WO2016127461A1 - 有机电致发光材料及其制备方法 - Google Patents

有机电致发光材料及其制备方法 Download PDF

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WO2016127461A1
WO2016127461A1 PCT/CN2015/073850 CN2015073850W WO2016127461A1 WO 2016127461 A1 WO2016127461 A1 WO 2016127461A1 CN 2015073850 W CN2015073850 W CN 2015073850W WO 2016127461 A1 WO2016127461 A1 WO 2016127461A1
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group
substituted
organic electroluminescent
carbon atoms
ring
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French (fr)
Inventor
张贯京
陈兴明
葛新科
张少鹏
方静芳
高伟明
梁艳妮
周荣
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Shenzhen Qianhai AnyCheck Information Technology Co Ltd
E Techno Information Technologies Co Ltd
Bio Tech Academy China Co Ltd
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Shenzhen Qianhai AnyCheck Information Technology Co Ltd
E Techno Information Technologies Co Ltd
Bio Tech Academy China Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials

Definitions

  • the invention relates to the field of biological detection technology, in particular to an organic electroluminescent material and a preparation method thereof.
  • organic electroluminescent materials have been used in the fields of display, imaging, etc. due to their special luminescent properties, but the existing applications only utilize the luminescent properties of organic electroluminescent materials, and simply utilize them in components that require luminescence.
  • the detection methods of biomarkers, DNA, antibodies, viruses, microorganisms, enzymes, pesticides and other biological macromolecules are constantly updated.
  • the existing detection methods usually use detection instruments.
  • these detection instruments have the disadvantages of large volume, low detection sensitivity, high price, and narrow application fields. Therefore, it is necessary to utilize the luminescent properties of the organic electroluminescent material in the field of detection of biological macromolecules to solve the shortcomings of the existing detection methods such as high detection cost, low detection sensitivity, and narrow application fields.
  • the main object of the present invention is to provide an organic electroluminescent material with high selectivity and high specificity, which can improve the sensitivity to detection of biological macromolecules.
  • the present invention provides an organic electroluminescent material represented by the following general formula (I):
  • A represents an organic electroluminescent compound molecule
  • B represents a functional group
  • AB represents a product after A is functionalized by B
  • C represents an antibody
  • C is bonded to A through B to obtain an organic electroluminescent material.
  • the A is a macrocyclic conjugated organic compound molecule.
  • the B is a carbon chain structure containing one or more of -OH, -SH, -CHO, -COOH, -SO 3 H, -NH 2 , -CH 2 -, RCO-.
  • R 1 and R 2 are functional groups
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms;
  • Ar 3 represents a substituted or unsubstituted monocyclic hydrocarbon group having 6 or less ring carbon atoms or a substituted or unsubstituted monocyclic heterocyclic group having 6 or less ring atoms;
  • n an integer from 0 to 3;
  • X 1 to X 8 and Y 1 to Y 8 each independently represent N or CR a ;
  • R a each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, and a substituted or unsubstituted group.
  • One of X 5 to X 8 and one of Y 1 to Y 4 are bonded via Ar 3 or directly bonded;
  • Formula (II) satisfies at least one of the following (1) and (2):
  • At least one of Ar 1 and Ar 2 is an aromatic hydrocarbon group having 6 to 30 ring carbon atoms substituted by a cyano group or 5 to 30 ring atoms substituted by a cyano group. Heterocyclic group;
  • X 1 ⁇ X 4 and Y is at least a 5 ⁇ Y 8 is at least one CR a, X R a 1 ⁇ X 4 and Y 5 ⁇ Y 8 is a cyano substituted into the An aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a heterocyclic group having 5 to 30 ring atoms substituted by a cyano group;
  • a plurality of R a when a plurality of R a is present, a plurality of R a may be the same or different.
  • the substituent is selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl halide having 1 to 20 carbon atoms.
  • At least one of Ar 1 and Ar 2 is a phenyl group substituted with a cyano group, a naphthyl group substituted with a cyano group, a phenanthryl group substituted with a cyano group, and a dibenzo group substituted with a cyano group.
  • X 6 and Y 3 are bonded via Ar 3 or directly.
  • the present invention also provides a method for preparing an organic electroluminescent material, the preparation method comprising the following steps:
  • Step 1 Under the argon gas flow, sequentially add an organic electroluminescent compound substrate, phenylboronic acid, tetrakis(triphenylphosphine)palladium, toluene, 2M sodium carbonate aqueous solution, and heat to reflux; after cooling the reaction solution to room temperature, The organic layer is separated, the organic solvent is distilled off under reduced pressure, and the obtained residue is purified by silica gel column chromatography to give intermediate 1;
  • Step 2 Under the argon gas stream, the intermediate 1, triphenylphosphine and o-dichlorobenzene are sequentially added and heated at 100 ° C to 200 ° C; the reaction solution is cooled to room temperature, and then purified by silica gel column chromatography.
  • Step 3 under the argon gas flow, sequentially add the organic electroluminescent compound molecule A containing the functional group B, tetrakis(triphenylphosphine)palladium, toluene, 2M aqueous sodium carbonate solution, and heating and refluxing; after cooling the reaction liquid to room temperature , the organic layer was separated, the organic solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to identify intermediate 3;
  • Step 4 Under the argon gas stream, sequentially add the intermediate 3, 4-bromobenzonitrile, tris(dibenzylideneacetone)dipalladium, tri-tert-butylphosphonium tetrafluoroborate, sodium t-butoxide, Anhydrous toluene, heated to reflux; the reaction mixture was cooled to room temperature, the organic layer was separated, the organic solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography to afford white solid AB;
  • Step 5 Mixing the solution of the white solid AB with one of the antibody, virus, bacteria, enzyme or biomarker protein to obtain an organic electroluminescent material of the formula AB-C.
  • the method for preparing the organic electroluminescent material comprises the following steps:
  • Step 1 Under the argon gas stream, 2-nitro-1,4-dibromobenzene (11.2 g, 40 mmol) was added sequentially. Phenylboronic acid (4.9 g, 40 mmol), tetrakis(triphenylphosphine)palladium (1.39 g, 1.2 mmol), toluene 120 mL, 2M sodium carbonate aqueous solution 60 mL, heated under reflux for 8 hr; a layer, the organic solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give 6.6 g of the intermediate 1 of yield 59%;
  • Step 2 under argon gas flow, add (6.6g, 23.7mmol) of intermediate 1, (15.6g, 59.3mmol) triphenylphosphine, o-dichlorobenzene 24mL, heated at 180 ° C for 8 hours; After cooling the liquid to room temperature, it was purified by silica gel column chromatography to obtain 4 g of intermediate 2 in a yield of 68%;
  • Step 3 under the argon gas stream, sequentially add the intermediate 2, the compound B containing the functional group B, tetrakis(triphenylphosphine)palladium (1.39 g, 1.2 mmol), toluene 120 mL, 2M sodium carbonate aqueous solution 60 mL, and heated to reflux 8 After the reaction solution is cooled to room temperature, the organic layer is separated, and the organic solvent is distilled off under reduced pressure, and the obtained residue is purified by silica gel column chromatography to identify intermediate 3;
  • Step 4 Under the argon gas stream, (2.03 g, 3.9 mmol) of intermediate 3, (0.71 g, 3.9 mmol) of 4-bromobenzonitrile, (0.071 g, 0.078 mmol) of tris (di) Benzylacetone) dipalladium, (0.091 g, 0.31 mmol) of tri-tert-butylphosphonium tetrafluoroborate, (0.53 g, 5.5 mmol) of sodium t-butoxide, 20 mL of anhydrous toluene, heated under reflux for 8 hours; After cooling the reaction mixture to room temperature, the organic layer was separated, the organic solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give 0.79 g of white solid AB;
  • Step 5 Mixing the solution of the white solid AB with one of the antibody, virus, bacteria, enzyme or biomarker protein to obtain an organic electroluminescent material of the formula AB-C.
  • the organic electroluminescent material provided by the invention can be applied to the field of biological macromolecule detection, thereby broadening the application field of the organic electroluminescent material and improving the detection sensitivity of the biological macromolecule.
  • the main object of the present invention is to solve the defects of the detection method of the existing biomacromolecules, such as high detection cost, low detection sensitivity, narrow application field, etc.
  • the innovation of the present invention is to provide a highly selective and highly specific organic electricity.
  • the above-mentioned object is achieved by applying an organic electroluminescent material to the field of biomacromolecule detection.
  • the organic electroluminescent material provided by the embodiment of the present invention is represented by the following general formula (I):
  • A represents an organic electroluminescent compound molecule
  • B represents a functional group
  • AB represents a product after A is functionalized by B
  • C represents an antibody
  • C is bonded to A through B to obtain an organic electroluminescent material.
  • A is a macrocyclic conjugated organic compound molecule
  • B is a carbon chain structure of a functional group contained on A, wherein the functional group may be selected from -OH, -SH, -CHO, -COOH, - One or more of SO 3 H, -NH 2 , -CH 2 -, RCO-.
  • the organic electroluminescent material can be specifically expressed as follows:
  • R 1 and R 2 are functional groups
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms;
  • Ar 3 represents a substituted or unsubstituted monocyclic hydrocarbon group having 6 or less ring carbon atoms or a substituted or unsubstituted monocyclic heterocyclic group having 6 or less ring atoms;
  • n an integer from 0 to 3;
  • X 1 to X 8 and Y 1 to Y 8 each independently represent N or CR a ;
  • R a each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, and a substituted or unsubstituted group.
  • One of X 5 to X 8 and one of Y 1 to Y 4 are bonded via AR 3 or directly bonded;
  • At least one of Ar 1 and Ar 2 is an aromatic hydrocarbon group having 6 to 30 ring carbon atoms substituted by a cyano group or 5 to 30 ring atoms substituted by a cyano group. Heterocyclic group;
  • X 1 ⁇ X 4 and Y is at least a 5 ⁇ Y 8 is at least one CR a, X R a 1 ⁇ X 4 and Y 5 ⁇ Y 8 is a cyano substituted into the An aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a heterocyclic group having 5 to 30 ring atoms substituted by a cyano group;
  • a plurality of R a when a plurality of R a is present, a plurality of R a may be the same or different.
  • an aromatic hydrocarbon group having 6 to 30 ring carbon atoms substituted by a cyano group and a heterocyclic group having 5 to 30 ring atoms substituted by a cyano group are further There may be a substituent other than a cyano group.
  • a non-condensed aromatic hydrocarbon group and a condensed aromatic hydrocarbon group may be selected, more specifically The choice of phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, tetraphenyl, fluoranthene, benzophenanyl, phenanthryl, fluorenyl, fluorenyl, 9,9-di Phenylfluorenyl, 9,9'-spirobis[9H-fluorenyl]-2-yl, 9,9-dimethylindenyl, benzo[c]phenanthryl, benzo[a]benzophenanthrenyl, Naphtho[1,2-c]phenanthryl, naphtho[1,2-a]benzophenanthrenyl, dibenzo[a,c]benzophenanyl, benzo[b]flu
  • a non-fused heterocyclic group and a fused heterocyclic group may be optionally selected. More specifically, it may be selected from a pyrrole ring, an isoindole ring, a benzofuran ring, an isobenzofuran ring, a dibenzothiophene ring, an isoquinoline ring, a quinoxaline ring, a phenanthridine ring, and a phenanthroline.
  • a porphin ring a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, an anthracene ring, a quinoline ring, an acridine ring, a pyrrolidine ring, a dioxane ring, a piperidine ring, a morpholine ring, Piperazine ring, carbazole ring, furan ring, thiophene ring, oxazole ring, oxadiazole ring, benzoxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring, benzene And a group formed by an imidazole ring, a pyran ring, a dibenzofuran ring, a benzo[c]dibenzofuran ring,
  • Ar 3 when Ar 3 is a substituted or unsubstituted monocyclic hydrocarbon group having 6 or less ring carbon atoms, a phenylene group, a cyclopentylene group, a cyclopentadienyl group or a cyclohexylene group may be selected.
  • a cyclopentylene group or the like is preferably a phenylene group.
  • Ar 3 when Ar 3 is a substituted or unsubstituted monocyclic heterocyclic group having 6 or less ring atoms, a pyridylene group, a pyrazinylene group, a pyridylene group or a furylene group may be selected. , thionylene and the like.
  • a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group or an isobutyl group may be selected.
  • n-pentyl n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecane Base, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, cyclopropyl, cyclobutyl, cyclopentyl, ring
  • the hexyl group, the cyclooctyl group, the adamantyl group and the like are preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group,
  • a trimethylsilyl group a triethylsilyl group, a tributylsilyl group, a dimethylethylsilyl group, a t-butyldimethyl group may be selected.
  • Silyl group vinyl dimethylsilyl group, propyldimethylsilyl group, dimethylisopropylsilyl group, dimethylpropylsilyl group, dimethylbutylsilyl group, two Methyl tert-butylsilyl, diethylisopropylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, diphenyl tert-butylsilyl, triphenylsilyl, etc.
  • It is preferably a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a vinyldimethylsilyl group or a propyldimethylsilyl group.
  • the halogen atom represented by R a may be selected from fluorine, chlorine, bromine, iodine or the like, and is preferably fluorine.
  • R a is also preferably a hydrogen atom or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms.
  • an aromatic hydrocarbon group having 6 to 30 ring atoms or a heterocyclic group having 5 to 30 ring atoms represented by Ar 1 and Ar 2 has a substituent
  • the substituent is selected.
  • any substituent in the case of "substituted or unsubstituted” and “may have a substituent” may be selected from a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, and a carbon number of 1 to 20 (preferably 1 to 6) an alkyl group, a cycloalkyl group having 3 to 20 (preferably 5 to 12) carbon atoms, an alkoxy group having 1 to 20 (preferably 1 to 5) carbon, or carbon a halogenated alkyl group having 1 to 20 (preferably 1 to 5) atoms, a halogenated alkoxy group having 1 to 20 (preferably 1 to 5) carbon atoms, and 1 to 10 (preferably 1 to 5) carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms used for any substituent may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and Amyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecane Base, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, and the like.
  • the cycloalkyl group having 3 to 20 carbon atoms used for the optional substituent may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group or an adamantyl group.
  • the alkoxy group having 1 to 20 carbon atoms used for any substituent may be a group having an alkyl group as the alkyl group.
  • the halogenated alkyl group having 1 to 20 carbon atoms used in any substituent may be a group obtained by substituting a part or all of hydrogen atoms of the alkyl group with a halogen atom.
  • the halogenated alkoxy group having 1 to 20 carbon atoms used for the optional substituent may be a group obtained by substituting a part or all of the hydrogen atoms of the alkoxy group with a halogen atom.
  • the alkylsilyl group having 1 to 10 carbon atoms used for the optional substituent may be selected from the group consisting of a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group, and a dimethylethylsilyl group.
  • a trimethylsilyl group a triethylsilyl group, a tributylsilyl group, and a dimethylethylsilyl group.
  • the aromatic hydrocarbon group having 6 to 30 ring carbon atoms used in the optional substituent may be the same as the aromatic hydrocarbon group represented by the above A 1 , A 2 and R a .
  • any of the substituents used is an aryloxy group having 6 to 30 ring carbon atoms, and the aryl moiety can be selected. a group of the aforementioned aromatic hydrocarbon group.
  • An arylsilyl group having 6 to 30 carbon atoms used for any substituent, and a phenyldimethylsilyl group, a diphenylmethylsilyl group, a diphenyl tert-butylsilyl group, a triphenyl group may be selected.
  • a silyl group or the like may be selected.
  • the heteroaryl group having 5 to 30 ring atoms may be used in any of the substituents, and the same groups as the above-mentioned heterocyclic groups represented by A 1 , A 2 and R a may be selected.
  • the optional substituent is preferably a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a heteroaryl group having 5 to 30 ring atoms. More preferably, it is a fluorine atom, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthrenyl group, a phenanthrenyl group, a fluorenyl group, a spirobifluorenyl group, a fluoranthene group, a dibenzofuran ring, an oxazole ring.
  • At least one of Ar 1 and Ar 2 is a phenyl group substituted by a cyano group, a naphthyl group substituted by a cyano group, a phenanthryl group substituted by a cyano group, or a cyano group.
  • X 6 and Y 3 are bonded via Ar 3 or directly.
  • the organic electroluminescent material of the present embodiment can apply the organic electroluminescent material to the field of biomacromolecule detection, thereby broadening the application field of the organic electroluminescent material and improving the detection sensitivity to biomacromolecules.
  • the invention also provides a preparation method of the organic electroluminescent material in the above embodiment, the preparation method comprising the following steps:
  • Step 1 Under the argon gas flow, sequentially add an organic electroluminescent compound substrate, phenylboronic acid, tetrakis(triphenylphosphine)palladium, toluene, 2M sodium carbonate aqueous solution, and heat to reflux; after cooling the reaction solution to room temperature, The organic layer is separated, the organic solvent is distilled off under reduced pressure, and the obtained residue is purified by silica gel column chromatography to give intermediate 1;
  • Step 2 Under the argon gas stream, the intermediate 1, triphenylphosphine and o-dichlorobenzene are sequentially added and heated at 100 ° C to 200 ° C; the reaction solution is cooled to room temperature, and then purified by silica gel column chromatography.
  • Step 3 under the argon gas flow, sequentially add the organic electroluminescent compound molecule A containing the functional group B, tetrakis(triphenylphosphine)palladium, toluene, 2M aqueous sodium carbonate solution, and heating and refluxing; after cooling the reaction liquid to room temperature , the organic layer was separated, the organic solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to identify intermediate 3;
  • Step 4 Under the argon gas stream, sequentially add the intermediate 3, 4-bromobenzonitrile, tris(dibenzylideneacetone)dipalladium, tri-tert-butylphosphonium tetrafluoroborate, sodium t-butoxide, Anhydrous toluene, heated to reflux; the reaction mixture was cooled to room temperature, the organic layer was separated, the organic solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography to afford white solid AB;
  • Step 5 Mixing the solution of the white solid AB with one of the antibody, virus, bacteria, enzyme or biomarker protein to obtain an organic electroluminescent material of the formula AB-C.
  • a method for preparing an organic electroluminescent material includes the following steps:
  • Step 1 Under the argon gas stream, 2-nitro-1,4-dibromobenzene (11.2 g, 40 mmol), phenylboronic acid (4.9 g, 40 mmol), and tetrakis(triphenylphosphine)palladium (1.39) were sequentially added. g, 1.2 mmol), 120 mL of toluene, 60 mL of 2M sodium carbonate aqueous solution, and heated under reflux for 8 hours; after cooling the reaction mixture to room temperature, the organic layer was separated, and the organic solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography. Purified, Obtaining 6.6 g of 59% yield of intermediate 1;
  • Step 2 under argon gas flow, add (6.6g, 23.7mmol) of intermediate 1, (15.6g, 59.3mmol) triphenylphosphine, o-dichlorobenzene 24mL, heated at 180 ° C for 8 hours; After cooling the liquid to room temperature, it was purified by silica gel column chromatography to obtain 4 g of intermediate 2 in a yield of 68%;
  • Step 3 under the argon gas stream, sequentially add the intermediate 2, the compound B containing the functional group B, tetrakis(triphenylphosphine)palladium (1.39 g, 1.2 mmol), toluene 120 mL, 2M sodium carbonate aqueous solution 60 mL, and heated to reflux 8 After the reaction solution is cooled to room temperature, the organic layer is separated, and the organic solvent is distilled off under reduced pressure, and the obtained residue is purified by silica gel column chromatography to identify intermediate 3;
  • Step 4 Under the argon gas stream, (2.03 g, 3.9 mmol) of intermediate 3, (0.71 g, 3.9 mmol) of 4-bromobenzonitrile, (0.071 g, 0.078 mmol) of tris (di) Benzylacetone) dipalladium, (0.091 g, 0.31 mmol) of tri-tert-butylphosphonium tetrafluoroborate, (0.53 g, 5.5 mmol) of sodium t-butoxide, 20 mL of anhydrous toluene, heated under reflux for 8 hours; After cooling the reaction mixture to room temperature, the organic layer was separated, the organic solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give 0.79 g of white solid AB;
  • Step 5 Mixing the solution of the white solid AB with one of the antibody, virus, bacteria, enzyme or biomarker protein to obtain an organic electroluminescent material of the formula AB-C.

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Abstract

本发明公开了一种有机电致发光材料，所述有机电致发光材料由以下通式表示：AB ∖ C;该通式中，A表示有机电致发光化合物分子，B表示官能团，AB表示A经B官能团化后的产物；C表示抗体，C通过B与A结合以获得有机电致发光材料。本发明所提供的有机电致发光材料，能够应用于生物大分子检测领域，从而拓宽了有机电致发光材料的应用领域，并且能够提高对生物大分子的检测灵敏度。

Description

有机电致发光材料及其制备方法 技术领域
本发明涉及生物检测技术领域，尤其涉及一种有机电致发光材料及其制备方法。
背景技术
目前，有机电致发光材料因其特殊的发光特性，已经应用于显示、成像等领域，但是现有的应用，仅仅只是利用有机电致发光材料的发光特性，简单将其利用在需要发光的元件中；然而，随着生物技术的发展，生物标记物蛋白、DNA、抗体、病毒、微生物、酶、农药等多种生物大分子的检测方法不断更新，现有的检测方法通常是使用检测仪器，但是这些检测仪器存在体积大、检测灵敏度低、价格昂贵、应用领域窄等缺点。因此，有必要将有机电致发光材料的发光特性利用在对生物大分子的检测领域，来解决现有的检测方法存在检测成本高、检测灵敏度低、应用领域窄等缺点。
发明内容
本发明的主要目的在于提供一种高选择性、高特异性的有机电致发光材料，能够提高对生物大分子检测的灵敏度。
为实现上述目的，本发明提供了一种有机电致发光材料，所述有机电致发光材料由以下通式(Ⅰ)表示：
AB-C   (Ⅰ)
式(Ⅰ)中，A表示有机电致发光化合物分子，B表示官能团，AB表示A经B官能团化后的产物；C表示抗体，C通过B与A结合以获得有机电致发光材料。
优选地，所述A为大环共轭有机化合物分子。
所述B为含-OH、-SH、-CHO、-COOH、-SO3H、-NH2、-CH2-、RCO-中一种或几种的碳链结构。
优选地，下述AB由以下通式(Ⅱ)表示：
Figure PCTCN2015073850-appb-000001
式(Ⅱ)中，R1，R2＝-(CH2)n-X，n＝0-32，X＝OH，SH，NH2，CH3，CHO，COOH，SO3H，R′CO；
R1、R2为官能团；
Ar1和Ar2分别独立地表示取代或未取代的成环碳原子数为6～30的芳香族烃基、或者取代或未取代的成环原子数为5～30的杂环基；
Ar3表示取代或未取代的成环碳原子数为6以下的单环烃基、或者取代或未取代的成环原子数为6以下的单环杂环基；
m表示0～3的整数；
X1～X8和Y1～Y8分别独立地表示N或者CRa；
Ra分别独立地表示氢原子、取代或未取代的成环碳原子数为6～30的芳香族烃基、取代或未取代的成环原子数为5～30的杂环基、取代或未取代的碳原子数为1～30的烷基、取代或未取代的甲硅烷基或者卤素原子；
X5～X8中的一个与Y1～Y4中的一个介由Ar3键合或者直接键合；
式(Ⅱ)满足下述(1)、(2)中的至少任一项：
(1)Ar1、Ar2中的至少1个是被氰基取代了的成环碳原子数为6～30的芳香族烃基、或者被氰基取代了的成环原子数为5～30的杂环基；
(2)X1～X4和Y5～Y8中的至少1个是CRa，X1～X4和Y5～Y8的Ra中的至少1个是被氰基取代了的成环碳原子数为6～30的芳香族烃基、或者被氰基取代了的成环原子数为5～30的杂环基；
其中，Ra存在多个时，多个Ra可以分别相同或不同。
优选地，所述Ar1和Ar2所示的成环碳原子数为6～30的芳香族烃基或者成环原子数为5～30的杂环基具有取代基时，该取代基是选自氰基、卤素原子、碳原子数为1～20的烷基、碳原子数为3～20的环烷基、碳原子数为1～20的烷氧基、碳原子数为1～20的卤代烷基、碳原子数为1～20的卤代烷氧基、碳原子数为1～10的烷基甲硅烷基、成环碳原子数为6～30的芳基、成环碳原子数为6～30的芳氧基、碳原子数为6～30的芳烷基和成环原子数为5～30的杂芳基 中的至少一种。
优选地，Ar1和Ar2中的至少1个为被氰基取代了的苯基、被氰基取代了的萘基、被氰基取代了的菲基、被氰基取代了的二苯并呋喃基、被氰基取代了的二苯并噻吩基、被氰基取代了的联苯基、被氰基取代了的三联苯基、被氰基取代了的9,9-二苯基芴基、被氰基取代了的9,9’-螺二[9H-芴]-2-基、被氰基取代了的9,9-二甲基芴基或者被氰基取代了的苯并菲基。
优选地，X6与Y3介由Ar3键合或直接键合。
优选地，m＝1或m＝2。
此外，为实现上述目的，本发明还提供一种有机电致发光材料的制备方法，所述制备方法包括如下步骤：
步骤一、在氩气气流下，依次添加有机电致发光化合物底物、苯基硼酸，四(三苯基膦)钯、甲苯、2M碳酸钠水溶液，加热回流；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，得到中间体1；
步骤二、在氩气气流下，依次添加中间体1、三苯基膦、邻二氯苯，以100℃-200℃加热；将反应液冷却至室温后，用硅胶柱色谱法进行纯化，得到有机电致发光化合物分子A；
步骤三、在氩气气流下，依次添加包含有官能团B的有机电致发光化合物分子A、四(三苯基膦)钯、甲苯、2M碳酸钠水溶液，加热回流；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，鉴定为中间体3；
步骤四、在氩气气流下，依次添加中间体3、4-溴苯并腈、三(二亚苄基丙酮)二钯、三叔丁基磷鎓四氟硼酸盐、叔丁醇钠、无水甲苯，加热回流；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，得到白色固体AB；
步骤五、将白色固体AB的溶液与抗体、病毒、细菌、酶或生物标记蛋白中的一种混合搅拌，获得通式为AB-C的有机电致发光材料。
优选地，所述有机电致发光材料的制备方法包括如下步骤：
步骤一、在氩气气流下，依次添加2-硝基-1,4-二溴苯(11.2g，40mmol)、 苯基硼酸(4.9g，40mmol)、四(三苯基膦)钯(1.39g，1.2mmol)、甲苯120mL、2M碳酸钠水溶液60mL，加热回流8小时；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，得到6.6g收率59％的中间体1；
步骤二、在氩气气流下，依次添加(6.6g，23.7mmol)的中间体1，(15.6g，59.3mmol)三苯基膦，邻二氯苯24mL，以180℃加热8小时；将反应液冷却至室温后，用硅胶柱色谱法进行纯化，得到4g收率68％的中间体2；
步骤三、在氩气气流下，依次添加中间体2、含官能团B的化合物A，四(三苯基膦)钯(1.39g，1.2mmol)、甲苯120mL、2M碳酸钠水溶液60mL，加热回流8小时；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，鉴定为中间体3；
步骤四、在氩气气流下，依次添加(2.03g，3.9mmol)的中间体3，(0.71g，3.9mmol)的4-溴苯并腈，(0.071g，0.078mmol)的三(二亚苄基丙酮)二钯，(0.091g，0.31mmol)的三叔丁基磷鎓四氟硼酸盐，(0.53g，5.5mmol)的叔丁醇钠、无水甲苯20mL，加热回流8小时；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，得到0.79g白色固体AB；
步骤五、将白色固体AB的溶液与抗体、病毒、细菌、酶或生物标记蛋白中的一种混合搅拌，获得通式为AB-C的有机电致发光材料。
本发明所提供的有机电致发光材料，能够应用于生物大分子检测领域，从而拓宽了有机电致发光材料的应用领域，并且能够提高对生物大分子的检测灵敏度。
具体实施方式
应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明的主要目的在于解决现有的生物大分子的检测方法存在检测成本高、检测灵敏度低、应用领域窄等缺点，本发明的创新点在于提供一种高选择性、高特异性的有机电致发光材料，将有机电致发光材料应用于生物大分子检测领域，从而实现上述目的。
本发明实施例提供的有机电致发光材料由以下通式(Ⅰ)表示：
AB-C   (Ⅰ)
式(Ⅰ)中，A表示有机电致发光化合物分子，B表示官能团，AB表示A经B官能团化后的产物；C表示抗体，C通过B与A结合以获得有机电致发光材料。
进一步地，在上述通式中，A为大环共轭有机化合物分子；B为包含于A上的官能团的碳链结构，其中，官能团可选择-OH、-SH、-CHO、-COOH、-SO3H、-NH2、-CH2-、RCO-中的一种或几种。
本实施例中，有机电致发光材料具体可表示为如下通式：
Figure PCTCN2015073850-appb-000002
式(Ⅱ)中，R1，R2＝-(CH2)n-X，n＝0-32，X＝OH，SH，NH2，CH3，CHO，COOH，SO3H，R′CO；
R1、R2为官能团；
Ar1和Ar2分别独立地表示取代或未取代的成环碳原子数为6～30的芳香族烃基、或者取代或未取代的成环原子数为5～30的杂环基；
Ar3表示取代或未取代的成环碳原子数为6以下的单环烃基、或者取代或未取代的成环原子数为6以下的单环杂环基；
m表示0～3的整数；
X1～X8和Y1～Y8分别独立地表示N或者CRa；
Ra分别独立地表示氢原子、取代或未取代的成环碳原子数为6～30的芳香族烃基、取代或未取代的成环原子数为5～30的杂环基、取代或未取代的碳原子数为1～30的烷基、取代或未取代的甲硅烷基或者卤素原子；
X5～X8中的一个与Y1～Y4中的一个介由AR3键合或者直接键合；
进而，式(Ⅱ)满足下述(1)、(2)中的至少任一项：
(1)Ar1、Ar2中的至少1个是被氰基取代了的成环碳原子数为6～30的芳香族烃基、或者被氰基取代了的成环原子数为5～30的杂环基；
(2)X1～X4和Y5～Y8中的至少1个是CRa，X1～X4和Y5～Y8的Ra中的至 少1个是被氰基取代了的成环碳原子数为6～30的芳香族烃基、或者被氰基取代了的成环原子数为5～30的杂环基；
其中，Ra存在多个时，多个Ra可以分别相同或不同。
需要说明的是，式(Ⅱ)中，被氰基取代了的成环碳原子数为6～30的芳香族烃基、被氰基取代了的成环原子数为5～30的杂环基还可以具有除了氰基以外的取代基。
在上述实施例中，Ar1、Ar2和Ra所示的成环碳原子数为6～30的芳香族烃基时，可选择非稠合芳香族烃基和稠合芳香族烃基，更具体而言，可选择苯基、萘基、菲基、联苯基、三联苯基、四联苯基、荧蒽基、苯并菲基、菲基、芴基、螺芴基、9,9-二苯基芴基、9,9’-螺二[9H-芴]-2-基、9,9-二甲基芴基、苯并[c]菲基、苯并[a]苯并菲基、萘并[1,2-c]菲基、萘并[1,2-a]苯并菲基、二苯并[a,c]苯并菲基、苯并[b]荧蒽基等，优选为苯基、萘基、联苯基、三联苯基、菲基、苯并菲基、芴基、螺二芴基、荧蒽基，进一步优选为苯基、1-萘基、2-萘基、联苯-2-基、联苯-3-基、联苯-4-基、菲-9-基、菲-3-基、菲-2-基、苯并菲-2-基、9,9-二甲基芴-2-基、荧蒽-3-基。
在上述实施例中，Ar1、Ar2和Ra所示的成环碳原子数为5～30的杂环基具有取代基时，可选择由非稠合杂环基和稠合杂环基，更具体而言，可选择由吡咯环、异吲哚环、苯并呋喃环、异苯并呋喃环、二苯并噻吩环、异喹啉环、喹喔啉环、菲啶环、菲咯啉环、吡啶环、吡嗪环、嘧啶环、哒嗪环、三嗪环、吲哚环、喹啉环、吖啶环、吡咯烷环、二噁烷环、哌啶环、吗啉环、哌嗪环、咔唑环、呋喃环、噻吩环、噁唑环、噁二唑环、苯并噁唑环、噻唑环、噻二唑环、苯并噻唑环、三唑环、咪唑环、苯并咪唑环、吡喃环、二苯并呋喃环、苯并[c]二苯并呋喃环以及它们的衍生物形成的基团等，优选为由二苯并呋喃环、咔唑环、二苯并噻吩环以及它们的衍生物形成的基团，进一步优选为二苯并呋喃-2-基、二苯并呋喃-4-基、9-苯基咔唑-3-基、9-苯基咔唑-2-基、二苯并噻吩-2-基、二苯并噻吩-4-基。
在上述实施例中，Ar3为取代或未取代的成环碳原子数为6以下的单环烃基时，可选择亚苯基、亚环戊烯基、亚环戊二烯基、亚环己基、亚环戊基等， 优选为亚苯基。
在上述实施例中，Ar3为取代或未取代的成环原子数为6以下的单环杂环基时，可选择亚吡咯基、亚吡嗪基(pyrazinylene)、亚吡啶基、亚呋喃基、亚噻吩基等。
在上述实施例中，Ra所示的碳原子数为1～30的烷基时，可选择甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、新戊基、1-甲基戊基、环丙基、环丁基、环戊基、环己基、环辛基、金刚烷基等，优选为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、环戊基、环己基。
Ra所示的取代或未取代的甲硅烷基时，可选择三甲基甲硅烷基、三乙基甲硅烷基、三丁基甲硅烷基、二甲基乙基甲硅烷基、叔丁基二甲基甲硅烷基、乙烯基二甲基甲硅烷基、丙基二甲基甲硅烷基、二甲基异丙基甲硅烷基、二甲基丙基甲硅烷基、二甲基丁基甲硅烷基、二甲基叔丁基甲硅烷基、二乙基异丙基甲硅烷基、苯基二甲基甲硅烷基、二苯基甲基甲硅烷基、二苯基叔丁基甲硅烷基、三苯基甲硅烷基等，优选为三甲基甲硅烷基、三乙基甲硅烷基、叔丁基二甲基甲硅烷基、乙烯基二甲基甲硅烷基、丙基二甲基甲硅烷基。
Ra所示的卤素原子，可选择氟、氯、溴、碘等，优选为氟。
另外，Ra也优选为氢原子、或者取代或未取代的成环碳原子数为6～30的芳香族烃基。
在上述实施例中，Ar1和Ar2所示的成环碳原子数为6～30的芳香族烃基或者成环原子数为5～30的杂环基具有取代基时，该取代基是选自氰基、卤素原子、碳原子数为1～20的烷基、碳原子数为3～20的环烷基、碳原子数为1～20的烷氧基、碳原子数为1～20的卤代烷基、碳原子数为1～20的卤代烷氧基、碳原子数为1～10的烷基甲硅烷基、成环碳原子数为6～30的芳基、成环碳原子数为6～30的芳氧基、碳原子数为6～30的芳烷基和成环原子数为5～30的杂芳基中的至少一种。
具体地，“取代或未取代”和“可以具有取代基”这一情况下的任意的取代基，可以选择卤素原子(氟、氯、溴、碘)、氰基、碳原子数为1～20(优选为1～6)的烷基、碳原子数为3～20(优选为5～12)的环烷基、碳原子数为1～20(优选为1～5)的烷氧基、碳原子数为1～20(优选为1～5)的卤代烷基、碳原子数为1～20(优选为1～5)的卤代烷氧基、碳原子数为1～10(优选为1～5)的烷基甲硅烷基、成环碳原子数为6～30(优选为6～18)的芳基、成环碳原子数为6～30(优选为6～18)的芳氧基、碳原子数为6～30(优选为6～18)的芳基甲硅烷基、碳原子数为7～30(优选为7～20)的芳烷基、以及成环原子数为5～30的(优选为5～18)杂芳基。
任意的取代基使用的碳原子数为1～20的烷基，可选择甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、新戊基、1-甲基戊基等。
任意的取代基使用的碳原子数为3～20的环烷基，可选择环丙基、环丁基、环戊基、环己基、环辛基、金刚烷基等。
任意的取代基使用的碳原子数为1～20的烷氧基，可选择烷基部位为前述烷基的基团。
任意的取代基使用的碳原子数为1～20的卤代烷基，可选择前述烷基的一部分或全部氢原子被卤素原子取代而成的基团。
任意的取代基使用的碳原子数为1～20的卤代烷氧基，可选择前述烷氧基的一部分或全部氢原子被卤素原子取代而成的基团。
任意的取代基使用的碳原子数为1～10的烷基甲硅烷基，可选择三甲基甲硅烷基、三乙基甲硅烷基、三丁基甲硅烷基、二甲基乙基甲硅烷基、叔丁基二甲基甲硅烷基、乙烯基二甲基甲硅烷基、丙基二甲基甲硅烷基、二甲基异丙基甲硅烷基、二甲基丙基甲硅烷基、二甲基丁基甲硅烷基、二甲基叔丁基甲硅烷基、二乙基异丙基甲硅烷基等。
任意的取代基使用的成环碳原子数为6～30的芳香族烃基，可选择与前述A1、A2和Ra所示的芳香族烃基相同的基团。
任意的取代基使用的成环碳原子数为6～30的芳氧基，可选择芳基部位为 前述芳香族烃基的基团。
任意的取代基使用的碳原子数为6～30的芳基甲硅烷基，可选择苯基二甲基甲硅烷基、二苯基甲基甲硅烷基、二苯基叔丁基甲硅烷基、三苯基甲硅烷基等。
任意的取代基使用的碳原子数为7～30的芳烷基，可选择苄基、2-苯基丙烷-2-基、1-苯基乙基、2-苯基乙基、1-苯基异丙基、2-苯基异丙基、苯基叔丁基、α-萘基甲基、1-α-萘基乙基、2-α-萘基乙基、1-α-萘基异丙基、2-α-萘基异丙基、β-萘基甲基、1-β-萘基乙基、2-β-萘基乙基、1-β-萘基异丙基、2-β-萘基异丙基、1-吡咯基甲基、2-(1-吡咯基)乙基、对甲基苄基、间甲基苄基、邻甲基苄基、对氯苄基、间氯苄基、邻氯苄基、对溴苄基、间溴苄基、邻溴苄基、对碘苄基、间碘苄基、邻碘苄基、对羟基苄基、间羟基苄基、邻羟基苄基、对氨基苄基、间氨基苄基、邻氨基苄基、对硝基苄基、间硝基苄基、邻硝基苄基、对氰基苄基、间氰基苄基、邻氰基苄基、1-羟基-2-苯基异丙基、1-氯-2-苯基异丙基等。
任意的取代基使用的成环原子数为5～30的杂芳基，可选择与前述A1、A2和Ra所示的杂环基相同的基团。
任意的取代基，优选为氟原子、氰基、碳原子数为1～20的烷基、成环碳原子数为6～30的芳香族烃基、成环原子数为5～30的杂芳基，更优选为氟原子、苯基、萘基、联苯基、三联苯基、菲基、苯并菲基、芴基、螺二芴基、荧蒽基、二苯并呋喃环、咔唑环、二苯并噻吩环和它们的衍生物所形成的基团、甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、环戊基、环己基。
在上述实施例中，Ar1和Ar2中的至少1个为被氰基取代了的苯基、被氰基取代了的萘基、被氰基取代了的菲基、被氰基取代了的二苯并呋喃基、被氰基取代了的二苯并噻吩基、被氰基取代了的联苯基、被氰基取代了的三联苯基、被氰基取代了的9,9-二苯基芴基、被氰基取代了的9,9’-螺二[9H-芴]-2-基、被氰基取代了的9,9-二甲基芴基或者被氰基取代了的苯并菲基。
在上述实施例中，X6与Y3介由Ar3键合或直接键合。
在上述实施例中，m的取值优选为m＝1，或m＝2。
本实施例的有机电致发光材料，能够将有机电致发光材料应用于生物大分子检测领域，从而拓宽了有机电致发光材料的应用领域，并且提高了对生物大分子的检测灵敏度。
本发明还提供一种上述实施例中有机电致发光材料的制备方法，所述制备方法包括如下步骤：
步骤一、在氩气气流下，依次添加有机电致发光化合物底物、苯基硼酸，四(三苯基膦)钯、甲苯、2M碳酸钠水溶液，加热回流；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，得到中间体1；
步骤二、在氩气气流下，依次添加中间体1、三苯基膦、邻二氯苯，以100℃-200℃加热；将反应液冷却至室温后，用硅胶柱色谱法进行纯化，得到有机电致发光化合物分子A；
步骤三、在氩气气流下，依次添加包含有官能团B的有机电致发光化合物分子A、四(三苯基膦)钯、甲苯、2M碳酸钠水溶液，加热回流；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，鉴定为中间体3；
步骤四、在氩气气流下，依次添加中间体3、4-溴苯并腈、三(二亚苄基丙酮)二钯、三叔丁基磷鎓四氟硼酸盐、叔丁醇钠、无水甲苯，加热回流；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，得到白色固体AB；
步骤五、将白色固体AB的溶液与抗体、病毒、细菌、酶或生物标记蛋白中的一种混合搅拌，获得通式为AB-C的有机电致发光材料。
作为本发明一优选实施例，有机电致发光材料的制备方法包括如下步骤：
步骤一、在氩气气流下，依次添加2-硝基-1,4-二溴苯(11.2g，40mmol)、苯基硼酸(4.9g，40mmol)、四(三苯基膦)钯(1.39g，1.2mmol)、甲苯120mL、2M碳酸钠水溶液60mL，加热回流8小时；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化， 得到6.6g收率59％的中间体1；
步骤二、在氩气气流下，依次添加(6.6g，23.7mmol)的中间体1，(15.6g，59.3mmol)三苯基膦，邻二氯苯24mL，以180℃加热8小时；将反应液冷却至室温后，用硅胶柱色谱法进行纯化，得到4g收率68％的中间体2；
步骤三、在氩气气流下，依次添加中间体2、含官能团B的化合物A，四(三苯基膦)钯(1.39g，1.2mmol)、甲苯120mL、2M碳酸钠水溶液60mL，加热回流8小时；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，鉴定为中间体3；
步骤四、在氩气气流下，依次添加(2.03g，3.9mmol)的中间体3，(0.71g，3.9mmol)的4-溴苯并腈，(0.071g，0.078mmol)的三(二亚苄基丙酮)二钯，(0.091g，0.31mmol)的三叔丁基磷鎓四氟硼酸盐，(0.53g，5.5mmol)的叔丁醇钠、无水甲苯20mL，加热回流8小时；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，得到0.79g白色固体AB；
步骤五、将白色固体AB的溶液与抗体、病毒、细菌、酶或生物标记蛋白中的一种混合搅拌，获得通式为AB-C的有机电致发光材料。
具体地，上述AB的制备反应路线如下：
Figure PCTCN2015073850-appb-000003
Figure PCTCN2015073850-appb-000004
Figure PCTCN2015073850-appb-000005
Figure PCTCN2015073850-appb-000006
Figure PCTCN2015073850-appb-000007
Figure PCTCN2015073850-appb-000008
Figure PCTCN2015073850-appb-000009
Figure PCTCN2015073850-appb-000010
以上仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (10)

  1. 一种有机电致发光材料，其特征在于，所述有机电致发光材料由以下通式(Ⅰ)表示：
    Figure PCTCN2015073850-appb-100001
    式(Ⅰ)中，A表示有机电致发光化合物分子，B表示官能团，AB表示A经B官能团化后的产物；C表示抗体，C通过B与A结合以获得有机电致发光材料。
  2. 如权利要求1所述的有机电致发光材料，其特征在于，所述A为大环共轭有机化合物分子。
  3. 如权利要求1所述的有机电致发光材料，其特征在于，所述B为含-OH、-SH、-CHO、-COOH、-SO3H、-NH2、-CH2-、RCO-中一种或几种的碳链结构。
  4. 如权利要求1所述的有机电致发光材料，其特征在于，所述AB由以下通式(Ⅱ)表示：
    Figure PCTCN2015073850-appb-100002
    式(Ⅱ)中，R1，R2＝-(CH2)n-X，n＝0-32，X＝OH，SH，NH2，CH3，CHO，COOH，SO3H，R′CO；
    R1、R2为官能团；
    Ar1和Ar2分别独立地表示取代或未取代的成环碳原子数为6～30的芳香族烃基、或者取代或未取代的成环原子数为5～30的杂环基；
    Ar3表示取代或未取代的成环碳原子数为6以下的单环烃基、或者取代或未取代的成环原子数为6以下的单环杂环基；
    m表示0～3的整数；
    X1～X8和Y1～Y8分别独立地表示N或者CRa；
    Ra分别独立地表示氢原子、取代或未取代的成环碳原子数为6～30的芳香族烃基、取代或未取代的成环原子数为5～30的杂环基、取代或未取代的碳原子数为1～30的烷基、取代或未取代的甲硅烷基或者卤素原子；
    X5～X8中的一个与Y1～Y4中的一个介由Ar3键合或者直接键合；
    式(Ⅱ)满足下述(1)、(2)中的至少任一项：
    (1)Ar1、Ar2中的至少1个是被氰基取代了的成环碳原子数为6～30的芳香族烃基、或者被氰基取代了的成环原子数为5～30的杂环基；
    (2)X1～X4和Y5～Y8中的至少1个是CRa，X1～X4和Y5～Y8的Ra中的至少1个是被氰基取代了的成环碳原子数为6～30的芳香族烃基、或者被氰基取代了的成环原子数为5～30的杂环基；
    其中，Ra存在多个时，多个Ra可以分别相同或不同。
  5. 如权利要求4所述的有机电致发光材料，其特征在于，所述Ar1和Ar2所示的成环碳原子数为6～30的芳香族烃基或者成环原子数为5～30的杂环基具有取代基时，该取代基是选自氰基、卤素原子、碳原子数为1～20的烷基、碳原子数为3～20的环烷基、碳原子数为1～20的烷氧基、碳原子数为1～20的卤代烷基、碳原子数为1～20的卤代烷氧基、碳原子数为1～10的烷基甲硅烷基、成环碳原子数为6～30的芳基、成环碳原子数为6～30的芳氧基、碳原子数为6～30的芳烷基和成环原子数为5～30的杂芳基中的至少一种。
  6. 如权利要求4所述的有机电致发光材料，其特征在于，Ar1和Ar2中的至少1个为被氰基取代了的苯基、被氰基取代了的萘基、被氰基取代了的菲基、被氰基取代了的二苯并呋喃基、被氰基取代了的二苯并噻吩基、被氰基取代了的联苯基、被氰基取代了的三联苯基、被氰基取代了的9,9-二苯基芴基、被氰基取代了的9,9’-螺二[9H-芴]-2-基、被氰基取代了的9,9-二甲基芴基或者被氰基取代了的苯并菲基。
  7. 如权利要求4所述的有机电致发光材料，其特征在于，X6与Y3介由Ar3键合或直接键合。
  8. 如权利要求4所述的有机电致发光材料，其特征在于，m＝1或m＝2。
  9. 一种如权利要求1－8所述的有机电致发光材料的制备方法，其特征在于，所述制备方法包括如下步骤：
    步骤一、在氩气气流下，依次添加有机电致发光化合物底物、苯基硼酸，四(三苯基膦)钯、甲苯、2M碳酸钠水溶液，加热回流；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，得到中间体1；
    步骤二、在氩气气流下，依次添加中间体1、三苯基膦、邻二氯苯，以100℃-200℃加热；将反应液冷却至室温后，用硅胶柱色谱法进行纯化，得到有机电致发光化合物分子A；
    步骤三、在氩气气流下，依次添加包含有官能团B的有机电致发光化合物分子A、四(三苯基膦)钯、甲苯、2M碳酸钠水溶液，加热回流；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，鉴定为中间体3；
    步骤四、在氩气气流下，依次添加中间体3、4-溴苯并腈、三(二亚苄基丙酮)二钯、三叔丁基磷鎓四氟硼酸盐、叔丁醇钠、无水甲苯，加热回流；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，得到白色固体AB；
    步骤五、将白色固体AB的溶液与抗体、病毒、细菌、酶或生物标记蛋白中的一种混合搅拌，获得通式为
    Figure PCTCN2015073850-appb-100003
    的有机电致发光材料。
  10. 如权利要求9所述的有机电致发光材料的制备方法，其特征在于，所述有机电致发光材料的制备方法包括如下步骤：
    步骤一、在氩气气流下，依次添加2-硝基-1,4-二溴苯(11.2g，40mmol)、苯基硼酸(4.9g，40mmol)、四(三苯基膦)钯(1.39g，1.2mmol)、甲苯120mL、2M碳酸钠水溶液60mL，加热回流8小时；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，得到6.6g收率59％的中间体1；
    步骤二、在氩气气流下，依次添加(6.6g，23.7mmol)的中间体1，(15.6g，59.3mmol)三苯基膦，邻二氯苯24mL，以180℃加热8小时；将反应液冷却至室温后，用硅胶柱色谱法进行纯化，得到4g收率68％的中间体2；
    步骤三、在氩气气流下，依次添加中间体2、含官能团B的化合物A，四(三苯基膦)钯(1.39g，1.2mmol)、甲苯120mL、2M碳酸钠水溶液60mL，加热回流8小时；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，鉴定为中间体3；
    步骤四、在氩气气流下，依次添加(2.03g，3.9mmol)的中间体3，(0.71g，3.9mmol)的4-溴苯并腈，(0.071g，0.078mmol)的三(二亚苄基丙酮)二钯，(0.091g，0.31mmol)的三叔丁基磷鎓四氟硼酸盐，(0.53g，5.5mmol)的叔丁醇钠、无水甲苯20mL，加热回流8小时；将反应液冷却至室温后，分离有机层，在减压下蒸馏去除有机溶剂，将所得残渣用硅胶柱色谱法进行纯化，得到0.79g白色固体AB；
    步骤五、将白色固体AB的溶液与抗体、病毒、细菌、酶或生物标记蛋白中的一种混合搅拌，获得通式为
    Figure PCTCN2015073850-appb-100004
    的有机电致发光材料。
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CN103896830A (zh) * 2014-03-24 2014-07-02 东南大学 一种三苯胺吡啶盐荧光分子及其制备方法

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