CN108976394A - Conjugated polymer, synthetic method and the method for detecting Etimicin concentration with it - Google Patents
Conjugated polymer, synthetic method and the method for detecting Etimicin concentration with it Download PDFInfo
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- CN108976394A CN108976394A CN201810869803.9A CN201810869803A CN108976394A CN 108976394 A CN108976394 A CN 108976394A CN 201810869803 A CN201810869803 A CN 201810869803A CN 108976394 A CN108976394 A CN 108976394A
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- etimicin
- solution
- conjugated polymer
- concentration
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- VEGXETMJINRLTH-ALRICIOSSA-N etimicin Chemical compound O1C[C@@](O)(C)[C@H](NC)[C@H](O)[C@H]1O[C@@H]1[C@H](O)[C@H](O[C@@H]2[C@@H](CC[C@@H](CN)O2)N)[C@@H](N)C[C@H]1N VEGXETMJINRLTH-ALRICIOSSA-N 0.000 title claims abstract description 100
- 229950009953 etimicin Drugs 0.000 title claims abstract description 100
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000010189 synthetic method Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 84
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000001514 detection method Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002835 absorbance Methods 0.000 claims abstract description 12
- 239000000872 buffer Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 229910052709 silver Inorganic materials 0.000 claims description 37
- 239000004332 silver Substances 0.000 claims description 37
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000012046 mixed solvent Substances 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 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 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
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- 238000003756 stirring Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 229940043279 diisopropylamine Drugs 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
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- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
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- 150000003222 pyridines Chemical class 0.000 claims description 6
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- POECFFCNUXZPJT-UHFFFAOYSA-M sodium;carbonic acid;hydrogen carbonate Chemical compound [Na+].OC(O)=O.OC([O-])=O POECFFCNUXZPJT-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
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- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- FEYDZHNIIMENOB-UHFFFAOYSA-N 2,6-dibromopyridine Chemical compound BrC1=CC=CC(Br)=N1 FEYDZHNIIMENOB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 206010067484 Adverse reaction Diseases 0.000 description 1
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/124—Copolymers alternating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G2261/10—Definition of the polymer structure
- C08G2261/22—Molecular weight
- C08G2261/228—Polymers, i.e. more than 10 repeat units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
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Abstract
Conjugated polymer, synthetic method and the method for detecting Etimicin concentration with it, the invention discloses conjugated polymer and its synthetic methods.The detection method are as follows: (1) aqueous solution of conjugated polymer, Nano silver solution are added in buffer, are stirred to react, stand, survey its fluorescence intensity；(2) solution for containing Etimicin to be measured is added, is stirred to react, stands, surveys its fluorescence intensity or absorbance；(3) molar concentration of Etimicin is calculated.Conjugated polymer of the present invention can be adsorbed in Nano silver grain surface in non-covalent mode, to realize fluorescence, colorimetric detection；Also water and organic solvent can be well soluble in；Synthetic method of the present invention is easy to operate, it is at low cost, be suitable for industrialized production；Conjugated polymer in conjunction with Nano silver grain, is constituted new nano composite system by detection method, hence it is evident that improves the sensitivity of Etimicin detection, simple and easy, detection is accurate, rapid, highly sensitive, and detection is linear good, and selectivity is good.
Description
Technical field
Present invention relates particularly to a kind of conjugated polymer, synthetic method and the methods for detecting Etimicin concentration with it.
Background technique
Etimicin (Etimicin, ETM) be China voluntarily develop anti-infective new drug (Chin.J.Antibiot.,
1995,20:401-406), extensive pharmacology, toxicity, pharmacodynamic study and clinical research show: ETM is that a kind of toxicity is low, treats
Imitate exact new aminoglycoside antibiotics.Etimicin dysentery, peritonitis, enteritis caused by teenager, children sensitive bacteria
Equal enteric infections disease, operation consent cleaning enteric cavity in the application in the relevant gastritis drug of helicobacter pylori, have splendid
Curative effect (CN106491515A, CN106727294A).The medical instrument has the spies such as efficient, safety, spectrum, antibacterial, drug resistance
Point, adverse reaction is low, anti-cross resistance good (J. Pharm. Biomed. Anal., 2012,70,212-223, Hum.
Exp. Toxicol., 2015,34 (5), 479-486).Since Etimicin does not have near ultraviolet absorption, measuring method master
There are microbial method, liquid chromatography-mass spectrography, HPLC method, HPLC ELSD detection method (HPLC-ELSD) etc.,
But these methods operation it is relatively complicated, time-consuming (assay office, 2011,30 (9): 22-25, Anal. Methods,
2017,9,3845-3851).
Fluorescence, colorimetric detection have the characteristics that it is simple, quick, sensitive, without marking, application has caused the pole of people
Big interest (CN106496197A, CN103323440A, CN106770103A).And conjugated polymer is a kind of novel highly sensitive
Fluorescence sense detection platform, have patent report for fluorine ion (CN105295009A), copper ion (CN101824139A),
The detection of biomolecule and cell (CN105348493A) etc. such as ATP(CN105348493A) and BSA(CN103588960A).So
And it is currently used for still belonging to blank in fluorescence, the conjugated polymer of colorimetric determination Etimicin and detection method.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of containing pyridine
With the conjugated polymer of sulfonate groups.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, provide a kind of behaviour
Make the synthetic method of conjugated polymer that is simple, at low cost, being suitable for industrialized production.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, provide one kind
Simple and easy, detection is accurate, rapid, highly sensitive, and lowest detection is limited to 8nmol/L, and detects linear good, the good inspection of selectivity
The method for surveying Etimicin concentration.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of conjugated polymer, the conjugated polymers
The general formula of the chemical structure of object are as follows:
,
Wherein, n=100~150.
The characteristics of conjugated polymer are as follows: with pyridine and sulfonate group is contained, can be adsorbed in non-covalent mode
Nano silver grain surface, to realize fluorescence, colorimetric detection；And due to introducing hydrophilic sulfonic group on conjugated polymer side chain
Group, it can be well soluble in the organic solvents such as water and methanol, this simple nanocomposite can be used to construct to according to
Highly sensitive, the highly selective detection for rice star.By viscosimetry measure the conjugated polymer molecular weight be 52000~
78000g/mol。
The present invention further solves technical solution used by its technical problem: a kind of synthesis side of conjugated polymer
Method, comprising the following steps:
(1) by the mixed solution of water, dimethylformamide and diisopropylamine, under inert atmosphere protection, 2,6- diacetylene is added
In the mixture of yl pyridines,-two iodo -2,5- dipropoxy sodium sulfonate benzene of Isosorbide-5-Nitrae and catalyst, heating reaction is cooled to room temperature,
Filtering, is washed with water obtained solid, obtains conjugated polymer, and by filtrate spin concentration, obtain concentrate；
(2) organic in the mixed solvent that concentrate obtained by step (1) is added to stirring is precipitated, centrifugation, obtained solid first uses first
Alcohol dissolution adds organic in the mixed solvent and settles >=2 times, obtains conjugated polymer.
The principle of synthetic method of the present invention is: polymer passes through catalysis Sonogashira polycondensation reaction under anaerobic
It obtains.
Preferably, in step (1), the water, the mixed solution of dimethylformamide and diisopropylamine and 2,6- diynyl
The mass ratio of the mixture of pyridine, bis- iodo -2,5- dipropoxy sodium sulfonate benzene of 1,4- and catalyst is that 50~150:1(is more excellent
Select 70~120:1).
Preferably, in step (1), the mass ratio of the water, dimethylformamide and diisopropylamine be 1~3.5:2.5~
More preferable 2~the 3:3.0 of 5.0:1(~4.5:1).Under the ratio, it is more advantageous to the formation of water-soluble polymer.
Preferably, in step (1), 2, the 6- diine yl pyridines,-two iodo -2,5- dipropoxy sodium sulfonate benzene of Isosorbide-5-Nitrae with
The mass ratio of catalyst is 0.6~1.0:4~6:1.By adjusting 2,6- diine yl pyridines and bis- iodo -2,5- dipropyl oxygen of 1,4-
The molar ratio of base sodium sulfonate benzene can realize the changes of contents of pyridine ring in conjugated polymer, and the more close polymer of molar ratio contains pyridine
Number of rings mesh is higher, the introducing of suitable pyridine ring, can effectively improve the rigidity of conjugated main chain, improve the sensitivity of detection, make
Conjugated polymer has superior performance.
Preferably, in step (1), the catalyst is tetra-triphenylphosphine palladium and cuprous iodide mass ratio is the mixed of 5~7:1
Close object.
The synthetic method of the tetra-triphenylphosphine palladium is: by PdCl2, triphenylphosphine and dimethyl sulfoxide be with mass ratio 1:5
More preferable 1:6~8:80~120~10:50~150() mixing, under nitrogen protection, stirring is warming up to 140~160 DEG C, protects
After 12~18 min of temperature reaction, solution colour is reddened by yellow, then with 0.5~1.5 mL/min of speed, with hydrazine hydrate and diformazan
The mass ratio of base sulfoxide is more preferable 1:70~90 1:60~100() hydrazine hydrate is instilled, it stands, cooling, filtering, filter residue ethyl alcohol
It washing >=4 times, ether washs >=2 times,.
The synthetic method of the 2,6- diacetylene pyridine is: by the tetra-triphenylphosphine palladium, CuI and 2,6- dibromo pyridine
With the mixing of 5~10:1:20 of mass ratio~50, under nitrogen protection, with above-mentioned mixed raw material and toluene-diisopropylamine mixed solution
Mass ratio be more preferable 1:8~12 1:6~18(), be added toluene: the volume ratio of diisopropylamine be 3~5:1 toluene-two it is different
Propylamine mixed solution, then with the speed of 0.5~1.0mL/min, toluene-diisopropylamine mixed solution and trimethyl silicane ethyl-acetylene
Mass ratio be 10~15:1, trimethyl silicane ethyl-acetylene is added, after reacting 10~15 h under room temperature, is filtered to remove insoluble matter, then
Using petroleum ether: the mixed solution that the volume ratio of methylene chloride is 4~6:1 is as solvent, with the purified column of silica gel column chromatography point
From obtaining pure intermediate products, then at normal temperature, pure intermediate products be dissolved in tetrahydro furan with 1:10~30 mass volume ratio (g/mL)
Mutter: the volume ratio of methanol is the in the mixed solvent of 1:0.8~1.2, mixed solvent and K2CO3Mass ratio be 1~10:1 be added
K2CO3, stir 10~15 h, filtering at room temperature, filtrate is concentrated, then with petroleum ether: the volume ratio of methylene chloride is the mixed of 1~2:1
Solution is closed as solvent, purifies column separation with silica gel column chromatography,.
The synthetic method of-two iodo -2,5- dipropoxy sodium sulfonate benzene of Isosorbide-5-Nitrae is: in a reservoir, first with mass ratio 3
~5:2~3:1 sequentially adds 1,4- bis- (propoxyl group sodium sulfonate) benzene, I2、KIO3, then successively with 10~15:8 of volume ratio~12:1
Glacial acetic acid, water and the concentrated sulfuric acid, Isosorbide-5-Nitrae-two (propoxyl group sodium sulfonate) benzene, I is added2、KIO3Quality sum and glacial acetic acid, water and dense sulphur
The mass volume ratio (g/mL) of the sum of sour volume is 1:5~8, after mixing, 10~15h of constant temperature reflux at 50~70 DEG C
Afterwards, ice bath is cooling, after filtering precipitating, successively intersects flushing with ethyl alcohol and cold water, obtains white powder product.Wherein, Isosorbide-5-Nitrae-two (third
Oxygroup sodium sulfonate) synthetic method of benzene is: in the NaOH solution that mass concentration is 8~12%, after being passed through nitrogen deoxygenation, with
The molar ratio of NaOH and hydroquinone be 2~3:1, be added hydroquinone, under nitrogen protection, with 1,3- propane sultone with
The molar ratio of hydroquinone is 2~3:1, and being rapidly added 1,3- propane sultone with dioxanes mass volume ratio (g/mL) is
The mixed solution of 0.1~0.2:1 after 3~5h is stirred at room temperature, forms the slurries of thick white, ice bath is cooling, vacuum mistake
Filter, successively intersects flushing with ethyl alcohol and acetone, obtains white powder product.
Preferably, in step (1), the temperature of the heating reaction is 60~70 DEG C, and the time is 12~36h.If temperature mistake
High or overlong time, then be difficult to obtain the conjugated polymer of suitable molecular weight size.
Preferably, in step (1), the temperature of the spin concentration is 50~70 DEG C, and the time is 8~12h, is concentrated into sticky
Shape.
Preferably, in step (1), the inert atmosphere is nitrogen.Inert atmosphere purity used in the present invention >=
99.9%。
Preferably, in step (2), the volume ratio of the concentrate and organic mixed solvent is 0.05~0.10:1.
Preferably, in step (2), the speed of the stirring is 50~65r/min.Revolving speed is too fast or too slow to be unfavorable for filling
Divide reaction.
Preferably, in step (2), the organic solvent is acetone and ether volume ratio is 1~2:1 mixed solvent.Make
With acetone-diethyl ether mixed liquor dissolved impurity, it is more advantageous to the separation of conjugated polymer.
Preferably, in step (2), the mass volume ratio (g/mL) of the solid and methanol is that 0.01~0.10:1(is more excellent
Select 0.02~0.06:1).Since methanol polarity is larger, target product can be preferably dissolved in methanol.
Preferably, in step (2), when sedimentation, the volume ratio of methanol and organic mixed solvent dissolved with solid is 1~2:1.
Sedimentation purpose is to improve the yield of conjugated polymer.
Concentrate is further processed in step (2), and the yield of conjugated polymer can be improved.
The present invention further solves technical solution used by its technical problem: a kind of detection Etimicin concentration
Method, comprising the following steps:
(1) aqueous solution of the conjugated polymer, Nano silver solution are added in buffer, after being stirred to react, stand, obtain
One system measures its fluorescence intensity F0；
(2) in the uniform system obtained by step (1), the solution for containing Etimicin to be measured is added, after being stirred to react, stands, surveys
Absorbance A when fixed its fluorescence intensity F or 650nm650With absorbance A when 393nm393；
(3) when using Fluorometric assay Etimicin, Y=(F is calculated0- F)/F0, when the molar concentration of Etimicin is 8.0 × 10-9
~2.0 × 10-7When mol/L, by formula Y=0.595+0.0518* of relationship between expression Etimicin and fluorescence intensity
logCEtimicin, R=0.997 calculates CEtimicin；When the molar concentration of Etimicin is > 2.0 × 10-7~5.0 × 10-6mol/L
When, by formula Y=2.04+ 0.267*logC of relationship between expression Etimicin and fluorescence intensityEtimicin, R=0.996,
Calculate CEtimicin；
When with colorimetric determination Etimicin, Y=A is calculated650/A393, when the concentration of Etimicin is 2.0 × 10-7~7.0 × 10-7When, by formula Y=- 0.0623+328000*C of relationship between expression Etimicin and absorbanceEtimicin, R=0.992 calculates
CEtimicin。
The basic ideas of Fluorometric assay of the present invention are: measuring conjugated polymer-silver nanoparticle before Etimicin is added
The fluorescence intensity of system, after Etimicin is added, the fluorescence in the system is quenched, and by the variation of detection fluorescence, then is passed through
The fluorescence intensity level under different Etimicin concentration is tested, the formula of relationship between expression Etimicin and fluorescence intensity is obtained,
Finally calculate Etimicin concentration.
The mechanism of Fluorometric assay of the present invention is as follows:
From the foregoing, it will be observed that conjugated polymer of the present invention has both excellent photoelectric property and water solubility, contain pyridyl group in conjugated polymer
The sensitivity of detection can be improved based on the strong electron donation of pyridine groups in group, and Nano silver grain has good delustring system
Number, conjugated polymer have good peptizaiton to Nano silver grain, and it is multiple that novel silver nanoparticle can be formed with Nano silver grain
Object is closed, Etimicin is added to containing after conjugated polymer-silver buffer solution, there are five basic nitrogen originals since Etimicin contains
Son and three hydroxyls, the amino of Etimicin can be adsorbed on the surface of Nano silver grain by electrostatic interaction, be made by electrostatic
With and along with hydrogen bond effect induction of Nano silver grain reunion, cause silver nanoparticle compound at 488 nm fluorescence it is sudden
It goes out, solution colour becomes blue from yellow, to realize the colorimetric detection and Visual retrieval of Etimicin.
The basic ideas of colorimetric determination of the present invention are: due to leading to conjugated polymer-silver nanoparticle after Etimicin is added
The reunion of particle causes the absorption intensity at 393nm and gradually decreases, while occurring new suction at long wave direction 650nm
Peak is received, intensity gradually increases, to realize the colorimetric detection and Visual retrieval of Etimicin.
Preferably, in step (1), the molar ratio of the conjugated polymer and nano silver is 1:3~7.Due to nano silver material
Material has certain quenching effect to conjugated polymer, and when the ratio of the conjugated polymer of addition and nano silver >=1, effect is more
It is good.
Preferably, in step (1), the volume of the sum of aqueous solution and Nano silver solution of the conjugated polymer and buffer
Than for 1:0.5~1.0.The volume of buffer reaches matched uniform system total volume, and more than half more can guarantee having for buffer system
Effect property.
Preferably, in step (1), the buffer is disodium hydrogen phosphate-citrate buffer solution that pH value is 6.5~8.5
Or the sodium carbonate-bicarbonate buffer that pH value is 8.5~9.5.
Preferably, the disodium hydrogen phosphate-citrate buffer solution is the disodium phosphate soln by 0.15~0.25mol/L
It is that 3~40:1 is formulated with volume ratio with the citric acid solution of 0.05~0.15mol/L.
Preferably, the sodium carbonate-bicarbonate buffer is by the sodium carbonate liquor of 0.05~0.15mol/L and 0.05
The sodium bicarbonate solution of~0.15mol/L, is formulated with volume ratio for 1:5~7.
Preferably, in step (1), the Nano silver solution is silver nano-particle solution, and the partial size of Nano silver grain is 10
~15nm.
Preferably, in step (1), the silver nano-particle solution the preparation method comprises the following steps: by silver nitrate solution and citric acid
Sodium solution is added to the water simultaneously, stirs and evenly mixs, and the sodium borohydride solution newly prepared is added in property again, continues to stir,.
Preferably, the volume ratio of the silver nitrate solution, sodium citrate solution and water be 0.01~0.015:0.002~
0.004:1。
Preferably, the volume ratio of the sodium borohydride solution and water is 0.008~0.010:1.
Preferably, the molar concentration of the silver nitrate solution is 0.01~0.03mol/L.
Preferably, the molar concentration of the sodium citrate solution is 0.2~0.3mol/L.
Preferably, the molar concentration of the sodium borohydride solution is 0.2~0.3mol/L.
Preferably, continue the time of stirring after sodium borohydride solution is added as 20~40min.
Preferably, in step (1), the time being stirred to react is 15~25 min.
Preferably, in step (1), the time of the standing is 10~30min.
Preferably, in step (2), the time being stirred to react is 15~30 min.
Preferably, in step (2), the time of the standing is 10~30min.
In step (3), fluorescence detection uses two equations, is respectively used under Etimicin low concentration and high concentration
More accurately detection, this is because being continuously increased with concentration, the fluorescence at 488 nm is gradually reduced, (F0- F)/F0Ratio
For value when Etimicin concentration is lower, variation is slower, and when concentration is higher, then variation is quick, thus has two sections of lines
Property range.
In the present invention, conjugated polymer is referred to as P2, Etimicin is referred to as etimicin, and silver nanoparticle ion is referred to as
AgNPs。
Beneficial effects of the present invention are as follows:
(1) conjugated polymer of the present invention contains with pyridine and sulfonate group is contained, and can be adsorbed in silver nanoparticle in non-covalent mode
Particle surface, to realize fluorescence, colorimetric detection；And due to introducing hydrophilic sulfonic acid group on conjugated polymer side chain, it
The organic solvents such as water and methanol can be well soluble in；Molecular weight is 52000~78000g/mol；
(2) synthetic method of the present invention it is easy to operate, it is at low cost, be suitable for industrialized production；
(3) detection method constitutes new nano composite system dexterously by conjugated polymer in conjunction with Nano silver grain,
The sensitivity of Etimicin detection is significantly improved, simple and easy, detection is accurate, rapid, highly sensitive, and detection is linear good, choosing
Selecting property is good, and in optimal conditions, the detection of fluorescence detection is limited to 8nmol/L, and the detection of colorimetric detection method is limited to 100 nmol/
L。
Detailed description of the invention
Fig. 1 is the TEM figure of 1 monodisperse nano grain of silver subsystem of reference example of the present invention；
Fig. 2 is the grain size distribution of 1 monodisperse nano grain of silver subsystem of reference example of the present invention；
Fig. 3 is the TEM figure of P2-AgNPs in 1-4 of embodiment of the present invention step (1)；
Fig. 4 is the TEM figure that the P2-AgNPs after Etimicin is added in 1-4 of embodiment of the present invention step (2)；
Fig. 5 is 1-4 of embodiment of the present invention conjugated polymer-nano grain of silver subsystem (pH=8.0) Fluorometric assay to different ions
Selective response histogram；
Fig. 6 is fluorescence response of 1-4 of the embodiment of the present invention conjugated polymer-nano grain of silver subsystem to various concentration Etimicin
Figure；
Fig. 7 is fluorescence response of 1-4 of the embodiment of the present invention conjugated polymer-nano grain of silver subsystem to various concentration Etimicin
Linear graph (in figure, CEtimicinIndicate concentration of the Etimicin in the mixed solution obtained by step (2))；
Fig. 8 is fluorescence response of the concentration to Etimicin of different Nano silver solutions in conjugated polymer-nano grain of silver subsystem
(1-1~1-5 of the embodiment of the present invention is the 5th~9 point from left to right to figure；In figure, CAgNPsThe nano silver for indicating that step (1) is added is molten
The concentration of liquid)；
Fig. 9 be in conjugated polymer-nano grain of silver subsystem buffer difference pH value to fluorescence response figure (this hair of Etimicin
Bright embodiment 2-1~2-3 is the 5th~7 point from left to right)；
Figure 10 is that (present invention is real for fluorescence response figure of the reaction time to Etimicin in conjugated polymer-nano grain of silver subsystem
Applying a 3-1~3-4 is the 8th~11 point from left to right)；
Figure 11 is fluorescence response of the concentration to Etimicin of different Nano silver solutions in conjugated polymer-nano grain of silver subsystem
(4-1~4-5 of the embodiment of the present invention is the 5th~9 point from left to right to figure；In figure, CAgNPsThe nano silver for indicating that step (1) is added is molten
The concentration of liquid)；
Figure 12 is selection of the colorimetric determination to different ions in 5 conjugated polymers of the embodiment of the present invention-nano grain of silver subsystem
Property response histogram；
Figure 13 is 5 conjugated polymers of the embodiment of the present invention-to the ultraviolet of various concentration Etimicin in nano grain of silver subsystem-it can
Light-exposed spectrogram；
Figure 14 is A in 5 conjugated polymers of the embodiment of the present invention-nano grain of silver subsystem650/A393It is linear with Etimicin concentration
Relational graph (in figure,C EtimicinIndicate concentration of the Etimicin in the mixed solution obtained by step (2)).
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Nitrogen used in the embodiment of the present invention is the high pure nitrogen of purity >=99.9%；Used in the embodiment of the present invention
Chemical reagent is obtained by routine business approach unless otherwise specified.
The synthetic method reference example 1 of tetra-triphenylphosphine palladium
By 0.8867 g(5 mmol) PdCl2, 6.5573 g(25 mmol) triphenylphosphine and 80 mL(88 g) dimethyl sulfoxide
Mixing, under nitrogen protection, stirring are warming up to 150 DEG C, and after insulation reaction 15min, solution colour is reddened by yellow, then with speed
1.0 mL/min are spent, 0.97 mL(20 mmol, 1g is instilled) hydrazine hydrate, it stands, cooling, filtering, filter residue is washed 5 times with ethyl alcohol,
Ether washs 3 times,.
The synthetic method reference example 2 of diacetylene pyridine
By 0.462 g(0.4 mmol of the gained of reference example 1) tetra-triphenylphosphine palladium, 0.076 g(0.4 mmol) CuI and 1.90 g(8
Mmol) 2,6- dibromo pyridine mixes, and under nitrogen protection, 30 mL toluene-diisopropylamine mixed solution (toluene: diisopropyl is added
The volume ratio of amine is 4:1, gross mass 22.4g), then with the speed of 0.8mL/min, 2.2 mL(1.529g are added) trimethyl silicane
Ethyl-acetylene is filtered to remove insoluble matter, then after reacting 12h under room temperature with petroleum ether: the volume ratio of methylene chloride is the mixing of 5:1
Solution purifies column separation as solvent, with silica gel column chromatography, the pure intermediate products of 1.7g is obtained, then at normal temperature, by pure centre
Product is dissolved in 36mL tetrahydrofuran: the volume ratio of methanol is the in the mixed solvent of 1:1, and 7.08 g K are added2CO3, stir at room temperature
12h is mixed, is filtered, filtrate concentration, then using petroleum ether: the mixed solution that the volume ratio of methylene chloride is 1.5:1 is used as solvent
Silica gel column chromatography purifies column separation,.
The synthetic method reference example 3 of two iodo -2,5- dipropoxy sodium sulfonate benzene
In three-necked bottle, 1.58 g Isosorbide-5-Nitrae-two (propoxyl group sodium sulfonate) benzene, 1.01 g I are sequentially added2、0.41g KIO3、10
ML glacial acetic acid, 7.5 mL water and the 0.75 mL concentrated sulfuric acid, after mixing, at 60 DEG C after constant temperature reflux 12h, ice bath is cooling, mistake
After filter precipitating, successively intersects flushing with ethyl alcohol and cold water, obtain white powder product.Wherein, Isosorbide-5-Nitrae-two (propoxyl group sodium sulfonate) benzene
Synthetic method be: the NaOH(50mmol for being 8% in 25mL mass concentration) in solution, after being passed through nitrogen deoxygenation, 2.21 g are added
(20 mmol) hydroquinone is rapidly added containing 6.21g(50 mmol under nitrogen protection) 1,3- propane sultone and
The mixed solution of 40mL dioxanes after 4h is stirred at room temperature, forms the slurries of thick white, and ice bath is cooling, vacuum filter, uses
Ethyl alcohol and acetone successively intersect flushing, obtain white powder product.
The preparation method reference example 4 of silver nano-particle solution
The sodium citrate solution of the silver nitrate solution of 1.2 mL, 0.02 mol/L and 0.32 mL 0.25mol/L is added simultaneously
It in 100mL water, stirs and evenly mixs, the 0.96mL 0.25mol/L sodium borohydride solution newly prepared is added in property again, continues to stir
30min,.
As shown in Figure 1, in silver nano-particle solution obtained by this reference example, the Nano silver grain containing uniform dispersion, grain
Diameter is 10~15nm.
As shown in Fig. 2, by the analysis of particle diameter distribution, in silver nano-particle solution obtained by this reference example, silver nanoparticle
The partial size of particle is distributed mainly on 10~15nm, consistent with Fig. 1.
As shown in figure 3, foring silver nanoparticle compound after conjugated polymer is added in silver nano-particle solution.
As shown in figure 4, in silver nanoparticle compound, after Etimicin further is added, the ammonia as contained by Etimicin
Base can be in conjunction with silver nanoparticle electrostatic interaction, and along with the effect of hydrogen bond, so that silver nanoparticle is reunited.
As shown in figure 5, having investigated the selectivity of fluorescence detection Etimicin, find relative to other 12 kinds of interfering substances,
After Etimicin only is added, fluorescence intensity ratio F/F0Just there is apparent decline, and other interfering substances do not have too substantially
Big variation, it is highly selective that this shows that P2-AgNPs nano composite system has the detection of Etimicin.
The preparation method reference example 5 of buffer
By 16.47 mL, the citric acid solution of the disodium phosphate soln of 0.2mol/L and 3.53 mL, 0.1mol/L are mixed, and are obtained
Disodium hydrogen phosphate-citrate buffer solution 1 of pH=7；
By 19.45 mL, the citric acid solution of the disodium phosphate soln of 0.1mol/L and 0.55 mL, 0.1mol/L are mixed, and are obtained
Disodium hydrogen phosphate-citrate buffer solution 2 of pH=8.
The sodium carbonate liquor of 1.4 mL is mixed with the sodium bicarbonate solution of 8.6 mL, obtains sodium carbonate-bicarbonate of pH=9
Sodium buffer 1.
Embodiment 1
Conjugated polymer:
Its general formula of the chemical structure are as follows:
,
Wherein, n=100~150, molecular weight are 52000~78000g/mol.
The synthetic method of conjugated polymer:
(1) by 5mL water, 7.5mL(7.11g) dimethylformamide and 2.5mL(1.79g) diisopropylamine mixed solution, in nitrogen
Under gas atmosphere protection, 2 gained 2,6- diacetylene pyridine of 0.025g reference example, 3 gained Isosorbide-5-Nitrae of 0.131g reference example-diiodo- is added
Generation -2,5- dipropoxy sodium sulfonate benzene and 0.03g catalyst (1 gained tetra-triphenylphosphine palladium of reference example and cuprous iodide mass ratio
For the mixture of 6:1) mixture in, at 65 DEG C, heating reaction 30h is cooled to room temperature, filters, it is solid that gained is washed with water
Body obtains conjugated polymer 1, and at 60 DEG C, by filtrate spin concentration 10h, until it is thick, obtain 0.2mL concentrate；
(2) 0.2mL concentrate obtained by step (1) is added to the organic mixed solvent (acetone of 4mL stirred with speed 60r/min
With ether volume ratio be 1.5:1 mixed solvent) in precipitating, centrifugation, gained 0.20g solid first use 4mL methanol dissolve, add
Sedimentation 2 times in the organic mixed solvent of 3mL (mixed solvent that acetone and ether volume ratio are 1.5:1), conjugated polymer 1 is obtained.
Embodiment 2
Conjugated polymer:
,
Wherein, n=100~110, molecular weight are 52000~57000g/mol.
The synthetic method of conjugated polymer:
(1) by 4mL water, 6mL(5.69g) dimethylformamide and 2mL(1.52g) diisopropylamine mixed solution, in nitrogen gas
Under atmosphere protection, 2 gained 2,6- diacetylene pyridine of 0.015g reference example,-two iodo -2 of 3 gained Isosorbide-5-Nitrae of 0.08g reference example is added,
(1 gained tetra-triphenylphosphine palladium of reference example and cuprous iodide mass ratio are 5:1 for 5- dipropoxy sodium sulfonate benzene and 0.018g catalyst
Mixture) mixture in, at 60 DEG C, heating reaction 36h, be cooled to room temperature, filter, solid is washed with water, must be conjugated
Polymer 2, and at 70 DEG C, by filtrate spin concentration 8h, until thick, 0.3mL obtains concentrate；
(2) 0.3mL concentrate obtained by step (1) is added to the organic mixed solvent (acetone of 4mL stirred with speed 55r/min
With ether volume ratio be 1:1 mixed solvent) in precipitating, centrifugation, gained 0.18g solid first use 4mL methanol dissolve, add
Sedimentation 2 times in the organic mixed solvent of 2mL (mixed solvent that acetone and ether volume ratio are 1:1), conjugated polymer 2 is obtained.
Embodiment 3
Conjugated polymer:
,
Wherein, n=100~135, molecular weight are 52000~70000g/mol.
The synthetic method of conjugated polymer:
(1) by 4.5mL water, 6.7mL(6.35g) dimethylformamide and 2mL(1.52g) diisopropylamine mixed solution, in nitrogen
Under gas atmosphere protection, 2 gained 2,6- diacetylene pyridine of 0.020g reference example, 3 gained Isosorbide-5-Nitrae of 0.104g reference example-diiodo- is added
Generation -2,5- dipropoxy sodium sulfonate benzene and 0.024g catalyst (1 gained tetra-triphenylphosphine palladium of reference example and cuprous iodide mass ratio
For the mixture of 7:1) mixture in, at 70 DEG C, heating reaction 20h, be cooled to room temperature, filter, solid is washed with water, obtains
Conjugated polymer 3, and at 50 DEG C, by filtrate spin concentration 12h, until it is thick, obtain 0.4mL concentrate；
(2) 0.4mL concentrate obtained by step (1) is added to the organic mixed solvent (acetone of 4mL stirred with speed 65r/min
With ether volume ratio be 2:1 mixed solvent) in precipitating, centrifugation, gained 0.15g solid first use 4mL methanol dissolve, add
Sedimentation 2 times in the organic mixed solvent of 2mL (mixed solvent that acetone and ether volume ratio are 2:1), conjugated polymer 3 is obtained.
With embodiment of the method 1-1~1-5 of conjugated polymers analyte detection Etimicin
(1) by 10 μ L, 1 × 10-3The aqueous solution of the conjugated polymer 1 of mol/L, respectively with 500 μ L, 4 gained silver of reference example received
The molar concentration that rice corpuscles solution is prepared is respectively 0.72 × 10-4 mol/L、0.84×10-4 mol/L、1.08×10-4 mol/
L、1.2×10-4 mol/L、1.32×10-4The Nano silver solution of mol/L is added to 500 μ L reference example, 5 gained phosphoric acid hydrogen two
Sodium-citrate buffer solution 2(pH=8) in, after being stirred to react 20min, stand 15min, respectively uniform system 1-1~1-5, divide
Its fluorescence intensity F is not measured0；
(2) respectively in uniform system 1-1~1-5 obtained by step (1), it is (theoretical dense that the solution containing Etimicin to be measured is added
Degree is 1 × 10-6Mol/L), after being stirred to react 20min, 15min is stood, measures its fluorescence intensity F respectively；
(3) Y=(F is calculated separately0- F)/F0=0.441,0.446,0.463,0.479,0.454, by expression Etimicin and fluorescence
Formula Y=2.04+ 0.267*logC of relationship between intensityEtimicin, R=0.996 calculates separately CEtimicin=1.03×10-6
Mol/L, 1.07 × 10-6Mol/L, 1.24 × 10-6Mol/L, 1.42 × 10-6Mol/L, 1.15 × 10-6mol/L。
As shown in Figure 3,4, by comparing mixed solution (i.e. conjugated polymer-obtained by 1-4 of embodiment of the present invention step (1)
Nano grain of silver subsystem, similarly hereinafter) in, the electron microscope before and after Etimicin is added in monodispersed conjugated polymer-Nano silver grain
It was found that conjugated polymer-nano grain of silver subsystem is oxidized etching after Etimicin is added, so that conjugated polymer
Fluorescence quenches, and achievees the purpose that detect Etimicin with this.
As shown in figure 5, different particles have different sound for mixed solution obtained by 1-4 of embodiment of the present invention step (1)
It answers, but Etimicin, fluorescence intensity ratio F/F is only added0Just there is apparent decline, and other chaff interferents do not have too substantially
Big variation illustrates that mixed solution obtained by the method for the present invention step (1) has good selectivity for Etimicin.
As shown in fig. 6, illustrating mixed solution obtained by 1-4 of embodiment of the present invention step (1) to various concentration Etimicin
Fluorescence has more apparent response difference.
As shown in fig. 7, being mixed solution obtained by 1-4 of embodiment of the present invention step (1) to various concentration Etimicin (8.0
×10-9Mol/L, 1.0 × 10-8Mol/L, 2.0 × 10-8Mol/L, 4.0 × 10-8Mol/L, 6.0 × 10-8Mol/L, 8.0
×10-8Mol/L, 1.0 × 10-7Mol/L, 2.0 × 10-7Mol/L, 3.0 × 10-7Mol/L, 4.0 × 10-7Mol/L, 5.0
×10-7Mol/L, 6.0 × 10-7Mol/L, 1.0 × 10-6Mol/L and 5.0 × 10-6Mol/L fluorescence response linear graph), when
The molar concentration of Etimicin is 8.0 × 10-9~2.0 × 10-7Mol/L, 2.0 × 10-7~5.0 × 10-6When mol/L, (F0-
F)/F0With logCEtimicinIn two sections of good linear relationships, and in this, as the calculation formula of step (3), calculate containing according to for rice
The unknown concentration of star solution.The detection of the method is limited to 8nmol/L.
With being continuously increased for concentration, the fluorescence at 488 nm is gradually reduced, (F0- F)/F0Ratio in Etimicin
Concentration lower (8.0 × 10-9~2.0 × 10-7When mol/L), reunion degree very little, the fluorescent quenching of P2 is slower, (F0- F)/F0
Ratio variation it is slower, and in the higher (> 2.0 × 10 of concentration-7~5.0 × 10-6When mol/L), reunion degree is very big, P2
Fluorescent quenching it is very fast, (F0- F)/F0Ratio variation quickly, thus have two sections of ranges of linearity.
As shown in figure 8, for Y=(F obtained by 1-1~1-5 of embodiment of the present invention step (3)0- F)/F0Curve graph (from a left side to
It is 5th~9 point right), it follows that in the Nano silver grain in the concentration range in system, with Nano silver grain concentration
Increase, (F0- F)/F0It is worth first increases and then decreases, when Nano silver grain concentration is 1.2 × 10-4When mol/L, (F0- F)/F0Value
Maximum, fluorescent quenching rate is maximum, therefore selects the concentration for optium concentration.
With embodiment of the method 2-1~2-3 of conjugated polymers analyte detection Etimicin
(1) by 10 μ L, 1 × 10-3The aqueous solution of the conjugated polymer 1 of mol/L and 500 μ L, 4 gained Nano silver grain of reference example
The molar concentration that solution is prepared is 1.2 × 10-4The Nano silver solution of mol/L is added separately to 500 μ L reference example, 5 gained phosphoric acid
Disodium hydrogen-citrate buffer solution 1(pH=7), disodium hydrogen phosphate-citrate buffer solution 2(pH=8), sodium carbonate-bicarbonate buffering
Liquid 1(pH=9) in, after being stirred to react 15min, stand 30min, respectively uniform system 2-1~2-3, it is strong to measure its fluorescence respectively
Spend F0；
(2) respectively in uniform system 2-1~2-3 obtained by step (1), it is (theoretical dense that the solution containing Etimicin to be measured is added
Degree is 8.0 × 10-7Mol/L), after being stirred to react 20min, 25min is stood, measures its fluorescence intensity F respectively；
(3) Y=(F is calculated separately0- F)/F0=0.409,0.417,0.406, by relationship between expression Etimicin and fluorescence intensity
Formula Y=2.04+ 0.267*logCEtimicin, R=0.996 calculates separately CEtimicinObtain 7.8 × 10-7Mol/L, 8.3 ×
10-7Mol/L, 7.6 × 10-7 mol/L。
As shown in figure 9, for Y=(F obtained by 2-1~2-3 of embodiment of the present invention step (3)0- F)/F0Curve graph (from a left side to
It is 5th~7 point right), it follows that in the pH value range, with the increase of pH value, (F0- F)/F0It is worth first increases and then decreases,
When pH value is 8, (F0- F)/F0Value is maximum, and fluorescent quenching rate is maximum, therefore it is best for selecting pH value=8.The reason is that: when pH value compared with
When low, the pyridine functional groups in conjugated polymer are easy protonation, and the pyridine groups of protonation are easy and adjacent sulfonic acid group
In conjunction with, lead to the reunion of conjugated polymer, and pH value is lower, Nano silver grain surface it is negatively charged number reduce, destroy quiet
Electric equilibrium can make Nano silver grain reunite.
With embodiment of the method 3-1~3-4 of conjugated polymers analyte detection Etimicin
(1) by 10 μ L, 1 × 10-3The aqueous solution of the conjugated polymer 1 of mol/L, with 500 μ L, 4 gained nano grain of silver of reference example
The molar concentration that sub- solution is prepared is 1.2 × 10-4The Nano silver solution of mol/L is added to 500 μ L reference example, 5 gained phosphoric acid hydrogen
Disodium-citrate buffer solution 2(pH=8) in, after being stirred to react 15min, stand 20min, respectively uniform system 3-1~3-4,
Its fluorescence intensity F is measured respectively0；
(2) in uniform system 3-1~3-4 obtained by the step (1), the solution containing Etimicin to be measured is added, and (theoretical concentration is
1.5×10-6Mol/L), glimmering after measurement standing 16min, 18 min, 20 min, 22 min respectively after being stirred to react 30min
Luminous intensity F；
(3) Y=(F is calculated separately0- F)/F0=0.466,0.477,0.490,0.493, by expression Etimicin and fluorescence intensity it
Between relationship formula Y=2.04+ 0.267*logCEtimicin, R=0.996 calculates separately CEtimicinObtain 1.27 × 10-6 mol/
L, 1.4 × 10-6Mol/L, 1.57 × 10-6Mol/L, 1.61 × 10-6 mol/L。
It as shown in Figure 10, is Y=(F obtained by 3-1~3-4 of embodiment of the present invention step (3)0- F)/F0Curve graph (from a left side to
It is 8th~11 point right), it follows that in the reaction time range, with the increase in reaction time, (F0- F)/F0Value is gradually
Increase, when reacted between when reaching 20 min, (F0- F)/F0Ratio tends towards stability, therefore selects 20min for optimum reacting time.
With embodiment of the method 4-1~4-5 of conjugated polymers analyte detection Etimicin
(1) by 10 μ L, 1 × 10-3The aqueous solution of the conjugated polymer 1 of mol/L, respectively with 500 μ L, 4 gained silver of reference example received
The molar concentration that rice corpuscles solution is prepared is respectively 0.72 × 10-4 mol/L、0.84×10-4 mol/L、1.08×10-4 mol/
L、1.2×10-4 mol/L、1.32×10-4The Nano silver solution of mol/L is added to 500 μ L reference example, 5 gained phosphoric acid hydrogen two
Sodium-citrate buffer solution 2(pH=8) in, after being stirred to react 20min, stand 15min, respectively uniform system 4-1~4-5, divide
Its fluorescence intensity F is not measured0；
(2) respectively in uniform system 4-1~4-5 obtained by step (1), it is (theoretical dense that the solution containing Etimicin to be measured is added
Degree is 1.5 × 10-7Mol/L), after being stirred to react 20min, 15min is stood, measures its fluorescence intensity F respectively；
(3) Y=(F is calculated separately0- F)/F0=0.238,0.239,0.240,0.244,0.237, by expression Etimicin and fluorescence
Formula Y=0.595+0.0518*logC of relationship between intensityEtimicin, R=0.997 calculates separately CEtimicin=1.28×10-7
Mol/L, 1.34 × 10-7Mol/L, 1.40 × 10-7Mol/L, 1.67 × 10-7Mol/L, 1.23 × 10-7 mol/L。
It as shown in figure 11, is Y=(F obtained by 4-1~4-5 of embodiment of the present invention step (3)0- F)/F0Curve graph (from a left side to
It is 5th~9 point right), it follows that in the Nano silver grain in the concentration range in system, with Nano silver grain concentration
Increase, (F0- F)/F0It is worth first increases and then decreases, when Nano silver grain concentration is 1.2 × 10-4When mol/L, (F0- F)/F0Value
Maximum, fluorescent quenching rate is maximum, therefore selects the concentration for optium concentration.
With the embodiment of the method 5 of conjugated polymers analyte detection Etimicin
(1) by 10 μ L, 1 × 10-3The aqueous solution of the conjugated polymer 1 of mol/L and 500 μ L, 4 gained Nano silver grain of reference example
The molar concentration that solution is prepared is 1.2 × 10-4The Nano silver solution of mol/L is added to 500 μ L reference example, 5 gained phosphoric acid hydrogen two
Sodium-citrate buffer solution 2(pH=8) in, after being stirred to react 20min, 15min is stood, uniform system is obtained；
(2) in the uniform system obtained by step (1), the solution containing Etimicin to be measured is added, and (theoretical concentration is 4 × 10- 7Mol/L), after being stirred to react 20min, 15min is stood, absorbance A when its 650nm is measured650With absorbance when 393nm
A393；
(3) Y=A is calculated650/A393=0.0666, by formula Y=- 0.0623+ of relationship between expression Etimicin and absorbance
328000*CEtimicin, R=0.992 calculates CEtimicinObtain 3.93 × 10-7mol/L。
As shown in figure 12, different particles have different sound for mixed solution obtained by 5 step of the embodiment of the present invention (2)
It answers, but Etimicin, absorbance ratio A is only added650/A393Just there is apparent rising, and other chaff interferents do not have substantially
Too big variation illustrates that the addition of Etimicin causes P2-AgNPs acutely to reunite, and influence of other interfering substances to system
It is not that very greatly, mixed solution obtained by the method for the present invention step (2) has good selectivity for Etimicin.
As shown in figure 13, illustrate mixed solution obtained by 5 step of the embodiment of the present invention (2) to the glimmering of various concentration Etimicin
Light has more apparent response difference.
As shown in figure 14, for mixed solution obtained by 5 step of the embodiment of the present invention (2) to various concentration Etimicin (1.0 ×
10-7Mol/L, 2.0 × 10-7Mol/L, 3.0 × 10-7Mol/L, 4.0 × 10-7Mol/L, 5.0 × 10-7Mol/L, 6.0 ×
10-7Mol/L, 7.0 × 10-7Mol/L, 8.0 × 10-7Mol/L, 9.0 × 10-7Mol/L and 1.0 × 10-6Mol/L)
Fluorescence response linear graph, when the concentration 2.0 × 10 of Etimicin-7~7.0 × 10-7When within the scope of mol/L, A650/A393With
CEtimicinIn good linear relationship, and in this, as the calculation formula of step (3), the unknown dense of the solution containing Etimicin is calculated
Degree.The detection of the method is limited to 100 nmol/L(S/N=3).
By the embodiment of the present invention 5 it is found that the process of Etimicin induction agglomeration is further by UV-Vis spectra, TEM
It confirms；The Etimicin standard solution of various concentration is added in P2-AgNPs solution, with being gradually increased for concentration, P2-
Absorbance value of the AgNPs at 393nm gradually decreases, and occurs new absorption band in long wave direction, and intensity gradually increases, this is
Reunion due to the P2-AgNPs and reunion along with P2 causes.
Claims (8)
1. a kind of conjugated polymer, it is characterised in that: the general formula of the chemical structure of the conjugated polymer are as follows:
,
Wherein, n=100~150.
2. a kind of synthetic method of conjugated polymer as described in claim 1, which comprises the following steps:
(1) by the mixed solution of water, dimethylformamide and diisopropylamine, under inert atmosphere protection, 2,6- diacetylene is added
In the mixture of yl pyridines,-two iodo -2,5- dipropoxy sodium sulfonate benzene of Isosorbide-5-Nitrae and catalyst, heating reaction is cooled to room temperature,
Filtering, is washed with water obtained solid, obtains conjugated polymer, and by filtrate spin concentration, obtain concentrate；
(2) organic in the mixed solvent that concentrate obtained by step (1) is added to stirring is precipitated, centrifugation, obtained solid first uses first
Alcohol dissolution adds organic in the mixed solvent and settles >=2 times, obtains conjugated polymer.
3. the synthetic method of conjugated polymer according to claim 2, it is characterised in that: in step (1), the water, diformazan
The mixed solution of base formamide and diisopropylamine and 2,6- diine yl pyridines, bis- iodo -2,5- dipropoxy sodium sulfonate benzene of 1,4-
Mass ratio with the mixture of catalyst is 50~150:1；The mass ratio of the water, dimethylformamide and diisopropylamine is 1
~3.5:2.5~5.0:1；The 2,6- diine yl pyridines, bis- iodo -2,5- dipropoxy sodium sulfonate benzene of 1,4- and catalyst
Mass ratio is 0.6~1.0:4~6:1；The catalyst is tetra-triphenylphosphine palladium and cuprous iodide mass ratio is the mixed of 5~7:1
Close object；The temperature of the heating reaction is 60~70 DEG C, and the time is 12~36h；The temperature of the spin concentration is 50~70 DEG C,
Time is 8~12h, is concentrated into thick；The inert atmosphere is nitrogen.
4. the synthetic method of the conjugated polymer according to Claims 2 or 3, it is characterised in that: in step (2), the concentration
The volume ratio of liquid and organic mixed solvent is 0.05~0.10:1；The speed of the stirring is 50~65r/min；It is described organic molten
The mixed solvent that agent is acetone and ether volume ratio is 1~2:1；The mass volume ratio of the solid and methanol be 0.01~
0.10:1；When sedimentation, the volume ratio of methanol and organic mixed solvent dissolved with solid is 1~2:1.
5. a kind of method of the conjugated polymers analyte detection Etimicin concentration described in claim 1, which is characterized in that including following
Step:
(1) aqueous solution of conjugated polymer described in claim 1, Nano silver solution are added in buffer, after being stirred to react,
It stands, obtains uniform system, measure its fluorescence intensity F0；
(2) in the uniform system obtained by step (1), the solution for containing Etimicin to be measured is added, after being stirred to react, stands, surveys
Absorbance A when fixed its fluorescence intensity F or 650nm650With absorbance A when 393nm393；
(3) when using Fluorometric assay Etimicin, Y=(F is calculated0- F)/F0, when the molar concentration of Etimicin is 8.0 × 10-9~
2.0×10-7When mol/L, by formula Y=0.595+0.0518* of relationship between expression Etimicin and fluorescence intensity
logCEtimicin, R=0.997 calculates CEtimicin；When the molar concentration of Etimicin is > 2.0 × 10-7~5.0 × 10-6mol/L
When, by formula Y=2.04+ 0.267*logC of relationship between expression Etimicin and fluorescence intensityEtimicin, R=0.996,
Calculate CEtimicin；
When with colorimetric determination Etimicin, Y=A is calculated650/A393, when the concentration of Etimicin is 2.0 × 10-7~7.0 × 10-7
When, by formula Y=- 0.0623+328000*C of relationship between expression Etimicin and absorbanceEtimicin, R=0.992 calculates
CEtimicin。
6. using the method for conjugated polymers analyte detection Etimicin concentration according to claim 5, it is characterised in that: step (1)
In, the molar ratio of the conjugated polymer and nano silver is 1:3~7；The aqueous solution and Nano silver solution of the conjugated polymer
The sum of with the volume ratio of buffer be 1:0.5~1.0；The buffer is disodium hydrogen phosphate-lemon that pH value is 6.5~8.5
The sodium carbonate-bicarbonate buffer that acid buffer or pH value are 8.5~9.5；Disodium hydrogen phosphate-the citrate buffer solution is
By the disodium phosphate soln of 0.15~0.25mol/L and the citric acid solution of 0.05~0.15mol/L, with volume ratio be 3~
40:1 is formulated；The sodium carbonate-bicarbonate buffer be by the sodium carbonate liquor of 0.05~0.15mol/L and 0.05~
The sodium bicarbonate solution of 0.15mol/L, is formulated with volume ratio for 1:5~7.
7. according to the method with conjugated polymers analyte detection Etimicin concentration of claim 5 or 6, it is characterised in that: step
(1) in, the Nano silver solution is silver nano-particle solution, and the partial size of Nano silver grain is 10~15nm；The nano grain of silver
Sub- solution the preparation method comprises the following steps: silver nitrate solution and sodium citrate solution are added to the water simultaneously, stir and evenly mix, property adds again
Enter the sodium borohydride solution newly prepared, continues to stir,；The volume ratio of the silver nitrate solution, sodium citrate solution and water
For 0.01~0.015:0.002~0.004:1；The volume ratio of the sodium borohydride solution and water is 0.008~0.010:1；Institute
The molar concentration for stating silver nitrate solution is 0.01~0.03mol/L；The molar concentration of the sodium citrate solution be 0.2~
0.3mol/L；The molar concentration of the sodium borohydride solution is 0.2~0.3mol/L；Continue to stir after sodium borohydride solution is added
Time be 20~40min.
8. using the method for conjugated polymers analyte detection Etimicin concentration according to one of claim 5~7, it is characterised in that:
In step (1), the time being stirred to react is 15~25 min；In step (1), the time of the standing is 10~30min；
In step (2), the time being stirred to react is 15~30 min；In step (2), the time of the standing is 10~30min.
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Application publication date: 20181211 |