Background In a vast variety of situations, it is important to know whether an enclosure, package, mailer, envelope, product, food package or any other transported or in transit item has been safely and rapidly decontaminated or elevated of a particular pathogen prior to receipt or opening of the item. To protect the safety of individuals involved in the transportation process or an individual who receives the item it is of key importance that the individuals coming in physical or remote contact with the item be given proper warning that the item has been safely decontaminated or sterilized prior to delivery.

Pathogens can be of a spore-like nature, a bacteria, or a virus which have happened to come in contact with an item being transported or has deliberately been placed in or on the item being transported. Pathogens can be highly infectious, virulent, and in some cases resistant to available medications. In each case, both decontamination of any transport item potentially harboring a pathogen as well as indication that the item has been safely decontaminated is imperative in order to reduce contact and potential health risks from handling.

Individuals involved in transport and receipt of an item would benefit from the immediate knowledge that an item has been properly decontaminated prior to encountering or contacting the item. These individuals include: a worker which picks up mail from a mail box, sorts it, and drives the mail to a local post office; a worker who sorts and distributes the

mail at the post office; an individual responsible for delivery of mail to an off site location; individuals at the off-site location who further distribute mail; subsequent delivery personnel who deliver the mail to a recipient; the recipient of a piece of mail; and individuals who the mail is ultimately sent to.

During the process of transport including pickup, routing, delivery, and receipt, any of a number of possible contacts are made between a piece of mail and an individual handling the piece. Each of these point contacts provides a risk of transferring an infectious agents from a potentially contaminated piece of mail, a package, an envelope, a product, or any other enclosure to a contacting person.

Relevant literature of interest includes U. S. Patent numbers: 4,859, 538; 5,144, 112; 5,156, 810; 5,189, 281; 5,273, 360; 5,415, 999; 5,685, 641; 5,788, 375; 5,918, 981; 6,046, 455; and 4,389, 217 SUMMARY OF THE INVENTION Rapid response decontamination indicating devices and methods for reporting successful rapid decontamination of transported or in transit items are provided. The devices comprise an intrinsic indicating unit having a composition capable of reporting that a decontamination step has taken place. The device reports both qualitatively and quantitatively that items produced and or transported which have the potential of being contaminated with a hazardous pathogen has been successfully decontaminated and is free of the pathogenic agent. The reporting indicator intrinsically responds to the physical, chemical, or energetic processes involved and imparted during decontamination. The device is prepared and embodied according to the decontamination process intended. Depending on the choice of decontamination processes and desired method of reporting successful decontamination, the device may give visual conformation or conformation when technically analyzed by an analog or digital method.

DESCRIPTION OF THE SPECIFIC EMBODIMENTS Rapid response decontamination indicating devices and methods for reporting successful rapid decontamination of transported or in transit items are provided. The devices comprise an intrinsic indicating unit having a composition capable of reporting that a decontamination step has taken place. The device reports both qualitatively and quantitatively that items produced and or transported which have the potential of being contaminated with a hazardous pathogen has been successfully decontaminated and is free of the pathogenic agent. The reporting indicator intrinsically responds to the physical, chemical, or energetic processes involved and imparted during decontamination. The device is prepared and embodied according to the decontamination process intended. Depending on the choice of decontamination processes and desired method of reporting successful decontamination, the device may give visual conformation or conformation when teclmically analyzed by an analog or digital method.

Desirably, any product producer who wishes to ensure that during transport and prior to receipt of the products they are responsible for that the items are both decontaminated and indicated as such are delivered to the recipient with full and adequate knowledge to the recipient that the delivered product has be decontaminated. Importantly, indicators for decontamination should be compatible with and considered for various forms of pathogenic agent transfer including skin contact, inhalation, and ingestion. The particular means of pathogen prorogation and transmission can be assessed during the selection of a particular indicator device.

Importantly, a direct and causative indication eliminates possible mishaps or mislabeling of an item which is reported to be decontaminated. Simple marking or cataloging of a transport item alone does not conclusively indicate that the item was properly decontaminated. By employing an indicating means which directly responds to the processes imparted by the decontamination event, all parties involved in sending, distributing and receiving a transportable item will have confidence that the item was properly decontaminated.

Efforts at reducing the spread of contamination can significantly more effective from knowledge of what transport enclosures or transport item have been decontaminated during the transportation or transit of suspected items. Pre and forewarning recipients that the decontamination or non-decontamination event has taken place provides the recipient with vital information to make judgments that may effect their safety. Thus the deployment and use of devices which report the status and completeness of pathogen decontamination can provide critical information and knowledge to those who may be impacted by the threat of possible contamination.

Indicator composition : Compositions can contain a chemical constituent which responds to a particular decontamination parameter. Compositions can include chemicals, molecules, matrices, formulations, mixtures, direct reporter molecules, indirect report chemistries, or the like. Usually an indicator composition will be formulated to be transferred to a particular substrate as well as sensitivity to a particular decontamination phenomena.

Inorganic and organic compounds or molecules can be utilized to be responsive to a decomposition phenomena. The molecular structure or matrix will be dictated by the energy or influence encountered during a decontamination process. Matrix components can also contain substances which stabilizes the indicating agent so that the agent only responds to an intended decontamination process. For example, it may be important to stabilize the indicating agent from temperatures encountered during transport whereas the indicator is intended to respond to irradiation. Alternatively, it may be important to stabilize an indicator against certain energy wavelengths encountered during transport yet ensure that the indicator responds to the specific wave lengths intended for use during the decontamination process.

For example, an indicator intended for gamma irradiation or electron beam irradiation can be protected from false triggering due to exposure from ultraviolet light by incorporating ultraviolet light blocking agents into the matrix. In this case, the effects of transient exposure to ultraviolet light during transport can be mitigated. Since electron beam or gamma radiation fully penetrates an article during exposure, the blocking agent intended will not effect the ability of the indicator to change properties during a decontamination event.

Ultraviolet light blocking agents can be those typically

used for blocking UV radiation. Alternatively, a UV protective layer can be applied over the indicating material which accomplishes blocking UV light, yet allows transmission of irradiating beams used in decontamination.

Indicator compositions for electron beam and cobalt 60 gamma irradiation: Cobalt 60 sources for gamma rays and electron beam sources are often used for radiating and decontaminating items of transfer or consumption. Organic and inorganic compounds capable of selectively undergoing a discernible, irreversible, and reportable change during the irradiation process are of importance.

Compositions include any chemistry sensitive to and capable of irreversibly chromically or chemically reporting that the composition has been exposed to a prescribed energy dose from irradiation beam which is sufficient to kill any pathogens present at the same time that the composition is irradiated. Irreversible indicating compounds can be monomolecular or polymeric in structure. It is imperative that the chemical structure reacts directly to the irradiation beam used for decontamination. The indicating material must absorb the irradiation it is bombarded with and alter in a way which results in a distinct and irreversible structural change which can be easily assessed. For example, the indicator may be a chromophore which develops a color or changes color in response to the radiation dose. It is desirable that the chromophore responds in color change intensity quantitatively to the amount of the dose applied during the decontamination process. It is also desirable that the indicator be broadly applicable to a wide range of different items under transport and that the indicator be low cost, simple to apply, and single use to ensure that there is no loss of information regarding the decontamination process.

Photochromic materials can include organic or inorganic compounds. For example, a naturally derived inorganic material such as fluorsilicate can be transformed in color by electron beam exposure or a cobalt 60 source. Polymers such as polyvinyl chloride (PVC) show a darkening and color change from a clear or pigmented color to darkened yellow color after irradiation with gamma rays. Compounds such as methylviologen in polycyano- polycadmate hosts can under go photo induced color changes. Conjugated organic chromophores can be changed from being colored to non-colored with adequate dosages of

gamma irradiation while other organic compound may undergo a electron state change due to energy induced bond formation or breakage. Also of interest are diacetylenic monomers which when exposed to gamma irradiation and or electron beam sources will polymerize to form highly colored polydiacetylenic compounds.

In the case of diacetylenic materials, the degree of exposure to a electron beam source will influence the degree of polymerization and consequently the depth of color indicated by the material. Thus, diacetylenic materials can be used to quantitatively report the radiation dosage over a broad range of doses with good incremental resolution in color density.

Exemplary dosages can range for the sub millirad range to greater than 1000 millirad. It is of particular importance to ensure that the chromatic change in the indicating element is irreversible in order to mitigate any potentially false readings. Diacetylenic materials when polymerized do not depolymerize and can be formulated to maintain their coloration without reversal.

Diacetylenic materials can be prepared in a variety of forms including hydrophilic, hydrophobic, and multi-phasic characteristics. For ease of application, stability, and activity it will be desirable to use a diacetylenic compound with characteristics suitable to format the material to be subjected to during actual usage. In the case of using an organic solvent for application, it is desirable to use a diacetylenic compound which is soluble in the solvent of interest. The diacetylene group can be coupled between two identical organic side groups to form a symmetric molecule or between two structurally different groups to form an asymmetric molecule. In the case of using a water based system for application, it will be desirable to use an analog of the diacetylenic compound that can be emulsified into an aqueous medium. For example, a lipid-like structure such as 10,12-pentacosadiynoic acid or 10,12-tricosadiynoic acid may be formulated into a micro-emulsion using compatible surfactants.

Indicator compositions for ultraviolet light treatment: Irreversible ultraviolet light responsive compounds or molecules can be utilized which indicate directly that an appropriate amount of ultraviolet light was used to decontaminate the surface of a surface suspected of contamination with a particular pathogen. The response time of the indicating

material to the irradiation process should be commensurate with the exposure time necessary to fully destroy a pathogen. The indicator response can be quantitative with respect to the amount of ultraviolet irradiation employed. A variety of materials available are known to change color or properties when exposed to ultraviolet light, however, it is important that the change be irreversible and cumulative in response to the irradiation dose being applied.

Ultraviolet light sensitive irreversible chromophores are of particular interest since it is likely that the use of ultraviolet light as a decontamination means will be used in more selected situations by an end recipient of a transport item. In this case, a distinct and easy to visualize color change is desirable since the application of the indicator and irradiation of the transport item may be performed by a less well trained individual as opposed to a professional in the distribution process.

The intensity, color density range, photochromic irreversibility, and ease of application provided by diacetylenic materials make them a important class of compounds as subjects for indicating completeness of ultraviolet light decontamination. Diacetylenic monomers are known to quantitatively change color from a non-colored essentially non-visible form to the blue polydiacetylenic form. Diacetylenic compounds can be formulated into various ink matrices or deployed in an adherent from to be placed on the transport item of interest.

Methods for the preparation and usage of various polydiacetylenic materials as photo sensitive dyes are known to those of skill in the art.

Various chemical analogs of diacetylenic compounds can be utilized. As described above, the diacetylene group can be coupled between two identical organic side group to form a symmetric molecule or between two structurally different groups to form an asymmetric molecule. In the case of using a water based system for application, it will be desirable to use a analog of the diacetylenic compound that can be emulsified into an aqueous medium. For example, a lipid-like structure such as 10, 12-pentacosadiynoic acid or 10,12- tricosadiynoic acid may be formulated into a micro-emulsion using compatible surfactants.

Indicator compositions for heat treatment: Irreversibly and thermally responsive compounds or molecular species or polymers can be utilized which respond directly to a temperature imparted on an item exposed to elevated temperatures during decontamination. The time response to an elevated temperature should be rapid and respond in the same time necessary to fully kill any potential contaminating pathogens.

Various class of thermochromic materials can be utilized to change color in response to specific temperature settings. Examples include: leucodyes, transition melting waxes with embedded colors, nano-pigments, molybdenum analogs, doped or undoped vandium dioxide, mercuric iodide, indolinospirochromenes, spiropyrans, polythiophenes, polybi-thiophenes, di- b-napthospiropyrans, and polydiacetylenic compounds. Whereas a wide variety of thermally responsive chromic change agents are available, however the criteria for thermochromic irreversible limits those materials which will meet the specific parameters.

Importantly, polydiacetylenic compounds serve not only as an effective class of irradiation sensitive indicators, they also meet the criteria imposed on using them for use as a class of indicators for temperature indicating materials for heat-based decontamination. Diacetylenic compounds in their ordered blue polymeric form change color immediately in response to temperature. Methods for the preparation and usage of various polydiacetylenic materials as thermally sensitive dyes can be found in U. S. Patent Numbers: 4,238, 352,5, 685,641, and 5,918, 981. The temperature range necessary to kill pathogenic agents is typically 160°F for 15 seconds. Polydiacetylenes transition from an ordered blue form to a disordered red form when a particular temperature is achieved. Polydiacetylenic compounds can be synthesized in a form which gives an irreversible color change response from the blue form to a red form.

Irreversible forms of polydiacetylenic materials can be made by reducing or eliminating intermolecular hydrogen bonding moieties.

Indicator compositions for vapor treatment: Chemically responsive molecular species can be employed which respond directly to the presence of gases and vapors typically used during decontamination processes. Often chlorine vapors, peroxide vapors, or plasma

ionized peroxide vapors are used. Chemical moieties sensitive to the presence of allowable concentrations of a specific decontamination vapor can be attached to a chromic change agent which, in turn, will change color due to the presence of the chemical vapor.

Decontamination vapor contact should result in an irreversible chromic change so that false readings are not encountered.

Indicator substrates: Indicator substrates can include any solid or liquid substrate that conveniently possesses the properties of integrating or supporting an indicating material or compound. Substrates can be planar or structured. Substrates can be made of common materials such as paper, plastic, metal, foils, fabrics, glass, ceramic, rubbers, food stuffs, digestible or non-digestible materials, natural products, nylon, various co-polymers, alloys, composite materials, woods, liquids including aqueous and non-aqueous, gels, laminating materials, ink bases, carrier materials, organic or inorganic materials, leather and other animal based substrates, particle based substances, micro particle based substances, and assorted other materials with compatible properties for carrying the agent capable of detecting and reporting decontamination.

The indicating material may be formulated into a liquid phase where the indicating liquid formulation is contained within an unbreakable vessel. The liquid-based indicator can be made to respond to a decontamination event in much the same way as a solid phase indicator.

Liquid phase indicators may find advantage as they can be made to circulate throughout a transport container or package. Also, liquid phase indicators can be placed in a flexible pouch which may confonn to a particular configuration during transport. Alternatively, liquid phase indicators may be configured for easier analysis for determination of the impact of a decontamination event compared to a solid phase indicator device.

Application and construction methods: The indicating material is formulated into a liquid base and applied to a substrate using a printing process. The liquid base can contain the indicating material, a matrix, upon application and drying adheres, supports, and or stabilizes the indicating material, and a liquid that is used as a medium to emulsify and transport the indicating material to a substrate. The liquid formulation can be used as an ink

which is formulated to be suitable for specific printing processes including: ink jet printing, pad printing, silk screen printing, off-set printing, spray coating, ball point pen marking, transfer printing, flexographic printing, stamping, roll-on printing, painting, dripping, dip coating, or the like. The liquid base should contain an agent at a concentration which can be adequately detected once the decontamination process has occurred.

Concentrations of the indicating material can be from 0. 01% by weight to saturating levels of greater than 50% by weight. Typically the indicating material will be present from 0.1% to 20% by weight compared to the formulation constituents; more usually, the indicating material will be present from 1% to 10% in the final formulation.

Liquids used to formulate the transfer composition can be organic solvents, oil based, polymer based, water based, or compatible media which can be used with a selected printing or transfer process. Liquid media may be solutions at room temperature or may require heating prior to the transfer process. Liquid carriers may be selected to be highly volatile for rapid drying or less volatile but practical for absorbing into a selected substrate.

A matrix component may be added to the formulation to facilitate adherence of the indicating material to a substrate, used as a thickening agent for particular printing process, or used in some cases as a stabilizing agent to prevent any false changes in the indicating material which could cause misinterpretation as to whether the device is properly reporting a decontamination event. For example, it may useful to use a matrix component which shields the indicating material for being falsely triggered by an energy source capable of causing the indicator to change but was not intended to cause the indicator to change.

The matrix component can be an organic polymer, a thermoset polymer, a silicon based material, a plastic or placticizer, a micro particle additive, a wax, a polyethylene glycol, a rubber, a sealant, a cellulosic material, natural byproduct, a synthetic additive, an ink stabilizer, an adhesive material, or the like which imparts the formulation with desirable properties for adhering, binding, stabilizing, thickening, depositing or orienting the indicating agent. The matrix component can be present in concentrations compatible with

the indicating material from 0.1% up to 50% by weight. More usually from 1% to 25% and typically from 5% to 10% by weight.

Hidden, encoded, and embedded indicators: In certain cases, it is desirable to utilize a decontamination indicator which although not visible by eye is visible by a process employing optical or chemical detection processes which electronically, digitally, or mechanically reports to an observer that the decontamination process has taken place. In cases where privacy, secrecy, confidentiality or the is elected to be maintained, it will be important to utilize an indicator means where knowledge of the decontamination process is maintained only by those employing the indicating means.

For example, dyes, compositions, materials, chemicals, or other reports can be employed which transition from an original state to a reportable secondary state when a decontamination process has taken place. In particular, a dye indicator may be used which is not visible by eye either prior to or after a decontamination process taking place. However, the indicating dye does undergo a transition from one state to another as a result of the impacting decontamination process. The state change in dye/indicator can be visualized using spectral, optical, or chemical analytical means. Fluorescence can be used where a dye is transformed from a non fluorescent state to a fluorescent state by a decontamination process. The resulting state change in the dye causes a detectable fluorescence change in the indicator which can be quantitatively detected, analyzed, and reported by compatible equipment.

Materials, chemicals, dyes, specialized molecules or the like can be used as reporters which are embedded, hidden, or encoded in a transport item. Electronic or wavelength specific devices may also be employed where the devices are not obviously present in the item of interest. In each of these cases, detection and reporting will utilize a compatible analytical means to report that a decontamination process was accomplished.

Transport items carrying a hidden, encoded, or embedded decontaminating indicating means may carry the indicator at a location which is specific or random but in any case identifiable to those inspecting for decontamination. For example, the indicating means

may be a hidden part of a printed graphic such as the methods in utilize in printing currency.

The indicator may be a part of the actual packaging material used for carrying a transport item. Alternatively, the indicator may be integrated directly into an ink used for printing on the item.

Visible indicators: Indicators may be utilized to provide various visual outputs. The output can be in the form of a message, a symbol, a graphic, a design, a printed note, a character, line art, high resolution art, an emblem, a mark, a fill pattern, a color zone, a changed image, a warning sign, lettering, a grid, a line and a diagram or the like. The form of the indicator can be modified to reinforce a particular emphasis or communication to the end recipient.

The language or communication in all cases should be discernible and convey an adequate understanding of decontamination.

The indicator comes in the form of an ink, a label, a stamp, internalized or impregnated into a packaging material or envelope, part of a postage mark, a piece of tap, a thermally transferred material, a spray coat, an embossed message, silk screen print, an adhesive, part of the dye coloring of a package, a copied item, an inserted item not directly a part of the transport piece, laminated items, an ink jet printed zone, a pad printed region or location, a roll on region, an offset printed domain, a typed item, a region formed by liquid transfer, or any practical or commercial method which can be utilized to create an indicator.

The visual output will also be dictated by the composition of the indicator. Various color change agents can be employed to report decontamination which may reveal or change to a particular color. Colors and color combinations may be useful for communicating a particular concern level or assurance message.

Tactile indicators: Tactile indicators can be utilized where the item of transport may be intended for receipt by a visually impaired person or receipt by a device capable of physically identifying that the item was properly decontaminated of potentially pathogenic materials.

Tactile decontamination indicators involve utilize a thermally responsive material that change shape as a result of a particular decontamination process. For example,

a plastic sheet can be imprinted or form to become a shape such as a dot, a letter, or a symbol.

When the plastic sheet is heated to above the thermal set point of the plastic, the dot, letter, or symbol will change shape due to the stress relief imparted on the plastic during formation of the indented dot or letter. The shape change or disappearance can be used as an indicating zone signifying that the plastic piece has been raised to a specific temperature. A plastic sheet can should be selected based on the its thermal set point so that it is applicable to the temperature range used for decontamination. There exist a variety of methods commonly know for forming features in plastics. Plastic compositions such as polystyrenes and high impact polystyrenes used for applications such as thermoforming make ideal candidates as tactile indicators. A tactile indicator once prepared can be cut out and attached to a transport object of interest. The formed plastic part can be used as an indicator by first feeling the presence of feature on the plastic device prior to decontamination heat treatment and the absence of the same feature after heat treatment.

Automated reporting indicators : Of interest are bar code based indicators which can be read optically by high speed optical reading systems which communicate to the distribution organization that the item was both properly decontaminated and properly sorted for subsequent delivery. UPC coding process as well as mail delivery coding can be used as an algorithm for implementing the indicating region.

Indicators utilized by recipient : It may be desirable for the end recipient of an item to personally utilize a decontamination method. A company or individual which is in receipt of a transport item may desire to perform a decontamination process in-house. In this case, it will be important for those involved to use an indicator which they themselves apply prior to a decontamination step. For example, the end recipient may wish to irradiate a piece of mail with a hand-held ultraviolet lamp to decontaminate any expose areas. Prior to irradiation and denomination, it will be highly desirable to mark the item with a ultraviolet sensitive indicator which tells the recipient that the irradiation process was performed properly.

During the irradiation step the mark will change color indicating that the process is progressing and at the end an endpoint color will ensue indicating that the process is complete.

Alternatively, a recipient may wish to decontaminate an item using a heating process. In this case it will be important for the recipient to utilize an indicator which reports that a high enough level of temperature was applied to the entire item to ensure that any potentially contaminating pathogens in the item were fully killed. It will be appropriate to utilize an irreversible temperature indicator that is calibrated to 160°F or above to ensure complete pathogen elimination. The indicator may also have the convenient capability to report that an adequate level of temperature was achieved and that further increases in temperature could result in flammable combustion and the risk of fire.

Indicators used by the end recipient could include or involve the use of a marker with an indicating ink, a label, a stamp, a decal, a tape, a card, a clip or any other convenient carrier of the sensitized indicating material. The particular embodiment of the indicator will depend on the type of decontamination process utilized and the type of item which is being decontaminated without any particular limitations except for cost, convenience, reliability, and accuracy.

Warning indicators reporting non-decontamination: It may be desirable that a reciprocal indicator may be utilized which warns that decontamination has not occurred at all or at least not successfully. In this case, the indicator would report in an amenable format that the transport item or package being received has not undergone any particular decontamination process.

A non-decontamination indicator may warn graphically that whereas during transport decontamination did not occur, that decontamination should be implemented prior to further contact or further transport. The indicator can be encoded in such a way that the transport item is recognizable either visually or using scanning or imaging. Thus, the item is routed appropriately to a decontamination center or area for subsequent decontamination.

A personal identification code system can be employed where the sender of an item encodes an identification number or message which is only revealed during the decontamination process. The code is predetermined and interpretable only by the individual or receiving

party. The code servers as multiple usage including decontamination, indication of who the sending party is, and selective information to the receiving party.

Postal workers, government agencies, military personnel, overnight delivery services, blood centers or blood donation services, food producers, beverage producers, pharmaceutical developers, health care product producers, cosmetic product producers, processors and producers and those involved at any level of preparation, packaging, transport, fulfillment, reselling, photo processing, mail order, internet selling and mailing, local and national distribution, logistics, warehousing, unpacking of palletized goods, shelving and merchandising, examining, checking, purchasing, and consumption would benefit from the knowledge that an item in transit that they come in contact with has been safely decontaminated from any pathogen that may have been introduced either intentionally or unintentionally. Indicators possessing the intrinsic property of directly reporting that an item has been successfully decontaminated during the transit process is described herein.

In consideration of protecting the food supply for example, cereal boxes or convenience foods intended for consumption by children could be supplied with an indicator that tells parents that the cereal box was properly treated during a decontamination process.

Alternatively, perishable partially hydrated foods which have the potential of facilitating the growth and culturing of a particular pathogen are of particular interest for decontamination.

Meats, cheeses, vegetables, milk and other dairy products, yogurt, tofu or the like may serve as mediums for pathogens to grow. An indicator on the package or conveniently placed in proximity of the food stuff will serve to acknowledge that the food was properly decontaminated prior to distribution to the consumer.

Those involved with product research and development, production, manufacturing, supply, distribution, overnight delivery, warehousing, packaging, re-packaging, of products, goods, materials and supplies other than ingestibles which are intended for consumer, commercial, military and defense, professional, agricultural, entertainment, travel, marketing, clothing and garment, institutional, industrial, mass mailers, e-commerce product shippers, ticket services, delivery services, publishers, printers, recyclers, meat co-packagers, non-perishable co- packers, water bottlers, educational, government, health care, athletics, media,

technology and software, environmental or other typical or non typical occupational uses will benefit from the knowledge that the item, objects or material of interest has been safely decontaminated from the presence of a pathogen that may have been present on the goods.

Of particular interest are indicators on items which can effectively harbor and release a pathogenic agent during the product's cycle from production to receipt from those who are designated to receive the item. For example, package goods which may appear tamper resistant but can actually be tampered with by injection or reversing the packaging assembly process will have an advantage if they contain a sensing indicator which tells recipients that the package or item was decontaminated from the possible presence of a pathogen prior to recipient.

A variety of means can be utilized to neutralize or kill pathogens contaminating items being transported and received including: gamma irradiation, prolonged temperatures above 160°F, chemical vapors, high vacuum, electrostatic discharge, high voltage exposure, extreme atmospheric pressure, and other means which can disrupt pathogens at the cellular or molecular level. In each case, it will be important to utilize an indicator which specifically reports that the intended decontamination process was performed according to the specifications of the intended decontamination process.

In the case of irradiation, it would be useful and informative to indicate to an individual coming in contact with a transport item that the item had been adequately irradiated at a radiation dose level that will ensure that any potential contaminating pathogen is killed and that the item is safely decontaminated. In the case of using temperatures, it is important to indicate to an individual that an adequate temperature was reached for the item to be safely decontaminated. In the case of using high vacuum, is important to use an indicator that reports that the item was safely decontaminated using an appropriate level of vacuum. In the case of electro static charge, it is important to indicate to an individual that an adequate level of charge was applied to the item to report that the item was decontaminated. In the case of using chemical vapors, it is important to indicate that an appropriate level of vapor exposure was presented to the item to ensure that it was safely decontaminated.

The indicator should quantitate the decontamination dose adequately to ensure that the decontamination process is fully lethal to all pathogens involved. The dose and indicator should coincide. The dose should result in completely killing pathogens to eliminate the possibility of developing resistant strains of the pathogens. The indicator should indicate that pathogenic lethality was complete.

Any individual transferring, routing, transporting, handling, or receiving an enclosed item such as a package, product, parcel, envelope, mail card, magazine, currency, tickets, print ads, inserts, free standing inserts (FSI's) newspaper, mailed advertisement or any other item of transport for evaluation or ingestion would benefit from direct knowledge that the item was, at the time the individual came in contact with the item, safe to handle or posses.

An indicator could be associated with the item prior to a decontamination process indicating the items decontamination history. The indicator should be easily and readily discernible by anyone who would benefit from the safety associated with the decontamination process. The indicator should be plainly apparent in a symbolic, graphic, written, marked, post marked, stamped, inked, labeled, tagged, permanent, or visual form such that the indicator directly reports that the decontamination process was successful. The indicator should be capable itself of sensing with accuracy and precision that the decontamination process occurred at a level known quantitatively to kill any possible harbored pathogen.

Ideally the indicator should be applied directly prior to the decontamination process and physically, chemically, thermally, electronically, colorimetrically, or the like respond in a visual, electronic or preferable means that is unambiguous to an individual coming in contact subsequent to the decontamination event.

Although a variety of chemical, electrical, physical, and tactile systems can be utilized as reporters for completion of a decontamination process, it is of particular interest to use a class of materials which respond to a range of different contamination methodologies.

Of interest are classes of chromic change agents which can be rapidly sensitized to particular physical and chemical effects encountered during the decontamination process.

Chromic change agents which indicate a colorimetric change are important in that they visually show a color or optical density change when they are triggered by a stimuli such as the energy transmitted during a decontamination event.

Various categories of temperature sensitive dyes and thennochromic agents are of interest since they can be specifically tuned to respond to the temperature levels imparted for base decontamination. Thermochromic agents utilized should indicate an irreversible color change to maintain memory that the decontamination process did in fact take place.

Various categories of irradiation sensitive dyes and photochromic agents are of interest since they can be specifically modified to respond to essential wave lengths and energy levels necessary to impart decontamination. For example, it will be important to use a radiation sensitive dye that reports that gamma rays emitted and penetrated at a particular energy level were used to decontaminate mail.

In particular, polydiacetylenic compounds act as chromic change agents that have a multiplicity of applications. For example, polydiacetylenic materials can be chemically structured to respond to particular temperature ranges and undergo an irreversible color transition from a blue ordered polymeric form to a red disordered form when a particular temperature level is reached.

Monomeric diacetylene forms of the material can be used to indicate exposure to radiation such as gamma radiation from a cobalt 60 source. Gamma radiation exposure to monomeric crystalline diacetylenic materials cause a polymerization reaction to occur which transforms the colorless monomer to a deeply colored polymer.

Monomeric diacetylenic materials are also readily polymerized from a colorless form to a deeply colored polymeric for using UV irradiation also known as a useful pathogen decontamination wave length. Intense UV irradiation at 245 nanometers conveniently polymerizes diacetylenes to colored polydiacetylenes and at the same time severs to decontaminate exposed surfaces.

Other polymeric forms of polydiacetylenic materials can be used to indicate the presence of chemical vapors capable of decontaminating enclosed or non-enclosed items of transfer. The blue form of the polymer exhibits a color transition to the disordered red form of the polymer when the polymer is directly exposed to vapors known to kill pathogen such as concentrated chlorine or solvent vapors such as chloroform or dichloromethane.

Institutes or companies may choose to use a combination of decontamination processes to rid potential pathogens from transported items. In this case, it will be desirable to have an indicator which identifies and reports that each of the processes were effectively employed.

For example, a combination irradiation and thermal sterilization may be utilized. In this case it will important to report both that irradiation was complete and that the appropriate temperature level was achieved.

A decontamination combination might be carried out together at one site or remotely at different geographical sites. In either case, it is important to plan, design, and implement an indicator which can discretely report a particular decontamination event. The indicator should be easily and readily discernible to the recipient of an item which possess a transported item.

Bottled, wrapped, folded, canned, sealed, bagged, enveloped, pouched, sleeved, boxed, cartooned, master cartooned, palletized, shrink wrapped, molded, thermoformed and other conventional or non-conventional packaging types can be conveniently designated with an indicator which directly indicates that the individual item has been properly decontaminated.

Companies which are in the business of decontamination such as those who develop or supply decontamination equipment or services can provide an important and integral service to those involved who come in contact with an item that such equipment or service has been applied to. The decontamination service or equipment maker can immediately apply an indicator prior to entering a decontamination device. The indicator will report that the item, or bulk of items, was appropriately treated and decontaminated.

An indicator can come in a wide range of different forms. The indicator may be intended to be made visible to an individual coming in contact with the item being transported.

Alternatively, the indicator may be intended to be discrete or not visible on an item. In this case, the indicator may be encoded or visible only be a technical or analytical means to those involved in the transport process but not to the end recipient of the item. There may be particular circumstances where the indicator is purposefully hidden from the end recipient to maintain secrecy from anyone involved in harmfully contaminating the transport item with a pathogenic substance.

Hazardous pathogens or agents : Any of a variety of infectious agents may be unintentionally or intentionally introduced into an item or enclosure to be transported or in transit. Pathogens may include bacteria, spores of bacteria, viruses, viral particles, a hazardous proteins, prions, DNA or RNA fragments encoding infectious or hazardous agents or molecules. The intended decontamination process utilized should have sufficient properties to render a pathogenic agent.

Points for introducing decontamination indicators: Integrated decontamination indicating devices can be implemented and deployed at any point along the continuum of preparation, transport, and receipt of an item being transported or in transit. Likewise, reporting and identification that a decontamination event has taken place can occur at any time immediately following the actual decontamination process.

The application or attachment of an intrinsic indicator can be produced as a part of an enclosure which will be used for transporting an item. The indicator can be formed into the packaging material or printed on the enclosure at the point of manufacturing the enclosure.

The indicator can be applied, adhered, or printed on the enclosure after the enclosure has been formed. The indicator can be applied, adhered, or integrated into an item intended to be placed into an enclosure and prior to transport. The indicator can be attached, printed, or adhered to an item of transport such as a piece of mail, a food article, or other item to be distributed after the item is enclosed in a vessel intended for transport.

An individual or sender sending an item to a recipient may elect to attach, adhere to, or place in an indicator into an item or an enclosure containing the item to be transported. Once the indicator is properly affixed to the item or enclosure, the individual or sender can then deliver the item or enclosure/item to a delivery service. Under certain circumstances, the indicator may also be placed within an enclosure prior to transport. In this way, the indicator is known to be contained only by the sender of an item. The delivery means, assuming that it possess a decontamination process, will then channel the item through the process in a way the indicator responds to the decontamination event. Any one having subsequent contact with the item may then gain knowledge that the item was properly decontaminated.

The indicator can be made available from a major producer or supplier of items relating to the preparation, delivery, and receipt of an object to be transported. The supplier may offer any of a variety of embodiments which contain an indicating device. For example, the manufacture, producer, supplier or distributor may carry a form of the indicator which is a part of paper, enclosed items notes or cards, Post-it notes, address labels, stamps used in an office stamping machine, paper clips, marking flags, staples, envelopes, pens and pencils, various tapes including shipping tape, folders, bands, rubber bands, string, reinforcing materials, protective shipping envelopes, fasteners, highlighters, ink jet cartridges, or the like.

Items containing the indicator can come in any convenient form typically used in the office and which promote use of the decontamination indicator.

Companies selling in-office postage meters can benefit from employing indicating inks that are formulated to respond to a particular decontamination process. Companies which sell printers or related copying and marking equipment benefit from inks or toners which contain an indicating ink or dye as a part of the medium used in the printing process. Companies already selling items typically associated with an item to be transported such as address labels, Post-it notes, envelopes, pens, pencils, or the like can readily as a part of their product offering sell the same items which have been modified to contain an indicating element. Companies involved with packaging of any sort where the package is ultimately transported and distributed to the public can benefit from employing a means to ensure whether the package and its contents were satisfactorily decontaminated. Drop off mail

services (e. g. Mail Boxes Etc. ) can benefit themselves and their customers by providing and attaching decontamination indicators to a package prior to bringing the package to the post office or carrier service.

If the transport item is to be transported by the United States Mail Service or any other carrier service, the service may be responsible for applying the indicating device. For example, the service may use a postage mark, ink mark associated with the item being transported, label, stamp, decal, tape, or any other substrate compatible with the indicator. The service can select any orientation for applying the indicator to a package or piece of mail. The service must apply the intrinsic indicator at any point prior to the item being decontaminated for the item to be able to respond directly to the energy delivered during the decontamination process. A carrier service (e. g. Federal Express Corporation) for example, can utilize a tracking label containing an indicating device. The indicator can be on any part of the tracking label including being part of the tracking bar code. This method of deploying the indicating device provides the advantage of maintaining uniformity in the method of use.

If the item is a food product such as perishable meats, dairy products, or vegetables, the decontamination indicator can be placed on the product to be decontaminated at any point prior to the decontamination event. In particular, with ground meats it is desirable to use irradiation such as electron beam exposure to decontaminate any possible food borne pathogens prior to delivering the food to a consumer or other recipient. In these cases, it may or may not be elected by the producer to identify and reveal to the receiver that the decontamination process did in fact occur. If it is desired to reveal to the receiver that decontamination did occur then it will be useful to utilize an intrinsic message that communicates to the receiver that the product being delivered was successfully decontaminated. Otherwise the producer may decide to imbed the indicator in a package or on a label in a way that the indicator can be interpreted by the producer or distribution channel but. not the end recipient of the product.

The producer or a segment of its distribution channel may elect to use any of a number of means to impart the indicator on the product to be transported. The method of applying, embedding, adhering or attaching the indicator will depend on the impact and knowledge intended to be gained by the producer, distributor, or recipient. The indicator may be implemented as simply as a mark from a marking device or be applied using a technology such as a high speed ink jet printing system. The mark may encode not only for the decontamination event, but also where and when the decontamination event took place.

Timing and location information revealed or encoded as a part of the indicating device has the advantage of informing those in further receipt of the transfer item that the item may have been subsequently handled and additional precautions should be taken.

Electron beam system providers used for decontamination (e. g. Sure Beam Corporation) directly utilize an integrated decontamination detection device which instantly reports that a piece of mail or food has been properly exposed to an electron beam source. To the providers advantage, an intrinsic indicator serves a multiple of purposes. The indicator can report that the intended decontamination either did or did not take place. The indicator can report quantitatively that all items taken under the decontamination process were fully or not fully treated. In this case, the indicator can be formulated to reveal a set optical density which can be used for calibrating the energy levels or radiation dosages utilized in the decontamination process. Low dose can be indicated by light levels of color change where as high and adequate doses can be indicated by dark levels of color change in the indicator. The indicator can be employed as a readable code which can assist in the subsequent routing of an item to a particular location in the distribution process. The indicator can be used in an inverse fashion where the indicator can identify that the decontamination process was unsuccessful and the item should be resubmitted for decontamination.

The decontamination provider may elect to expose or embed the indicator for internal or external usage of the information the indicator is programmed to impart. The provider may also find use for the indicator as a means to fine tune the decontamination process in a way which calibrates the decontamination unit to a particular pathogen, a particular package configuration, the type of items under exposure (e. g. some may be damaged by excessive exposure), to reduce energy costs (e. g. power requirements may be conserved), as well as

having the flexibility of how to report that the decontamination process occurred and how the knowledge is revealed to the recipients of the item post contamination. For example as public sentiment of pathogenic decontamination changes with time, the message communicated by the visual output from the intrinsic indicator can be adapted.

Providers of equipment, services, or supplies of vapor phase for plasma phase decontamination systems or components (e. g. Surgikos, a Johnson & Johnson Company and provider of vapor phase peroxide treatment) can benefit from utilizing a decontamination indicator which reports that the process that they are associated with had been effectively deployed. Materials utilized as indicators for gas or vapor phase decontamination treatments must be compatible with the process used by the respective party.

Those involved in the distribution process such as a trucking company, a train freight company, a warehouser, a co-packager, a retail distribution center, a logistics company, an airline, mail order companies, cataloging companies which ship products, internet companies involved in shipping products to customers or other businesses, fulfillment centers used for commercially advertised products, sweepstakes enterprises, photo processors and finishers, a local delivery service, a retail store, a mass merchandising center, or the like may elect to employ a decontamination indicator prior to the decontamination process or utilize information derived from an indicator placed on an item that was exposed to decontamination prior to possessing the item of transport. In either case, those involved in the distribution process can benefit from decontamination device reporting to use the information for their internal purposes for conveying the information to anyone who will receive the items that the distribution system is distributing.

The final recipient of an item which has been transported to them will benefit from information provided by an integrated intrinsic decontamination indicator. The recipient may elect to open, not open, return, or report an item they received depending on the information they interpret on the indicator.

It may be desirable to provide the recipient with a transportable decontamination unit for home or office use which includes both an ultraviolet light box for illumination and decontamination and a kit containing UV sensitive decontamination indicators and markers.

The kit can include protective disposable gloves, a respirator mask and protective eye ware.

The kit can also include a sanitizing solvent such as ethanol or isopropanol.

The following examples are offered by way of illustration and not by way of limitation.

EXAMPLES EXAMPLE 1: Ink for applying indicating material.

An ink was prepared by solubilizing 5% by weight monomeric 10,12-pentacosadiynoic acid in clear solvent ink base (LetrasetC, England). Solubility was maintained at higher concentrations by adding additional solvents such a dichloromethane. The ink found use for felt tip printing, swabbing, for ink jet printing, various makers, pad printing, stamps and stamping systems, spraying, permanent on labels, applied to adherent notes, and the like. The was found useful for decontamination methods including gamma irradiation, UV irradiation (254 nanometers), and thermal decontamination where the monomer was first polymerized to a blue color and then used as an irreversible thermochromic indicating agent when exposed to temperatures above 160°F.

EXAMPLE 2: Adjusting indicator sensitivity.

Lower temperature transition inks were prepared using shorter chain diynoic acid molecules and higher temperature transition inks were prepared using longer chain diynoic acid molecules. Sensitivities to irradiation doses were adjusted by adding like-kind materials which effect the color development process. For example, 10,12 tricosadiynoic acid was added at up to 20% weight compared to 10m 12 pentacosadiynoic acid. The co-mixture was found to be more sensitive to irradiation doses than either of the individual components

alone. The depth of color formed by a particular ink produced was adjusted by increasing or decreasing the concentration of the indicating material.

EXAMPLE 3: Postmark indicating electron beam exposure.

A postmark stamp was treated with the ink base described above. The postmark stamp was applied over a stamp in a fashion identical to that typically used by the postal service. The ink base dried immediately after contact. Identically marked envelopes were subjected to different irradiation means including electron beam irradiation and UV irradiation (254 nanometers). In each case, the postmark transformed from an invisible form to a deep blue postmark design upon exposure to irradiation doses known to kill pathogens. Various forms of the mark or other marks were evaluated. In each case, it was found that the ink turned color in response to the degree of irradiation.

EXAMPLE 4: Postage stamp for temperature exposure.

A graphic stamp was created on an adhesive label using an ink base containing an indicating material similar to the ink base described above. The printed stamp was irradiated with UV light (254 nanometers) to expose the graphic embedded on the stamp. The stamp graphic turned deep blue to give the appearance of a typical postage stamp utilized by the United States Postal Service. An envelope containing the stamp was placed in a heating unit and raised to a temperature of 160°F for 15 seconds. The dark blue graphic on the stamp immediately and completely changed color to a bright red color. The color change confirmed that the envelope, its contents and the indicating stamp were all properly raised to a temperature known to kill pathogenic agents. Higher and lower temperature transition color changing inks were applied using the same methodology in order to create the same decontamination indicator, but adjusted to different temperature ranges.

EXAMPLE 5: Ink jet printed bar codes for automated process.

A bar code for scanning was integrated with an ink base containing an indicating material similar to the ink bas described above. The bar code included one or more bars which were printed with the ink in a transparent form and the remaining bars printed with conventional black ink. The bar code was readable in one form prior to the code being exposed to an irradiation decontamination source. After exposure to UV (254 nanometers), a Cobalt 60 source or an electron beam source, the indicating bars in a code will change to an optical density and coloration such that when the code is rescanned the code itself will automatically indicate that a decontamination process was successful. Bar code scanning optics can be accordingly adjusted in the apparatus to accommodate optical density levels and provide end point determination for objective analysis of the decontamination event.

Bar codes with application to thermal decontamination were prepared using inks and methods described above. Thermally sensitive bar code bars selectively change color when heat from thermal decontamination is applied. Bars in a code will change to an optical density and coloration such that when the code is rescanned, the code itself will automatically indicate that a decontamination process was successful. Bar code scanning optics can be accordingly adjusted in the apparatus to accommodate optical density levels and provide end point determination for objective analysis of the decontamination event.

EXAMPLE 6: Packages integrating indicating decontamination component.

A graphic was printed on to a cereal box using an ink base containing an indicating material similar to the ink base described above. The graphic was irradiated with LTV light (254 nanometers) to expose the graphic embedded on the box. The box graphic turned deep blue to give the full desired appearance. The box was placed in a heating unit and raised to a temperature of 160°F for 15 seconds. The dark blue graphic on the box immediately and completely changed color to a bright red color. The color change confirmed that the box, its contents and the indicating graphic were all properly raised to a temperature known to kill pathogenic agents. Higher and lower temperature transition color changing inks were applied using the same methodology in order to create the same decontamination indicator, but adjusted to different temperature ranges.

EXAMPLE 7: Embedded fluorescence indicating decontamination device.

A graphic was printed on to an envelope was over coated using an ink base containing an indicating material similar to the ink base described above. The overlay graphic was irradiated with UV light (254 nanometers) to convert the diacetylenic monomer to the polydiacetylene form. The blue polydiaectylenic form is non-fluorescent in the blue unheated state. The envelope was placed in a heating unit and raised to a temperature of 160°F for 15 seconds. On heating the polydiacetylenic ink converted to the red fluorescent form. Although the color change was not visible by eye, it was visible using fluorescence imaging. The graphic when exposed to filtered green light emitted fluorescent orange light which was detected using both fluorescence microscopy and fluorescence imaging. Spectral imaging provides a convenient means for inspection automation and discrete analysis where the decontamination monitoring process can be securely evaluated without alerting anyone unintended to share the information.

EXAMPLE 8: Marker for at home use.

A marker containing an indicating ink was prepared using the ink base described above. A blank felt tip pen enclosure (Letraset (g), England) was filled with the ink to a saturating level. The clear ink was visible as a wetted line or mark when the felt tip was placed on a paper envelope or other porous surface. The mark became invisible after the ink solvent dried. The mark, when exposed to a hand held UV light (254 nanometers), emitted a radiation dose necessary to kill a pathogen, turned color to a dark blue hue. The color change in the mark was used to indicate that any pathogen and potentially present was destroyed.

The marker and UV lamp combination served as a practical means to an end recipient to both decontaminate a surface and show that the surface was effectively decontaminated.

EXAMPLE 9: Food package label.

An indicating message was ink jet printed on to a meat package label to form the word "SAFELY IRRADIATED"with an ink base containing an indicating material similar to the ink base described above. The message was printed with the ink in a transparent form. After exposure with a Cobalt 60 source or an electron beam source, the message changed to an optical density and coloration such that when the message could be easily read by eye. Other forms of messages were printed to communicate various safety slogans. The resulting color change in the printed message was irreversible under all the meat storage conditions evaluated including refrigerator temperatures, freezing and thawing.

EXAMPLE 10: Configuration indicating exposure did not take place.

A conformation indicator confirming that irradiation decontamination did not take place was prepared using a two color printing process. An outlined graphic was printed using a color matched blue hue on an adhesive label (Avery Dennison Corporation, CA). The printed graphic contained the wording"Not Decontaminated If Box Uncolored"and a box which is printed with the indicating ink described above. The label was over-coated with a UV blocking transparent tape (Scotch Tape@) such that the message and box were clearly visible.

The box remains uncolored as long the label is not exposed to a gamma radiation source or an electron beam source. The indicator help alert the recipient of a piece of mail or purchased package that the item has not been decontaminated using an irradiation source.

It is evident from the above description and results by using an indicator that intrinsically responds to a irradiation, vapor phase chemical, heating, pressure, other energetic event capable of decontaminating an item that the device provides the major advantage of obtaining vital information as to the completeness of a decontamination process. It is also evident that by incorporating such a device into an item to be transported or in transit that there is a wide variety of means of integrating and utilizing the knowledge gained from the device. It is further evident that individuals involved in the sending, transporting and receiving of an item which possesses the indicating device will have the advantage of making informed decisions

about how to handle an item they received as it may have a significant impact on their health and safety.

All publication and patent application mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.

The invention now being fully described, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit of scope of the appended claims.