EP1354097B1 - Paper comprising bodies which comprise at least one biochemical marker - Google Patents
Paper comprising bodies which comprise at least one biochemical marker Download PDFInfo
- Publication number
- EP1354097B1 EP1354097B1 EP02712007A EP02712007A EP1354097B1 EP 1354097 B1 EP1354097 B1 EP 1354097B1 EP 02712007 A EP02712007 A EP 02712007A EP 02712007 A EP02712007 A EP 02712007A EP 1354097 B1 EP1354097 B1 EP 1354097B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bodies
- biochemical marker
- paper
- fiber
- carrying
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
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- 239000003150 biochemical marker Substances 0.000 title claims abstract description 62
- 239000000835 fiber Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 21
- 125000003729 nucleotide group Chemical group 0.000 claims description 18
- 239000002773 nucleotide Substances 0.000 claims description 17
- 239000004005 microsphere Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920000297 Rayon Polymers 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 230000005284 excitation Effects 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000012408 PCR amplification Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 230000002285 radioactive effect Effects 0.000 claims description 2
- 230000000007 visual effect Effects 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 239000011147 inorganic material Substances 0.000 claims 1
- 230000003321 amplification Effects 0.000 description 15
- 238000003199 nucleic acid amplification method Methods 0.000 description 15
- 108020004414 DNA Proteins 0.000 description 12
- 108091028043 Nucleic acid sequence Proteins 0.000 description 8
- 238000003752 polymerase chain reaction Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000000295 complement effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000003753 real-time PCR Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 108091027568 Single-stranded nucleotide Proteins 0.000 description 2
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical compound NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 description 2
- XJLITJHUQRBWPN-UHFFFAOYSA-N 2-acetamidoacetic acid;4-[2-(4-carbamimidoylphenyl)iminohydrazinyl]benzenecarboximidamide Chemical compound CC(=O)NCC(O)=O.C1=CC(C(=N)N)=CC=C1NN=NC1=CC=C(C(N)=N)C=C1 XJLITJHUQRBWPN-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 238000007400 DNA extraction Methods 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229940104302 cytosine Drugs 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000001317 epifluorescence microscopy Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
- D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
- D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
- D21H21/46—Elements suited for chemical verification or impeding chemical tampering, e.g. by use of eradicators
-
- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/249933—Fiber embedded in or on the surface of a natural or synthetic rubber matrix
-
- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/249933—Fiber embedded in or on the surface of a natural or synthetic rubber matrix
- Y10T428/249934—Fibers are aligned substantially parallel
- Y10T428/249936—Fiber is precoated
-
- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/249933—Fiber embedded in or on the surface of a natural or synthetic rubber matrix
- Y10T428/249937—Fiber is precoated
-
- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/249942—Fibers are aligned substantially parallel
- Y10T428/249944—Fiber is precoated
-
- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/249948—Fiber is precoated
Definitions
- the present invention relates to a novel paper.
- an ink intended for printing an object microspheres of about 0.01 ⁇ m to about 5 ⁇ m in diameter, each carrying at least one nucleotide sequence.
- To identify the object it is then necessary firstly to identify the microspheres using a suitable microscope, then to take a sample of ink from the microsphere zone and purify it in order to extract the nucleotide sequence, then amplify the latter by PCR (Polymerase Chain Reaction) until the amount necessary for the analysis is obtained, the amplification and the analysis being carried out using specific primers.
- the ink is generally removed by scraping, which has the disadvantage of damaging the object.
- the invention aims in particular to meet this need.
- the invention thus relates to a new paper according to claim 1.
- the bodies used are bodies having a good affinity with the paper, so as to remain attached to the latter during conventional processing and use thereof, especially during printing.
- the carrier bodies of the biochemical marker are advantageously incorporated into the fibrous mass paper before the paper is delivered to end users.
- the extraction of the carrier bodies of the biochemical marker can be carried out easily, mechanically, without destroying the appearance of the paper, for example using tweezers, under visual control with the help of a microscope possibly.
- the largest dimension of said body is preferably of the order of one to a few mm, for example between 1 and 10 mm.
- the bodies used are fibers or fiber agglomerates, such agglomerates can form boards, the fibers can be natural, artificial or synthetic.
- the length of the fibers carrying the biochemical marker may for example be between 3 and 10 mm, being preferably close to 5 mm.
- the diameter or larger dimension of the boards carrying the biochemical marker may be greater than 2 mm, for example.
- fibers When fibers are used, they can be made in many ways, depending on the nature of their main constituent.
- thermoplastic materials such as polyamide or polypropylene.
- the biochemical marker can be incorporated into the bodies intended to carry it in multiple ways, during or after the manufacture of said bodies.
- the biochemical marker may be incorporated into the material intended to constitute the fibers before the elaboration of the latter by spinning or extrusion, or after their manufacture by a dyeing process or the like.
- the biochemical marker can be deposited on the paper intended to form the boards by a surface treatment, in particular using a sizing press or an impregnator.
- the biochemical marker can be further chemically grafted onto the fibers or other bodies used, with establishment of a strong chemical bond between the biochemical marker and the fiber or other body.
- the bodies carrying the biochemical marker may be colored or not, the color proving to facilitate their identification within the fibrous mass of the paper.
- the bodies carrying the biochemical marker may be colorless but present fluorescence in the infrared or ultraviolet, their removal then taking place under adequate lighting.
- the bodies carrying the biochemical marker may be colorless in appearance but have a fluorescence whose absorption and emission characteristics are between 400 and 800 nm.
- the revelation of the bodies is obtained under adequate illumination and through an optical filter that selects the fluorescence emission in a visible wavelength range.
- the optical principle of revealing fluorescences of the visible domain is described more precisely in the patent application. PCT / FR01 / 02480 whose content is incorporated for reference.
- the carrier bodies of the biochemical marker can be incorporated into the fibrous mass paper in various ways.
- the bodies carrying the biochemical marker can be applied in sowing, their distribution in the fibrous paper mass then being random, but preferably they are applied so as to form a relatively narrow band, which has the advantage of reducing the amount of biochemical marker used.
- the paper may comprise other security elements in addition to the bodies carrying the biochemical marker, these security elements constituting at least one additional means of authentication and / or identification.
- the bodies carrying the biochemical marker may have other properties of authentication, in particular be radioactive, magnetic, or may present electromagnetic resonance properties at particular frequencies and / or change their appearance depending on the angle of observation or under the action of an excitation source such as radiation.
- the carrier bodies of the biochemical marker may in particular contain microspheres detectable by epifluorescence microscopy, these pond microspheres bound or not to the biochemical marker.
- the microspheres may be mineral particles marked with a specific fluorescence by covalent bond, as described in the patent application W00130936 .
- the bodies carrying the biochemical marker can be in particular fluorescent, thermochromic or photochromic fibers.
- the density of carrying bodies of the biochemical marker may be very low and, for example, less than 10 bodies per dm 2 of paper when the distribution of said bodies is random and extends to the entire paper, or less than 10 bodies per linear dm when the bodies are confined in a band.
- Each body may have more than 10 7 sequences for example.
- the biochemical marker may be embedded in the material constituting said bodies, as indicated above, or be present at their surface only, or both.
- the biochemical marker will preferably be embedded in the material constituting the bodies, which makes it possible to protect it against physical attacks, in particular abrasion, or chemical attacks, in particular by falsification products.
- the biochemical marker When the biochemical marker is provided by a surface treatment, it will preferably be bonded to the carrier body by virtue of a highly crosslinked binder in order to protect it, such a binder possibly being in particular a polyurethane crosslinked with an azidine or a crosslinked styrene-acrylate copolymer. with melamine-formaldehyde.
- biochemical marker it will be preferable to use single-strand sequences of at least 70 nucleotides, for example at least 80 nucleotides. Use will preferably be at least 10 5 sequences such carrier body.
- Such a biochemical marker offers a large number of coding possibilities and is extremely difficult to detect.
- telomere sequences telomere sequences of 70 to 110 nucleotides in number less than 10 11 molecules requires “amplification”.
- amplification is meant the process of duplicating DNA sequences by a polymerase chain reaction commonly referred to as PCR.
- Performing the amplification of the sequence requires at least one primer (strand of DNA complementary to one end of the sequence to be amplified)
- the sequence may comprise a sequence of nucleotides encoding identification information, in addition to the sequence of nucleotides complementary to the abovementioned primer.
- a means of DNA authentication may advantageously be the use of specific fluorimetric probes which by hybridization with a central region of the duplicated PCR sequences emit a fluorescent signal which can be measured by a laser. The intensity of the fluorescent signal is correlated with a number of amplified sequences.
- the advantage of this technique is that it allows to validate in real time an amplification then called quantitative amplification.
- biochemical markers including double-stranded natural DNA or molecular semaphores.
- the invention further relates to a papermaking process according to claim 18.
- the bodies carrying the biochemical marker may be introduced in bulk or by surface treatment.
- the bodies may be distributed throughout the width or only part of it.
- the biochemical marker is advantageously introduced into a masterbatch used during their extrusion.
- the invention further relates to a method for authenticating and / or identifying a paper in which have been incorporated during the paper manufacturing process bodies carrying at least one biochemical marker according to claim 23.
- the method may further comprise the step of separating the sequences from the matrix of the body to which they are attached or incorporated, wherein the body matrix is the constituent material of the body.
- the step of separating the template and DNA sequences from the DNA extraction and purification step is described.
- the extraction of the marker can go through a step of dissolving the body matrix by means of one or more suitable solvents.
- the method may comprise the step of authenticating the DNA by a PCR reaction by means of specific primers.
- the amplification can be validated in real time and the amplified DNA identified. The paper is then identified.
- this amplification may be followed by analysis, for example by sequencing, to identify the DNA sequence that has been introduced into the paper.
- the invention also relates to fibers or boards according to claim 27, preferably comprising at least one nucleotide sequence, advantageously single-stranded and comprising at least 70 nucleotides, in particular at least 80 nucleotides.
- FIG. 1 to 3 a paper sheet 1 according to the invention, comprising a fibrous paper mass 2, consisting essentially of cellulose fibers for example, and a plurality of bodies 3, each carrying a specific biochemical marker, as will be specified in the after.
- the bodies 3 are constituted on the Figures 1 and 2 by fibers and on the figure 3 by boards.
- the average length of the fibers 3 is 5 mm, their diameter is 25 ⁇ m, and their specific volume is close to 1.
- the fibers 3 are confined in a limited area of the width in the example of the figure 2 , thus forming a relatively narrow band 4.
- the fibers 3 can be made by spinning, mainly from viscose for example, or by extrusion of polypropylene for example, other materials and other manufacturing processes are of course usable.
- the biochemical marker consists of nucleotide sequences.
- sequences 5 can be dispersed in the mass of the body 3, on its surface or both.
- Each body 3 comprises in the example described between about 10 5 and 10 8 sequences, each sequence consisting of a single strand of DNA preferably comprising between 70 and 110 nucleotides, for example between 80 and 100 nucleotides.
- biochemical markers comprising nucleotide sequences are given in the patent US 5,763,176 and in the international applications WO94 / 0491 and WO00 / 61799 , which will be usefully referred to, such markers being marketed by the company Cypher Sciences in particular.
- the nucleotide sequence comprises, in a manner known per se, a series of bases chosen for example from the following list: adenine A, cytosine C, guanine G, thymine T, the latter being able to be replaced by uracil, other compounds and nucleotide derivatives which may be further used, if appropriate.
- FIG. 6 schematically, a sequence which has end regions 7 and 8 each composed of a predetermined sequence of bases and a central region 9 constituting the sequence carrying the identification information.
- the end regions 7 and 8 are intended to recognize complementary primers during amplification by PCR, and comprise for example between 20 and 25 bases each.
- the central region 9 comprises, for example, between 30 and 60 bases, part of which is intended to be recognized by specific fluorimetric probes. Only six bases have been represented for the sake of simplification.
- the bodies 3 can be incorporated in the paper in various ways, depending on the distribution of the bodies 3 that is desired on the surface of the paper.
- They may be mixed with a bath used in the papermaking process, for example an impregnating bath, gluing press or coating.
- the bodies 3 are first identified and then sampled at step 10, as shown in FIG. figure 7 .
- This sampling can be carried out with or without a microscope, by means of tweezers for example, without altering the appearance of the paper.
- the number of bodies 3 taken can be very small and be equal to ten for example.
- the matrix is dissolved in step 11 in order to extract the biochemical marker.
- the bodies 3 taken are constituted by viscose fibers, they can be placed in a bath of ethyl acetate which is slightly heated. As the ethyl acetate evaporates, solvent is added until the fibers are completely dissolved. A mixture of water and ethanol for precipitating the DNA is added at the end of the dissolution.
- the bodies 3 taken are made of polypropylene fibers, they are placed for example in an extraction cartridge of a Soxhlet extractor marketed for example by the company Merck and which is operated with xylene.
- the product of the dissolution is then purified, for example using a kit purification brand "DNeasy” and marketed by QIAGEN.
- the purification procedure may include separating the biochemical marker from the dissolved matrix.
- step 12 quantitative amplification by PCR is performed in step 12 using specific primers and specific fluorimetric probes.
- the specific primers allow the amplification of the sequences 5, whereas the fluorimetric probes make it possible to measure in real time the quantity of amplified DNA.
- PCR amplification requires the use of specific primers.
- sequence 5 can be carried out according to the characteristics described in the patent application WO00 / 61799 , which allows a quantitative PCR.
- Such semaphores comprise a DNA loop at the ends of which are grafted a fluorescent molecule and a cache molecule.
- the loop recognizes on a strand of DNA the complementary sequence, it opens and becomes fluorescent, and in the negative it remains folded and emits no light.
- double-stranded natural DNA can still be used.
- the amplification can be carried out without specific primer.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Paper (AREA)
- Sampling And Sample Adjustment (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Credit Cards Or The Like (AREA)
Abstract
Description
La présente invention concerne un nouveau papier.The present invention relates to a novel paper.
Il est connu par le brevet
Il est notamment connu d'incorporer à une encre destinée à l'impression d'un objet des microsphères de 0,01 µm à 5 µm environ de diamètre, porteuses chacune d'au moins une séquence de nucléotides. Pour identifier l'objet, il est alors nécessaire dans un premier temps de repérer les microsphères à l'aide d'un microscope adéquat, puis de prélever dans la zone des microsphères repérée un échantillon d'encre et de le purifier afin d'extraire la séquence de nucléotides, puis d'amplifier cette dernière par PCR (Polymerase Chain Réaction) jusqu'à l'obtention de la quantité nécessaire pour l'analyse, l'amplification et l'analyse étant effectuées au moyen d'amorces spécifiques. L'encre est généralement prélevée par grattage, ce qui présente l'inconvénient d'endommager l'objet.It is in particular known to incorporate in an ink intended for printing an object microspheres of about 0.01 μm to about 5 μm in diameter, each carrying at least one nucleotide sequence. To identify the object, it is then necessary firstly to identify the microspheres using a suitable microscope, then to take a sample of ink from the microsphere zone and purify it in order to extract the nucleotide sequence, then amplify the latter by PCR (Polymerase Chain Reaction) until the amount necessary for the analysis is obtained, the amplification and the analysis being carried out using specific primers. The ink is generally removed by scraping, which has the disadvantage of damaging the object.
Il existe un besoin pour authentifier et/ou identifier un objet sans réaliser d'analyse destructive de l'objet.There is a need to authenticate and / or identify an object without performing destructive analysis of the object.
Un tel besoin d'authentification et/ou d'identification existe notamment pour lets papiers destinés à des utilisations diverses, en particulier les papiers destinés à servir de support à des ouvres d'art ou les papiers utilisés pour la fabrication de documents de sécurité, de documents de valeur ou de vignettes, par exemple des passeports, des billets de banque ou des étiquettes destinées à être apposés sur des articles ou des emballages.Such a need for authentication and / or identification exists in particular for papers intended for various uses, in particular papers intended to support works of art or the papers used for the manufacture of security documents, valuable documents or vignettes, such as passports, banknotes or labels intended to be affixed to articles or packaging.
L'invention vise notamment à répondre à ce besoin.The invention aims in particular to meet this need.
L'invention a ainsi pour objet un nouveau papier selon la revendication 1.The invention thus relates to a new paper according to
Les corps utilisés sont des corps ayant une bonne affinité avec le papier, de manière à rester solidaires de ce dernier lors des procédés de transformation et d'utilisation usuels de celui-ci, notamment lors de l'impression.The bodies used are bodies having a good affinity with the paper, so as to remain attached to the latter during conventional processing and use thereof, especially during printing.
Les corps porteurs du marqueur biochimique sont avantageusement incorporés à la masse fibreuse papetière avant que le papier ne soit livré aux utilisateurs finaux.The carrier bodies of the biochemical marker are advantageously incorporated into the fibrous mass paper before the paper is delivered to end users.
L'extraction des corps porteurs du marqueur biochimique peut s'effectuer facilement, de manière mécanique, sans détruire l'aspect du papier, par exemple à l'aide de brucelles, sous contrôle visuel à l'aide d'un microscope éventuellement.The extraction of the carrier bodies of the biochemical marker can be carried out easily, mechanically, without destroying the appearance of the paper, for example using tweezers, under visual control with the help of a microscope possibly.
Pour faciliter leur enlèvement, la plus grande dimension desdits corps est de préférence de l'ordre d'un à quelques mm, par exemple comprise entre 1 et 10 mm.To facilitate their removal, the largest dimension of said body is preferably of the order of one to a few mm, for example between 1 and 10 mm.
Les corps utilisés sont des fibres ou agglomérats de fibres, de tels agglomérats pouvant former des planchettes, les fibres pouvant être naturelles, artificielles ou synthétiques.The bodies used are fibers or fiber agglomerates, such agglomerates can form boards, the fibers can be natural, artificial or synthetic.
La longueur des fibres porteuses du marqueur biochimique peut être par exemple comprise entre 3 et 10 mm, étant préférentiellement voisine de 5 mm.The length of the fibers carrying the biochemical marker may for example be between 3 and 10 mm, being preferably close to 5 mm.
Le diamètre ou plus grande dimension des planchettes porteuses du marqueur biochimique peut être supérieur à 2 mm, par exemple.The diameter or larger dimension of the boards carrying the biochemical marker may be greater than 2 mm, for example.
Lorsque des fibres sont utilisées, ces dernières peuvent être réalisées de multiples manières, selon la nature de leur constituant principal.When fibers are used, they can be made in many ways, depending on the nature of their main constituent.
On peut notamment les réaliser par filage lorsqu'elles sont constituées de viscose essentiellement, ou par extrusion lorsqu'elles sont réalisées dans une matière thermoplastique telle que le polyamide ou le polypropylène.They may in particular be made by spinning when they consist essentially of viscose, or by extrusion when they are made of a thermoplastic material such as polyamide or polypropylene.
Le marqueur biochimique peut être incorporé aux corps destinés à le porter de multiples manières, pendant ou après la fabrication desdits corps.The biochemical marker can be incorporated into the bodies intended to carry it in multiple ways, during or after the manufacture of said bodies.
Lorsque lesdits corps sont des fibres, le marqueur biochimique peut être incorporé à la matière destinée à constituer les fibres avant l'élaboration de ces dernières par filage ou extrusion, ou après leur fabrication par un procédé de teinture ou autre.When said bodies are fibers, the biochemical marker may be incorporated into the material intended to constitute the fibers before the elaboration of the latter by spinning or extrusion, or after their manufacture by a dyeing process or the like.
Lorsque les corps sont des agglomérats de fibres tels que des planchettes, le marqueur biochimique peut être déposé sur le papier destiné à constituer les planchettes par un traitement de surface, notamment à l'aide d'une presse encolleuse sou d'une imprégnatrice.When the bodies are agglomerates of fibers such as boards, the biochemical marker can be deposited on the paper intended to form the boards by a surface treatment, in particular using a sizing press or an impregnator.
Le marqueur biochimique peut encore être greffé chimiquement sur les fibres ou autres corps utilisés, avec établissement d'une liaison chimique forte entre le marqueur biochimique et la fibre ou autre corps.The biochemical marker can be further chemically grafted onto the fibers or other bodies used, with establishment of a strong chemical bond between the biochemical marker and the fiber or other body.
Les corps porteurs du marqueur biochimique peuvent être colorés ou non, la coloration prouvant faciliter leur repérage au sein de là masse fibreuse du papier.The bodies carrying the biochemical marker may be colored or not, the color proving to facilitate their identification within the fibrous mass of the paper.
Les corps porteurs du marqueur biochimique peuvent être incolores mais présenter une fluorescence dans l'infrarouge ou l'ultraviolet, leur prélèvement s'effectuant alors sous un éclairage adéquat.The bodies carrying the biochemical marker may be colorless but present fluorescence in the infrared or ultraviolet, their removal then taking place under adequate lighting.
Les corps porteurs du marqueur biochimique peuvent être incolores en apparence mais présenter une fluorescence dont les caractéristiques d'absorption et d'émission sont comprises entre 400 et 800 nm. La révélation des corps est obtenue sous éclairage adéquat et à travers un filtre optique qui sélectionne l'émission de fluorescence dans une plage de longueurs d'ondes du visible. Le principe optique de révélation des fluorescences du domaine du visible est décrit plus précisément dans la demande de brevet
Les corps porteurs du marqueur biochimique peuvent être incorporés à la masse fibreuse papetière de différentes façons.The carrier bodies of the biochemical marker can be incorporated into the fibrous mass paper in various ways.
Les corps porteurs du marqueur biochimique peuvent être appliqués en semis, leur répartition dans la masse fibreuse papetière étant alors aléatoire, mais de préférence, ils sont appliqués de manière à former une bande relativement étroite, ce qui présente l'avantage de réduire la quantité de marqueur biochimique utilisée.The bodies carrying the biochemical marker can be applied in sowing, their distribution in the fibrous paper mass then being random, but preferably they are applied so as to form a relatively narrow band, which has the advantage of reducing the amount of biochemical marker used.
Le papier peut comporter d'autres éléments de sécurité en plus des corps porteurs du marqueur biochimique, ces éléments de sécurité constituant au moins un moyen d'authentification et/ou d'identification supplémentaire.The paper may comprise other security elements in addition to the bodies carrying the biochemical marker, these security elements constituting at least one additional means of authentication and / or identification.
Les corps porteurs du marqueur biochimique peuvent présenter d'autres propriétés d'authentification, notamment être radioactifs, magnétiques, ou encore présenter des propriétés de résonance électromagnétique à des fréquences particulières et/ou changer d'aspect selon l'angle d'observation ou sous l'action d'une source d'excitation tel qu'un rayonnement.The bodies carrying the biochemical marker may have other properties of authentication, in particular be radioactive, magnetic, or may present electromagnetic resonance properties at particular frequencies and / or change their appearance depending on the angle of observation or under the action of an excitation source such as radiation.
Les corps porteurs du marqueur biochimique peuvent notamment contenir des microsphères détectables par microscopie à épifluorescence, ces microsphères étang liées ou non au marqueur biochimique. Les microsphères peuvent être des particules minérales marquées d'une fluorescence spécifique par liaison covalente, comme décrit dans la demande de brevet
Les corps porteurs du marqueur biochimique peuvent être notamment des fibres fluorescentes, thermochromes ou photochromes.The bodies carrying the biochemical marker can be in particular fluorescent, thermochromic or photochromic fibers.
La densité de corps porteurs du marqueur biochimique peut être très faible et inférieure par exemple à 10 corps par dm2 de papier lorsque la répartition desdits corps est aléatoire et s'étend à l'ensemble du papier, ou inférieure à 10 corps par dm linéaire lorsque les corps sont confinés dans une bande. Chaque corps peut comporter plus de 107 séquences par exemple.The density of carrying bodies of the biochemical marker may be very low and, for example, less than 10 bodies per dm 2 of paper when the distribution of said bodies is random and extends to the entire paper, or less than 10 bodies per linear dm when the bodies are confined in a band. Each body may have more than 10 7 sequences for example.
Le marqueur biochimique peut être noyé dans la matière constituant lesdits corps, comme indiqué plus haut, ou être présent à leur surface uniquement, ou les deux.The biochemical marker may be embedded in the material constituting said bodies, as indicated above, or be present at their surface only, or both.
Le marqueur biochimique sera préférentiellement noyé dans la matière constituant les corps, ce qui permet de le protéger contre les attaques physiques, notamment l'abrasion, ou chimiques, notamment par les produits de falsification.The biochemical marker will preferably be embedded in the material constituting the bodies, which makes it possible to protect it against physical attacks, in particular abrasion, or chemical attacks, in particular by falsification products.
Lorsque le marqueur biochimique est apporté par un traitement de surface, il sera de préférence lié au corps porteur grâce à un liant très réticulé afin de le protéger, un tel liant pouvant être notamment un polyuréthane réticulé par une azidine ou un copolymère styrène-acrylate réticulé avec une mélamine-formol.When the biochemical marker is provided by a surface treatment, it will preferably be bonded to the carrier body by virtue of a highly crosslinked binder in order to protect it, such a binder possibly being in particular a polyurethane crosslinked with an azidine or a crosslinked styrene-acrylate copolymer. with melamine-formaldehyde.
Comme marqueur biochimique, on utilisera de préférence des séquences monobrin d'au moins 70 nucléotides, par exemple au moins 80 nucléotides. On utilisera de préférence au moins 105 de telles séquences par corps porteur.As the biochemical marker, it will be preferable to use single-strand sequences of at least 70 nucleotides, for example at least 80 nucleotides. Use will preferably be at least 10 5 sequences such carrier body.
Un tel marqueur biochimique offre un grand nombre de possibilités de codage et s'avère extrêmement difficile à détecter.Such a biochemical marker offers a large number of coding possibilities and is extremely difficult to detect.
La détection de séquence d'ADN de 70 à 110 nucléotides en nombre inférieur à 1011 molécules nécessite une « amplification ». On entend par « amplification » le processus qui consiste à dupliquer des séquences d'ADN par une réaction de polymérisation en chaîne appelée communément PCR.Detection of DNA sequences of 70 to 110 nucleotides in number less than 10 11 molecules requires "amplification". By "amplification" is meant the process of duplicating DNA sequences by a polymerase chain reaction commonly referred to as PCR.
La réalisation de l'amplification de la séquence nécessite au moins une amorce (brin d'ADN complémentaire d'une extrémité de la séquence à amplifier)Performing the amplification of the sequence requires at least one primer (strand of DNA complementary to one end of the sequence to be amplified)
En l'absence d'une telle amorce, l'amplification ne peut avoir lieu, ce qui offre déjà un moyen permettant de limiter l'accès à la détection de la séquence d'ADN.In the absence of such a primer, amplification can not take place, which already provides a means of limiting access to the detection of the DNA sequence.
La séquence peut comporter une suite de nucléotides codant des informations d'identification, en plus de la suite de nucléotides complémentaire de l'amorce précitée.The sequence may comprise a sequence of nucleotides encoding identification information, in addition to the sequence of nucleotides complementary to the abovementioned primer.
Un moyen d'authentification de l'ADN peut être avantageusement l'utilisation de sondes fluorimétriques spécifiques qui par hybridation avec une région centrale des séquences dupliquées par PCR émettent un signal fluorescent qui peut être mesuré par un laser. L'intensité du signal fluorescent est corrélée à un nombre de séquences amplifiées. L'avantage de cette technique est qu'elle permet de valider en temps réel une amplification appelée alors amplification quantitative.A means of DNA authentication may advantageously be the use of specific fluorimetric probes which by hybridization with a central region of the duplicated PCR sequences emit a fluorescent signal which can be measured by a laser. The intensity of the fluorescent signal is correlated with a number of amplified sequences. The advantage of this technique is that it allows to validate in real time an amplification then called quantitative amplification.
Comme séquences monobrin d'au moins 70 nucléotides, on utilisera de préférence des séquences réalisées selon les enseignements de la demande de brevet
D'autres marqueurs biochimiques sont utilisables, notamment de l'ADN naturel double brin ou des sémaphores moléculaires.Other biochemical markers can be used, including double-stranded natural DNA or molecular semaphores.
L'invention a encore pour objet un procédé de fabrication de papier, selon la revendication 18.The invention further relates to a papermaking process according to claim 18.
Les corps porteurs du marqueur biochimique peuvent être introduits en masse ou par un traitement de surface.The bodies carrying the biochemical marker may be introduced in bulk or by surface treatment.
On peut notamment mélanger lesdits corps à un bain, notamment d'imprégnation, de presse encolleuse ou de couchage, utilisé lors du traitement de la masse fibreuse papetière.In particular, it is possible to mix said bodies with a bath, in particular impregnation, gluing or coating, used during the treatment of the paper fibrous mass.
Les corps peuvent être répartis sur toute la laize ou sur une partie seulement de celle-ci.The bodies may be distributed throughout the width or only part of it.
Concernant la fabrication desdits corps, lorsque ces derniers sont constitués par des fibres extrudées, le marqueur biochimique est avantageusement introduit dans un mélange maître utilisé lors de leur extrusion.As regards the manufacture of said bodies, when the latter consist of extruded fibers, the biochemical marker is advantageously introduced into a masterbatch used during their extrusion.
L'invention a encore pour objet un procédé d'authentification et/ou d'identification d'un papier dans lequel ont été incorporés lors du processus de fabrication du papier des corps porteurs d'au moins un marqueur biochimique selon la revendications 23.The invention further relates to a method for authenticating and / or identifying a paper in which have been incorporated during the paper manufacturing process bodies carrying at least one biochemical marker according to claim 23.
Lorsque le marqueur biochimique est une séquence de nucléotides monobrin, le procédé peut comporter en outre l'étape consistant à séparer les séquences de la matrice du corps auquel elles sont rattachées ou incorporées, la matrice du corps étant la matière constituante du corps. On qualifie l'étape de séparation de la matrice et des séquences ADN d'étape d'extraction et de purification d'ADN. Lorsque le marqueur biochimique est incorporé à la matrice du corps, l'extraction du marqueur peut passer par une étape de dissolution de la matrice du corps au moyen d'un ou plusieurs solvants adéquats.When the biochemical marker is a single-stranded nucleotide sequence, the method may further comprise the step of separating the sequences from the matrix of the body to which they are attached or incorporated, wherein the body matrix is the constituent material of the body. The step of separating the template and DNA sequences from the DNA extraction and purification step is described. When the biochemical marker is incorporated into the body matrix, the extraction of the marker can go through a step of dissolving the body matrix by means of one or more suitable solvents.
Lorsque le marqueur biochimique est une séquence de nucléotides monobrin, le procédé peut comporter l'étape d'authentification de l'ADN par une réaction de PCR au moyen d'amorces spécifiques.When the biochemical marker is a single-stranded nucleotide sequence, the method may comprise the step of authenticating the DNA by a PCR reaction by means of specific primers.
En réalisant une amplification quantitative au moyen d'amorces spécifiques et de sondes fluorimétriques spécifiques, on peut valider en temps réel l'amplification et identifier l'ADN amplifié. Le papier est alors identifié.By performing quantitative amplification using specific primers and specific fluorimetric probes, the amplification can be validated in real time and the amplified DNA identified. The paper is then identified.
Dans le cas d'amplification par PCR non quantitative, cette amplification peut être suivie d'une analyse par exemple par un séquençage, afin d'identifier la séquence d'ADN qui a été introduite dans le papier.In the case of non-quantitative PCR amplification, this amplification may be followed by analysis, for example by sequencing, to identify the DNA sequence that has been introduced into the paper.
L'invention a encore pour objet des fibres ou planchettes selon la revendication 27 comprenant de préférence au moins une séquence de nucléotides, avantageusement monobrin et comprenant au moins 70 nucléotides, notamment au moins 80 nucléotides.The invention also relates to fibers or boards according to claim 27, preferably comprising at least one nucleotide sequence, advantageously single-stranded and comprising at least 70 nucleotides, in particular at least 80 nucleotides.
D'autres caractéristiques et avantages de la présente invention ressortiront à la lecture de la description détaillé qui va suivre, d'exemples de mise en oeuvre non limitatifs, et à l'examen du dessin annexé, sur lequel :
- la
figure 1 est une vue schématique de face d'un papier conforme à un premier exemple de mise en oeuvre de l'invention, - la
figure 2 est une vue schématique de face d'un papier conforme à un deuxième exemple de mise en oeuvre de l'invention, - la
figure 3 est une vue schématique et partielle de face d'un papier comportant des planchettes revêtues d'un marqueur biochimique, - les
figures 4 sont des sections transversales de deux exemples de fibres porteuses chacune d'un marqueur biochimique,et 5 - la
figure 6 représente de manière schématique une séquence de nucléotides servant de marqueur biochimique, et - la
figure 7 est un schéma en blocus illustrant de manière schématique différentes étapes d'un procédé d'identification.
- the
figure 1 is a schematic front view of a paper according to a first embodiment of the invention, - the
figure 2 is a diagrammatic front view of a paper according to a second example of implementation of the invention, - the
figure 3 is a schematic and partial front view of a paper comprising boards coated with a biochemical marker, - the
Figures 4 and 5 are cross-sections of two examples of fibers each carrying a biochemical marker, - the
figure 6 schematically represents a nucleotide sequence serving as a biochemical marker, and - the
figure 7 is a block diagram illustrating schematically different steps of an identification process.
On a représenté aux
Les corps 3 sont constitués sur les
Dans l'exemple des
Leur répartition à la surface de la masse fibreuse papetière 2 est aléatoire dans l'exemple de la
En revanche, les fibres 3 sont confinées dans une zone limitée de la laize dans l'exemple de la
Les fibres 3 peuvent être réalisées par filage, principalement à partir de viscose par exemple, ou par extrusion de polypropylène par exemple, d'autres matériaux et d'autres procédés de fabrication étant bien entendu utilisables.The
Le marqueur biochimique est constitué, dans l'exemple illustré, par des séquences 5 de nucléotides.In the illustrated example, the biochemical marker consists of nucleotide sequences.
Ces séquences 5 ont été représentées à échelle agrandie sur les
Pour chaque corps 3, les séquences 5 peuvent être dispersées dans la masse du corps 3, à sa surface ou les deux.For each
Chaque corps 3 comporte dans l'exemple décrit entre environ 105 et 108 séquences, chaque séquence 5 étant constituée par un simple brin d'ADN comprenant de préférence entre 70 et 110 nucléotides, par exemple entre 80 et 100 nucléotides.Each
Des exemples de marqueurs biochimiques comprenant des séquences de nucléotides sont donnés dans le brevet
La séquence 5 de nucléotides comporte de façon connue en soi une suite de bases choisies par exemple dans la liste suivante : adénine A, cytosine C, guanine G, thymine T, cette dernière pouvant être remplacée par de l'uracile, d'autres composés et dérivés de nucléotides pouvant être encore utilisés, le cas échéant.The nucleotide sequence comprises, in a manner known per se, a series of bases chosen for example from the following list: adenine A, cytosine C, guanine G, thymine T, the latter being able to be replaced by uracil, other compounds and nucleotide derivatives which may be further used, if appropriate.
On a représenté à la
Les régions extrêmes 7 et 8 sont destinées à reconnaître des amorces complémentaires lors de l'amplification par PCR, et comportent par exemple entre 20 et 25 bases chacune.The
Seules trois ou quatre bases ont été représentées à la
La région centrale 9 comporte par exemple entre 30 et 60 bases dont une partie est destinée à être reconnue par des sondes fluorimétriques spécifiques. Seules six bases ont été représentées dans un souci de simplification.The
Les corps 3 peuvent être incorporés au papier de diverses manières, selon la répartition des corps 3 que l'on souhaite à la surface du papier.The
Ils peuvent être mélangés à un bain utilisé lors du processus de fabrication du papier, par exemple un bain d'imprégnation, de presse encolleuse ou de couchage.They may be mixed with a bath used in the papermaking process, for example an impregnating bath, gluing press or coating.
Ils peuvent encore être pulvérisés à la surface du papier.They can still be sprayed on the surface of the paper.
Pour authentifier et/ou identifier un papier conforme à l'invention, on commence par repérer les corps 3 et on procède ensuite à leur prélèvement à l'étape 10, comme illustré à la
Ce prélèvement peut s'effectuer à l'aide ou non d'un microscope, au moyen de brucelles par exemple, sans altérer l'aspect du papier.This sampling can be carried out with or without a microscope, by means of tweezers for example, without altering the appearance of the paper.
Le nombre de corps 3 prélevés peut être très faible et être égal à dix par exemple.The number of
Une fois les corps 3 prélevés, on en dissout la matrice à l'étape 11 afin d'en extraire le marqueur biochimique.Once the
Lorsque les corps 3 prélevés sont constitués par des fibres de viscose, on peut les placer dans un bain d'acétate d'éthyle que l'on chauffe légèrement. Au fur et à mesure que l'acétate d'éthyle s'évaporé, on rajoute du solvant jusqu'à dissolution complète des fibres. On ajoute en fin de dissolution un mélange d'eau et d'éthanol destiné à précipiter l'ADN.When the
Lorsque les corps 3 prélevés sont constitués par des fibres de polypropylène, on les place par exemple dans une cartouche d'extraction d'un extracteur Soxhlet commercialisé par exemple par la société MERCK et que l'on fait fonctionner avec du xylène.When the
Le produit de la dissolution est ensuite purifié par exemple en utilisant un kit de purification de marque « DNeasy » et commercialisé par la société QIAGEN. La procédure de purification peut consister à séparer le marqueur biochimique de la matrice dissoute.The product of the dissolution is then purified, for example using a kit purification brand "DNeasy" and marketed by QIAGEN. The purification procedure may include separating the biochemical marker from the dissolved matrix.
Une fois les séquences 5 de nucléotides extraites et purifiées, on effectue à l'étape 12 une amplification quantitative par PCR à l'aide d'amorces spécifiques et de sondes fluorimétriques spécifiques. Les amorces spécifiques permettent l'amplification des séquences 5, tandis que les sondes fluorimétriques permettent de mesurer en temps réel la quantité d'ADN amplifiée.Once the nucleotide sequences are extracted and purified, quantitative amplification by PCR is performed in
L'amplification par PCR nécessite l'utilisation d'amorces spécifiques.PCR amplification requires the use of specific primers.
Ainsi, seule une personne disposant de ces amorces spécifiques est capable de procéder à amplification.Thus, only a person with these specific primers is able to amplify.
La séquence 5 peut être réalisée selon les caractéristiques décrites dans la demande de brevet
Bien entendu, l'invention n'est pas limitée aux exemples qui viennent d'être donnés.Of course, the invention is not limited to the examples that have just been given.
On peut notamment utiliser d'autres marqueurs biochimiques que ceux décrits dans la les demandes internationales
De tels sémaphores comportent une boucle d'ADN aux extrémités de laquelle sont greffées une molécule fluorescente et une molécule cache.Such semaphores comprise a DNA loop at the ends of which are grafted a fluorescent molecule and a cache molecule.
Si la boucle reconnaît sur un brin d'ADN la séquence complémentaire, elle s'ouvre et devient fluorescente, et dans la négative elle reste repliée et n'émet pas de lumière.If the loop recognizes on a strand of DNA the complementary sequence, it opens and becomes fluorescent, and in the negative it remains folded and emits no light.
On peut encore utiliser comme marqueur biochimique de l'ADN naturel double brin.As a biochemical marker, double-stranded natural DNA can still be used.
Dans ce cas, l'amplification peut s'effectuer sans amorce spécifique.In this case, the amplification can be carried out without specific primer.
Claims (36)
- Paper (1) comprising:- bodies (3) being configured for an individual extraction out of the paper, having a largest dimension lying in the range 100 µm to 10 mm,- at least one biochemical marker (5) carried by the bodies, wherein the bodies are fibers or fiber agglomerates.
- Paper according to claim 1, in which the bodies are fibers, wherein the length of the fibers lies in the range 3 mm to 10 mm.
- Paper according to claim 1, in which the bodies are fiber agglomerates constituting spots, wherein the spots are greater than 2 mm in diameter.
- Paper according to claim 1 or 2, wherein the bodies are extruded fibers, the biochemical marker being mixed with an ingredient of the fibers prior to extrusion.
- Paper according to claim 1 or 2, the bodies being fibers, wherein the fibers (3) are viscose based.
- Paper according to any preceding claim, wherein the bodies (3) carrying the biochemical marker (5) are colored.
- Paper according to any preceding claim, wherein the bodies (3) carrying the biochemical marker (5) fluoresce in the infrared or the ultraviolet.
- Paper according to any claim 1 to 6, wherein the bodies (3) carrying the biochemical marker (5) fluoresce in the visible and are observed under specific excitation through a filter.
- Paper according to any preceding claim, wherein the bodies (3) carrying the biochemical marker (5) also contain fluorescent microspheres.
- Paper according to any preceding claim, wherein the bodies (3) carrying the biochemical marker present other authentification properties.
- Paper according to any preceding claim, wherein the distribution of the bodies (3) carrying the biochemical marker (5) in the papermaking mass (2) is random.
- Paper according to any claim 1 to 10, wherein the bodies (3) carrying the biochemical marker (5) are confined in a strip (4).
- Paper according to any preceding claim, wherein the density of bodies (3) carrying the biochemical marker (5) is less than ten bodies per dm2 of paper when the distribution of bodies is random and includes all of the paper, or less than ten bodies per linear dm when the bodies are confined in a strip.
- Paper according to any preceding claim, wherein the biochemical marker is constituted by sequences of nucleotides.
- Paper according to claim 14, wherein each body includes more than 107 sequences.
- Paper according to claim 14 or 15 wherein each sequence is a single strand sequence.
- Paper according to any preceding claim, wherein the biochemical marker is bound to a binder
- A method of manufacturing paper, the method comprising:- incorporating bodies in the mass of papermaking fiber (2) during the process of making the paper, the bodies (3) having a largest dimension lying in the range 100 µm to 10 mm and carrying at least one biochemical marker (5), wherein the bodies comprise fibers or fiber agglomerates.
- A method according to the preceding claim, wherein the bodies carrying the biochemical marker (5) are mixed in a bath used during treatment of the papermaking masts,
- A method according to claim 18 or 19, wherein the biochemical marker (5) is initially introduced into a master mixture used for making the fibers (3) by extrusion.
- A method according to claim 18 or 19, wherein the fibers (3) are made by spinning viscose.
- A method according to claim 18, wherein the fibers (3) are made by extruding polypropylene.
- A method of authenticating and/or identifying paper in which bodies have been incorporated during the papermaking process, bodies carrying at least one biochemical marker, the method including the steps consisting in identifying and taking under visual control at least one body (3) carrying the biochemical marker (5) from the paper, the largest dimension of said body lying in the range 100 µm to 10 mm.
- A method according to the preceding claim, wherein the biochemical marker is extracted from the body by dissolving the matrix of said body and by purifying the product of the dissolution.
- A method according to claim 23, wherein the biochemical marker comprises at least one single strand (5) sequence of nucleotides, and wherein PCR amplification is performed by means of specific primers.
- A method according to the preceding claim, wherein the DNA is identified in real time and quantitatively by performing PCR.
- A fiber or a spot (3) having a largest dimension in the range of 100 µm to 10 mm constituting a body including at least one biochemical marker.
- A fiber according to claim 27, wherein the length of the fiber lies in the range 3 mm to 10 mm.
- A spot according to claim 27, presenting a diameter greater than 2 mm.
- A fiber according to claim 27, comprising an extruded matrix.
- A fiber according to claim 27, the fiber being based on viscose.
- A fiber or spot according to claim 27, wherein it fluoresces in the infrared or the ultraviolet.
- A fiber or spot according to claim 27, wherein it fluoresces in the visible and is observed under specific excitation through a filter.
- A fiber or spot according to claim 27, including at least one fluorescent microsphere, in particular based on inorganic material.
- A fiber or spot according to claim 27 comprising other authentification properties, especially being radioactive or magnetic, or presenting properties of electromagnetic resonance at particular frequencies and/or changing appearance with changing viewing angle or under the action of an excitation source such as a source of radiation.
- A fiber or spot according to claim 27, including more than 107 sequences,
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0100805A FR2819831A1 (en) | 2001-01-22 | 2001-01-22 | PAPER COMPRISING BODIES CARRYING AT LEAST ONE BIOCHEMICAL MARKER |
FR0100805 | 2001-01-22 | ||
PCT/FR2002/000209 WO2002057548A1 (en) | 2001-01-22 | 2002-01-18 | Paper comprising bodies which comprise at least one biochemical marker |
Publications (2)
Publication Number | Publication Date |
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EP1354097A1 EP1354097A1 (en) | 2003-10-22 |
EP1354097B1 true EP1354097B1 (en) | 2012-01-11 |
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Application Number | Title | Priority Date | Filing Date |
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EP02712007A Expired - Lifetime EP1354097B1 (en) | 2001-01-22 | 2002-01-18 | Paper comprising bodies which comprise at least one biochemical marker |
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US (1) | US7235289B2 (en) |
EP (1) | EP1354097B1 (en) |
AT (1) | ATE541091T1 (en) |
BR (1) | BRPI0206645B1 (en) |
FR (1) | FR2819831A1 (en) |
WO (1) | WO2002057548A1 (en) |
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DE10122836A1 (en) * | 2001-05-11 | 2002-11-28 | November Ag Molekulare Medizin | Security thread for forgery-proof marking of objects comprises a fiber to which a string of nucleic acid molecules is attached, such that they can be verified using a string of complementary molecules |
GB2392868B (en) | 2002-09-16 | 2006-02-01 | D W Spinks | Rainbow fibres |
CN100422440C (en) * | 2002-11-18 | 2008-10-01 | 中国印钞造币总公司 | Fiber anticounterfeit paper and manufacture method thereof |
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 |
US8372648B2 (en) | 2003-04-16 | 2013-02-12 | APDN (B.V.I.), Inc. | Optical reporter compositions |
US20050112610A1 (en) * | 2003-04-16 | 2005-05-26 | Applied Dna Sciences, Inc. | System and method for marking textiles with nucleic acids |
US20090286250A1 (en) * | 2006-05-19 | 2009-11-19 | James Arthur Hayward | Incorporating soluble security markers into cyanoacrylate solutions |
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 |
US8124333B2 (en) * | 2003-04-16 | 2012-02-28 | APDN, Inc. | Methods for covalent linking of optical reporters |
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 |
WO2006127558A2 (en) * | 2005-05-20 | 2006-11-30 | Applied Dna Sciences, Inc | System and method for authenticating multiple components associated with a particular product |
US9790538B2 (en) | 2013-03-07 | 2017-10-17 | Apdn (B.V.I.) Inc. | Alkaline activation for immobilization of DNA taggants |
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 |
AT504704B1 (en) * | 2006-06-14 | 2008-12-15 | Chemiefaser Lenzing Ag | FIBER-CONTAINING OBJECT |
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 |
FR2943074B1 (en) * | 2009-03-13 | 2011-05-20 | Arjowiggins Security | LASER MARKABLE SUBSTRATE AND METHOD FOR MANUFACTURING THE SAME |
FR2995114B1 (en) * | 2012-09-03 | 2015-09-04 | Arjowiggins Security | METHOD FOR AUTHENTICATION FROM THE CONTENT OF BIO-SOURCEE MATERIAL |
US9266370B2 (en) | 2012-10-10 | 2016-02-23 | Apdn (B.V.I) Inc. | DNA marking of previously undistinguished items for traceability |
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 |
US9243283B2 (en) | 2012-11-19 | 2016-01-26 | Src, Inc. | System and method for authentication and tamper detection using nucleic acid taggants |
US9963740B2 (en) | 2013-03-07 | 2018-05-08 | APDN (B.V.I.), Inc. | Method and device for marking articles |
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US10745825B2 (en) | 2014-03-18 | 2020-08-18 | Apdn (B.V.I.) Inc. | Encrypted optical markers for security applications |
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DE102014220289B4 (en) * | 2014-10-07 | 2016-12-29 | Bundesdruckerei Gmbh | Process for the preparation of modified regenerated cellulose and its use |
US10760182B2 (en) | 2014-12-16 | 2020-09-01 | Apdn (B.V.I.) Inc. | Method and device for marking fibrous materials |
US10519605B2 (en) | 2016-04-11 | 2019-12-31 | APDN (B.V.I.), Inc. | Method of marking cellulosic products |
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 |
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GB9314394D0 (en) * | 1993-07-12 | 1993-08-25 | Slater James H | A security device using an ultrasensitive microtrace for protecting materials,articles and items |
CA2206486A1 (en) * | 1994-12-08 | 1996-06-13 | Peter Alestrom | Chemical labelling of objects |
US5869160A (en) * | 1996-06-07 | 1999-02-09 | Avery Dennison Corporation | Release coated liners and security labels containing such release coated liners |
FR2818672B1 (en) * | 2000-12-22 | 2003-02-21 | Arjo Wiggins Sa | SECURITY PAPER COMPRISING AN AREA RESPONDING TO APOLAR SOLVENTS |
FR2838228B1 (en) * | 2002-04-03 | 2005-03-25 | Arjo Wiggins | SECURITY DOCUMENT WITH MARKER |
-
2001
- 2001-01-22 FR FR0100805A patent/FR2819831A1/en not_active Withdrawn
-
2002
- 2002-01-18 US US10/466,627 patent/US7235289B2/en not_active Expired - Fee Related
- 2002-01-18 BR BRPI0206645-9A patent/BRPI0206645B1/en not_active IP Right Cessation
- 2002-01-18 AT AT02712007T patent/ATE541091T1/en active
- 2002-01-18 EP EP02712007A patent/EP1354097B1/en not_active Expired - Lifetime
- 2002-01-18 WO PCT/FR2002/000209 patent/WO2002057548A1/en not_active Application Discontinuation
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BRPI0206645B1 (en) | 2015-03-17 |
US20040063117A1 (en) | 2004-04-01 |
WO2002057548A1 (en) | 2002-07-25 |
EP1354097A1 (en) | 2003-10-22 |
US7235289B2 (en) | 2007-06-26 |
BR0206645A (en) | 2004-02-25 |
ATE541091T1 (en) | 2012-01-15 |
FR2819831A1 (en) | 2002-07-26 |
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