WO2012152531A1

WO2012152531A1 - Packaging having an indicator area

Info

Publication number: WO2012152531A1
Application number: PCT/EP2012/056807
Authority: WO
Inventors: Gerhard J. Mohr; Anna HEZINGER; Sabine Trupp; Jennifer Schmidt; Matthias Stich
Original assignee: Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority date: 2011-05-11
Filing date: 2012-04-13
Publication date: 2012-11-15
Also published as: DE102011075667A1

Abstract

Embodiments of the present invention provide packaging (100) having an indicator area (102) which has a plurality of micro/nanoparticles (104) to which an indicator dye for detecting an analyte is directly bound. The indicator area (102) may be used to detect rotting food or as a freshness sensor.

Description

PACKAGING WITH INDICATOR RANGE

description

Embodiments of the present invention relate to a package having an indicator region, e.g. B. on a food package with an indicator area for detecting spoiled food. Further exemplary embodiments of the present invention relate to a fresh sensor.

In the packaging of food, medicines, equipment and raw materials may, for. B. during transport or storage, form undesirable substances that restrict the use of the packaged goods or impossible. Especially with foodstuffs and medicines, spoilage of the packaged goods due to incorrect or too long storage should be emphasized. The release of undesirable substances may take place in the case of food through a spoilage process, e.g. B. triggered by contamination with microorganisms. For medicines, proper storage and keeping of the best before date are particularly important. The APV guideline (APV = Arbeitsgemeinschaft der Pharmazeutischen Verfahrenstechnik) stipulates that at least 90% of the active substance must still be present. The decomposition of the active ingredients, but also the added auxiliaries can lead to the formation of harmful substances. The storage and transport of equipment may interfere with the transfer of undesirable substances from the packaging material or the means of transport, which may lead to contamination of the sample by chemicals. But also by damage to the device, eg. B. leakage of coolant, such impairment of functionality, but also a threat to the health of the consumer. Raw materials for the food and pharmaceutical industries as well as for the chemical industry are subject to strict input controls. Again, by improper storage, packaging or transport may be a deterioration in the quality, which may lead to the formation of undesirable substances or contamination with chemicals.

In US 2010/0209521 A I, the use of metal-based sensory pigments in the packaging of foods, pharmaceuticals, paper and electronic

Products described. Here, a chemically reactive polymer layer (up to 500 nm thick) is applied to metal-based particles, on the polymer layer then dye-bearing nanoparticles (1-100 nm) are bound. In analyte contact (eg. DNA, water, C0 ₂ , organic vapors and solvents), the particle system changes its optical properties. The change in optical properties occurs due to a change in the properties of the polymer layer between dye nanoparticles and metal particles. The change in optical properties is read by means of "resonance amplified optical absorption of light".

Furthermore, US Pat. No. 6,624,147 B2 describes the selective recognition of biogenic amines from spoiled foods by the use of molecularly imprinted polymers. The polymers are incorporated as test strips in food packaging. The indicator used here is a metal-ligand complex of nickel, which shows a color change on reaction with biogenic amines.

Furthermore, DE 10021313 A1 describes a shelf-life indicator which can be integrated into a food packaging and changes its absorption behavior when a certain pH value, a temperature, a humidity value or a certain time has elapsed. In particular, the use of pH-sensitive dyes is emphasized here. In addition, US 6149952 describes the determination of the presence of contaminated bacteria in packaged foods. Here, a hydrophilic polymer matrix is used, in which indicators for C0 ₂ , CO, H ₂ 0, S0 ₂ , H ₂ and NH _{3 are} embedded. These analytes are released by spoilage bacteria. The above-mentioned US 2010/020952 AI refers to metal-based particle systems, which are read with a special method. Here, the change in optical properties does not occur due to a structural change of the dye in the nanoparticles, but is caused by a reaction of the inferior polymer layer.

Furthermore, the above-mentioned US 6924147 B2, DE 10021313 AI and US 6149952 relate to a limited number of analytes, they also use systems in which, the indicator dye is incorporated directly into a polymer matrix. In the case of US Pat. No. 6,924,147 B2, the indicator dye is polymerized directly into the matrix, and molecular embossing achieves selectivity only with respect to biogenic diamines of a specific chain length. In contrast, DE 100213131 AI and US 6149952 use nonspecific indicator molecules that hardly allow any differentiation with respect to the analyte. The present invention is therefore based on the object to provide a concept for controlling a packaged goods, which avoids the disadvantages mentioned above or at least reduced.

This object is achieved by a package having an indicator region according to claim 1 and a method for producing a package having an indicator region according to claim 20. Embodiments of the present invention provide a package having an indicator region having a plurality of micro-Z nanoparticles to which Indicator dye is directly bound to accept an analyte.

In embodiments, the indicator dye can be easily handled and versatile by being directly attached to the plurality of micro- / nanoparticles. For example, a simple application of the indicator dye with the plurality of micro-Z nanoparticles 1 n to or into the packaging is possible both before and during the production of the packaging. In the manufacture of the indicator dye with the plurality of micro-Z nanoparticles z. B. as a suspension and sprayed on the packaging, printed or gerake.lt be. Furthermore, the suspension can be pulled as a film and the film can be applied to the packaging. Furthermore, the immediate binding of the indicator dye to the plurality of micro Z nanoparticles leads to a faster response of the indicator dye over known systems by shorter diffusion paths.

Embodiments of the present invention will be explained below with reference to the accompanying drawings. Show it:

Fig. 1 is a schematic view of a package with an indicator region according to an embodiment of the present invention.

Fig. 2 is a flowchart of a method for producing a package with a.

Indicator area according to an embodiment of the present invention. In the following description of the embodiments of the invention, the same or equivalent elements are provided with the same reference numerals in the figures, so that their description in the different embodiments is interchangeable. FIG. 1 shows a schematic view of a packaging 100 with an indicator region 102 according to an export example of the present invention. The indicator region 102 comprises a plurality of micro-Z nanoparticles 104 to which an indicator dye for detecting an analyte is directly bound.

In embodiments, by directly bonding the indicator dye to the plurality of micro-Z nanoparticles 104, a package 100 having an easy-to-handle and versatile indicator region 102 may be provided. For example, a consumer is enabled by the inventive package 100, without opening the package 100 to control the quality of the packaged goods and optionally, for. As in the case of food or drugs, to avoid a health impairment. Furthermore, in the case of equipment or raw materials quickly and easily recognized impairment of functionality and quality and possible consequential damage can be avoided by the use.

For this purpose, the indicator dye may have an optical property and be designed to selectively change the optical property upon contact with the analyte. Further, the indicator dye may be formed such that the optical property that selectively changes due to the contact with the analyte is an absorption wavelength, an absorption intensity, an emission wavelength, an emission intensity, or a fluorescence decay time. For example, the analyte may be a biogenic amine formed in a food decomposition process, where the indicator dye reacts with the analyte and changes color.

The package 100 may include the indicator area 102 in an interior of the package 100. Furthermore, the package 100 may include a foil in the indicator region 100. Furthermore, the package 100 may be transparent in the indicator area. Thus it is for a consumer z. B. possible to control the contents of the package 100 from the outside, without opening the package 100 itself.

The indicator dye may be bonded directly to the plurality of micro Z nanoparticles 104 by means of a chemical bond. The chemical bond z. B. be an atomic bond or covalent bond. In the case of an atomic bond, the indicator dye is firmly bound to the plurality of micro-Z nanoparticles 104. Thereby, a leakage of the indicator dye from the indicator region 102, which has the plurality of micro-Z nanoparticles 104, and an associated eventual contamination of the packaged goods can be avoided. Furthermore, the packaging 100 in the Indicator region 102 have a semipermeable barrier layer, the z. B. may be formed to pass the analyte. In addition, leakage of microparticles / nanoparticles 104 out of the indicator region 102 can be avoided by the semipermeable barrier layer.

In embodiments, the plurality of microscope / nanoparticles 104 to which the indicator dye is directly bound to detect the analyte may be processed into an indicator strip applied to the package 100 or integrated into the package 100 can. In this case, the indicator region 102 of the package 100 has the indicator strip.

A release of the analyte, z. As an undesirable and / or harmful substance may, while optically with the indicator strip (based for example on absorption, reflection, luminescence, SP (SPR = Surface Plasmon Resonance, dt. Surface plasmon resonance) or IR (IR = infrared absorption or Raman absorption)), the z. B. in the

Packaging 100 is integrated, proven. This can be achieved by the production of indicator strips which can be integrated into the package 100 and which are based on different types of analytes, eg. B, undesirable and / or detectable substances, hereinafter: amines, carbon dioxide, alcohols, aldehydes, carboxylic acids, reactive oxygen species (including hydrogen peroxide), saccharides, thiols, diols, nitrogen oxides, ketones, organophosphorus compounds, cations, anions, carbon monoxide and amino acids , For this purpose, suitable reversible or irreversible indicator dyes can be used with appropriate receptor functionalities. These tailor-made indicator dyes are chemically stable (covalently) bonded to the majority of silicone / nanoparticles 104 from suitable organic or inorganic polymers. As already mentioned, the plurality of micro nanoparticles 104 can then be processed into an indicator strip, either directly or embedded in a suitable natural or artificial polymer matrix. If necessary, the indicator strip can be supplemented by a suitable semipermeable barrier layer in order, for. B. food and drug packaging guidelines. The stable chemical immobilization of the indicator dyes can prevent potential contamination of the packaged product, and further, the barrier layer can suppress potential migration of polymer and dye components into the material. The most important advantage of the packaging 100 with the indicator strip based on micro / nanoparticles 104 is its ease of use and versatility. The use of such an indicator strip allows the consumer to quickly and easily simply to make a statement about the condition of the packaged goods without direct contact.

The use of the plurality of micro-Z nanoparticles 104 has the advantage of faster response through shorter diffusion paths over known systems. Due to the small dimensions of the plurality of micro-Z nanoparticles 104, the z. B. in the range of 10 to 150 nm or in the range of 3 to 600 nm, results in a faster reaction of the embedded indicator dye on the analyte compared with the embedding thicker Polymermatrizes.

Furthermore, the plurality of micro / nanoparticles 104 may be porous. Thus, selectivities to the analytes, and thus the reliability of the color change, can be accounted for by the porosity of the plurality of micro / nanoparticles 104. Here, depending on the porosity or type of pores, the diffusion of the desired analyte can be advantageously controlled. This makes it possible to greatly improve the selectivity of the indicator strip to a few analytes.

For example, in the case of micro- / nanoparticles, it is also not possible to use a plurality of dyes at the same time, embedded in different micro-nanoparticles of the majority of micro-nanoparticles 104. These can recognize several analytes in parallel. Alternatively, in luminescence measurements, an inert dye can be added to reference the signal. This further increases the reliability of the statement of the indicator strip. Further, the micro Z nanoparticles of the plurality of micro Z nanoparticles 104 may have a core and a shell. In other words, the micro-Z nanoparticles can be designed in a core-shell construction. In this case, the core of the micro-Z nanoparticle of the plurality of micro-Z nanoparticles 104 may comprise the indicator dye, and the micro-nanoparticle cladding shell may control a solubility of the micro-Z nanoparticle in polymer materials. Thus, the core may include indicator chemistry, while the shell controls the solubility of the micro Z nanoparticle in polymeric materials.

Alternatively, the core of the micro-Z nanoparticle of the plurality of micro-Z nanoparticles 104 may be magnetic, with a first portion of the cladding of the micro-Z nanoparticle having a reference dye and a second portion of the cladding having the indicator dye. Thus, the core may be magnetic while the first shell includes a reference dye and the second shell may include the indicator dye. Alternatively, the shell of the micro-Z nanoparticle of the plurality of micro Z nanoparticles may have 104 pores, the pores being selectively permeable to a gas, and wherein the core of the micro Z nanoparticle comprises the indicator dye, wherein the indicator dye is configured to trap the gas in to detect its ionic form. Thus, the shell may have a specific porosity which selectively allows only gases to pass, while in the core there is an indicator dye for ions, which then deletes the gas in its ionic form.

Alternatively, the shell of the micro-z-nanoparticle of the plurality of microcomponents can

10 / nanoparticles 104 comprise an enzyme for chemically reacting the analyte, wherein a product is formed in the chemical reaction, and wherein the core of the micro-Z nanoparticle comprises the indicator dye and a reference dye, wherein the indicator dye is adapted to detect the product. Thus, a reference dye and an indicator dye may be present in the core while an envelope may be present in the shell.

• 15 zym which chemically converts the analyte to be examined, because this reaction subsequently produces a product, which is then detected by the indicator.

Above all, the use of the plurality of micro-Z nanoparticles 104 offers the possibility of a stable immobilization of the indicator dye and thus an underpressure.

20 contamination of the sample or the packaged goods (eg food, medicines, etc.). The indicator dye can be chemically stabilized (covalently) incorporated into the matrix of the particulate-forming polymer. Thus, they can no longer escape from the micro-Z nanoparticles and contaminate the material to be examined. This contributes greatly to the safety of the indicator strip for the consumer. The majority of

Optionally, ro-ZNanoparti no 104 may be incorporated into a polymer layer, crosslinked, or applied directly to a substrate, such as a film.

For example, in the manufacture of the package, it is possible to form the plurality of micro-Z nanoparticles 104 with (suitable) polymers into a film, mesh or foam

_* 30 to extrude, and the film, the net or the foam on the package 100 in the

Apply indicator region 102. Moreover, in the manufacture of the package 100, it is possible to extrude the plurality of micro-Z nanoparticles 104 with (suitable) polymers to the package 100.

Thus, a major advantage of micro-Z nanoparticles is their significantly improved processability over other formulations, as evidenced by their good roll-to-roll processability, ink-jet printing, screen printing, and extrusion. This is a great advantage on a favorable large-scale production of the indicator strip. The indicator dyes attached to the plurality of micro Z nanoparticles 104 carry specific receptor clutter to provide selective analyte recognition. An example of detection of amines is the tri fluoroacetyl group-amine interaction. Receptors that cause a visible change in the control surface for reactive oxygen species may be, for example, edox systems, often using metal-ligand complexes and the recognition reaction then taking place at the metal center. Fluorescein sulfonate grafts are selective receptor hydrogen peroxide receptors, maleimide functions are selective receptor groups for thiols, tricyanovinyl groups are selective receptor groups for primary and secondary amines, pyrylium functions are selective receptor primes for primary amines, hydrazine functions are selective receptor groups for aldehydes and ketones, amino groups are selective receptor clusters for aldehydes and ketones, boronic acid functions are selective receptor groups for diols, 1,2-D at the inobenzene groups are selective receptor groups for nitrogen oxides, aldehyde functions are selective receptor groups for amino acids. Crown ethers, calixarenes, and cryptands are selective receptor moieties for cations and anions, and metalpoly- phyrin complexes are selective receptor functions for carbon monoxide, amines, and nitrogen oxides.

The indicator dyes directly attached to the plurality of micro-Z nanoparticles 104 can also be used for product authentication of foods, medicines, and other goods through their selective recognition reaction. The color changes and the optical properties of the indicator strip are then unique to a specific product and can not be counterfeited. For this purpose, different colored micro / nanoparticle systems can be combined.

The package 100 of the present invention may be used to control the health of the packaged good (e.g., food or medicines) by the consumer at the time of purchase or at home. Further, the inventive package 100 can be used for rapid controls of base materials and equipment during warehousing and transportation.

Further exemplary embodiments of the present invention relate to an indicator strip (or sensor film) which can be integrated into the package 100 and can take over the quality control there. The indicator dye of the indicator strip can warn of spoiled food by a color change. For packaged foods, such as. Fish or meat, it is hardly possible for the consumer to distinguish between scher and already inedible goods. Also, the best before date is no guarantee.

The inventive package 100 having the indicator region 102 comprising a plurality of micro-Z nanoparticles 104 to which an indicator dye for detecting an analyte is directly bound may e.g. B. warn consumers of spoiled goods.

In the case of food packaging, the indicator strip (sensor film) can be integrated into the inside of the packaging 1.00 and react to biogenic amines (molecules that are formed during the decomposition process of food, especially fish and meat). Biogenic amines are also responsible for the unpleasant Gerach. Once these are released into the air in the package 100, the indicator dye of the indicator strip reacts with them and changes color, e.g. From yellow to blue. The color change of the indicator strip can thus assume a warning function. This is not only interesting to detect inedible products. Many people are hypersensitive to certain amines. A warning is even more important to them.

The information of the inventive packaging according to the present invention 100 with the indicator area 102 is based on the actual control of the packaged goods, z. B. in contrast to the best before date not on an estimate. Food. At the same time, the packaging 100 according to the invention with the indicator area is very cost-effective in comparison to other solutions, for example electronic sensors. In addition, it is necessary that things that can come into direct contact with food meet high standards. In the case of the packaging 100 according to the invention with the indicator region 102, food safety is ensured by a semipermeable barrier layer between the indicator strip and the packaged foods. This barrier layer can, for. B. be designed to pass only gaseous amines. The indicator dye (indicator chemicals) can not pass.

In addition, the indicator region 102 of the packaging 100 can be read out with a measuring module. Employees of the food and packaging industry can thus directly control the packaged goods in order, for. B. to test its freshness. The measuring module can objectively evaluate the color reaction and provide a more accurate result than the human eye. Furthermore, with the measuring module, color intermediate stages can be determined exactly. The following is a description of a method for producing the inventive package 100 with the indicator region 102 having a plurality of micro-Z nanoparticles 104 to which an indicator dye for detecting an analyte is directly bound.

2 shows a flowchart of a method for producing a packaging 100 according to an embodiment of the present invention. In a first step 130, a plurality of micro-Z nanoparticles 104 to which an indicator dye for detecting an analyte is directly bound are provided. In. In a second step 132, the plurality of micro-Z nanoparticles 104 are applied to the package in an indicator region 102.

In the method of manufacturing the package 100, a suspension may further be provided having the plurality of micro-Z nanoparticles, wherein at the second step 132, the suspension is applied to the package in the indicator area. Furthermore, the suspension can be applied to the packaging 100 as indicator strips or integrated into the packaging 100.

The suspension can be sprayed, latticed or printed onto the indicator region 102 of the packaging 100. Alternatively, the suspension can be drawn as a film and the film can be applied in the indicator region 102 of the packaging 100.

The embodiments described above are merely illustrative of the principles of the present invention. It will be understood that modifications and variations of the arrangements and details described herein will be apparent to others of ordinary skill in the art. Therefore, it is intended that the invention be limited only by the scope of the appended claims, rather than by the specific details presented in the description and explanation of the embodiments herein.

Claims

claims

Packing (100) with one. Indicator region (102), wherein the indicator region (102) comprises a plurality of micro-nanoparticles (104) to which an indicator dye is directly bound to detect an anion.

The packaging (100) of claim 1, wherein the indicator dye is chemically bonded directly to the plurality of micro Z nanoparticles (104).

Packaging (100) according to claim 2, wherein the chemical bond is an atomic bond.

The package (100) of any one of claims 1 to 3, wherein the indicator dye has an optical property and is configured to selectively alter the optical property upon contact with the analyte.

The package (100) of claim 4, wherein the indicator dye is such that the optical property that selectively changes due to contact with the analyte is an absorption wavelength, an absorption intensity, an emission wavelength, an emission intensity, or a fluorescence decay time.

The package (100) of claim 4 or 5 wherein the analyte is an amine, a carbon dioxide, an aldehyde, a carboxylic acid, a reactive oxygen species, a hydrogen peroxide, a saccharide, a thiol, a diol, a nitric oxide, a ketone, an organophosphorus compound , a cation, an anion, a carbon monoxide or an amino acid.

The package (100) of claim 6, wherein the indicator dye has a receptor group for the analyte, wherein the receptor group is a trifluorooctyl group for the amine; a redox system for the oxygen species; a fluorescein sulfonate group for the hydrogen peroxide; a maleimide function for the thiol; a tricyanovinyl group for the amine; a pyrylium function for the amine; a hydrazine unkt ion for the aldehyde or ketone; an amino group for the aldehyde or ketone; a boric acid function for the diol; a 1,2-diaminobenzene group for the nitric oxide; an aldehyde group for the amino acid; a crown ether group pe for the cation or anion; a calixarene group for the cation or anion; a cryptand group for the cation or anion; or a metal polyphyrin complex for the carbon monoxide, amine or nitrogen oxides.

The package (100) of any one of claims 1 to 7, wherein the plurality of micro Z nanoparticles (104) are polymers and embedded in a polymer matrix.

The package (100) of any one of claims 1 to 8, wherein the plurality of micro Z nanoparticles (104) are porous.

The package (100) of any one of claims 1 to 9, wherein the micro / nanoparticles of the plurality of micro Z nanoparticles (104) comprise a core and a shell.

The package (100) of claim 10, wherein the core of the micro Z nanoparticle of the plurality of micro Z nanoparticles (104) comprises the indicator dye, and wherein the shell of the micro nanoparticle controls solubility of the micro Z nanoparticle in polymeric materials.

Packaging (100) according to claim 10, wherein the core of the micro-Z nanoparticle of the

A plurality of micro-Z nanoparticles (104) is magnetic, and wherein a first portion of the shell of the micro-Z nanoparticle comprises a reference dye and a second portion of the shell comprises the indicator dye.

The package (100) of claim 10, wherein the shell of the micro Z nanoparticle of the plurality of micro Z nanoparticles (104) has pores, wherein the pores are selectively permeable to a gas, and wherein the core of the micro Z nanoparticle comprises the indicator dye, the indicator dye is formed to detect the gas in its ionic form.

The package (100) of claim 10, wherein the shell of the micro-Z nanoparticle of the plurality of micro-Z nanoparticles (104) comprises an enzyme for chemically reacting the analyte, wherein the chemical reaction produces a product, and wherein the core of the micro-Z nanoparticle the indicator dye and a reference dye, wherein the indicator dye is formed to detect the product. The package (100) of any one of claims 1 to 14, wherein the package (100) comprises the indicator area (102) in an interior of the package (100).

16. The package (100) of claim 15, wherein the package (100) in the indicator area (102) comprises a film.

The package (100) of claim 15 or 16, wherein the package is transparent in the indicator area (102).

The package (100) of any one of claims 1 to 17, wherein the package (100) in the indicator region (102) comprises a semipermeable barrier layer.

19. A package (100) according to any one of claims 1 to 17, wherein the package (100) is a package for food, medicines, equipment or raw materials.

20. Method for producing a packaging with the following steps:

Providing a plurality of micro-Z nanoparticles to which an indicator dye for detecting an analyte is directly bound; and

Producing the package so that the package has an indicator region, wherein the indicator region comprises the plurality of icro-nanoparticles to which the indicator dye is directly bound to detect the analyte.

21. The method of claim 20, further comprising the step of:

Providing a suspension comprising the plurality of micro-Z nanoparticles; wherein, when the package is created, the suspension is applied to the package in the indicator area.

22. The method of claim 21, wherein in applying the suspension in the indicator region of the package, the suspension in the indicator region is sprayed, latticed or printed on the package. 23. The method of claim 21, wherein in the application of the suspension in the indicator region of the package, the suspension is drawn as a film and the film is applied to the packaging in the indicator region.

24. The method according to claim 20, further comprising the following step:

Extruding the plurality of micro-Z nanoparticles with polymers into a film, mesh or foam; wherein, when the packaging is produced, the film, the net or the foam is applied to the packaging in the indicator region,

25. The method of claim 20, wherein in forming the package, the plurality of microparticles are polymer-extruded into the package.