatings and materials obtained therefrom, are characterized by being able to be used, among other areas, in the detection of amines such as cadaverine, putrescine, ethylenediamine, trimethylamine and / or gas phase morpholine. In one embodiment, the detection of amines is performed in food products.
    One embodiment relates to a textile fiber coated with at least one copolymer of the present invention.
    Another embodiment relates to the use of a copolymer of formula (1) of the invention, or of a material comprising it, or of a textile fiber or textile material coated with said copolymer of formula (1), for the detection of amines In the gas phase.
    In a preferred embodiment said amines are biogenic amino.
    In a reallization the biogenic amine is selected from B-ethylenediamine, spermine, spermidine, cadaverine, histamine, trimethylamine, morpholine, piperazine, tryptamine, tyramine, B-phenylenediamine or putrescine. In a preferred embodiment, the color change occurs when there is B-ethylenediamine, cadaverine, trimethylamine, morpholine and / or
    25 putrescine present in the middle. In another embodiment, a fluorescence change occurs in the presence of B-ethylenediamine, cadaverine, morpholine and / or putrescine.
    A preferred embodiment relates to the use of copolymers with structures of formula I according to the present invention, where the amine is cadaverine. In another preferred embodiment the amine is putrescine. In another preferred embodiment the amine is ethylenediamine.
    In a further embodiment said amines are detected and / or quantified in said copolymer,
    or in said textile fiber, by at least one method independently selected from:
    the use of a calorimetric scale comprising at least two different shades of color, where each of said shades defines a concentration range of said amines; the use of the RGB parameters of a digital photograph; o the use of spectroscopic techniques;
    In general, and for the purposes of the present invention, RGB is a colorimetric representation model with which it is possible to represent a color by mixing by adding the three primary light colors. To indicate in what proportion each of the primary colors are in a given hue, a value is assigned to each of the primary colors, so that the value "O" means that it does not intervene in the studied hue and, as that this value increases, it is understood that it contributes more intensity to this tone.
    Another embodiment of the present invention relates to a method of determining the level of deterioration of a food comprising:
    (to) introducing a copolymer of formula (1), or a material comprising it, into a container containing said food, and where said copolymer, or the support comprising it, is not in direct contact with the food,
    (b) detecting and / or quantifying in said copolymer, or in the material comprising it, at least one gas phase biogenic amine produced by said food, by at least one method independently selected from:
    the use of a colorimetric scale comprising at least two different color tones, where each of said tones defines a concentration range of said amines; the use of the RGB parameters of a digital photograph; o the use of spectroscopic techniques;
    For the purposes of the present invention it is defined as a colorimetric scale at a scale comprising at least two type shades that each represent the color of the copolymer of formula (1) of the invention in the presence of a known amine concentration range. In this way, the comparison of the color obtained by contacting the copolymer of formula (1) with an unknown amount of amine in the gas phase, with the color of the type shades of the colorimetric scale provides a measure of the amine concentration range that is detected
    An embodiment of the invention also relates to porous membranes obtained by chemical and / or physical foaming processes from the solid membranes or coatings described previously. Examples of the physical foaming process are the dissolution of high pressure gas (CO2 and / or Nú, and as chemical foaming processes some non-limiting examples are included such as leaching from salts or mixtures of polymers or the use of agents of foaming endo or exothermic chemicals that produce the cellular structure by heating and releasing the gas, and in general any foaming process that originates a porous structure within the solid membrane.
    DESCRIPTION OF THE FIGURES
    Figure 1. Characterization of compound (V) a, 5-bromo-1, 2-dihydroacenaphthylene, intermediate of the synthesis of a compound of formula (VIII) to: 1A chemical structure; 1 B infrared spectrum; 1C proton magnetic resonance (1 H NMR); 10 carbon magnetic resonance (NMR "e).
    Figure 2. Characterization of compound (VI) a, 6-bromobenzo [de] isochromoen-1,3-dione, intermediate of the synthesis of 4-bromo-1, B-Naphthalimide as an example of a compound of formula (VIII): 2A chemical structure; 2B infrared spectrum; 2C proton magnetic resonance (1 H NMR); 20 carbon magnetic resonance (13C NMR).
    Figure 3. Characterization of compound (VII) a, 5- (6-bromo-1, 3-dioxo-1 H-benzo [de] isoquinolin-2 (3H) -yl) isophthalic acid, intermediate synthesis of 4- Bromo-1, BNaftalimide as an example of a compound of formula (VIII) a: 3A chemical structure; 3B infrared spectrum; 3C proton magnetic resonance imaging (1 H NMR); (d) carbon magnetic resonance (NMR BC).
    Figure 4. Characterization of 5- (6-bromo-1, 3-dioxo-1 H-benzo [de] isoquinolin-2 (3H) -yl) -N 1, N3 diphenylisophthalamide. Derived from the compound of formula (VIII) obtained by reacting the acid chlorides with aniline, according to Example 2: 4A chemical structure; 4B infrared spectrum; 4C proton magnetic resonance (1 H NMR); 40 carbon magnetic resonance (NMR BC).
    Figure 5. Characterization of 5- (1,3-dioxo-6- (piperazin-1-yl) -1 H-benzo [de] isoquinolin-2 (3H) -yl-N1, N3-diphenylisophthalamide. Compound obtained by exposure a piperazine of the aniline derivative of the sensor monomer of formula (VIII) a, characterized in Figure 4, according to Example 3: 5A chemical structure; 5B infrared spectrum; 5C proton magnetic resonance (1 H NMR); 50 resonance carbon magnetic (DC NMR).
    Figure 6. Characterization of 5- (6-morpholino-1,3-dioxo-1 H-benzo [de] isoquinolin-2 (3H) -yl) N1, N3-diphenylisophthalamide. Compound obtained by exposure to morpholine of the aniline derivative of the sensor monomer of formula (VIII) a, characterized in Figure 4 according to Example 3: 6A chemical structure, 6B infrared spectrum; 6C proton magnetic resonance (1 H NMR); 60 carbon magnetic resonance (13C NMR).
    Figure 7. Characterization of 5- (6- «2-aminoethyl) amino) -1,3-dioxo-1 H-benzo [de] isoquinolin2 (3H) -yl) -N1, N3-diphenylisophthalamide. Compound obtained by exposure to ethylenediamine of the derivative with aniline of the sensor monomer of formula (VIII) a, characterized in Figure 4 according to Example 3: 7 A chemical structure; 7B infrared spectrum; 7C proton magnetic resonance (1 H NMR); 70 carbon magnetic resonance (13C NMR).
    Figure 8. Characterization of 5- (6- (butylamino) -1, 3-dioxo-1 H-benzo [de) isoquinolin-2 (3H) -yl) N1, N3-diphenylisophthalamide. Compound obtained by exposure to ethylenamine of the aniline derivative of the sensor monomer of formula (VIII) a, characterized in Figure 4 according to Example 3: 8A chemical structure; 8B infrared spectrum; 8C proton magnetic resonance (1 H NMR); 80 carbon magnetic resonance (13C NMR).
    Figure 9. Characterization of a copolymer of formula IV obtained in Example 4: 9A chemical structure; 9B infrared spectrum; 9C proton magnetic resonance (1 H NMR); 90 carbon magnetic resonance (13C NMR).
    Figure 10. Copolymer of formula (IV) in the form of a membrane prepared according to Example 5, and coated on cotton fabric comprising said copolymer of formula (IV) prepared according to Example 6, exposed to ethylenediamine vapors according to the procedure described in Example 5: Exposure of independent pieces of material at increasing concentrations of ethylenediamine (samples 1 to 7), in which the gray scale corresponds to a color scale where the darkest gray corresponds to the orange color and high fluorescence and the gray colors lighter correspond to very pale yellow colors, practically white and very low fluorescence). Figure 10A shows the color change of the membranes (circular shapes) and of the cotton fabric coverings (quadrangular shapes) with natural light. Figure 10B shows the fluorescence change of the membranes (circular shapes) and of the cotton fabric coatings (quadrangular shapes) with 365nm ultraviolet light. The graph in Figure 10C shows the relationship between the ppm of ethylenediamine added and the intensity of the orange color obtained by the detection of said amine, translated into component B (CB) of the RGB parameters obtained by means of visible light photography of the Digital camera of a mobile phone, as well as exponential adjustment.
    Figure 11 Copolymer of formula (IV) in the form of a membrane prepared according to Example 5, and coated on cotton fabric comprising said copolymer of formula (IV) prepared according to Example 6, exposed to putrescine vapors according to the procedure described in Example 7: Exposure of independent pieces of material at increasing concentrations of putrescine (samples 1 to 7, in which the gray scale corresponds to a color scale where the darkest gray corresponds to the orange color and high fluorescence and the lightest gray colors they correspond to very pale yellow colors, practically white and very low fluorescence). Figure 11A shows the color change of the membranes (circular shapes) and of the cotton fabric coverings (quadrangular shapes) with natural light. Figure 118 shows the fluorescence change of the membranes (circular shapes) and of the cotton fabric coatings (quadrangular shapes) with 365nm ultraviolet light. The graph in Figure 11 C shows the relationship between the putrescine ppm added and the intensity of the orange color obtained by the detection of said amine, translated into component B (CB) of the RGB parameters obtained by means of visible light photography of the digital camera of a mobile phone, as well as the potential setting.
    Figure 12. Copolymer of formula (IV) in the form of a membrane prepared according to Example 5, and coating on cotton fabric comprising said copolymer of formula (IV) prepared according to Example 6, exposed to cadaverine vapors according to the procedure described in Example 7: Exposure of independent pieces of material at increasing concentrations of cadaverine (samples 1 to 7, in which the gray scale corresponds to a color scale where the darkest gray corresponds to the orange color and high fluorescence and the lightest gray colors they correspond to very pale yellow colors, practically white and very low fluorescence). Figure 12A shows the color change of the membranes (circular shapes) and of the cotton fabric coverings (quadrangular shapes) with natural light. Figure 12B shows the fluorescence change of the membranes (circular shapes) and of the cotton fabric coatings (quadrangular shapes) with 365nm ultraviolet light. The graph in Figure 12C shows the relationship between the ppm of cadaverine added and the intensity of the orange color obtained by the detection of said amine, translated into component B (eB) of the RGB parameters obtained by means of visible light photography of the Digital camera of a mobile phone, as well as polynomial adjustment.
    EXAMPLES
    The following illustrative examples are not intended to be limiting and describe:
    a) the preparation of a sensor monomer of formula (VIII) a, 5- (6-bromo-1, 3-dioxo-1 Hbenzo [de] isoquinolin-2 (3H) -yl) isophthalic acid (Example 1);
    b) obtaining a derivative of the sensor monomer of formula (VIII) a obtained in Example 1 with aniline for characterization of the compound of formula (VIII) a (Example 2);
    c) the detection of piperazine, morpholine, ethylenediamine and ethylenamine, with the derivative of the sensor monomer of formula (VIII) obtained in Example 2 (Example 3); d) the preparation of a copolymer of formula (IV), comprising the monomer of formula (VIII) prepared in Example 1 (Example 4); e) the preparation of a sensor membrane from the copolymer of formula (IV) obtained in Example 4 (Example 5); f) the preparation of a cotton fabric coating from the copolymer of formula (IV) obtained in Example 4 (Example 6);
    g) the procedure for the application as a colorimetric and fluorimetric sensor, both of the sensing membrane of Example 5 and of the textile coating of Example 6, against the presence of amino vapors (Example 7).
    Example 1. Synthesis of a sensor monomer.
    This example illustrates the preparation and characterization of the sensor monomer 5- (6-bromo-1, 3dioxo-1 H-benzo [de] isoquinolin-2 (3H) -yl) isophthalic acid (VIII) a, which was carried out by The following synthetic route:
    36 grams (0.2 moles) of N-Bromosuccinimide were dissolved in 50 ml of DMF, and said
    5 solution was added dropwise on a suspension of acenaphthene (30.8 grams, 0.2 moles) in 50 ml of DMF. The mixture was stirred for two hours and precipitated in cold water. After a few minutes, the brown solid was filtered and recrystallized from ethanol. Yield: 97%. The characterization of the compound obtained is included in Figure 1. Figure 1A shows the chemical structure of the compound obtained, Figure 18 is a spectrum of
    10 infrared characterization and Figures 1C and 10 show the 13 H NMR and 13C spectra respectively.
    1.2. Synthesis of the 6-bromobenzol of Jisocromeno-1 3-dione (VIL.
    In a pressure flask 10 g (42.9 mmol) of compound (V) are added to a solution of 80 ml of glacial acetic acid and 31.97 grams (107.25 mmol) of sodium dichromate dihydrate. The mixture was stirred at the boiling temperature of the solvent for 5 hours. Then, the mixture was cooled to room temperature and a volume of water was added to precipitate the compound. Finally, the product was filtered and washed with plenty of water. The yield was 87%. The characterization of the compound obtained is included in Figure 2. Figure 2A shows the chemical structure of the compound obtained, Figure 28 is a spectrum of
    20 infrared characterization and Figures 2C and 20 show the 1HRMN and 13C spectra respectively.
    1.3. Synthesis of 5- (6-Bromo-1 3-dioxo-1 H-benzol from Jisoguinolin-2 (3H) -jD isophthalic acid (Vllt •.
    In a pressure flask, 1.02 grams (3.68 mmol) of compound (VI) "667 mg (3.68 mmol) of 5-aminoisophthalic acid and 906 mg (11.04 25 mmol) of sodium acetate were suspended in 25 ml of glacial acetic acid The mixture was stirred at 100 ° C for 2 hours and filtered hot The solid was washed with hot acetic acid, hot water and hot ethanol The yield was 60% The characterization of the compound obtained is included in the Figure 3. Figure 3A
    (Goes
    M
    xx:
    or Yr o
    O ~ C ~ C ~ O
    ,,
    el el (VIII) a
    shows the chemical structure of the compound obtained, Figure 3B is an infrared characterization spectrum and Figures 3e and 3D show the 1HRMN and 13C spectra respectively.
    1.4. Synthesis of 5- (6-bromo-l 3-dioxo-l H-benzoldelisoguinolin-2 (3H) -jllisophthaloyl dichloride (VIIIl ,.
    In a round bottom flask, 3 g (6.81 mmol) of compound (VII) ... are placed together with approximately 30 mL of SOCL2. A few drops of N, N-dimethylformamide are added as catalyst. The mixture is heated to 75 ° C and stirred for 30 minutes. The solution is distilled under vacuum. The solid obtained is refluxed overnight with 70 mL of heptane, filtered, and the solid is dried under vacuum to prevent exposure to moisture. The yield was 51%.
    Example 2: Obtaining a derivative of the compound of formula (VII!) ... from Example 1.
    In order to characterize the compound of formula (VIII) ... obtained in Example 1, and given the high reactivity of the acid chloride groups, the compound of formula was reacted
    (VIII) ... with aniline as follows: to a solution of aniline (1.54 g, 16.54 mmol) in 15 ml of DMA 6.89 mmol of the acid dichloride with formula (VIII) was added to, with ice bath and under nitrogen atmosphere. It was stirred vigorously for 30 minutes. The mixture was subsequently stirred at room temperature for another 3.5 hours, and precipitated in water. Finally the solid is washed with plenty of water. Yield: 97%. The chemical structure of the resulting compound can be seen in Figure 4A, while Figures 4B, 4C and 4D show the infrared spectra, 1 H NMR and 13C respectively.
    Example 3: Detection of amines by the compound of formula (VIII) a of Example 1.
    3.1: Piperazine detection:
    To exemplify the detection of an amine by a compound of formula (VIII), piperazine and the compound of formula (Viii) have been used in this example ....
    Since the compound of formula (VIII) ... contains acid chloride groups very sensitive to hydrolysis, the aniline-derived compound obtained in Example 2 and whose structure is described in Fig. 4A was used in this example.
    The derivative obtained in Example 2 contains gas phase amine sensing groups by nucleophilic substitution reaction between a halogen (Sr group at position 4-1, 8-naphthalimide) and an amine group, as described : To a solution of the compound derived with aniline obtained in Example 2 (0.2 g, 0.34 mmol) and 2 ml of DMA, 1.69 mmol of piperazine were added. The reaction was stirred at 110 ° C for 4 hours, cooled to room temperature, and precipitated in water. The solid was filtered and washed with water. In this case, the Sr group reacts with an amino group of the piperazine to give rise to the chemical structure product represented in Figure 5A. Fig. 58, 5C and 50 represent its infrared, proton magnetic resonance (1 H NMR) and carbon magnetic resonance (13 C NMR) spectra respectively.
    3.2: Morpholine Detection:
    To exemplify the detection of an amine by a compound of formula (VIII), morpholine has been used in this example.
    As in the previous example, since the compound of formula (VII I) a contains acid chloride groups very sensitive to hydrolysis, the aniline-derived compound obtained in Example 2 was used.
    The derivative obtained in Example 2 contains sensor groups of amino acids in the gas phase, by nucleophilic substitution reaction between a halogen (Sr group at position 4-1, 8-naphthalimide) and an amine group, such as It is described: to a solution of the compound derived with aniline obtained in Example 2 (0.2 g, 0.34 mmol) and 2 ml of DMA, were added
    1.69 mmol of morioline. The reaction was stirred at 110 ° C for 4 hours, cooled to room temperature, and precipitated in water. The solid was filtered and washed with water. In this case, the Sr group reacts with the morpholine amino group to give rise to the chemical structure product represented in Figure 6A. Fig. 68, 6C and 60 represent their infrared, proton magnetic resonance (1 H NMR) and carbon magnetic resonance (13 C NMR) spectra respectively.
    3.3: Detection of ethylenediamine:
    To exemplify the detection of an amine by a compound of formula (VIII), ethylenediamine has been used in this example.
    As in the previous example, since the compound of formula (VII I) a contains acid chloride groups very sensitive to hydrolysis, the aniline-derived compound obtained in Example 2 was used.
    The derivative obtained in Example 2 contains sensor groups of amino acids in the gas phase, by nucleophilic substitution reaction between a halogen (Sr group at position 4-of 1, B-naphthalimide) and an amine group, such as It is described: to a solution of the compound derived with aniline obtained in Example 2 (0.2 g, 0.34 mmol) and 2 ml of DMA, 1.69 mmol of ethylenediamine were added. The reaction was stirred at 110 ° C for 4 hours, cooled to room temperature, and precipitated in water. The solid was filtered and washed with water. In this case, the Sr group reacts with an amino group of ethylenediamine to give rise to the product of chemical structure represented in Figure 7A. Fig. 7B, 7C and 7D represent their infrared, proton magnetic resonance (1 H NMR) and carbon magnetic resonance (13 C NMR) spectra respectively.
    3.4: Detection of ethylenamine:
    To exemplify the detection of an amine by a compound of formula (VIII), ethylenamine has been used in this example.
    As in the previous example, since the compound of formula (VIII) a contains acid chloride groups very sensitive to hydrolysis, the aniline-derived compound obtained in Example 2 was used.
    The derivative obtained in Example 2 contains sensor groups of amino acids in the gas phase, by nucleophilic substitution reaction between a halogen (Sr group at position 4-of 1,8-naphthalimide) and an amine group, such as It is described: to a solution of the compound derived with aniline obtained in Example 2 (0.2 g, 0.34 mmol) and 2 ml of DMA, were added
    1.69 mmol of ethylenamine. The reaction was stirred at 110 ° C for 4 hours, cooled to room temperature, and precipitated in water. The solid was filtered and washed with water. In this case, the Sr group reacts with the amino group of ethylenamine to give rise to the product of chemical structure represented in Figure 8A. Fig. 8B, 8C and 80 represent their infrared, proton magnetic resonance (1 H NMR) and carbon magnetic resonance (13 C NMR) spectra respectively.
    Example 4. Preparation of a copolymer of formula (IV), comprising the above sensor monomer of formula (VlIlla obtained in Example 1.
    In a three-neck round bottom flask provided with nitrogen and mechanical stirring, 5.73 mL of N, N-dimethylacetamide and 0.62 g (5.73 mmol) of m-phenylenediamine are added at room temperature and stirred until complete dissolution. The system is then cooled to O oc and 0.27 9 (0.57 mmol) of compound (VIII), and 1.04 9 (5.15 mmol) of isophthaloyl chloride are added in small portions for 5 minutes. The mixture is allowed to react at 0 ° C for 30 minutes and then at room temperature for 3.5 hours. The final solution precipitates over slowly distilled water, forming a polymer, which is thoroughly washed with water and acetone. The yield was quantitative.
    The polymer of formula (IV) is characterized in Figure 9, where Figure 9A represents the chemical structure; and Figures 9B, 9C and 9D are the infrared spectrum; proton magnetic resonance imaging (1H NMR); And carbon magnetic resonance (13C NMR) respectively.
    Example 5. Preparation of a sensor membrane from a copolymer of formula (IV) obtained in Example 4.
    For the preparation of a sensor membrane from the copolymer obtained in example 2, a solution of 0.21 g of copolymer of formula (IV) in 3 mL of N, N-dimethylacetamide is prepared. The solution is filtered, placed on a level glass inside a flask at 60 oC for 6 hours and another 4 hours at 100 oC. a membrane is obtained by casting by solvent removal. Subsequently the membrane is cut into 6 mm diameter discs.
    Example 6. Preparation of a cotton fabric coating from a copolymer of formula (IV) obtained in Example 4.
    Cotton coatings from the copolymer of formula (IV) are prepared by dipping a previously washed cotton cloth in a solution of said copolymer of formula (IV) (0.1 g) in N, N-dimethylacetamide (2 mL ) and allowing the solvent to evaporate for 8 hours in a flask at 60 oC and another 4 hours at 100 ° C. Next, the cotton fabrics are cut into rectangles of 6x8 mm.
    Example 7. Procedure for the application as a calorimetric and fluorimetric sensor of both the sensing membrane of Example 5 and the textile coating of Example 6 against the presence of amine vapors.
    This example illustrates the behavior as a colorimetric sensor of membranes and coated fabrics prepared in Examples 5 and 6 against biogenic amines. The disks of the membranes and the rectangles of the fabrics are placed inside closed vials of 0.5 L capacity, together with different amounts of the different biogenic amines that are to be detected. The vials are kept thermostatted at 20 oC for 24 hours. The presence of biogenic amines produced an observable color change in the prepared coatings and membranes and is proportional to the concentration of the amines within the closed vial.
    The detection of the animals was performed by changing the color analyzed with natural light,
    or by fluorescence, with 365 nm ultraviolet light. The quantification was performed by measuring the intensity of the orange color, translated into component B (eS) of the RGS parameters obtained by visible light photography with a digital camera.
    7.1: Detection and quantification of ethylenediamine:
    The membrane discs of the copolymer of formula (IV) prepared according to Example 5, and the rectangles of fabrics coated by said copolymer, prepared according to Example 6 were exposed according to what is described in this example at increasing concentrations of ethylenediamine between 0.79 and 80.35 mg / l.
    Figures 10A and 10B show the change in color and fluorescence, respectively, of
    10 membrane samples of formula (IV) (circular shapes from 1 to 7) and samples of cotton fabric coated with said copolymer of formula (IV) (rectangular shapes from 1 to 7). Said samples were exposed increasing concentrations (from 1 to 7) of ethylenediamine in accordance with the above.
    In figure 10A the lighter gray colors correspond to very pale yellow colors
    15 and low concentrations of ethylenediamine, and the darker gray colors correspond to orange colors and high concentrations of ethylenediamine. As the concentration of ethylenediamine (from 1 to 7) increases, the transition from pale yellow (light gray) to increasingly intense oranges (dark gray) is observed.
    Figure 10B shows the fluorescence change with 365 nm ultraviolet light. By way of
    20 analogous to Figure 10A, as the concentration of ethylenediamine increases (from 1 to 7), an increasingly intense fluorescence is observed.
    Quantification of ethylenediamine was performed by measuring the orange color, translated
    to the S component of the RGB parameters obtained by visible light photography with
    a digital camera as shown in figure 10C. A limit of
    25 detection of 0.22 ppm and a quantification limit of 0.67 ppm. The exponential adjustment of this quantification is shown in Table 1:
    Equation y -exp (a + b * x + c * xI 2)
    R2 setting 0.9938
    Standard error value
    D toS, 18D080,02481
    D b-0.216290.01524
    D and0, D02044.03E-04
    Table 1
    7.2: Detection and quantification of putrescine: The membrane discs of the copolymer of formula (IV) prepared according to Example 5, and the rectangles of fabrics coated by said copolymer, prepared according to Example 6 were
    5 exposed as described in this example to putrescine concentrations
    increasing values between 0.79 and 78.57 mg / l.
    Figures 11A and 118 show the change in color and fluorescence, respectively, of
    membrane samples of formula (IV) (circular forms 1 to 7) and tissue samples of
    cotton coated with said copolymer of formula (IV) (rectangular shapes from 1 to 7).
    10 Said samples were exposed increasing concentrations (from 1 to 7) of putrescine in accordance with the above.
    In figure 11A the lighter gray colors correspond to very pale yellow colors
    and low concentrations of putrescine, and the darker gray colors correspond to
    Orange colors and high concentrations of putrescine. As the
    The concentration of putrescine (from 1 to 7) shows the passage of pale yellow (light gray) colors to increasingly intense oranges (dark gray).
    Figure 118 shows the fluorescence change with 365 nm ultraviolet light. By way of
    analogous to Figure 11A, as the concentration of putrescine (from 1 to 7) increases
    observe an increasingly intense fluorescence.
    20 The quantification of putrescine was performed by measuring the orange color, translated into component B of the RGB parameters obtained by visible light photography with a digital camera as shown in Figure 11C. A detection limit of 3.5 ppm and a quantification limit of 10.6 ppm were obtained. The exponential adjustment of this quantification is shown in Table 2:
    Equation y = l.O / (a + b * x + c * x "2) Adjust R2 0.96507
    Value Standard error B a 0.00555 2.41E-04 B b S, 84E-04 l, l2E-04 B e -2.33E-06 3, OOE-06
    Table 2
    7.3: Detection and quantification of cadaverine:
    The membrane discs of the copolymer of formula (IV) prepared according to Example 5, and the rectangles of fabrics coated by said copolymer, prepared according to Example 6 were exposed according to what is described in this example at concentrations of cadaverine
    increasing values between 0.77 and 75.56 mg / l.
    Figures 12A and 128 show the color and fluorescence change, respectively, of
    membrane samples of formula (IV) (circular forms 1 to 7) and tissue samples of
    cotton coated with said copolymer of formula (IV) (rectangular shapes from 1 to 7).
    10 Said samples were exposed increasing concentrations (from 1 to 7) of cadaverine in accordance with the above.
    In figure 12A the lighter gray colors correspond to very pale yellow colors
    and low concentrations of cadaverine, and the darkest gray colors correspond to
    Orange colors and high concentrations of cadaverine. As the
    The concentration of cadaverine (from 1 to 7) shows the passage of pale yellow (light gray) colors to increasingly intense oranges (dark gray).
    Figure 12B shows the fluorescence change with 365 nm ultraviolet light. By way of
    analogous to Figure 12A, as the concentration of cadaverine (from 1 to 7) increases
    observe an increasingly intense fluorescence.
    20 The quantification of the cadaverine was performed by measuring the orange color, translated
    to component B of the RGB parameters obtained by visible light photography with
    a digital photo camera as shown in figure 12C. A limit of
    detection of 0.58 ppm and a quantification limit of 1.75 ppm. It is shown in Table 3 on
    exponential adjustment of said quantification:
    Equation y = A + B * x + C * x "'2
    Aju ste R2 0.99685 Value Standard error
    B A 155.76396 1.67586 B B -3.04196 0.75968 B e -0.29105 0.04864
    Table 3
    权利要求:
    Claims (14)
    [1]
    1. A copolymer of formula (1) comprising at least one unit X:
    x (1)
    5 where
    Ra is a group independently selected from alkyl, aryl or heteroaryl;Rb is a group independently selected from aryl or heteroaryl alkyl;Z1 and Z2 are each and independently H or halogen, and where Z, and Z2 are notthey can be both H.
    [2]
    2. A copolymer according to claim 1, further comprising at least one Y unit:
    I I 1I 11
     i H H O 0+
    N-Ra-N-C-Rc-C and
    where units X and Y are in a molar ratio of 0.01: 99.99 to 100: 0, and 15 where Re is a group independently selected from alkyl, aryl or heteroaryl, and wherein said copolymer is a copolymer of formula (111).
    [3]
    3. A copolymer according to claim 2, wherein Ra, Rb and Re are each and independently a group selected from:
    F3C CF3 or
    f) 'C'Q
     v-ü-yy
    Noel
    [4]
    4. A copolymer according to claim 3, wherein said copolymer is a copolymer of formula (IV), wherein the X units are groups
    H H O O
     No N 
    0CQ
    NO
    I '"'"
    4 4
    Br
    x
    and where the Y units are groups:
    OR
    Y
    A copolymer according to any one of claims 2 to 4, wherein the X and Y units are in a molar ratio of 0.5: 9: 5 to 1.5: 8.5.
    [6]
    6. Textile fiber coated with at least one copolymer of any one of claims 1 to 5.
    [7]
    7. Use of a copolymer of any one of claims 1 to 4, or of the fibers of claim 5, for the detection of amines in the gas phase.
    [8]
    8. Use according to claim 6, wherein said amino acids are detected and / or quantified in said copolymer, or in said textile fiber, by at least one method independently selected from:
    the use of a colorimetric scale comprising at least two different shades of color, where each of said shades defines a concentration range of said amines; the use of the RGB parameters of a digital photograph; or the use of spectroscopic techniques.
    [9]
    9. Method of determining the level of deterioration of a food comprising:
    (to) introducing a copolymer of claims 1 to 5, or a material comprising it, into a container containing said food, and wherein said copolymer, or the support comprising it, is not in direct contact with the food,
    (b) detecting and / or quantifying in said copolymer, or in the material comprising it, at least one gas phase biogenic amine produced by said food, by at least one method independently selected from:
    - the use of a calorimetric scale comprising at least two different color shades, where each of said shades defines a concentration range of said amines; -the use of the RGB parameters of a digital photograph; or -the use of spectroscopic techniques;
    [10]
    10. Compound of formula (VIII):
    o o
    CI) lR (lCII
    ~
    z, Z, (VIII)
    where Rb is a group selected from alkyl, aryl or heteroaryl; Zl and Z2 are each and independently H or halogen, and where Zl and Z2 cannot be both H.
    [11 ]
    eleven . Method of obtaining a copolymer of formula (1), wherein said method comprises performing a polycondensation of the compound of formula (VIII) of claim 10, with at least one other monomer comprising two amino groups of formula H2N-Ra-NH2.
    12. Method of obtaining according to claim 11, wherein the polycondensation further comprises a third monomer selected from a CI-C (Q) Rc · C (O) -CI dichloride or a carboxylic acid HO (CO) - Rc- (CO) OH, where Re is a group independently selected from alkyl, aryl or heleroaryl.
    13. Method of obtaining according to claim 12, wherein Ra, Rb and Rc are each independently selected from:
    F3C CF3 or
    ~ O); Ü
     v-ü-yy
    Noel
    [14]
    14. Method of obtaining according to claim 13, wherein the third monomer is
    a CI-C (O) -Re-C (O) -CI acid dichloride, and where the molar ratio between H2N-Ra5 NH2 Y diamine of the total CI-C (O) -Rc-C acid dichloride ( O) -CI together with the compound of formula
    (VIII) is 1: 1, and the molar ratio between CI-C (O) -Rc C (Q) -CI acid dichloride and compound of formula (VIII) is between 1.1: 9.9 to 9.9: 1.1.
    [15]
    15. Method of obtaining according to claim 14, wherein Ro., Rb and Re are each a phenyl group.
    [16]
    16. Use of the compound of formula (VIII) of claim 10 for the manufacture of a gas phase amines detector polymer, or of a textile fiber coated with said polymer.
    [17]
    17. Use of the compound of formula (VIII) of claim 10 for the detection of amines in the gas phase.
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    US8697792B2|2009-09-24|2014-04-15|Basf Se|Migration-free coloured copolycondensates for colouring polymers|
    ES2557332A1|2014-07-23|2016-01-25|Universidad De Burgos|Chromogenic sensors for amines |
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