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Bioluminescent Novelty Items Biolumineszente Neuheiten Nouveaux Articles Bioluminescents

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Bioluminescent Novelty Items Biolumineszente Neuheiten Nouveaux Articles Bioluminescents Europäisches Patentamt *EP000879383B1* (19) European Patent Office Office européen des brevets (11) EP 0 879 383 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.7: F21K 2/00, F21K 2/06, of the grant of the patent: F41C 3/00, B05B 17/08, 21.05.2003 Bulletin 2003/21 A23L 1/03, A23L 2/00, (21) Application number: 97905731.2 A23G 1/00, A23G 9/02, A23K 1/18, D06Q 1/00 (22) Date of filing: 03.02.1997 (86) International application number: PCT/US97/01699 (87) International publication number: WO 97/029319 (14.08.1997 Gazette 1997/35) (54) BIOLUMINESCENT NOVELTY ITEMS BIOLUMINESZENTE NEUHEITEN NOUVEAUX ARTICLES BIOLUMINESCENTS (84) Designated Contracting States: (56) References cited: AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC EP-A- 0 246 174 EP-A- 0 302 819 NL PT SE WO-A-92/04577 WO-A-94/04918 Designated Extension States: DE-A- 3 935 974 FR-A- 2 292 595 AL LT LV RO SI FR-A- 2 674 223 GB-A- 1 105 927 US-A- 3 511 612 US-A- 4 534 317 (30) Priority: 06.02.1996 US 597274 US-A- 4 563 726 US-A- 4 765 510 25.11.1996 US 757046 US-A- 5 383 100 US-A- 5 405 056 US-A- 5 405 905 (43) Date of publication of application: 25.11.1998 Bulletin 1998/48 • DATABASE WPI Section Ch, Week 9546, Derwent Publications Ltd., London, GB; Class (73) Proprietor: Bryan, Bruce J. B04, AN 95-354274 & JP,A,7 241 192 (HARATA Beverly Hills, CA 90210 (US) K) 19 September 1995 • DATABASE INSPEC INSTITUTE OF (72) Inventor: Bryan, Bruce J. ELECTRICAL ENGINEERS, STEVENAGE, GB Beverly Hills, CA 90210 (US) Inspec No. 3715919 GAUTIER S M ET AL ’Alternate determination of ATP and NADH with (74) Representative: Goldin, Douglas Michael a single bioluminescence-based fiber-optic J.A. KEMP & CO. sensor’ & 5TH INTERNATIONAL CONFERENCE 14 South Square ON SOLID-STATE SENSORS AND ACTUATORS Gray’s Inn AND EUROSENSORS III, MONTREUX, London WC1R 5JJ (GB) SWITZERLAND, 25-30 JUNE 1989, vol.B1, no.1-6, ISSN 0925-4005, SENSORS AND ACTUATORS B (CHEMICAL), JAN. 1990, SWITZERLAND pages 580 - 584 • DATABASE WPI Section Ch, Week 9501, Derwent Publications Ltd., London, GB; Class B04, AN 95-006227 & WO,A,94 26100 (CNRS CENT NAT RECH SCI) 24 November 1994 Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 0 879 383 B1 Printed by Jouve, 75001 PARIS (FR) EP 0 879 383 B1 Description [0001] The present invention relates to combinations of systems for producing bioluminescent light and articles of manufacture including toys, fountains, personal care items, fairy dust, beverages, soft drinks, foods, textile and paper 5 products. The resulting combinations are novelty items, which, by virtue of the combination, glow or produce or expel a bioluminescent composition. [0002] Luminescence is a phenomenon in which energy is specifically channelled to a molecule to produce an excited state. Return to a lower energy state is accompanied by release of a photon (hγ). Luminescence includes a fluoresence, phosphorescence, chemiluminescence and bioluminescence. Bioluminescence is the process by which living organ- 10 isms emit light that is visible to other organisms. Luminescence may be represented as follows: A + B → X* + Y 15 X* → X + hγ, where X* is an electronically excited molecule and hγ represents light emission upon return of X* to a lower energy state. Where the luminescence is bioluminescence, creation of the excited state derives from an enzyme catalyzed 20 reaction. The colour of the emitted light in a bioluminescent (or chemiluminescent or other luminescent) reaction is characteristic of the excited molecule, and is independent from its source of excitation and temperature. [0003] An essential condition for bioluminescence is the use of molecular oxygen, either bound or free in the presence of a luciferase. Luciferases, are oxygenases, that act on a substrate, luciferin, in the presence of molecular oxygen and transform the substrate to an excited state. Upon return to a lower energy level, energy is released in the form of 25 light [for reviews see, e.g., McElroy et al. (1966) in Molecular Architecture in Cell Physiology, Hayashi et al., eds., Prentice-Hall, Inc., Englewood Cliffs, NJ, pp. 63-80; Ward et al., Chapter 7 in Chemi-and Bioluminescence, Burr, ed., Marcel Dekker, Inc. NY, pp.321-358; Hastings, J. W. in (1995) Cell Physiology;Source Book, N. Sperelakis (ed.), Ac- ademic Press, pp 665-681; Luminescence, Narcosis and Life in the Deep Sea, Johnson, Vantage Press, NY, see, esp. pp. 50-56]. 30 [0004] Though rare overall, bioluminescence is more common in marine organisms than in terrestrial organisms. Bioluminescence has developed from as many as thirty evolutionarily distinct origins and, thus, is manifested in a variety of ways so that the biochemical and physiological mechanisms responsible for bioluminescence in different organisms are distinct. Bioluminescent species span many genera and include microscopic organisms, such as bacteria [primarily marine bacteria including Vibrio species], fungi, algae and dinoflagellates, to marine organisms, including 35 arthropods, mollusks, echinoderms, and chordates, and terrestrial organism including annelid worms and insects. [0005] Bioluminescence, as well as other types of chemiluminescence, is used for quantitative determinations of specific substances in biology and medicine. For example, luciferase genes have been cloned and exploited as reporter genes in numerous assays, for many purposes. Since the different luciferase systems have different specific require- ments, they may be used to detect and quantify a variety of substances. The majority of commercial bioluminescence 40 applications are based on firefly [Photinus pyralis] luciferase. One of the first and still widely used assays involves the use of firefly luciferase to detect the presence of ATP. It is also used to detect and quantify other substrates or co- factors in the reaction. Any reaction that produces or utilizes NAD(H), NADP(H) or long chain aldehyde, either directly or indirectly, can be coupled to the light-emitting reaction of bacterial luciferase. [0006] Another luciferase system that has been used commercially for analytical purposes is the Aequorin system. 45 The purified jellyfish photoprotein, aequorin, is used to detect and quantify intracellular Ca2+ and its changes under various experimental conditions. The Aequorin photoprotein is relatively small [,20kDa], nontoxic, and can be injected into cells in quantities adequate to detect calcium over a large concentration range [3 X 10-7 to 10-4 M]. [0007] Because of their analytical utility, many luciferases and substrates have been studied and well-characterized and are commercially available [e.g., firefly luciferase is available from Sigma, St. Louis, MO, and Boehringer Mannheim 50 Biochemicals,Indianapolis, IN; recombinantly produced firefly luciferase and other reagents based on this gene or for use with this protein are available from Promega Corporation, Madison, WI; the aequorin photoprotein luciferase from jellyfish and luciferase from Renilla are commercially available from Sealite Sciences, Bogart, GA; coelenterazine, the naturally-occurring substrate for these luciferases, is available from Molecular Probes, Eugene, OR]. These luciferases and related reagents are used as reagents for diagnostics, quality control, environmental testing and other such anal- 55 yses. These reagents have not been used in connection with entertainment and recreation for the glow, illumination and color produced upon generation of bioluminescence. [0008] Thus, it is an object herein to exploit bioluminescence for use as a recreational product in combination with articles of manufacture to produce novelty items, including toys, personal care items, foods, fountains, beverages, soft 2 EP 0 879 383 B1 drinks, fairy dust, textile and paper products. It is also an object herein to provide such combinations and to provide means for producing and using such combinations. SUMMARY OF THE INVENTION 5 [0009] The invention provides a novelty item, comprising: a) an article of manufacture selected from among toys, fountains, personal care items, fairy dust, beverages, soft drinks, foods, textile and paper products; and 10 b) a fluorescent protein or one or more components of a bioluminescence generating system chosen from a luci- ferase and a luciferin. [0010] Suitably, the article of manufacture is chosen from among toy guns, pellet guns, greeting cards, fingerpaints, foot bags, slimy play material, clothing, bubble making toys and bubbles therefor, balloons, bath powders, body lotions, 15 gels, body powders, body creams, toothpastes, mouthwashes, soaps, body paints, bubble bath, board game toys, egg-shaped toys, toy cigarettes, dolls, sparklers, magic wand toys, wrapping paper, gelatins, icings, frostings, fairy dust, beer, wine, champagne, soft drinks, ice cubes, ice and dry ice. [0011] Systems and apparatus for generating bioluminescence, and combinations of these systems and apparatus with inanimate articles of manufacture to produce novelty items are provided. These novelty items, which are articles 20 of manufacture, are designed for entertainment, recreation and amusement, and include, but are not limited to: toys, particularly squirt guns, toy cigarettes, lanterns,
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