Classifications

• • 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
• • 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
  • G07D7/06—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 wave or particle radiation
  • G07D7/12—Visible light, infrared or ultraviolet radiation

Definitions

• the invention relates to an article including a chemiluminescent substance.
• the invention further relates to methods and a device, which detect the presence of chemiluminescence for purposes of communicating information associated with the article.
• Useful applications of the invention include confirmation of the authenticity of an article or its contents, or conversely forgery detection.
• Counterfeiting has become a global and highly profitable business. Counterfeiters don't have to cover research and development, marketing, and advertising costs, and most of the expense goes into making goods appear convincingly authentic, rather than making the goods perform well. Moreover, convicted counterfeiters often receive minimal fines.
• Counterfeit products are not limited to pharmaceuticals. They can include any number of manufactured products, as well as natural products. For example, counterfeit products can include cigarettes, textiles, software and luxury goods. Therefore, there is a need for methods to outwit the counterfeiters in the marketplace.
• an article such as an article of manufacture, would include a marker which is imperceptible to the human eye and which is not present in the counterfeit. This would permit detection of counterfeiting or forgery.
• chemiluminescent composition which can be caused to emit one or more signals, the detection of which being indicative of information about the article associated with the chemiluminescent composition.
• the presence of one or more signals per se may be an indication of information about the article.
• a person using the invention would look for the presence of a chemiluminescent signal or emission as an indication that the article associated with the chemiluminescent composition (from which the signal was generated) was authentic or associated with one or more pieces of information or date relating to the article, as further described herein.
• the light emission or emissions (signals) may be correlated with a key or code which translates the emission(s) into information about the product.
• the chemiluminescent signals may vary in complexity and may produce various detection results which may directly or indirectly indicate the desired information about the article, as further described herein.
• Various detection devices including devices which use software, may be employed to detect and/or interpret the results and/or display the information encoded in the signal(s) into an understandable format.
• the present invention provides a method that includes providing a surface associated with an article; and providing a composition on the surface, wherein the composition includes at least one compound capable of producing a chemiluminescent signal alone or in combination with other reagents.
• the method further includes subjecting the article to a triggering source which elicits the chemiluminescent signal; and identifying unique information contained in the chemiluminescent signal, wherein the unique information is associated with the article.
• the invention further provides a method that includes providing a surface associated with an article; and providing a composition on the surface at a predetermined location on the surface, wherein the composition comprises a dioxetane.
• This method further includes subjecting the article to heat which elicits the chemiluminescent signal; and identifying unique information contained in a chemiluminescent signal, wherein the unique information is associated with the article.
• composition includes at least one compound capable of producing a chemiluminescent signal, alone or in combination with other reagents, wherein unique information associated with the article is contained in the signal.
• the present invention also provides a device for detecting forgery of an article.
• the device includes a heating source; and a detection element.
• the detection element detects light emitted by a chemiluminescent substance and converts the detected light into a detectable signal.
• the present invention provides methods which are useful for the rapid and cost- effective identification of product forgeries.
• the present invention uses chemiluminescence for forgery detection.
• Chemiluminescence is the generation of light by chemical reaction.
• Chemiluminescent substances may produce a chemiluminescent signal either alone or alone with other agents.
• chemiluminescence for forgery detection has many advantages. For example, many chemiluminescent substances are both stable and invisible to the naked eye. Also, chemiluminescent substances can be applied to a variety of surfaces, such as paper and polymeric surfaces. The chemiluminescent substances can be applied to surfaces, such as paper or cloth, by printing techniques. The chemiluminescent substance can be combined with existing dyes used for printing, or used separately. Moreover, a simple and portable device can be used to trigger and detect chemiluminescence. These and other advantages will be discussed in further detail below.
• the present invention involves providing a surface associated with an article; and providing a composition on the surface of the article.
• the composition includes at least one compound which is capable of producing a chemiluminescent signal alone or in combination with other reagents.
• the composition can further include reagents for the enhancement of the chemiluminescent signal.
• the article including the chemiluminescent substance is subjected to a triggering source which elicits the chemiluminescent signal.
• the triggering source may be selected from the following: heat, light, chemical, pressure and combinations thereof.
• Unique information which is contained in or indicated by the chemiluminescent signal may then be identified.
• the signal or signals may be correlated with a key or code which corresponds with data or information. This unique information is desirably associated with the authentic article and would therefore be indicative of the presence of an authentic article
• the chemiluminescent signal may be produced at a predetermined location on the surface.
• a non- visible chemiluminescent substance(s) can be directly applied or printed on a secret location on labels or packaging.
• the location of the dry chemiluminescent material would preferably be difficult to detect.
• the composition is invisible to the human eye.
• the composition of the chemiluminescent material will be difficult to reproduce by counterfeiters.
• One purpose of the present invention is to determine the authenticity of a product by making, marking, or labeling the product or its packaging with substances which are chemiluminescent. These substances are routinely undetectable unless triggered by a special device designed for such a purpose.
• the device preferably both triggers and detects chemiluminescence.
• the chemiluminescent substances can be combined with normal ink (dyes), or be printed alone.
• the unique information contained in the chemiluminescent signal is encoded.
• the information needed to decode the unique information in the chemiluminescent signal can be known by the manufacturer of an authentic article.
• the decoding information can include the location of the applied composition on the surface of the article.
• the manufacturer can notify a customs inspector or a pharmacist that the article is authentic if a chemiluminescent signal is produced at a discrete location on the surface of an article.
• the composition may have been applied to the top left hand corner of a drug label. When the top left hand corner of the label is placed into a suitable detection device, and chemiluminescence is "triggered" by a device designed for this purpose, a chemiluminescent signal would be produced at the disclosed location on the label. This allows for authentication of the drug.
• the unique information obtained from a positive hit can be that of the manufacturer's name.
• the unique information can include other types of information as well.
• the unique information includes at least one of the following: manufacturer's name, batch number, expiration date, characteristics of the article, lot number, a code and combinations thereof.
• the chemiluminescent substance(s) can be printed in the form of an identifying pattern, such as a bar code or characteristic image.
• the bar code/image can contain the unique information to identify the product.
• the chemiluminescent composition applied to the surface of the article can consist of a plurality of light-emitting substances.
• the composition includes chemiluminescent substances with different wavelengths.
• the composition includes chemiluminescent substances with different triggering temperatures.
• the composition includes chemiluminescent substances with different decay rates.
• an exact combination of different colors or wavelengths can encompass the unique information in the form of a code to identify the authentic product.
• an exact combination of chemiluminescent substances of different colors or wavelengths is applied in a particular pattern. Various combinations and patterns are possible, and the present invention is not limited in this regard.
• the unique information contained in the code can be compared with information that has been provided about the article. For example, the comparison of the unique information with the provided information can indicate whether or not the article is authentic or a counterfeit.
• the information provided can be visible indicia.
• the provided information can be information on the article, on packaging for the article, on separate information provided with the article, and combinations thereof.
• an inspector may come across drug bottles that include labels that look like the labels for an authentic drug from the manufacturer. However, when the label is subjected to triggering and detection, the inspector may discover that a chemiluminescent signal is absent. Moreover, even if a chemiluminescent signal is detected, it is possible that the drugs may still be counterfeit.
• the code or particular image contained in a chemiluminescent signal can be important. For example, if the visible indicia on the label shows that the drugs are from Lot No. 10, the manufacturer can verify for the inspector that Lot No. 10 has associated with it a signal with an image including two circles and a triangle, for example. If the inspector finds that this particular image is not present in this signal, this is an indication that the article is not authentic.
• information about an authentic article may be transferred from a manufacturer location to a distributor location, such as a pharmacy, by any suitable means. As described above, this information may include the location of a signal on the surface of the authentic article.
• a pharmacist may receive by mail a package from the manufacturer including a sheet that indicates that for a given lot and batch number, the signal will be located on the bottom right hand corner of the label. The pharmacist may then take a bottle showing this lot number and batch number, and will use a device to determine whether a chemiluminescent signal is emitted at the discrete location where the manufacturer has specified. If the signal is not present at this location, the drug may be counterfeit, or is not from a specified lot.
• the article for authentication can be an article of manufacture.
• the article is a natural product.
• the article can be a consumer good.
• the article can also be a drug or bioactive agent.
• the article can be currency.
• the article can be selected from the following: foods, drinks, clothing, electronics, cigarettes, cosmetics, jewelry, computer hardware, computer software, mechanical parts, accessories and shoes.
• Accessories can include, but are not limited to, purses, wallets, belts, etc.
• the present invention is not limited to particular articles.
• the surface associated with the article can include any number of surfaces.
• the surface associated with the article can be selected from, but is not limited to, the following: paper, plastic, metal, glass, a natural surface and combinations thereof. With respect to natural surfaces, these would include surfaces such as fruit peels, vegetable peels, animal skins, leather, fibers, etc.
• the surface is selected from, but is not limited to, the following: surface of the article, a surface of a label on the article, a surface of a sheet of instructions or descriptions for the article, a surface of an accessory fitted to the article, a surface of a shipping document for the article, and a surface of a container used for shipping the article. •
• the composition on the surface of the article includes at least one compound that is capable of producing a chemiluminescent signal alone or in combination with other reagents.
• the compound can be a photoactive indicator or precursor.
• the compound is selected from the following: dioxetanes, dioxetane diones, dioxetane carboxylates, peroxyoxalates, oxalates, luciferins, endoperoxides, acridine, acridinium salts, luminols, phthalates, hydrazines, hydrazides, olefins, tetrapyrroles, porphyrins, metalloporphoryins, isoluminols, peroxy compounds, xanthines and combinations thereof.
• the compound is a stable dioxetane, which can be directly applied to or incorporated within an article.
• An example of a suitable stable dioxetane for use with the present invention is 3-(2'-spiroademantane)-4-methoxy-4-(3"- hydroxy phenyl- 1,2-dioxetane).
• the temperature at which chemiluminescent substances decay to produce light is unique to the chemiluminescent substance.
• the aforementioned dioxetane can be triggered to decay to produce light at temperatures of about 60-65°C.
• a plurality of chemiluminescent substances with different trigger temperatures can encode information about the product.
• chemiluminescent precursors for example, a stable dioxetane can be generated in situ by coating at least a portion of an article with an olefin reagent and a sensitizer. Subsequent to exposure of the coated article to light and oxygen, the sensitizer is promoted to an excited state, which allows for transfer of its excess energy to ambient oxygen, with the resultant formation of singlet oxygen. The singlet oxygen therein produced reacts with the olefin reagent to form a stable chemiluminescent dioxetane which when subjected to an appropriate triggering source, such as heat, decomposes to emit light on the article.
• an appropriate triggering source such as heat
• the triggering source to which the article is subjected is selected from the following: heat, light, chemical, pressure and combinations thereof.
• the triggering and detection is performed in a dry state.
• the methods of the present invention are performed non- enzymatically.
• the methods of the present invention include the step of identifying unique information contained in the chemiluminescent signal.
• the unique information is associated with the article.
• the identifying step includes capturing the chemiluminescent signal with a photoimaging device.
• a photoimaging device Any number of photoimaging devices can be used.
• the photoimaging device can be selected from one of the following: X-ray film, photodiode, photomultiplying tube and Charge-Coupled Device (CCD) camera.
• the detection element detects light emitted by a chemiluminescent substance and converts detected light into a detectable signal.
• a device can further include a processing unit.
• a processing unit can include a programmed microprocessor which measures any deviations between information provided about the article, such as visible indicia, and unique information contained in the signal to determine if the article is a forgery.
• the device can also include a reader.
• An example of a suitable detection element which would be a light detecting device, is a photodiode.
• a photodiode For example, if light is detected, the photodiode would send out a current.
• Certain photodiodes send out a current (i.e., detect) light between 380-555 nm. This type of photodiode detects bluish-green light, such as that emitted upon decomposition of the following dioxetane: 3-(2'-spiroademantane)-4-methoxy-4-(3 "-hydroxy phenyl- 1,2- dioxetane).
• a photodiode suitable for detecting bluish-green light is available from Epigap (Berlin, Germany).
• the figure is a schematic representation of one embodiment of a suitable forgery detection device according to the present invention.
• the device may be a handheld device, if desired.
• the device would include a light-tight enclosure, a power supply, a heating element and a detection element.
• the heating element includes Peltier heating elements that are capable of heating to temperatures of greater than 85 0 C.
• the detection element is a photodiode or photomultiplying tube.
• a sample such as an article according to the present invention, is placed on the heating element in direct contact with the detection element (e.g., photodiode or photomultiplying tube).
• the detection element e.g., photodiode or photomultiplying tube.
• the heating element e.g., Peltier element
• a method of the present invention includes providing a surface associated with an article; and providing a composition on the surface of a predetermined location on the surface, wherein the composition includes a dioxetane.
• the method further includes subjecting the article to heat, which elicits the chemiluminescent signal; and identifying unique information contained in the chemiluminescent signal, wherein the unique information is associated with the article.
• the methods of the present invention can include providing information about the article, and comparing the provided information with the unique information.
• the comparison of the unique information with the provided information indicates whether or not the article is authentic.
• this predetermined location may be known only to the manufacturer of the authentic article.
• the manufacturer would know other information, as well. For example, by knowing the exact dioxetane applied, the manufacturer would also know a suitable triggering temperature for that dioxetane, and a suitable detection element for that dioxetane (e.g., a suitable photodiode for detecting a dioxetane of a certain wavelength).
• the chemiluminescent signal produced through decomposition of the dioxetane is captured with any suitable photoimaging device, such as those described above. These include, but are not limited to, photodiodes.
• the unique information contained in the signal produced upon decomposition of the dioxetane may include any of the types of unique information described above. For example, unique information may include a manufacturer's name, batch number, expiration date, characteristics of the article, lot number, code and combinations thereof.
• the information to decode the unique information in the signal produced by decomposition of the dioxetane may be known only to the manufacturer of the authentic article.
• the dioxetane may be an invisible marker, and only the manufacturer may know its location on the surface of the article.
• only the manufacturer may know the exact composition applied to the article (for e.g., the exact dioxetane applied). Therefore, only the manufacturer would know suitable triggering/detection conditions.
• the composition can be applied in the form of a bar code, which can be translated into a batch number, expiration date, etc. with the help of a programmed microprocessor and reader, for example.
• the methods of the present invention are useful for detecting forgery of an article.
• the methods of the present invention are also useful for preventing forgery distribution. This is accomplished by providing an article having associated therewith a surface to which a chemiluminescent substance is applied.
• the present invention provides an article having associated therewith a surface to which is applied a composition that includes at least one compound capable of producing a chemiluminescent signal.
• the signal is produced either alone or in combination with other reagents.
• the unique information associated with the article is contained in the signal.
• the unique information when compared with information provided about the article (e.g., visible indicia), indicates whether or not the article is authentic.
• information provided about the article e.g., visible indicia
• Information provided by the counterfeiter could be on the article, on packaging for the article, and separate information provided with the article, and combinations thereof.
• the purpose of the methods and device of the present invention is to determine any deviations between the information provided by the counterfeiter and the unique information contained in the chemiluminescent signal to determine if the article is a forgery.
• the unique information contained in the signal on the surface of the provided article is the same as that described above.
• This information can be encoded, wherein the information needed to decode the unique information may be known only to the manufacturer of the authentic article.
• the information to decode the unique information can be the predetermined location of the chemiluminescent substance on the surface of the article, a pattern, an image, etc.
• an article of the present invention can be an article of manufacture or a natural product. In one example, the article can be selected from a consumer good, a drug, a bioactive agent and currency. However, the article is not limited to these particular embodiments. Particular examples of articles are the same as those described above.
• any number of other photoactive indicators or precursors can be included in the composition that is on/in the article. Suitable examples of these are described above.
• the applied chemiluminescent composition can further include reagents for the enhancement of the chemiluminescent signal.
• a variety of surfaces can be associated with the article.
• a chemiluminescent substance can be applied or incorporated within paper, plastic, metal, glass, a natural surface and combinations thereof.
• the article surface can be a surface of the article, a surface of a label on the article, a surface of a sheet of instructions or descriptions for the article, a surface of an accessory fitted to the article, a surface of a shipping document for the article and a surface of a container used for shipping the article.
• Stable chemiluminescent substances can be applied to various article surfaces, including paper and polymeric surfaces using printing or other techniques, such as spraying, painting, dipping, etc. Once adhered to the surface, the dry chemiluminescent substance can be subjected to a triggering source to decompose. This elicits the chemiluminescent signal.
• the triggering source used on the article is selected from heat, light, chemical and combinations thereof.
• suitable chemicals that can be used to cleave protecting groups on stable dioxetanes are described in U.S. Patent No. 6,613,578 Bl to Moller, et al., which is incorporated herein by reference.
• the triggering source is heat, whereby a simple and portable device could be used to trigger and detect chemiluminescence.
• a suitable device for this purpose can include a heating source; and a detection element capable of detecting light emitted from the chemiluminescent substance and converting the detected light into a detectable signal.
• the composition of the chemiluminescent material applied to the article will be difficult to reproduce by counterfeiters.
• the composition can include a combination of chemiluminescent substances having different triggering temperatures and/or different wavelengths and/or different decay rates.
• the location of the dry chemiluminescent material will be difficult to detect, since it will preferably be non- visible to the human eye.
• the exact pattern, image, or code associated with the signal will be difficult to reproduce.
• the end result should be that counterfeiting of an article including such chemiluminescent substances should be kept at a pretty low level.
• Other advantages of the present invention include the fact that the chemiluminescent substances can be easily applied in labels or packing using simple printing techniques.
• chemiluminescent materials can be mixed with existing inks, or applied separately. Also, chemiluminescence can be triggered and detected using a simple portable device, which can even be handheld, such that it can be held directly next to a label for forgery detection, for example.
• AU of the aforementioned advantages make the present invention not only useful to outwit the counterfeiters in the marketplace, but also make it practical for those whose job or desire it is to detect forgery of an article and prevent forgery distribution.
• Example 1 Dioxetane created in situ on nylon polymer surface and on paper surface, triggered and detected with polaroid film.
• Example 2 Dioxetane created in situ on Nylon/Glass interface, triggered and detected with Polaroid film.
• control paper "sandwiched" (pressed together) with glass slide, DCMB-side facing paper
• Example 3 Dilution series of dioxetane created in situ on nylon polymer surface and on paper surface, triggered and detected with polaroid film
• Example 4 Lifetime Study. Triggering after 1 day, 5 days, 1 month, 2 months.
• Example 5 Dioxetane applied on nylon polymer surface and on paper surface, triggered and detected with polaroid film.
• Example 6 Dilution series of dioxetane applied on nylon polymer surface and on paper surface, triggered and detected with polaroid film
• Example 7 Lifetime Study. Triggering after 1 day, 5 days, 1 month, 2 months.

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• 2006
  • 2006-04-25 EP EP06751427A patent/EP1889231A1/de not_active Withdrawn
  • 2006-04-25 WO PCT/US2006/015728 patent/WO2006118889A1/en active Application Filing

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