WO2002093504A2 - Fil de securite pour le marquage infalsifiable d'objets - Google Patents

Fil de securite pour le marquage infalsifiable d'objets Download PDF

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Publication number
WO2002093504A2
WO2002093504A2 PCT/EP2002/005079 EP0205079W WO02093504A2 WO 2002093504 A2 WO2002093504 A2 WO 2002093504A2 EP 0205079 W EP0205079 W EP 0205079W WO 02093504 A2 WO02093504 A2 WO 02093504A2
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WO
WIPO (PCT)
Prior art keywords
nucleic acid
acid molecules
security thread
fiber
security
Prior art date
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PCT/EP2002/005079
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German (de)
English (en)
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WO2002093504A3 (fr
Inventor
Hans Kosak
André JOSTEN
Original Assignee
november Aktiengesellschaft Gesellschaft für Molekulare Medizin
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by november Aktiengesellschaft Gesellschaft für Molekulare Medizin filed Critical november Aktiengesellschaft Gesellschaft für Molekulare Medizin
Priority to DE10292112T priority Critical patent/DE10292112D2/de
Priority to AU2002312885A priority patent/AU2002312885A1/en
Priority to US10/477,158 priority patent/US20050214532A1/en
Publication of WO2002093504A2 publication Critical patent/WO2002093504A2/fr
Publication of WO2002093504A3 publication Critical patent/WO2002093504A3/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/68—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving nucleic acids
    • C12Q1/6813—Hybridisation assays
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/14—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using chemical means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber

Definitions

  • the invention relates to a security thread for counterfeit-proof marking of objects and a method for counterfeit-proof marking and identification of objects.
  • a method for concealed security marking of objects is known from EP 0 408 424 B1, in which a chemical compound is applied to the object.
  • a nucleic acid with a selected sequence, which is applied to the object in solution, is proposed as the chemical compound.
  • the nucleic acid can then be detected using a suitable detection means, whereby the object is identified.
  • this method has the disadvantage that the applied nucleic acids are incorporated into the object, which is to be done in particular by impregnating the object with the nucleic acid-containing solution. However, this presupposes that the object can absorb the nucleic acid.
  • the nucleic acid be carried on a suitable carrier
  • WO 01/09607 AI describes a microarray in which, for the detection of substances possibly contained in a solution, a multiplicity of fibers are held in a predetermined fixed position relative to one another on a carrier. Each of the fibers is provided with a special chemical detection reagent on its surface. For the detection, a solution possibly containing the substances sought is brought into contact with the microarray and a check is carried out to determine whether and if so on which fibers a reaction takes place. From this it can be concluded whether and if so which of the substances searched for are contained in the solution. - Such microarrays are unsuitable for forgery-proof marking of objects. The identification of a detection reaction taking place on the fibers requires a lot of equipment. It cannot be carried out on site.
  • DE 197 38 816 AI describes a method for marking solid, liquid and gaseous substances.
  • a synthetically produced nucleic acid sequence formed from several sequence sections is detachably connected to the object to be marked.
  • the nucleic acid sequence is removed from the object and detected by means of PCR using predetermined primers.
  • the known method is complex because of the need to separate the nucleic acids and to carry out a PCR required for identification. Identification cannot be carried out on site.
  • the object of the invention is to eliminate the disadvantages of the prior art.
  • a simple possibility for counterfeit-proof marking of objects is to be specified.
  • the marking should be as simple and inexpensive to produce as possible and accessible to conventional textile processing methods.
  • an identification method that can be carried out easily and with which the tamper-proof marking can be identified on site is to be specified.
  • a security thread for counterfeit-proof marking of objects with at least one fiber, nucleic acid molecules being bound to a fiber surface of the fiber, each having one end thereof and the other end of the nucleic acid molecules le is free in each case, so that complementary nucleic acid molecules can be bound to the nucleic acid molecules.
  • Nucleic acid molecules in the sense of the present invention are understood to mean organic molecules which have a specific affinity for organic molecules which are complementary thereto. The specific affinity causes specific binding of such molecules. For example, is a strand of DNA that hybridizes with a complementary counter strand.
  • Other suitable nucleic acid molecules are e.g. RNA, PNA, proteins, peptides, synthetic oligonucleotides and the like.
  • the proposed security thread is suitable for reliable labeling and identification because of the nucleic acid molecules N bound to it.
  • the nucleic acid molecules N can be bound to the fiber surface in defined positions. Binding is preferably carried out where the fiber surface has a corresponding functional group.
  • the nucleic acid molecules N bound to the fiber surface can be specifically detected by means of complementary nucleic acid molecules N ⁇ .
  • the fiber can basically be formed from any fibrous material.
  • the fiber is advantageously formed from a natural or synthetic polymer.
  • the natural polymer is expediently selected from the following group: cellulose, chitin, silk, wool, cotton, hemp, flax or derivatives of these polymers.
  • the synthetic polymer is expediently selected from the following group: polyamide, polyacrylonitrile, nylon, polypropylene, polyvinylidene fluoride, polycarbonate, polystyrene or derivatives of these polymers.
  • the fiber can also consist of inorganic materials such as glass, quartz or a metal, in particular gold or platinum.
  • the type of binding of the nucleic acid molecules N to the fiber surface depends on the chemical nature of the fiber material and the intended use of the fiber.
  • the nucleic acid molecules N are preferably connected to the fiber via a defined bond.
  • a defined bond is understood to mean a known chemical bond.
  • undefined bonds such as those found in UV-cross-linked DNA on nylon, are bonds in which it is not possible to specify the atoms of the nucleic acid molecules from which the binding to the fiber takes place.
  • the number of bonds with which a nucleic acid molecule N is bound to the fiber is unknown.
  • the binding of the nucleic acid molecules N to the fiber via defined bonds offers the advantage that the type of binding of all nucleic acid molecules N to the fiber is largely identical.
  • the nucleic acid molecules N can be linked to the fiber at defined positions, so that the change in the activity and the accessibility of the nucleic acid molecules N caused by the binding is the same and known.
  • the nucleic acid molecule N can be bound to the fiber surface via a covalent bond.
  • the high binding coefficient of a covalent bond prevents simple removal of the nucleic acid molecules N from the fiber surface, for example by using a solvent.
  • the nucleic acid molecule N is preferably bound to the fiber surface via a carboxy, phosphate, amino, thiol, psoralen, cholesteryl or digoxigenin group.
  • the nucleic acid molecule is expediently bound to the fiber surface via an intermediate layer, preferably containing streptavidin. Such binding is particularly preferred because of its high affinity constant. This bond cannot be broken even using a strong base such as caustic soda.
  • the intermediate layer can also be a functionalized silane layer.
  • the nucleic acid molecules N can be bound to quartz / glass fibers via derivatized silanes.
  • the fiber surface is silylated. Nucleic acid molecules containing SH groups can bind to gold fibers.
  • Not all surface groups of the fiber suitable for binding with a nucleic acid molecule N have to be saturated with a nucleic acid molecule.
  • the free functional groups remaining after the attachment of the nucleic acid molecules to the fiber surface can remain in this state or can be saturated by suitable reactions.
  • Free thiol groups can, for example, be oxidized to disulfides or reacted with low molecular weight substances such as iodoacetamide.
  • nucleic acid molecules N with the same specific sequence in each case or different nucleic acid molecules N1, N2, that is to say nucleic acid molecules with a different sequence can be bound to the fiber surface.
  • nucleic acid molecules with a non-specific sequence can be bound to the fiber.
  • the nucleic acid molecules N are preferably bound to defined areas of the fiber surface.
  • the diameter of the fibers can be 100 nm to 100 ⁇ m.
  • Such fibers can be used to produce security threads using known methods.
  • the security thread can comprise at least one further fiber.
  • the fibers of a security thread are held together by the geometric arrangement of the fibers, for example twisting, or by chemical crosslinking of the fibers with one another.
  • Several physical properties of a security thread such as length and tensile strength, are greater than those of a fiber.
  • the security thread according to the invention can be formed from fibers of different materials.
  • fibers modified with different nucleic acid molecules N, Nl, N2 can also be used. The diameter of the is expediently
  • the security thread according to the invention is expediently incorporated into textiles.
  • the textiles can have security threads modified with different nucleic acid molecules.
  • Known processes such as spinning, weaving, knitting, crocheting, knots,
  • the nucleic acid-modified security threads can form a pattern in the textile that can be created using the complementary nucleic acid Molecular N v is detectable.
  • This pattern can be implemented, for example, as a geometric pattern in the form of a symbol or a bar code.
  • a label in particular for textiles, which contains at least one security thread according to the invention.
  • the label can of course also contain security threads that have been modified with different nucleic acids.
  • Such a label can, for example, be sewn into textiles, shoes or headgear.
  • a nucleic acid micro-arrangement in the form of a matrix is formed from several security threads.
  • the matrix can be produced by textile-technical processing of the security threads.
  • a tamper-proof marking is provided, in which one
  • Base body at least one security thread according to the invention is applied.
  • the base body can be produced from a fabric, paper or non-woven material that enables liquid transport to the security thread. It can also have a suction pad.
  • the aforementioned features enable targeted transport, for example of an identification liquid, to the security thread.
  • a cover preferably made of a plastic film, can be applied to the base body.
  • the cover expediently has a first opening, preferably closed off from a plastic film, for the application of detection liquid.
  • the cover can also have a second opening, preferably closed with a transparent film, for observing the security thread. After removing the cover, the detection liquid can be applied to the base body. There it is transported by capillary forces to the at least one security thread.
  • Complementary nucleic acid molecules contained in the identification liquid are preferably designed here in such a way that they hybridize at room temperature with the nucleic acid molecules bound to the fiber surface.
  • the hybridization expediently causes a fluorescence reaction. This can be identified optically by the cover by means of a reading device or, with a suitable design, even with the naked eye.
  • the steps lit. c and lit. d performed on the marked object. It is therefore not necessary to remove the security thread from the marked item.
  • the proposed identification procedure can be carried out directly on site.
  • the steps lit. c and d performed in less than 5 min. This is achieved in particular by the fact that the nucleic acid molecules used for labeling and identification are already at room temperature, i.e. hybridize in a temperature range of 18 to 25 ° C. In particular, no heating is required.
  • steps lit. c and d only one solution or suspension can be used. This also simplifies the process.
  • the steps lit. c and d can be carried out without a washing step.
  • the detection can be carried out by means of specific hybridization and a change in the optical properties brought about as a result of the hybridization, preferably by means of fluorescence or color reaction.
  • so-called “molecular beacons” can be used, each of which is specific for a sequence of the nucleic acid olec are cool and change their fluorescence after a specific binding, preferably at room temperature, with a complementary nucleic acid.
  • the marking is detected by applying a solution containing molecular beacons.
  • the molecular beacons have nucleic acid molecules complementary to the nucleic acid molecules used for the labeling. In the case of hybridization, the bond between the nucleic acid molecules and the nucleic acid molecules complementary thereto can be carried out directly at the label
  • Fluorescence measurement take place.
  • a particular advantage of using molecular beacons is that the marking can be detected without washing steps and directly on the • marked object. It is a one-step proof. It is also advantageous that detection is possible within a few minutes.
  • the detection is carried out by means of laminar flow.
  • a solution or suspension which contains labeled nucleic acid molecules complementary to the nucleic acid molecules used for the labeling is applied to an absorbent area of a carrier.
  • the solution or suspension is transported to the security thread by capillary forces.
  • the labeled complementary nucleic acid molecule is held on the security thread by hybridization. Excess complementary nucleic acid molecules are transported on by capillary forces.
  • the marking is detected by binding the marked complementary nucleic acid molecules to the nucleic acid molecules immobilized on the security thread.
  • the location of the proof and the location of the task of the identification means are different from each other. No washing steps are required in this process either. Also this identification can take place directly on site at the marked object.
  • the hybridization sample can be coupled directly or indirectly with an enzyme that converts a substrate to an insoluble dye. This dye can then be detected as a precipitate at the hybridization site.
  • the specific hybridization can also be detected using a hybridization sample that is directly or indirectly bound to particles. The immobilization of the particles at the site of the hybridization is then used to detect the specific hybridization.
  • nucleic acid molecules N, Nl, N2 By binding different nucleic acid molecules N, Nl, N2 to one or more fibers, the unauthorized imitation or falsification of the label is difficult.
  • non-specific nucleic acid sequences can also be bound to the fiber surface, so that non-specific nucleic acid detection does not lead to the disclosure of the specific label.
  • the sequence of the nucleic acid molecules attached to the security threads should only be known to authorized persons. Objects with such security threads can be marked at a specific position on or in the object. It can also have visible visual markings.
  • the security threads thus make it possible to identify textiles, in particular items of clothing, in a forgery-proof manner.
  • at least one security thread is expediently incorporated into the label, which is attached to the textile. It is essential in connection with the present invention that the nucleic acid molecules are bound to the fibers forming the security thread before the security threads are processed.
  • the security threads can also be used to generate security markings in the form of microarrays of nucleic acid molecules N.
  • a suitable arrangement or matrix of the nucleic acid molecules N can be achieved with a textile fabric made from the security threads. These tissues can thus be used as nucleic acid microarrays. They have the advantage that they are comparatively simple and inexpensive to manufacture.
  • the nucleic acid-modified security threads can be processed by textile technology processes such as weaving, knitting, crocheting, knotting, sewing or embroidery.
  • the security threads can also be applied to a fixed matrix at defined positions in a specific arrangement, for example in the form of a brush or tufts, without forming a fabric.
  • a plastic surface can be used as a matrix, through which security threads are drawn perpendicular to the surface at defined positions.
  • a nucleic acid microarray is thus created by producing nucleic acid-modified security threads by attaching the specific nucleic acid molecules N to defined areas of the fiber surfaces and forming a matrix using these nucleic acid-modified security threads.
  • the fibers can be modified with different nucleic acids in different areas.
  • fibers modified differently with nucleic acids can be used.
  • the nucleic acid-modified security threads can comprise different nucleic acid-modified fibers and also fibers not modified with nucleic acids.
  • the security threads have the properties mentioned above.
  • 5 shows a synthesis of nucleic acid molecules N on a fiber
  • 6 shows a parallel synthesis of different nucleic acid molecules N on a fiber
  • 11a to b show a second embodiment of a label with nucleic acid-modified threads.
  • Fig. 1 the directional binding of nucleic acid molecules N to a fiber F is shown schematically.
  • Steps are generated on the surface of the fiber F by a suitable activation or reaction of linker groups L which are suitable for coupling to activated nucleic acid molecules N.
  • linker groups L which are suitable for coupling to activated nucleic acid molecules N.
  • This step is not necessary if the fiber surface already has suitable functional groups.
  • free cysteine or amino groups are suitable for coupling activated nucleic acid molecules N.
  • SH groups can be generated in the wool or silk proteins by reducing disulfide groups.
  • nucleic acid molecules N are bound to the free linker groups L, so that the nucleic acid molecules acid-modified fiber FN is obtained.
  • the nucleic acid molecules N are expediently modified with coupling groups K.
  • Suitable coupling groups K are, for example, free SH or amino groups.
  • Nucleic acid molecules N with such coupling groups K can be obtained by oligonucleotide synthesis.
  • the terminal position of the coupling group K provides good accessibility of the nucleic acid N at a hybridization of a complementary strand.
  • the nucleic acid N can also be bound to the fiber F via homofunctional or heterofunctional crosslinkers.
  • Binding to cellulose-containing fibers can take place by oxidation of sugars to aldehydes.
  • the aldehydes can be linked covalently to amino-containing nucleic acid molecules N to form Schiff's bases and then reduced to amides.
  • Polycarbonate fibers can be linked to amino-containing nucleic acid molecules N by means of carbodiimide.
  • Other plastics such as polypropylene, can be covalently linked to nucleic acid molecules N after activation in the plasma.
  • Gold threads can be bound to nucleic acid molecules N containing thiol groups.
  • Glass or quartz fibers can be activated by means of silanization and then connected to the nucleic acid molecules N.
  • the linker group L can also be bound to the fiber F via a spacer.
  • Polyglycol, polyimine, dextran, polyether can be used as spacers. With the help of the spacers, steric hindrance of the nucleic acids N during hybridization can be reduced, a certain surface layer fertilizer generated, an unspecific binding to the fiber F is reduced and the number of coupling groups K for the nucleic acid molecules N is increased.
  • the nucleic acid-modified fiber FN is brought into contact with nucleic acid molecules N ⁇ which have a sequence complementary to the nucleic acid molecules N.
  • the complementary nucleic acid molecules N x can have a signal group S.
  • the signal group S for example, a modified electrical or optical signal can be generated after the hybridization.
  • the signal group S can be a fluorophore, an antigen or an enzyme.
  • a fiber FN which has linker groups L, is divided into spatially separate reaction areas RB1, RB2, RB3. Each reaction area is implemented separately with different nucleic acids Nl, N2, N3.
  • a fiber FN1N2N3 is obtained in which different nucleic acids N1, N2, N3 are bound to defined sections.
  • FIG. 4 shows the specific detection of different nucleic acid molecules N1, N2, N3, which are bound to different sections of a fiber FN1N2N3, by hybridization with complementary nucleic acid molecules N ⁇ 1, N x 2, N ⁇ 3.
  • the fiber FN1N2N3 is brought into contact with the complementary nucleic acid molecules N 1, N * 2, N 3.
  • the specific hybridization can be detected on the basis of the signal groups S1, S2, S3 bound to the nucleic acid molecules N1, N2, N3.
  • the signal groups S1, S2, S3 can be identical or different groups. By using different signal groups S1, S2, S3, for example fluorophores, patterns can be generated on the fiber.
  • nucleic acid molecules N show a synthesis of nucleic acid molecules N on a fiber F.
  • the nucleic acid molecules N are oligonucleotides synthesized from individual nucleotides.
  • a fiber F is covalently provided with formation blocks Ba for the attachment of further nucleotides.
  • an activated nucleotide (b, c, d, e, f, g) is added to the already bound nucleotides.
  • a FBabcdefg fiber to which a defined sequence of nucleotides is fixed is obtained by the synthesis.
  • FIG. 6 shows a parallel synthesis of different nucleic acids N on a fiber F.
  • the fiber F is divided into reaction areas RB1, RB2, RB3.
  • Each section is implemented separately with different activated education blocks Bai, Ba2, Ba3.
  • an activated nucleotide (b, c, d, e, f, g) is added to the previously immobilized nucleotide in each reaction area.
  • the synthesis gives a fiber FN1N2N3 to which different oligonucleotides N1, N2, N3 are bound in defined sections.
  • FIG. 7a to c show the parallel production of nucleic acid arrays on planar carrier materials M.
  • a Number n of planar carrier materials M placed on top of one another (FIG. 7a).
  • Different nucleic acid-modified threads FN1, FN2, FN3 are passed through the carrier materials M at defined positions.
  • the security threads are then separated between the carrier materials M.
  • FIG. 8a to c schematically show a method for producing security threads Fd from fibers F.
  • the fibers shown in FIG. 8a are modified with nucleic acid molecules N, whereby fibers FN are obtained (FIG. 8b).
  • the fibers FN are spun into threads Fd in a spinning machine S (FIG. 8c).
  • FIGS. 9a to c show a first embodiment of a marking 1 with nucleic acid-modified security threads Fd.
  • Four nucleic acid-modified security threads Fd are applied in parallel to a rectangular base body 2.
  • a suction pad 2 is also located on the base body 2.
  • the base body 2 is formed by a matrix which enables a lateral flow of a liquid. If the base body 2 is contacted with a liquid, it transports the liquid to the applied security threads Fd and the suction pad 3.
  • the base body 2 can be formed from a fabric, absorbent paper or non-woven fabric, which are expediently applied to a liquid-impermeable plastic film. The plastic film prevents liquid from escaping into the environment and protects the marking.
  • An adhesive plastic film can be used to apply the marking 1 to the object to be marked.
  • the security threads Fd are in contact with the base body 2, so that a transfer of liquid that is applied to the base body 2 is possible.
  • the absorbent pad 3 absorbs most of the liquid applied, so that only a minimal amount of liquid remains in the base body 1.
  • the suction pad 3 is formed from a fabric with a high liquid binding capacity.
  • the marker 1 can comprise one or more nucleic acid-modified security threads Fd.
  • Nucleic acid molecules N with different but known sequences can be bound to the security threads Fd.
  • unknown substances such as randomly generated DNA can be bound in order to make the analysis of the security threads Fd more difficult.
  • Such randomly generated substances do not bind any detection liquid, so that one is possible to check the detection liquid.
  • security threads can be used that contain a substance such as DEAE cellulose that binds non-specifically nucleic acid molecules. Such a security thread, which binds any nucleic acid molecules N ⁇ , is used to control the detection liquid.
  • the use of several security threads Fd makes it possible to form complex markings.
  • a pattern can be formed which is only revealed if all nucleic acid molecules on the security threads Fd are identified.
  • the security threads Fd can also form geometric patterns, for example numbers, letters, symbols, barcodes.
  • the cover 4 expediently consists of an opaque material which covers the base body 2 and two Has recesses 4.1 and .2.
  • the cover 4 serves to protect the marking 1 against mechanical stress, chemical stress or radiation.
  • the first recess 4.1 shows the location on which a detection liquid for detecting the marking 1 is applied.
  • the recess 4.1 can be closed, for example with a plastic film, and can only be opened if the marking 1 is to be identified. Such a closure serves to protect against contamination, for example by fat or similar substances, which could impair the flow behavior of the base body 1.
  • the second recess 4.2 forms a viewing window which enables a view of the security threads Fd.
  • the viewing window can be closed with a transparent film to protect the security threads Fd.
  • the security threads Fd can then be seen through the viewing window 4.2, as shown in FIG. 9c. Before the identification of the marking 1, the security threads Fd can be invisible to the eye.
  • 10a to d is a method for detecting the in
  • FIG. 9 shown marking 1, the marking 1 in Fig. 10a to c is shown for better illustration without a cover.
  • a defined volume of a detection liquid is given through the recess 4.1 on the base body 2 to identify the marking 1.
  • the detection liquid contains nucleic acid molecules N 1 which are complementary to the nucleic acid molecules N bound to the security threads Fd.
  • the nucleic acid molecules N 1 used for the detection can be labeled by means of dye molecules, fluorogenic, gold or latex particles, so that the detection of a specific hybridization with nucleic acid acid molecules N is facilitated.
  • the complementary single-stranded nucleic acid molecule N used for the detection preferably has a refolding. This increases the specificity of the hybridization.
  • FIG. 10b shows the lateral flow of the detection liquid in the direction of the suction pad 3 after the end of the lateral flow. The vast majority of the
  • Fig. 10d shows the mark 1 with cover 4 after the identification of the mark 1.
  • the thicker security threads Fd show the proof of the mark 1.
  • the detection process is completed within a few seconds to minutes.
  • colored particles such as gold particles, to which the nucleic acid molecules N ⁇ are bound, only the eye and no further aids such as a photometric detector are necessary to detect the marking. This means that toxic or radioactive components can be dispensed with.
  • FIG. 11a to b show a second embodiment of a marking 1 with nucleic acid-modified security threads Fd.
  • FIG. 11a four nucleic acid-modified security threads Fd and a suction pad 3 are arranged on the base body 2.
  • a cover 4 is applied, which has two recesses 4.1, 4.2 (Fig. 11b).
  • the recess 4.1 is used to apply the detection liquid on the security threads Fd.
  • the recess 4.2 is used to observe the detection of the marking 1.
  • the security threads Fd themselves serve the lateral flow of the detection liquid.
  • nucleic acid-modified fibers The production of nucleic acid-modified fibers and their detection is explained below using an example.
  • Cellulose threads with bound oligonucleotides N are incubated in 100 ⁇ l 10 mM TrisCl, 1 mM EDTA with 1 ⁇ M complementary oligonucleotides N 1 at 37 ° C. for 30 min.
  • the Oligonu- kleotide N have a sequence complementary to the oligonucleotides and N are labeled with a biotin group at the 5 -end ⁇ .
  • the cotton is washed five times with 10 ml of TBS and incubated for 1 h in an electrophoresis chamber at a voltage of 100 V in 10 mM trisacetate, 1 mM EDTA (pH 8).
  • Dynal superparamagnetic particles
  • the threads were washed in 0.1 M Na 2 CO 3 solution pH 9.5 and 10 cm of the threads in 1 ml of 1 fM oligonucleotide N in 0.1 M Na 2 CO 3 solution were incubated at RT for four hours. To saturate any aldehyde groups still present, the suspension was brought to 1% ethanolamine and 2 mM EDTA and incubated at RT overnight. Unbound oligonucleotides were removed by intensive washing in 1% SDS solution in 10 mM TrisHCl, 1 mM EDTA, pH 8.8.
  • N ⁇ nucleic acid molecule which is complementary to the nucleic acid molecule N RB reaction area

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Abstract

L'invention concerne un fil de sécurité servant au marquage infalsifiable d'objets et comprenant au moins une fibre (F). Des molécules d'acide nucléique (N) sont liées par une de leurs extrémités à une surface de cette fibre. L'autre extrémité des molécules d'acide nucléique (N) est libre de sorte que des molécules d'acide nucléique complémentaires (N') peuvent se lier aux molécules d'acide nucléique (N).
PCT/EP2002/005079 2001-05-11 2002-05-08 Fil de securite pour le marquage infalsifiable d'objets WO2002093504A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE10292112T DE10292112D2 (de) 2001-05-11 2002-05-08 Sicherheitsfaden zur fälschungssicheren Markierung von Gegenständen
AU2002312885A AU2002312885A1 (en) 2001-05-11 2002-05-08 Method for the forgery-proof marking and identification of objects
US10/477,158 US20050214532A1 (en) 2001-05-11 2002-05-08 Secueity thread for the forgery-proof making of objects

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10122836A DE10122836A1 (de) 2001-05-11 2001-05-11 Faser, Faden und Verfahren zur Markierung und Identifizierung
DE10122836.8 2001-05-11

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WO2002093504A2 true WO2002093504A2 (fr) 2002-11-21
WO2002093504A3 WO2002093504A3 (fr) 2004-03-18

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PCT/EP2002/005079 WO2002093504A2 (fr) 2001-05-11 2002-05-08 Fil de securite pour le marquage infalsifiable d'objets

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US (1) US20050214532A1 (fr)
AU (1) AU2002312885A1 (fr)
DE (2) DE10122836A1 (fr)
WO (1) WO2002093504A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016193164A1 (fr) * 2015-05-29 2016-12-08 Selectamark Security Systems Plc Compositions utilisées pour le marquage de sécurité

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100285985A1 (en) * 2003-04-15 2010-11-11 Applied Dna Sciences, Inc. Methods and Systems for the Generation of Plurality of Security Markers and the Detection Therof
US20090286250A1 (en) * 2006-05-19 2009-11-19 James Arthur Hayward Incorporating soluble security markers into cyanoacrylate solutions
US20050112610A1 (en) * 2003-04-16 2005-05-26 Applied Dna Sciences, Inc. System and method for marking textiles with nucleic acids
US8372648B2 (en) 2003-04-16 2013-02-12 APDN (B.V.I.), Inc. Optical reporter compositions
US8426216B2 (en) * 2003-04-16 2013-04-23 APDN (B.V.I.), Inc. Methods for authenticating articles with optical reporters
US8415164B2 (en) 2003-04-16 2013-04-09 Apdn (B.V.I.) Inc. System and method for secure document printing and detection
US8415165B2 (en) * 2003-04-16 2013-04-09 APDN (B.V.I.), Inc. System and method for authenticating sports identification goods
US8420400B2 (en) 2003-04-16 2013-04-16 APDN (B.V.I.), Inc. System and method for authenticating tablets
US8124333B2 (en) * 2003-04-16 2012-02-28 APDN, Inc. Methods for covalent linking of optical reporters
KR101110767B1 (ko) 2003-07-14 2012-02-24 플렉스 프로덕츠, 인코포레이티드 노출 및/또는 은폐 패턴층을 갖는 보안 물품과 그 제조 방법
WO2007035581A2 (fr) * 2005-09-17 2007-03-29 Champion Thread Company Procédé d’application de marqueur de textile et textile ainsi produit
US10741034B2 (en) 2006-05-19 2020-08-11 Apdn (B.V.I.) Inc. Security system and method of marking an inventory item and/or person in the vicinity
US9790538B2 (en) 2013-03-07 2017-10-17 Apdn (B.V.I.) Inc. Alkaline activation for immobilization of DNA taggants
CA2598007A1 (fr) 2006-08-29 2008-02-29 Jds Uniphase Corporation Article imprime avec un revetement a effet special
TWI310414B (en) * 2007-01-09 2009-06-01 Oriental Inst Technology Dna falsity-proof fiber and manufacturing method thereof
FR2925535B1 (fr) * 2007-12-21 2011-05-06 Arjowiggins Licensing Sas Feuille de securite comprenant un substrat fibreux comportant au moins un filigrane
US8669079B2 (en) 2008-11-12 2014-03-11 Cara Therapeutics, Inc. Methods for genetic analysis of textiles made of Gossypium barbadense and Gossypium hirsutum cotton
US8940485B2 (en) * 2008-11-12 2015-01-27 Apdn (B.V.I.) Inc. Methods for genotyping mature cotton fibers and textiles
US9297032B2 (en) 2012-10-10 2016-03-29 Apdn (B.V.I.) Inc. Use of perturbants to facilitate incorporation and recovery of taggants from polymerized coatings
US9266370B2 (en) 2012-10-10 2016-02-23 Apdn (B.V.I) Inc. DNA marking of previously undistinguished items for traceability
US9963740B2 (en) * 2013-03-07 2018-05-08 APDN (B.V.I.), Inc. Method and device for marking articles
CA2926436A1 (fr) 2013-10-07 2015-04-16 Judith Murrah Lecteur multimode d'image et spectral
CN106103121B (zh) 2014-03-18 2019-12-06 亚普蒂恩(B.V.I.)公司 用于安全应用的加密光学标记物
US10745825B2 (en) 2014-03-18 2020-08-18 Apdn (B.V.I.) Inc. Encrypted optical markers for security applications
US10760182B2 (en) 2014-12-16 2020-09-01 Apdn (B.V.I.) Inc. Method and device for marking fibrous materials
CN109070130B (zh) 2016-04-11 2022-03-22 亚普蒂恩（B V I）公司 用于标记纤维素产品的方法
US10995371B2 (en) 2016-10-13 2021-05-04 Apdn (B.V.I.) Inc. Composition and method of DNA marking elastomeric material
US10920274B2 (en) 2017-02-21 2021-02-16 Apdn (B.V.I.) Inc. Nucleic acid coated submicron particles for authentication
US20210338157A1 (en) * 2020-04-30 2021-11-04 The Regents Of The University Of California Pacifier sensor for biomarker monitoring

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987006383A1 (fr) * 1986-04-09 1987-10-22 Biotal Limited Marquage d'articles qu'on desire authentifier
WO1998006084A1 (fr) * 1996-08-02 1998-02-12 Beijing Sanzhu Xinda Biological Probe Co., Ltd. Methode a technique analytique de code d'acide nucleique utilisee dans des etiquettes infalsifiables
WO2000053739A1 (fr) * 1999-03-05 2000-09-14 Mitsubishi Rayon Co., Ltd. Fibres contenant des acides nucleiques immobilises, alignement de fibres contenant des acides nucleiques immobilises et coupe transversale de telles fibres

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4617261A (en) * 1984-03-21 1986-10-14 Cetus Corporation Process for labeling nucleic acids and hybridization probes
FR2649518B1 (fr) * 1989-07-07 1991-10-18 Bioprobe Systems Sa Procede et dispositif de marquage crypte de haute securite pour la protection d'objets de valeur
GB9314394D0 (en) * 1993-07-12 1993-08-25 Slater James H A security device using an ultrasensitive microtrace for protecting materials,articles and items
DE19548528A1 (de) * 1995-12-22 1997-06-26 Giesecke & Devrient Gmbh Sicherheitsdokument mit einem Sicherheitselement und Verfahren zu dessen Herstellung
DE19738816A1 (de) * 1997-09-05 1999-03-11 November Ag Molekulare Medizin Verfahren zur Markierung von festen, flüssigen oder gasförmigen Substanzen
US5974150A (en) * 1997-09-30 1999-10-26 Tracer Detection Technology Corp. System and method for authentication of goods
US6692031B2 (en) * 1998-12-31 2004-02-17 Mcgrew Stephen P. Quantum dot security device and method
AU773978B2 (en) * 1999-04-07 2004-06-10 Dennis Michael Connolly High resolution DNA detection methods and devices
EP1179185B1 (fr) * 1999-05-07 2009-08-12 Life Technologies Corporation Procede de detection d'une substance a analyser au moyen de nanocristaux semiconducteurs
US6713309B1 (en) * 1999-07-30 2004-03-30 Large Scale Proteomics Corporation Microarrays and their manufacture
US20050032226A1 (en) * 1999-10-01 2005-02-10 Natan Michael J. Encoded nanoparticles in paper manufacture
DE10000629C5 (de) * 2000-01-10 2010-06-02 november Aktiengesellschaft, Gesellschaft für Molekulare Medizin Verfahren zur Identifizierung einer auf einen festen Körper aufgebrachten Markierung
GB0015147D0 (en) * 2000-06-21 2000-08-09 Jacobs Michael Tracking system
FR2819831A1 (fr) * 2001-01-22 2002-07-26 Arjo Wiggins Sa Papier comportant des corps porteurs d'au moins un marqueur biochimique
US6706314B2 (en) * 2001-03-15 2004-03-16 Amesbury Trust Method of labelling an object
GB0123278D0 (en) * 2001-09-27 2001-11-21 Ucb Sa Labelled articles and uses thereof
WO2003038000A1 (fr) * 2001-11-02 2003-05-08 november Aktiengesellschaft Gesellschaft für Molekulare Medizin Solution de marquage pour l'identification infalsifiable d'un objet de valeur, marquage realise a l'aide de cette solution de marquage et procede de marquage d'un objet de valeur
US20040166520A1 (en) * 2003-01-03 2004-08-26 Connolly D. Michael Identifying items with nucleic acid taggants
US20040219533A1 (en) * 2003-04-29 2004-11-04 Jim Davis Biological bar code
US20050026181A1 (en) * 2003-04-29 2005-02-03 Genvault Corporation Bio bar-code

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987006383A1 (fr) * 1986-04-09 1987-10-22 Biotal Limited Marquage d'articles qu'on desire authentifier
WO1998006084A1 (fr) * 1996-08-02 1998-02-12 Beijing Sanzhu Xinda Biological Probe Co., Ltd. Methode a technique analytique de code d'acide nucleique utilisee dans des etiquettes infalsifiables
WO2000053739A1 (fr) * 1999-03-05 2000-09-14 Mitsubishi Rayon Co., Ltd. Fibres contenant des acides nucleiques immobilises, alignement de fibres contenant des acides nucleiques immobilises et coupe transversale de telles fibres

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016193164A1 (fr) * 2015-05-29 2016-12-08 Selectamark Security Systems Plc Compositions utilisées pour le marquage de sécurité
US11549143B2 (en) 2015-05-29 2023-01-10 Selectamark Security Systems Plc Compositions for use in security marking

Also Published As

Publication number Publication date
AU2002312885A1 (en) 2002-11-25
US20050214532A1 (en) 2005-09-29
WO2002093504A3 (fr) 2004-03-18
DE10292112D2 (de) 2004-04-15
DE10122836A1 (de) 2002-11-28

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