CN106497136B - A kind of nir dye and its preparation method and application of half flower cyanines structure - Google Patents
A kind of nir dye and its preparation method and application of half flower cyanines structure Download PDFInfo
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- CN106497136B CN106497136B CN201610838403.2A CN201610838403A CN106497136B CN 106497136 B CN106497136 B CN 106497136B CN 201610838403 A CN201610838403 A CN 201610838403A CN 106497136 B CN106497136 B CN 106497136B
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- flower cyanines
- half flower
- nir dye
- cyanines structure
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 244000139794 beach naupaka Species 0.000 title 1
- 244000258825 Scaevola taccada Species 0.000 claims abstract description 25
- -1 methoxyl group Chemical group 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003384 imaging method Methods 0.000 claims description 3
- 238000007626 photothermal therapy Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 36
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 abstract description 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 abstract description 5
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 abstract description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 abstract description 3
- 229960001755 resorcinol Drugs 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 210000003739 neck Anatomy 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000012805 post-processing Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000003935 benzaldehydes Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GDIYMWAMJKRXRE-UHFFFAOYSA-N (2z)-2-[(2e)-2-[2-chloro-3-[(z)-2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]cyclohex-2-en-1-ylidene]ethylidene]-1,3,3-trimethylindole Chemical compound CC1(C)C2=CC=CC=C2N(C)C1=CC=C1C(Cl)=C(C=CC=2C(C3=CC=CC=C3[N+]=2C)(C)C)CCC1 GDIYMWAMJKRXRE-UHFFFAOYSA-N 0.000 description 1
- FLHJIAFUWHPJRT-UHFFFAOYSA-N 2,3,3-trimethylindole Chemical compound C1=CC=C2C(C)(C)C(C)=NC2=C1 FLHJIAFUWHPJRT-UHFFFAOYSA-N 0.000 description 1
- BTQAJGSMXCDDAJ-UHFFFAOYSA-N 2,4,6-trihydroxybenzaldehyde Chemical class OC1=CC(O)=C(C=O)C(O)=C1 BTQAJGSMXCDDAJ-UHFFFAOYSA-N 0.000 description 1
- YVJYSSUIRUZWMP-WUKNDPDISA-N CCN(c1c(C2(C)C)cccc1)[I]=C2/C=C/C1=C2Oc(cc(c(-c3nc(cccc4)c4[nH]3)c3)O)c3C=C2CCC1 Chemical compound CCN(c1c(C2(C)C)cccc1)[I]=C2/C=C/C1=C2Oc(cc(c(-c3nc(cccc4)c4[nH]3)c3)O)c3C=C2CCC1 YVJYSSUIRUZWMP-WUKNDPDISA-N 0.000 description 1
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 1
- IKYOKBYKZLQMSY-UHFFFAOYSA-N Oc1cc(O)c(-c2nc(cccc3)c3[nH]2)c(O)c1 Chemical compound Oc1cc(O)c(-c2nc(cccc3)c3[nH]2)c(O)c1 IKYOKBYKZLQMSY-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-N disulfurous acid Chemical compound OS(=O)S(O)(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- 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, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention provides a kind of nir dye and its preparation method and application of half flower cyanines structure, the structural formula of the dyestuff as shown in formula I,R1For straight chain, branch or cyclic alkyl with 1 to 32 carbon atom；R2For hydrogen, bromine, methoxyl group, N, one kind in N dimethylaminos, ethyoxyl, hydroxyl, Carboxvmethoxv or acetyl methoxyl group.The dyestuff is made with Cy7 cyanine dyes and the resorcin reaction with benzimidazole.The present invention introduces benzimidazole group in the dyestuff of half flower cyanines structure, and gained dyestuff not only has absorption and transmitting near infrared region, and has response to the pH value of environment.
Description
Technical field
The invention belongs to organic near infrared fluorescent dye technical fields, and in particular to a kind of near-infrared dye of half flower cyanines structure
Material and its preparation method and application.
Background technology
Near infrared fluorescent dye is a kind of Functional dye, close since it has good absorption in near-infrared region
Infrared technique suffers from solar cell, oncotherapy, radio frequency identification system, anti-counterfeit printing etc. widely answers
With.
For cyanine dye as one kind in nir dye, part has obtained practical application, and constantly has new type to gush
It is existing.Near-infrared methine cyanine dye Absorption and emission spectra be located near infrared region (>650nm), relative to visible fluorescence area (<
For 650nm) detecting, in near-infrared fluorescent area, the fluorescent absorption and fluorescence intensity very little of biological sample matrix, thus background is dry
It disturbs and substantially reduces, and since the biquadratic of scattered light intensity and wavelength is inversely proportional, with the increase of wavelength, Raman scattering subtracts rapidly
It is small, so that scattering interference is also greatly reduced.The one kind of seven methines as methine cyanine dye, absorbing wavelength is longer, and background interference is more
It is small, it is applied to biology sample detection for conventional fluorescent detection, there are deeper tissue penetration depths, to biological group
The damage smaller knitted, so its application prospect is also more wide.
The half flower cyanines structure dyestuff based on the synthesis of seven methine indole cyanine dyes, has stronger absorption and transmitting near infrared region
Performance can be used for photo-thermal therapy and photoacoustic imaging field；And have response effect for the pH value of environment, it may be used as close red
The fluorescence probe of outskirt；In addition the photo-thermal of the dyestuff and chemical stability comparison heptamethine cyanine are carried there has also been prodigious
It rises.
Invention content
The technical issues of solution：The half flower cyanines structure that the purpose of the present invention is to provide a kind of with benzimidazole it is close red
Outer dyestuff and preparation method thereof, the dyestuff have near infrared absorption and emitting performance, good photo-thermal and chemical stability.
Technical solution：One aspect of the present invention provides a kind of nir dye of half flower cyanines structure, structural formula such as I institute of formula
Show：
Wherein, R1For straight chain, branch or cyclic alkyl with 1 to 32 carbon atom；R2For hydrogen, bromine, methoxyl group, N, N
One kind in dimethylamino, ethyoxyl, hydroxyl, Carboxvmethoxv or acetyl methoxyl group.
The preparation method of the nir dye of above-mentioned half flower cyanines structure, includes the following steps：
First by compound and the formylated cyclohexanone after 2,3,3- trimethyl -1-H- indolylethyls at 100 DEG C
The cyanine dye of Cy7 structures is obtained by the reaction；Then band is obtained by the reaction at 160 DEG C with o-phenylenediamine and 2,4- 4-dihydroxy benzaldehydes
There is the resorcinol of benzimidazole；Finally at 50 DEG C, using n,N-Dimethylformamide as solvent, with Cy7 cyanine dyes and band
The resorcin reaction for having benzimidazole is detached using column chromatography method to get the nir dye of cyanines structure is spent to described half.
The present invention also provides half flower cyanines structure dyestuffs being coordinated with boron, and structural formula is as shown in formula II：
Wherein, R1For straight chain, branch or cyclic alkyl with 1 to 32 carbon atom；R2For hydrogen, bromine, methoxyl group, N, N
One kind in dimethylamino, ethyoxyl, hydroxyl, Carboxvmethoxv or acetyl methoxyl group.
The preparation method of the above-mentioned half flower cyanines structure dyestuff with boron coordination be by the nir dye of half flower cyanines structure with
Boron trifluoride ether is reacted, and detailed process is as follows：
Application of the nir dye of above-mentioned half flower cyanines structure in photoacoustic imaging field.
Application of the nir dye of above-mentioned half flower cyanines structure in photo-thermal therapy field.
Application of the nir dye of above-mentioned half flower cyanines structure in fluorescence sense field.
Advantageous effect：The present invention introduces benzimidazole group in the dyestuff of half flower cyanines structure, and gained dyestuff not only exists
Near infrared region has absorption and transmitting, and has response to the pH value of environment.Hemicyanine dye after boron coordination is not only close red
Exterior domain has absorption and transmitting, has response to the pH value of environment, and its photo-thermal is improved with chemical stability.
Description of the drawings
Fig. 1 is ultraviolet-ray visible absorbing of the nir dye of half flower cyanines structure of embodiment 1 under acid and alkaline condition
Spectrum；
Fig. 2 is emission spectrum of the nir dye of half flower cyanines structure of embodiment 1 under acid and alkaline condition.
Specific implementation mode
The content of patent for a better understanding of the present invention is further illustrated the present invention below by specific example
Technical solution.Specifically include synthesis, property measures.But these embodiments are not intended to limit the present invention.
Embodiment 1
The preparation of the half flower cyanines structure dyestuff with benzimidazole structure, R1For ethyl, R2For H.
The synthesis of compound C1：
2,3,3- tri-methyl indole (478mg, 3mmol) of solid material is added into bottle with two necks to seal afterwards, vacuumizes, nitrogen charging
Gas 3 times；Then solvent anhydrous acetonitrile 10mL and liquid charging stock iodoethane (515mg, 3.3mmol) are injected into bottle with two necks, 70
15h is stirred to react at DEG C.Post-processing：Mixture after reaction is cooled to room temperature, the petroleum ether of 20mL is added under stiring.Stirring
It is filtered after 2h, obtains the solid powder 567mg of pink, yield 60%.1H NMR(400MHz,DMSO)δ8.00–7.91(m,
1H), 7.89-7.77 (m, 1H), 7.66-7.56 (m, 2H), 4.47 (q, J=7.3Hz, 2H), 2.81 (s, 3H), 1.51 (s,
6H), 1.42 (t, J=7.3Hz, 3H).
The synthesis of compound C2：
N,N-Dimethylformamide (1.14g, 13.1mmol) and dichloromethane (3mL) are added in bottle with two necks, and
Cooling 10min in ice-water bath.Phosphorus oxychloride (2g, 13.1mmol) and the mixed solution of dichloromethane (3mL) are added dropwise again
In the mixed solution good to above-mentioned cooling, 10min is stirred.Into above-mentioned mixed liquor inject cyclohexanone (430mg, 4.38mmol) and
The mixed solution of dichloromethane (3mL) stirs 10min.In N2Environment is stirred to react 6h at 80 DEG C.Post-processing：It will be mixed after reaction
After conjunction object is cooled to room temperature, it is poured slowly into 160g ice water, has yellow solid precipitation, stand overnight.Suction filtration obtains 613mg yellow
Powder, yield 80%.It is not further processed to direct plunge into and react in next step.
The synthesis of compound C3：
Raw material C1 (315mg, 1mmol), C2 (87.3mg, 0.5mmol), potassium acetate (45mg) are added in bottle with two necks,
Sealing, vacuum nitrogen gas 3 times.Solvent acetic acid acid anhydride 8Ml is injected, 2h is stirred to react at 100 DEG C.Post-processing：It will be mixed after reaction
Object is cooled to room temperature, and is filtered, is washed with a small amount of acetic anhydride, and the powder 287.6mg that green carries metallic luster, yield are obtained
90%.1H NMR (400MHz, DMSO) δ 8.25 (d, J=14.1Hz, 1H), 7.62 (d, J=7.4Hz, 1H), 7.47-7.39
(m, 2H), 7.32-7.22 (m, 1H), 6.30 (d, J=14.2Hz, 1H), 4.23 (q, J=7.0Hz, 2H), 2.69 (dd, J=
15.1,9.0Hz, 2H), 1.88-1.79 (m, 1H), 1.68 (d, J=22.1Hz, 6H), 1.29 (t, J=7.1Hz, 3H).
The synthesis of compound C4：
By raw material o-phenylenediamine (216mg, 2mmol), 2,4- 4-dihydroxy benzaldehydes (276mg, 2.2mmol) and pyrosulfurous acid
Sodium (190mg, 2mmol) is packed into bottle with two necks, is then injected into solvent n,N-Dimethylformamide 15mL, 4 are stirred to react at 160 DEG C
Hour.Post-processing：After mixture is cooled to room temperature after reacting, 50mL deionized waters are added, it is solid that suction filtration obtains yellow powder
Body.Obtained solid is dissolved in ethyl acetate, silica white is added and was spin-dried for column purification, obtains pale yellow powder 295mg, yield
65%.1H NMR (400MHz, DMSO) δ 13.17 (s, 1H), 12.90 (s, 1H), 9.97 (s, 1H), 7.82 (d, J=8.4Hz,
1H), 7.57 (d, J=30.2Hz, 2H), 7.21 (s, 2H), 6.42 (d, J=7.7Hz, 1H), 6.38 (s, 1H).
The synthesis of compound C5：
Raw material C4 (160mg, 0.7mmol) is fitted into bottle with two necks, is sealed, vacuum nitrogen gas 3 times.Inject solvent N, N-
Dimethylformamide 5mL and triethylamine (70.7mg, 0.7mmol), are stirred at room temperature 10 minutes.By raw material C3 (150mg,
It 0.23mmol) is dissolved in the DMF of 5mL, injects in reaction bulb.It is stirred to react at 50 DEG C 4 hours.Post-processing：It is mixed after toward reaction
It closes in object and pours into 50mL dichloromethane, washed organic phase 3 times with 20mL deionized waters.The organic phase anhydrous slufuric acid that will be obtained
Sodium is dried, and is spin-dried for, and is crossed column and is purified to obtain black blue powders 62mg, yield 42%.1H NMR(400MHz,DMSO)δ8.40(s,
1H), 8.22 (d, J=13.2Hz, 1H), 7.77 (s, 1H), 7.62 (s, 2H), 7.52 (d, J=6.6Hz, 1H), 7.35 (d, J=
6.7Hz, 1H), 7.29 (s, 1H), 7.17 (s, 1H), 7.13-7.17 (2H), 6.55 (s, 1H), 6.00 (d, J=13.0Hz,
1H), 4.09 (q, J=8.9Hz, 2H), 3.58 (t, J=7.0Hz, 2H), 2.69 (t, J=7.2Hz, 2H), 2.59 (t, J=
7.0Hz,2H),1.77(s,3H),1.67(s,6H)。
The synthesis of compound C6：
Raw material C5 (100mg, 0.16mmol) is fitted into bottle with two necks, is sealed, vacuum nitrogen gas 3 times.Inject solvent four
The mixed solution of hydrogen furans 5mL and boron trifluoride ether (0.1mL, excessive), are stirred at room temperature 15 hours.Post-processing：Reaction
The direct column of crossing of mixture purifies to obtain black blue powders 55mg, yield 52% afterwards.1H NMR(400MHz,DMSO)δ13.20(s,
1H), 8.47 (s, 1H), 8.19 (d, J=13.6Hz, 1H), 7.89 (s, 1H), 7.67-7.64 (m, 1H), 7.57 (d, J=
6.8Hz, 1H), 7.49 (d, J=7.6Hz, 1H), 7.31 (d, J=7.6Hz, 1H), 7.19 (d, J=7.9Hz, 1H), 7.12
(dd, J=8.6,4.6Hz, 3H), 6.43 (s, 1H), 5.92 (d, J=13.9Hz, 1H), 4.03 (d, J=6.8Hz, 2H),
2.72-2.68 (m, 2H), 2.64 (d, J=6.0Hz, 2H), 1.81 (t, J=12.6Hz, 3H), 1.76 (d, J=4.0Hz, 2H),
1.67(s,6H)。
The ultraviolet-visible spectrum test of the half flower cyanines structure dyestuff C5 with benzimidazole：Prepare the dilute of two kinds of compounds
Solution (10-5M, solvent are respectively the PBS buffer solution of pH=3.0 and pH=9.0), 2mL compound solutions are pipetted in fluorescence colorimetric
In ware, the test of Absorption and emission spectra is then carried out, such as Fig. 1 and Fig. 2.Test data shows：The compound is glimmering in near-infrared
Light area has good absorption and emission characteristic, and under alkaline condition, the absorption of the compound and emission peak are compared in acidity
Under the conditions of red shift.
Embodiment 2
The preparation of the half flower cyanines structure dyestuff with benzimidazole structure, R1For ethyl, R2For hydroxyl.
The synthesis of compound C1, C2, C3 are the same as embodiment 1.
The synthesis of compound C4：
By raw material o-phenylenediamine (216mg, 2mmol), 2,4,6- tri hydroxybenzaldehydes (311mg, 2.2mmol) and burnt sulfurous
Sour sodium (190mg, 2mmol) is packed into bottle with two necks, is then injected into solvent n,N-Dimethylformamide 15mL, is stirred at 160 DEG C anti-
It answers 4 hours.Post-processing：After mixture is cooled to room temperature after reacting, 50mL deionized waters are added, suction filtration obtains yellow powder
Solid.Obtained solid is dissolved in ethyl acetate, silica white is added and was spin-dried for column purification, obtains pale yellow powder 290mg, produces
Rate 60%.1H NMR (400MHz, Chloroform) δ 9.07 (s, 1H), 7.57 (d, J=5.6Hz, 2H), 7.25 (d, J=
2.9Hz, 2H), 6.36 (d, J=11.4Hz, 3H), 6.04-5.99 (m, 2H).
The synthesis of compound C5：
Raw material C4 (170mg, 0.7mmol) is fitted into bottle with two necks, is sealed, vacuum nitrogen gas 3 times.Inject solvent N, N-
Dimethylformamide 5mL and triethylamine (70.7mg, 0.7mmol), are stirred at room temperature 10 minutes.By raw material C3 (150mg,
It 0.23mmol) is dissolved in the DMF of 5mL, injects in reaction bulb.It is stirred to react at 50 DEG C 4 hours.Post-processing：It is mixed after toward reaction
It closes in object and pours into 50mL dichloromethane, washed organic phase 3 times with 20mL deionized waters.The organic phase anhydrous slufuric acid that will be obtained
Sodium is dried, and is spin-dried for, and is crossed column and is purified to obtain black blue powders 46mg, yield 40%.1H NMR(400MHz,Chloroform)δ
9.10 (s, 1H), 8.09 (s, 1H), 7.69 (s, 1H), 7.63-7.56 (m, 3H), 7.24 (d, J=2.4Hz, 2H), 7.16 (s,
1H),6.99(s,1H),6.81(s,1H),6.69(s,1H),6.43(s,1H),5.58(s,1H),5.26(s,1H),3.73(s,
1H),3.47(s,1H),2.86(s,2H),2.19(s,2H),1.70(s,2H),1.47(s,3H),1.39(s,6H)。
The synthesis of compound C6：
Raw material C5 (100mg, 0.15mmol) is fitted into bottle with two necks, is sealed, vacuum nitrogen gas 3 times.Inject solvent four
The mixed solution of hydrogen furans 5mL and boron trifluoride ether (0.1mL, excessive), are stirred at room temperature 15 hours.Post-processing：Reaction
The direct column of crossing of mixture purifies to obtain black blue powders 45mg, yield 42% afterwards.1H NMR(400MHz,Chloroform)δ
9.80 (s, 1H), 8.12 (s, 1H), 7.69 (s, 1H), 7.66-7.58 (m, 3H), 7.23 (d, J=2.4Hz, 2H), 7.11 (s,
1H),6.93(s,1H),6.60(s,1H),6.41(s,1H),5.57(s,1H),5.21(s,1H),3.73(s,1H),3.41(s,
1H),2.85(s,2H),2.11(s,2H),1.72(s,2H),1.50(s,3H),1.32(s,6H)。
Claims (5)
1. a kind of nir dye of half flower cyanines structure, it is characterised in that：Its structural formula is as shown in formula II：
Wherein, R1For straight chain, branch or cyclic alkyl with 1 to 32 carbon atom；R2For hydrogen, bromine, methoxyl group, N, N diformazans
One kind in amino, ethyoxyl, hydroxyl, Carboxvmethoxv or acetyl methoxyl group.
2. the preparation method of the nir dye of half flower cyanines structure described in claim 1, it is characterised in that：Including following step
Suddenly：
3. the nir dye of half flower cyanines structure described in claim 1 is in the application in photoacoustic imaging field.
4. the nir dye of half flower cyanines structure described in claim 1 is in the application in photo-thermal therapy field.
5. the nir dye of half flower cyanines structure described in claim 1 is in the application in fluorescence sense field.
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