CN106045905B - A kind of compound and preparation method thereof for assisting metal-enhanced fluorescence - Google Patents
A kind of compound and preparation method thereof for assisting metal-enhanced fluorescence Download PDFInfo
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- CN106045905B CN106045905B CN201610405347.3A CN201610405347A CN106045905B CN 106045905 B CN106045905 B CN 106045905B CN 201610405347 A CN201610405347 A CN 201610405347A CN 106045905 B CN106045905 B CN 106045905B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 19
- 150000002367 halogens Chemical class 0.000 claims abstract description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- -1 nitrite anions Chemical class 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- VJTJVFFICHLTKX-UHFFFAOYSA-N dipyridin-2-yldiazene Chemical compound N1=CC=CC=C1N=NC1=CC=CC=N1 VJTJVFFICHLTKX-UHFFFAOYSA-N 0.000 claims description 14
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 11
- 239000011630 iodine Substances 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 claims description 9
- 229960004979 fampridine Drugs 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000006149 azo coupling reaction Methods 0.000 claims description 4
- 238000006266 etherification reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000001965 increasing effect Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 9
- 238000001514 detection method Methods 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 239000002082 metal nanoparticle Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 108020004414 DNA Proteins 0.000 description 2
- 108091081062 Repeated sequence (DNA) Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 108091028043 Nucleic acid sequence Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002114 biscuit porcelain Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
-
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention provides a kind of preparation methods of compound for assisting metal-enhanced fluorescence, include the following steps：1) the fabricated in situ Nano silver grain in the dyestuff containing pyridine groups；2) the compound dissolution by the silver-being prepared containing pyridine groups dyestuff in a solvent, is added dropwise the solution containing halogenic molecule, double halogen key compounds of the silver-halogenic molecule-containing pyridine groups dyestuff is prepared.Double halogen key compounds of the invention have the characteristic that can assist metal-enhanced fluorescence, have wide potential application in fields such as biomedicine detections, and increase the distance between metal and dyestuff by introducing halogen key in the present invention to enhance fluorescence.
Description
Technical field
The present invention relates to one kind can assist the new method of metal-enhanced fluorescence material and fluorescent material based on the method
Preparation, in particular to a kind of double halogen keys being prepared using halogen, Nano silver grain and dyestuff containing pyridine groups as raw material
Compound and preparation method thereof.
Background technique
Currently, it is close for carrying out the study on the modification of molecular fluorescence using surface enhanced effect of the metal nanoparticle to electromagnetic field
One of the hot spot of international research, is related to the numerous areas such as spectroscopy, material, biology, chemistry, medicine over year.And fluorophor with
One of an important factor for distance of metal Nano structure is influence fluorophor fluorescence intensity, only when fluorophor and metal are received
When the distance of rice structure is appropriate, metal Nano structure
The global radiation attenuation rate for increasing fluorophor can be just played there are caused radiation decrement, improve fluorophor
Quantum yield, shorten its fluorescence lifetime.Therefore, in the application of metal-enhanced fluorescence (MEF), often by fluorogen and metal watch
Face or particle are artificially separated by a distance, and inquire into influence and available maximum fluorescence of the distance to metal-enhanced fluorescence
The suitable distance of enhancing.
Document report separate fluorogen and metal surface or the common method of particle there are several types of：(1) inorganic layer is utilized
SiO2Separate fluorogen and metal surface or particle.Such as one layer of SiO is coated on Ag film surface layer2, then by the life of labeling dye fluorogen
Object molecule and SiO2Bonding；Or the surface chemistry coated Si O in Ag nanoparticle2, form Ag@SiO2Core-shell structure, by fluorescence
Molecular dopant is in SiO2In shell, or and SiO2Layer surface formed chemical bonding, between fluorescent molecule and metal surface or particle away from
From SiO can be passed through2The thickness of layer is adjusted.(2) fluorescent molecule and metal watch are separated using the DNA sequence dna with determining chain length
Face or particle.As Ginger et al. by Ag film or be fixed on substrate surface Ag nanoparticle and simple sequence DNA be chemically bonded, and
With the complementary simple sequence DNA hydridization marked through fluorescent molecule.Therefore, the distance between fluorescent molecule and metal surface are accurate
DNA double chain length may be selected the DNA of different chain length to connect fluorogen and metal surface, adjust distance between the two with this.
(3) fluorescent molecule and metal surface or particle are separated using bio-macromolecule layer.(4) fluorescent molecule is separated using multi-layer film structure
With metal surface.Can not only people be made to gain more insight into metal nanoparticle comprehensive research of metal-enhanced fluorescence effect
Surface plasma volume property especially for the new biomedical spectral investigation method of development and can further increase detection sensitivity
Establish important theoretical basis.
Summary of the invention
Present invention aim to address subproblems present in existing metalfluorescent technology, provide a kind of assistance metal increasing
Compound of hyperfluorescence and preparation method thereof.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of preparation method of compound that assisting metal-enhanced fluorescence, includes the following steps：
(1) 4-aminopyridine and phenol existing for the nitrite anions under the conditions of diazo coupling occurs, obtain intermediate
4- hydroxy benzenes azo pyridine；
(2) filtering is precipitated, is washed, again after etherification reaction occurs for 4- hydroxy benzenes azo pyridine and chloralkane or brominated alkanes
Column chromatography, which is carried out, with the mixed solvent of petroleum ether and ethyl acetate after crystallization, drying generates azo pyridine alkoxy benzene；
(3) iodine or bromine are dissolved in organic solvent, are then added drop-wise to the solution of the azo pyridine alkoxy benzene of step (2)
In, stirring is settled out iodine key or bromine key compound；
(4) it is derivative to obtain metal-halogen-azo pyridine for the fabricated in situ Nano silver grain in iodine key or bromine key compound
Double halogen key compounds of object；
The chemical formula of 4- hydroxy benzenes azo pyridine is as follows in the step (1)：
The chemical formula of azo pyridine alkoxy benzene in the step (2) is as follows：
Wherein, R is the linear or branched alkyl group of C10~C24, and X is Cl or Br；
The reaction process of the step (3) is as follows：
Wherein, X is I or Br；
According to the mass fraction, 0.5 part of silver acetate is substantially dissolved in acetonitrile solution by thermal reduction by the step (4)
In, then 1.9 parts of iodine keys or 1.6 parts of bromine key compounds are added in the acetonitrile solution of dissolution silver acetate, 0.5- is stirred by ultrasonic
Acetonitrile solvent is removed after 1h, gradient increased temperature obtains after being cooled to room temperature to 110-120 DEG C under vacuum conditions by said mixture
The double halogen key compounds of metal-halogen-azo pyridine derivative.
Preferably, the R is the linear or branched alkyl group of C10~C18.
Preferably, the diazo coupling of the step (1) be by by sodium nitrite and phenol be placed in sodium hydroxide or
The mixed solution is added drop-wise in the aqueous hydrochloric acid solution containing 4-aminopyridine after being cooled to 0-5 DEG C in potassium hydroxide solution, ice
The pH of reaction mixture is adjusted to 6~7 after bath stirring 0.5-2h, precipitating is washed, recrystallizes, is dried to obtain centre by filtering
Body 4- hydroxy benzenes azo pyridine.
Preferably, according to the mass fraction, the sodium nitrite is 4 parts, and phenol is 5 parts；Sodium hydroxide or potassium hydroxide are molten
Liquid is 10% (w/w)；Contain 6 parts of 4-aminopyridine in the aqueous hydrochloric acid solution containing 4-aminopyridine, the volume of hydrochloric acid and water
Than being 5:4.
Preferably, according to the mass fraction, the etherification reaction of the step (2) is by 4- hydroxy benzenes azo pyridine and iodate
Potassium, part potassium carbonate are dissolved in organic solvent, to the mixed solution and dripping chloralkane or the solution of brominated alkanes, are heated to reflux
Reaction；The volume ratio of the petroleum ether and ethyl acetate is 1:1 or 1:2.
Preferably, according to the mass fraction, the 4- hydroxy benzenes azo pyridine is 2 parts, and potassium iodide is 0.005 part, potassium carbonate
It is 6.9 parts；Organic solvent is dimethyl sulfoxide (DMSO)；Heating temperature is 120-140 DEG C, reflux time 5-12h.
Preferably, the organic solvent of the step (3) is chloroform or n-hexane；Stirring is stirring 2 hours at room temperature.
Preferably, the solution of the azo pyridine alkoxy benzene of the step (3) is that azo pyridine alkoxy benzene is substantially soluble in
The solution formed in chloroform or n-hexane；According to the mass fraction, the azo pyridine alkoxy benzene is 1.8 parts.
Another aspect of the present invention, a kind of compound for assisting metal-enhanced fluorescence, the compound pass through the above method
It is prepared.
Beneficial effects of the present invention：Double halogen key compounds of the invention are due to introducing double halogen keys as azo dyes and metal
Bridge between nanoparticle, increases the distance between dyestuff and metal nanoparticle, so that having can assist metal to enhance
The characteristic of fluorescence, also, the distance between this dyestuff and metal nanoparticle can be by the different halogens of selection (such as
I2) be adjusted, the effect of regulation metal-enhanced fluorescence intensity is further functioned as, is had extensively in fields such as biomedicine detections
Wealthy potential application, and increase the distance between metal and dyestuff by introducing halogen key in the present invention to enhance the system of fluorescence
Preparation Method is simple and easy, application easy to spread.
Detailed description of the invention
Fig. 1 is the fluorescent emission figure of A12AzPy, 12Br, A12AzPy-Ag and 12Br-Ag (0.6wt%) in acetone,
The concentration of middle Ag nanoparticle in the base is 10wt%；
Fig. 2 is fluorescence emission peak of the A12AzPy-Ag (0.6wt%) under the excitation wavelength of 352nm；
Fig. 3 is fluorescence emission peak of the 12Br-Ag (0.6wt%) under the excitation wavelength of 393nm；
Fig. 4 is the fluorescence emission peak of the 12Br-Ag of various concentration in acetone, and wherein Ag nanoparticle is in 12Br matrix
Concentration be 10wt%；
Fig. 5 is the fluorescence emission peak of the 12I-Ag (0.6wt%) of different Ag doping concentration in acetone.
Specific embodiment
In order to better illustrate the present invention, with reference to the attached drawing in the embodiment of the present invention, in the embodiment of the present invention
Technical solution is clearly and completely described.
Embodiment 1：The synthesis of compound 1b
1. the synthesis of intermediate 4- hydroxy benzenes azo pyridine
4.00g (58mmol) sodium nitrite and 5.00g (53mmol) phenol are placed in 10% (w/w) sodium hydrate aqueous solution
In (20ml), and it is cooled to 0 DEG C.Above-mentioned mixed solution is added dropwise to containing 6.00g (64mmol) 4-aminopyridine
45ml hydrochloric acid solution (25ml 11N hydrochloric acid and 20ml water) in.0.5h is stirred under ice bath.Then, with 10% (w/w) hydroxide
Sodium water solution adjusts the pH value of reaction mixture to 6~7.The precipitating of yellow is obtained by filtration.It washes, recrystallize, be dried to obtain
Yellow solid.Yield：38.0%.
2. the synthesis of azo pyridine dodecyloxy benzene (being denoted as A12AzPy)
By 4- hydroxy benzenes azo pyridine (2.00g, 0.1mol), potassium iodide (0.005g, 0.03mmol) and potassium carbonate
(6.9g, 0.005mol) is dissolved in DMSO (20ml) solution.It is added dropwise dropwise into above-mentioned mixed solution and contains 1- chlorinated dodecane
DMSO (10ml) solution of (2.05g, 0.01mol).It is heated to 130 DEG C of back flow reaction 5h.It has reacted and has been placed on mistake in 200ml water
Filter obtains bisque precipitating.It washes, recrystallize, be dried to obtain yellow orange solid.Then with petroleum ether and ethyl acetate volume
Than being 1:1 mixed solvent carries out column chromatography, collects front-end volatiles.Vacuum is spin-dried for solvent in front-end volatiles, obtains light orange color powder.
Yield：61.0%.
Structural analysis data are as follows：
IR (KBr, cm-1)：2918cm-1And 2849cm-1Place is the characteristic absorption peak of alkyl chain, 1254cm-1For C-O-C's
Characteristic absorption peak.
1H-NMR (400MHz, CDCI3):δ8.77(2H,d,Ar-H),δ7.95(2H,d,Ar-H),δ7.71(2H,d,Ar-
H),δ7.03(2H,d,Ar-H),δ4.06(2H,t,-O-CH2-),δ1.85(2H,m,-CH2-),δ1.46(2H,m,-CH2-),δ
1.27(16H,m,-C8H16-),δ0.90(3H,t,-CH3)。
3. the synthesis of bromine key compound
The bromine water of 0.035g (0.5mmol) is added drop-wise to the azo pyridine dodecyloxy benzene for being dissolved in 5ml chloroform
In the solution of (0.1835g, 0.5mmol), 2h is stirred at room temperature.Filter and be dried to obtain the precipitating of Chinese red.Yield：
91.0%.
4. the synthesis of pair halogen key compound
Above-mentioned steps 1,2,3,4 can indicate with following reaction equations, and in the present embodiment, XR is 1- chlorinated dodecane, R is-
C12H23；
Embodiment 2：The synthesis of compound 1a
Reaction step only replaces bromine water with elemental iodine in step 3 with embodiment 1, obtains iodine key compound and (is denoted as
12I)。
Double halogen key compounds made of above-described embodiment have following feature：
Double halogen key compounds obtained above are dissolved in acetone, the more former compound A12AzPy of fluorescent characteristic,
A13AzPy, 12Br and 12I are remarkably reinforced.
Fig. 1-5 shows the azo pyridine alkoxy benzene (A12AzPy) prepared in above-described embodiment, halogen key compound
(12Br and 12I) and double halogen key compound (fluorescence curves of 1a to 1b), it can be seen that the fluorescence of double halogen key compounds is compared with raw material
A12AzPy, 12Br and 12I tool increase significantly, wherein since the distance of I-I is greater than the distance of Br-Br, double iodine key chemical combination
The fluorescence intensity of object is greater than the fluorescence intensity of double bromine key compounds.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection of claims
Subject to range.
Claims (6)
1. a kind of preparation method for the compound for assisting metal-enhanced fluorescence, which is characterized in that include the following steps：
(1) 4-aminopyridine and phenol existing for the nitrite anions under the conditions of diazo coupling occurs, obtain intermediate 4- hydroxyl
Base benzeneazo pyridine；
(2) 4- hydroxy benzenes azo pyridine is precipitated with filtering after chloralkane or brominated alkanes generation etherification reaction, washing, is tied again
Column chromatography, which is carried out, with the mixed solvent of petroleum ether and ethyl acetate after brilliant, dry generates azo pyridine alkoxy benzene；
(3) iodine or bromine are dissolved in organic solvent, are then added drop-wise in the solution of the azo pyridine alkoxy benzene of step (2), stir
It mixes, is settled out iodine key or bromine key compound；
(4) the fabricated in situ Nano silver grain in iodine key or bromine key compound, obtains metal-halogen-azo pyridine derivative
Double halogen key compounds；
The chemical formula of 4- hydroxy benzenes azo pyridine is as follows in the step (1)：
The chemical formula of azo pyridine alkoxy benzene in the step (2) is as follows：
Wherein, the R is the linear or branched alkyl group of C10~C18, and X is Cl or Br；
The reaction process of the step (3) is as follows：
Wherein, X is I or Br；
According to the mass fraction, 0.5 part of silver acetate is substantially dissolved in acetonitrile solution by the step (4) by thermal reduction, so
1.9 parts of iodine keys or 1.6 parts of bromine key compounds are added to afterwards in the acetonitrile solution of dissolution silver acetate, are removed after 0.5-1h is stirred by ultrasonic
Fall acetonitrile solvent, gradient increased temperature obtains metal-after being cooled to room temperature to 110-120 DEG C under vacuum conditions by said mixture
The double halogen key compounds of halogen-azo pyridine derivative；
According to the mass fraction, the etherification reaction of the step (2) is to be dissolved in 4- hydroxy benzenes azo pyridine and potassium iodide, potassium carbonate
In organic solvent, to the mixed solution and dripping chloralkane or the solution of brominated alkanes, heating reflux reaction；The petroleum ether
Volume ratio with ethyl acetate is 1:1 or 1:2；
The organic solvent of the step (3) is chloroform or n-hexane；Stirring is stirring 2 hours at room temperature.
2. preparation method according to claim 1, which is characterized in that the diazo coupling of the step (1) is to pass through
Sodium nitrite and phenol are placed in sodium hydroxide or potassium hydroxide solution after being cooled to 0-5 DEG C for the mixed solution to be added drop-wise to and be contained
Have in the aqueous hydrochloric acid solution of 4-aminopyridine, the pH of reaction mixture is adjusted to 6~7 after ice bath stirring 0.5-2h, filters, it will
Precipitating is washed, is recrystallized, being dried to obtain intermediate 4- hydroxy benzenes azo pyridine.
3. preparation method according to claim 2, which is characterized in that according to the mass fraction, the sodium nitrite is 4 parts,
Phenol is 5 parts；Sodium hydroxide or potassium hydroxide solution are 10% (w/w)；In the aqueous hydrochloric acid solution containing 4-aminopyridine
Containing 6 parts of 4-aminopyridine, the volume ratio of hydrochloric acid and water is 5:4.
4. preparation method according to claim 1, which is characterized in that according to the mass fraction, the 4- hydroxyl benzeneazo pyrrole
Pyridine is 2 parts, and potassium iodide is 0.005 part, and potassium carbonate is 6.9 parts；Organic solvent is dimethyl sulfoxide (DMSO)；Heating temperature is
120-140 DEG C, reflux time 5-12h.
5. preparation method according to claim 1, which is characterized in that the azo pyridine alkoxy benzene of the step (3)
Solution is that azo pyridine alkoxy benzene is substantially soluble in the solution formed in chloroform or n-hexane；According to the mass fraction, the azo
Pyridine alkoxy benzene is 1.8 parts.
6. the compound of the assistance metal-enhanced fluorescence of -5 any method preparations according to claim 1, which is characterized in that
The compound is prepared by the above method.
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| CN104030978A (en) * | 2014-06-25 | 2014-09-10 | 北京大学 | High-stability bromine-bond liquid crystal and preparation method thereof |
| CN104031652A (en) * | 2014-06-25 | 2014-09-10 | 北京大学 | Iodine bond liquid crystal with reversible photoinduced phase transition behavior and preparation method thereof |
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| CN104030978A (en) * | 2014-06-25 | 2014-09-10 | 北京大学 | High-stability bromine-bond liquid crystal and preparation method thereof |
| CN104031652A (en) * | 2014-06-25 | 2014-09-10 | 北京大学 | Iodine bond liquid crystal with reversible photoinduced phase transition behavior and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Photoresponsive liquid crystals based on halogen bonding of azopyridines;Yinjie Chen ET AL.,;《Chem. Commun.》;20141231;第50卷;第9647-9648页 * |
| 基于偶氮吡啶衍生物的超分子功能材料的研究;陈寅杰;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20150915(第09期);第35页图4-2，倒数第1-2段，第36页第1段和第37页第1段 * |
| 表面增强荧光研究进展;吕凤婷等;《化学进展》;20070331;第19卷(第2/3期);第257页左栏倒数第13-16行，右栏第2-3行 * |
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