US3840377A - Supersensitized silver halide photographic emulsions - Google Patents

Supersensitized silver halide photographic emulsions Download PDF

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US3840377A
US3840377A US00237041A US23704172A US3840377A US 3840377 A US3840377 A US 3840377A US 00237041 A US00237041 A US 00237041A US 23704172 A US23704172 A US 23704172A US 3840377 A US3840377 A US 3840377A
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silver halide
alkyl group
beta
halide photographic
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A Sato
A Ogawa
M Sonoda
N Miyasaka
K Shiba
H Takei
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed

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  • ABSTRACT A silver halide photographic emulsion containing a supersensitizing amount of the combination comprising at least one of the sensitizing -naphthoxazole represented by the following General Formulatl).
  • the present invention relates to a gelatino silver halide photographic emulsion which is spectrally sensitized by at least two sensitizing dyes exhibiting a super sensitizing effect on each other and in particular, it relates to a silver halide photographic emulsion having an increased spectral sensitivity in the green wave length region. 2.
  • the approach in spectral sensitization techniques for the green-sensitive silver halide emulsion for a natural color sensitive material is to locate the maximum sensitive wave length in the wave length region of from 560 nm. to 570 nm. and to increase the sensitivity at the shorter wave length side of from 520 nm. to 530 nm.
  • intensifying screens or fluorescent screens are frequently used together with silver halide photographic films for increasing the re cording sensitivity to X-rays. Because excessive exposure to X-ray radiation is hazardous to humans various attempts have been made for increasing the recoding sensitivity to X-rays to improve the reproducibility of details by using X-rays in an amount as low as possible and by expanding the X-ray recording range. For example, not only techniques for highly sensitizing silver halide photographic emulsions but also systems for using an X-ray image intensifier and for using a solid-state light amplifier have been developed. In any of these cases, however, the X-ray image is recorded finally on a gelatino silver halide light-sensitive material as a fluorescent image.
  • blue fluorescent substances such as calcium tungstate, zinc sulfide activated by silver, and barium sulfate activated by silver
  • green fluorescent substances such as zinc sulfide cadmium activated by silver.
  • the maximum emission energy of the latter fluorescent substance is about 540 nm. and the intensity distribution of the emission energy is as shown in FIG. 7 of the accompanyingdrawings. Also, as is clear from the above explanation, the
  • such a fluorescent substance is suitable as a fluorescent substance which is used for observing X-rays directly with the naked eye. That is to say, it is advantageous to use a fluorescent screen in which the fluorescent substance for reproducing an X-ray image on a fluorescent screen and observing the reproduced image with the naked eye or taking X-ray photograph of the image.
  • a fluorescent screen employing a green fluorescent substance is used in such an X-ray photographic method.
  • an X-ray light-sensitive material which is usually a socalled indirect X-ray photographic material, be treated easily in processings such as development and fixing and in particular it is desirable that such a lightsensitive material be handled in a room in whichthe level of light is as high as possible.
  • Such an X-ray photographic material is, in fact, handled under a safety light by using, for instance, Filter No. 7 made by the Fuji Photo Film Co., Ltd.
  • the spectral transmittance curve of Filter No. 7 is illustrated in FIG. 8 of the accompanying drawings.
  • an X-ray photographic material having a silver halide photographic emulsion layer be highly sensitive to the radiation emitted from a green fluorescent substance excited by X- rays and not very sensitive to ordinary light.
  • the fluorescent substance, P-2 has at least one maximum emission energy at about 545 nm., P-4 at about 560 nm., P-22D at about 525 nm., P-3l at about 520 nm., and P-2O at about 560 nm.
  • the developing and fixing steps of light-sensitive materials using silver halide photographic emulsions are shortened to 60 to seconds each.
  • the sensitizing dyes contained in the photographic emulsion layers of the light-sensitive materials are hardly washed out and then the photographs obtained by the processings are apt to be stained by the remaining dyes, which is one factor by which the photographic images are degraded.
  • the spectral sensitization in the green wavelength region is also conducted by'a merocyanine dye, a hemicyanine dye, or a trinuclear cyanine dye.
  • a technique is unsuitable for sensitization in a narrow and specific wave length region and the spectral sensitivity distribution obtained by such a sensitizing means is too broad.
  • it is difficult to obtain a high sensitivity and in particular, such a technique is disadvantageous in the spectral sensitization of high-sensitive silver iodo-bromide photographic emulsions due to its low sensitizing power.
  • F urthermore the aforesaid spectral sensitization has the disadvantage that it is not easy to find a super-sensitizer for the sensitizing dye.
  • An object of this invention is, therefore','to provide a silver halide photographic emulsion which is spectrally sensitized, which has a high green sensitivity and which gives rise to less color stains.
  • a second object of this invention is to provide a silver halide photographic emulsion which is suitable for making medical X-ray photographic light-sensitive materials having a high sensitivity to the radiation emitted from a green fluorescent substance and having a high stability to a safety light.
  • a third object of this invention is to provide a silver halide photographic emulsion having a high sensitivity in, particularly, in the wave length region of 520 540 nm. and giving less color stains.
  • a fourth object of this invention is to provide a silver halide photographic emulsion having a spectral sensitivity which is suitable for recording in a cathode ray tube type display system.
  • a fifth object of this invention is to provide a spectrally sensitized silver halide photographic emulsion which is suitable for use in a rapid processing system yet which is resistant to the formation of color stains as well as the harmful actions of antifoggants and a developing promotors.
  • Z represents a non-metallic atomic group necessary for forming a benzthiazole nucleus or a benzselenazole nucleus
  • Z represents a non-metallic atomic group necessary for forming a benzene nucleus
  • R and R each represents an alkyl group having from one to about six carbon atoms, a substituted lower alkyl group conventionally used in cyanine dyes, or an aliphatic hydrocarbon group having an unsaturated bond
  • X represents an anion and m is lor 2, m being I when the dye forms an intramolecular salt; and at least one of the sensitizing dyes represented by the General Formula a I.
  • General Formula (II) wherein Z, represents a non-metallic atomic group necessary for forming a benzoxazole nucleus, at B, B-naphthoxazole nucleus, or a.,8-naphthoxazole nucleus; Z represents a non-metallic atomic group necessary for forming a benzene nucleus; R and R each represents an alkyl group having from one to about six carbon atoms, a substituted alkyl group conventionally used in cyanine dyes, or an aliphatic hydrocarbon group having an unsaturated bond; at least one of said R and R being an alkyl group having at least one of a sulfo group, a carboxyl group or-a hydroxyl group; R represents an alkyl group having from one to about six carbon atoms, a substituted alkyl group conventionally used in cyanine dyes, an ary
  • Z represents an atomic group necessary for forming a benzthiazole nucleus or a benzselenazole nucleus
  • benzene nucleus of Z may be unsubstituted or may be substituted by a lower alkyl group having from one to about six, preferably from one to four, carbon atoms (such as a S-methyl group, a 6-methyl group, a S-ethyl group, a 6-propyl group, etc.,), an alkoxyl group (such as a 6-methoxy group, a 4-ethoxy group, etc.,), a hydroxyl group (such as a S-hydroxyl group, a 4-hydroxyl group, etc.,), a halogen atom (such as a 5-chloro substituent, a 6-bromo substituent, etc.,), an aryl group (such as a S-phenyl group etc., a sulfoaryl group (such as a 5-sulfophenyl group, etc.,), a carboxy aryl group, a N-alkyl .substituted amino group (such as a N
  • the benzene nucleus may be unsubstituted or may be substituted by lower alkyl group having from one to about six, preferably from one to four, carbon atoms (such as a S-methyl group, a 4-ethy1 group, etc.,), a halogen atom (such as a chlorine atom, a bromine atom, an iodine atom, etc.,), or an alkoxyl group (such as a S-methoxy group, etc.,).
  • lower alkyl group having from one to about six, preferably from one to four, carbon atoms (such as a S-methyl group, a 4-ethy1 group, etc.,), a halogen atom (such as a chlorine atom, a bromine atom, an iodine atom, etc.,), or an alkoxyl group (such as a S-methoxy group, etc.,).
  • R, and R each represents a lower alkyl group having from one to about six, preferably from one to four, carbon atoms (such as an ethyl group, a propyl group, a butyl group, etc.,) or such a substituted alkyl group as is conventionally used in cyanine dyes such as an aralkyl group (e.g., a benzyl group), an alkyl group having a sulfo group (e.g., a sulfoalkyl group such as a sulfobutyl group, a hydroxy sulfo alkyl group such as a B-hydroxysulfoethyl group, a sulfoalkoxyalkyl group such as a sulfopropoxyethyl group, a sulfoarylalkyl group such as a p-sulfophenylethyl group, a sulfoalkyl aminoal
  • a sulfoalkylthioalkyl group such as a C H,SC H SO H group, etc.,
  • an alkyl group having a carboxyl group and an alophatic hydrocarbon group having an unsaturated bond (e.g., allyl).
  • X represents an anion conventionally used for forming a cyanine dye such as a bromide ion, an iodide ion, a p-toluene-sulfonic acid ion, a perchlorate ion, a methyl sulfate ion, an ethyl sulfate ion, or a benzenesulfonate ion.
  • m is 1 or 2; and where m is 1 the sensitizing dye of the General Formula (1) forms a intramolecular salt (betaine like structure), i.e., in such a case no extra anion need be present.
  • the General Formula (l1) 2 represents an atomic group necessary for forming a B,,8-naphthoxazole nucleus, a B-naphthoxazole nucleus, or a benzoxazole nucleus, in which the nucleus may be unsubstituted or may be substituted with a lower alkyl group having from one to six, preferably from one to four, carbon atoms (such as a 6-methyl group, a S-ethyl group, etc.,) a halogen atom (such as a 5-chloro substituent, a S-bromo substituent, etc., an alkyl group (such as a 6-methyl group, etc.,), an alkoxyl group (such.
  • a S-methoxy group such as a S-methoxy group, 7-ethoxy group, etc.,
  • a hydroxyalkyl group such as a 5- hydroxymethyl group, etc.,
  • an alkoxycarbonyl group such as a S-methoxycarbonyl group, etc.,
  • an aryl group such as a S-phenyl group etc.,
  • a sulfoaryl group such as a 5-sulfophenyl group, or a carboxyaryl group etc.,).
  • Z represents a non-metallic atomic group necessary for forming a benzene nucleus, in which the benzene nucleus may be unsubstituted or may be substituted by a substituent conventionally known as a substituent of the benzimidazole nucleus in a cyanine dye nucleus.
  • the substituent can be a halogen atom such as a chlorine atom, a bromine atom, an iodine atom; a cyano group; an alkoxycarbonyl group; a trifluoromethyl group; a carbamoyl group, an alkyl substituted carbamoyl group, such as a methylcarbamoyl group or a dimethylcarbamoyl group; a sulfamoyl group, an alkyl substituted sulfamoyl group, such as methyl sulfamoyl and dimethyl sulfamoyl, etc.
  • a halogen atom such as a chlorine atom, a bromine atom, an iodine atom
  • a cyano group such as a methylcarbamoyl group or a dimethylcarbamoyl group
  • a sulfamoyl group an alkyl substituted sulfamoy
  • R and R each represents a lower alkyl group having from one to six, preferably from one to four carbon atoms e.g., a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, an unsaturated aliphatic hydrocarbon group for instance, an allyl group, or a substituted alkyl group conventionally used as a substituent on a nitrogen atom in the cyanine nucleus.
  • Such nucleus N-substituted groups can be groups such as a hydroxyalkyl group, an alkyl group having a sulfo group (such as a y-sulfobutyl group, a y-sulfobutyl group, a sulfopropoxy ethoxy ethoxy ethyl group etc.,),analkyl group having a carboxy'gr'oup (such as a B-carboxyethyl group; a 2-(2 carboxyethoxy) ethyl group etc.,), or an aralkyl group (such as a benzyl group etc.,).
  • R and R may further represent a B-methoxyethyl group, a B-ethoxyelthyl group, a- ,B-methallyl group, a benzyl group, a ,B-phenylethyl group, a B-acetoxyethyl
  • Groups R and R may be substituted by the substituents described in the specifications of, e.g., German Pat. No. 929,080; US. Pat. Nos. 2,537,880 and 2,776,280; British Pat. No. 1,001,480; and Japanese I Patent Publication No. 4843/1965; Japanese Patent Publication No. 5829/1960; Japanese Patent Publication No. 141 12/ 1965; Japanese Patent Publication No.
  • R or R is alkyl group having at least one of sulfo group, carb oxyl group and hydroxyl group.
  • R represents a lower alkyl group having from one to about six, preferably from one to four, (such as a methyl group, an ethyl group, a propyl group, etc.,), an unsaturated aliphatic hydrocarbon'group (such as an allyl group, etc.,), a substituted alkyl group and an aryl group (such as a phenyl group).
  • an aralkyl group such as a benzyl group, etc.,
  • a hydroxyalkyl group such as a ,B-hydroxylethyl group, etc.
  • R and R each represents a sulfoalkyl group or an alkyl group; at least one of R and R being a sulfoalkyl group.
  • An important feature of this invention is the discovery of the imidaoxacarbocyanine dye of a so-called' asymmetric nucleus represented by the General Formula (II) and the pseudocyanine dye represented by the General Formula (I).
  • the pseudocyanine dye of the General Formula (I) when used together with the carbocyanine dye of the General Formula (II), the maximum sensitivity can be obtained by employing the pseudocyanine dye of the General Formula (I) at a level of only a few percent of the amount required where the pseudocyanine dye is used alone. Consequently. the aforesaid difficulties are overcome by the present invention.
  • the sensitizing dye of the General Formula (II) sensitizes essentially in the wave length region substantially corresponding to the objects of this invention in giving a strong and sharp J-aggregate, i.e., a J-band.
  • the sensitizing dye of the General Formula (II) is used together with the pseudocyanine dye of the General F ormula (l)
  • the J-aggregate is properly partitioned and the spectra] absorption region is shifted toward the blue to give a spectral sensitivity distribution corresponding better the emission energy distribution shown in FIG. 7 of the accompanying drawings.
  • the maximum sensitivity is obtained in a small range of the amount of the dye and the formation of color stains is less.
  • the formation of color stains tends to increase rapidly when the amount of the same dye added is increased and the stronger aggregates are formed. Accordingly, the fundamental features of this invention will be understood on consideration of these circumstances.
  • sensitizing dyes used in this invention are illustrated herein below although the sensitizing dyes of this invention are not to be interpreted as limited to these specific dyes.
  • Examples of the sensitizing dyes represented by the General Formula (I) are as follows:
  • GHzCHaOHCHs CzHs (CHzhBOr' tion is particularly advantageous for the spectral sensitization of gelatino silver halide photographic emulsions.
  • the spectral sensitizing method of this invention is also usefully applied to a photographic emulsion containing other hydrophilic polymers than gelatin, such as agar-agar, collodion, water-soluble cellulose derivatives, polyvinyl alcohols, copolymers of polyvinyl pyrrolidone, synthetic hydrophilic resins, natural hydrophilic polymers, and gelatin derivatives.
  • a mixed silver halide emulsion containing silver chloride, silver bromide, or silver iodide or a mixed silver halide thereof such as silver bromoiodide and silver iodochlorobromide is suitable.
  • conventional methods of sensitization may be employed on a silver halide photographic emulsion which is spectrally sensitized by the sensitizing method of this invention, for instance, chemical sensitization such as sulfur sensitization, reduction sensitization, gold sensitization, sensitization by a metal belonging to the Group VIII of the periodic table and Noble metals. Combinations of these methods may also be used.
  • the photographic emulsion spectrally sensitized by the present invention may be preparedby incorporating the sensitizing dyes represented by the General Formula (l) and the General Formula (II) in the photographic emulsion using conventional techniques.
  • Each of the sensitizing dyes of the general formulae is generally added to a photographic emulsion as a solution-thereof in a water-miscible solvent such as methanol, ethanol, water, cellosolve, or a water-miscible ketone such as methylethyl ketone, methyl ketone and ethyl ketone.
  • the sensitizing dye may be added to a photographic emulsion as a dispersion of a solution in a weakly soluble 'oil in water or a hydrophilic colloid.
  • the addition ratio of the sensitizing dye of the General Formula (I) to the sensitizing dye of the General Formula (ll) to be incorporated in the photographicemulsion may be varied over a wide range, for example,
  • the amount of each of the sensitizing dyes employed in this invention range from I X mol to l X 10 mol per mol of silver depending upon the characteristics of the photographic emulsion.
  • the photographic emulsion of this invention may further be subjected to conventional supersensitization techniques.
  • the spectrally sensitized photographic emulsion of this invention may further contain additives conventionally employed in the art, such as sensitizers, stabilizers, color toning agents, hardening agents, surface active agents, antifoggants, plasticizers, developing promotors, color couplers, and fluorescent brightening agents.
  • the photographic emulsion of this invention may be applied to an appropriate support such as a glass sheet, a cellulose ester derivative film, a polyethylene terephthalate film, a synthetic resin film, a barayta-coated paper, a resin-coated paper, or a synthetic paper using conventional techniques.
  • an appropriate support such as a glass sheet, a cellulose ester derivative film, a polyethylene terephthalate film, a synthetic resin film, a barayta-coated paper, a resin-coated paper, or a synthetic paper using conventional techniques.
  • the silver halide photographic emulsion of this invention may be used as a light-sensitive material suitable for cathode ray tube display.
  • a silver halide photographic emulsion was prepared by using individually each of the sensitizing dyes of the General Formula (I) and the General Formula (ll) and also a comparison silver halide photographic emulsion was prepared by using each of the comparison sensitizing dyes represented by the Formula (T) and Formula (U) shown below.
  • Each of the silver halide photographic emulsions thus prepared was applied to a triacetyl cellulose film base.
  • the light-sensitive photographic films thus prepared were each exposed to day light radiation of 64 lux (corresponding to 5,400 K) through a yellow filter (made by the Fuji Photo Film Co., a filter passing light of wave lengths longer than 460'nm.), a green filter (made by the Fuji Photo Film Co., a filter passing'light of wave lengths of 480-620 nm. and having a maximum penetration coefficient at a wave length of 530 nm.), or a blue filter (made by the Fuji Photo Film Co., a filter passing light of wave lengths of 400-490nrn. and having a maximum penetration coefficient at a wave length of 450 nm.). They were then developed for 2 mi utes at 24C in a developing solution haveing the following composition:
  • the yellow sensitivity and the .green sensitivity are the relative values when the sensic o m parison Dye CIzH CzHs
  • FIG 1(1) FIG.I(2)
  • a green filter made by the Fuji Photo Film Co., a filter passing light of wave lengths of 480-650 nm., having a maximum penetration coefficient at a wave length of 530 nm.
  • a green filter made by the Fuji Photo Film Co., a filter passing light of wave lengths of 480-650 nm., having a maximum penetration coefficient at a wave length of 530 nm.
  • the sensitivity is shown by the relative sensitivity when the sensitivity of the silver halide photographic emulsion containing the dye (20) amples l 29.
  • the results obtained are shown in the From measure shown in thetablsfitcaii b seen that the green sensitivity is super-additively increased, which is one of the objects of this invention, by using at least one of the sensitizing dyes of the General Formula (l) and at least one of the sensitizing dyes of the General Formula (II).
  • FIG. 1, FIG. 2, FIG. 3 and FIG. 4 are spectrograms obtained by using the combinations of the sensitizing dyes of the General Formula (I) and the General Formula (II) according to the present invention.
  • FIG. 5 and FIG. 6 are the spectrograms obtained by using'the comparison sensitizing dyes of the Formula (T) and the Formula (U) respectively.
  • the numbers in the parentheses the examples shown in the above table to which the curves correspond.
  • FIG. 7 is a graph showing the spectral energy distribution of light emitted by exciting by X-rays the fluoresecnt substance of a fluorescent screen usually used for X-ray photography.
  • FIG. 8 is a graph showing the spectral penetrationco-.
  • the sensitized region of the light-sensitive film extends to 596 nm. as shown by the curve (4) of FIG. 2 but when the dye (N) is used together with the sensitizing dye (5) of the General Formula (II), the sensitized wave length end of the light-sensitive film shifts to the shorter wave length side and also the sensitivity reduction in the longer wave length side is sharp as is shown by the curve (6) of FIG. 2.
  • the green sensitivity of the light-sensitive film prepared by using the combination of the sensitizing dyes according to the present invention is about 1.6 times higher than that of the light-sensitive film obtained by using the sensitizing dye individually.
  • the photographic emulsion of this invention is less fogged by exposure to a safety light and also the spectral sensitivity distribution of the photographic emulsion fits the energy distribution of the light emitted from the green fluorescent substance of the X-ray fluorescent screen as shown in FIG. 7.
  • a silver halide photographic emulsion containing a supersensitizing amount of the combination comprising at least one of the sensitizing dyes represented by the following General Formula (I) l l )m1 General Formula (I) wherein Z, represents a non-metallic atomic group necessary for forming a benzothiazole nucleus or a benzoselenazole nucleus; Z represents a non-metallic atomic group necessary for forming a benzene nucleus; R, and R each represent an alkyl group having from one to about six carbon atoms, a substituted lower alkyl group conventionally used in cyanine dyes selected from the General Formula (II) wherein 2;, represents a benzoxazole nucleus, Z, represents a non-metallic atomic group necessary for forming a benzene nucleus; R and R each represents an alkyl group having from one to about six carbon atoms, a substituted alkyl group conventionally used in cyanine dye
  • An photographic light-sensitive material comprising a support havingthereon at least one layer of the silver halide photographic emulsion as set forth in claim 1.
  • alkyl group having a sulfo group is selected from the group consisting of a sulfo alkyl group, a hydroxy(sulfo) alkyl group, a sulfo alkoxy alkyl group, a sulfo phenyl alkyl group, a sulfo-alkyl amino alkyl group, a sulfo-alkyl amino alkyl group and a sulfoalkyl thio-alkyl group.
  • An photographic light-sensitive material comprising a support having thereon at least one layer of the silver halide photographic emulsion as set forth in claim 4.
  • a silver halide photographic emulsion containing a supersensitizing amount of the combination comprising at least one of the sensitizing dyes represented by the following General Formula (I') gi z General Formula (I') wherein R and R each represents a methyl group, an
  • R represents a hydrogen atom, a methyl group, or an ethyl group; and at least one of the sensitizing dyes represented by the following General Formula (ll') General Formula (11) wherein W, and W; each represents a hydrogen atom, a chlorine atom, or a methoxycarbonyl group and R and R each represents a sulfoalkyl group or an alkyl group; at least one of R ⁇ , and R being a sulfoalkyl group.
  • both of R and R have at least one sulfo group.

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US00237041A 1971-03-23 1972-03-22 Supersensitized silver halide photographic emulsions Expired - Lifetime US3840377A (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2005056689A2 (en) 2003-12-05 2005-06-23 Molecular Probes, Inc. Cyanine dye compounds
US7598390B2 (en) 2005-05-11 2009-10-06 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use
US7776529B2 (en) 2003-12-05 2010-08-17 Life Technologies Corporation Methine-substituted cyanine dye compounds

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2014896A1 (de) * 1969-03-27 1970-11-05 Fuji Photo Film Co., Ltd., Kanagawa (Japan) Spektral-sensibiIisierte photographische Silberhalogenidemulsionen

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US20100120051A1 (en) * 2003-12-05 2010-05-13 Life Technologies Corporation Cyanine dye compounds
WO2005056689A3 (en) * 2003-12-05 2005-10-13 Molecular Probes Inc Cyanine dye compounds
US7446202B2 (en) 2003-12-05 2008-11-04 Molecular Probes, Inc. Cyanine dye compounds
US20090047683A1 (en) * 2003-12-05 2009-02-19 Invitrogen Corporation Cyanine dye compounds
WO2005056689A2 (en) 2003-12-05 2005-06-23 Molecular Probes, Inc. Cyanine dye compounds
US7655409B2 (en) 2003-12-05 2010-02-02 Life Technologies Corporation Cyanine dye compounds
US9040561B2 (en) 2003-12-05 2015-05-26 Life Technologies Corporation Methine-substituted cyanine dye compounds
US7776529B2 (en) 2003-12-05 2010-08-17 Life Technologies Corporation Methine-substituted cyanine dye compounds
US7842811B2 (en) 2003-12-05 2010-11-30 Life Technologies Corporation Cyanine dye compounds
US10005908B2 (en) 2003-12-05 2018-06-26 Life Technologies Corporation Methine-substituted cyanine dye compounds
US8470529B2 (en) 2003-12-05 2013-06-25 Life Technologies Corporation Methine-substituted cyanine dye compounds
EP2607431A1 (en) * 2003-12-05 2013-06-26 Life Technologies Corporation Cyanine dye compounds
US9403985B2 (en) 2003-12-05 2016-08-02 Life Technologies Corporation Methine-substituted cyanine dye compounds
US7598390B2 (en) 2005-05-11 2009-10-06 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use
US9115397B2 (en) 2005-05-11 2015-08-25 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use
US9366676B2 (en) 2005-05-11 2016-06-14 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use
US8865904B2 (en) 2005-05-11 2014-10-21 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use
US7943777B2 (en) 2005-05-11 2011-05-17 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use

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DE2214208A1 (de) 1972-10-26
FR2135136A1 (Direct) 1972-12-15

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