CN106565679B - A kind of iron ion detection reagent and its preparation method and application - Google Patents
A kind of iron ion detection reagent and its preparation method and application Download PDFInfo
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- CN106565679B CN106565679B CN201610933781.9A CN201610933781A CN106565679B CN 106565679 B CN106565679 B CN 106565679B CN 201610933781 A CN201610933781 A CN 201610933781A CN 106565679 B CN106565679 B CN 106565679B
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- iron ion
- detection reagent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
The invention belongs to a kind of iron ion detection reagent, structure is as follows:；Acetonitrile is removed under reduced pressure step 1: Anhydrous potassium carbonate is alkali, and base acridine and near amino thiophenols react 12h under conditions of being heated to reflux between 2,9- bis- bromomethyls using anhydrous acetonitrile as solvent in synthesis, is added with saturation NaHCO3Through CH after solution2Cl2Extraction collects organic phase, through anhydrous MgSO4After drying, solvent is removed under reduced pressure and obtains crude product, crude product is purified through column separation, obtains compound 2；Step 2: using ethyl alcohol as solvent, compound 2 and 2- formylpyridine nitrogen protection, be heated to reflux under conditions of react 12h, ethyl alcohol is removed under reduced pressure after sodium borohydride reduction 12h is added, saturation NaHCO is added3Through CH after solution2Cl2Extraction collects organic phase, through anhydrous MgSO4After drying, solvent is removed under reduced pressure and obtains crude product, crude product through column separation purify to get.
Description
Technical field
The invention belongs to metal ion detection fields, and in particular to a kind of iron ion detection reagent and preparation method thereof and answer
With.
Background technique
Iron is one of indispensable element in life entity, and very important effect is played in the vital movement of organism, is related to
Every physiological activity of organism, such as the synthesis of the contraction of muscle, DNA and RNA, enzymatic, nerve conduction, intracellular penetration
Pressure adjusting and maintenance acid-base balance etc..The reduction of intracellular iron content will lead to the disorder of life system, and excessive iron is same
Sample is harmful even fatal to body.Therefore, realize it is highly selective, iron detected in living cells in high sensitivity seem pole
Its is important.The method of existing frequently-used detection iron ion (III) mainly has atomic absorption method, spectrophotometry, inductive coupling etc.
Ionomer emission spectrum method, inductively coupled plasma mass spectrometry, electrochemical process and fluorescence analysis etc., these methods respectively have excellent
Disadvantage.In recent years, fluorescence probe method had been a great concern, since the technology is not only easy to operate, at low cost, sensitivity
High, selectivity good, response time is short etc. outstanding advantages.Therefore, to its research and exploration, for determining for metal ion
Property and quantitative detection field have very important meaning, exploitation Novel iron ion (III) detection reagent can also be generated very big
Influence.
Summary of the invention
The object of the present invention is to provide a kind of iron ion detection reagents and its preparation method and application.
To achieve the above object, the technical solution adopted by the present invention is that, a kind of iron ion detection reagent, the iron ion is examined
The structure of test agent is as follows:
。
The iron ion detection reagent is synthesized in two steps；Step 1: Anhydrous potassium carbonate is alkali using anhydrous acetonitrile as solvent,
Base acridine and near amino thiophenols react 12h under conditions of being heated to reflux between 2,9- bis- bromomethyls, and acetonitrile is removed under reduced pressure, and are added
With saturation NaHCO3Solution (20mL) is by CH2Cl2(3 × 20 mL) extraction, collects organic phase, through anhydrous MgSO4After drying, subtract
Pressure removes solvent and obtains crude product, and crude product is passed through silica gel column chromatography separating-purifying (petrol ether/ethyl acetate=10:1), obtained
To compound 2；The structural formula of compound 2 is as follows:
；
Step 2: using ethyl alcohol as solvent, compound 2 and 2- formylpyridine in nitrogen protection, the condition being heated to reflux
Ethyl alcohol is removed under reduced pressure after sodium borohydride reduction 12h is added in lower reaction 12h, is added with saturation NaHCO3Solution (20mL) by
CH2Cl2(3 × 20 mL) extraction, collects organic phase, through anhydrous MgSO4After drying, solvent is removed under reduced pressure and obtains crude product, it is thick to produce
Object passes through silica gel column chromatography separating-purifying (petrol ether/ethyl acetate=5:1), obtains the iron ion detection reagent.
The beneficial effect comprise that: iron ion (III) detection reagent provided by the invention has can be in aqueous solution
In qualitatively and quantitatively detect Fe3+Performance, have qualitatively and quantitatively detect iron ion (III) application prospect, detect pole
Limit is up to 4.60 × 10-7M.；And iron ion detection reagent preparation process of the invention is simple, and yield is up to 80%.
Specific embodiment
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto.
Embodiment 1
The synthetic route of the iron ion detection reagent of embodiment 1 is as follows:
。
The specific synthesis process of compound 2 is as follows: taking 2,9- dibromo methylacridine (compound 1,1mmol), adjacent aminobenzene
Thiophenol (2.1mmol) and Anhydrous potassium carbonate (2.1mmol) are added in 10 milliliters of anhydrous acetonitrile, then heat under nitrogen protection
12h is reacted under conditions of reflux, acetonitrile is removed under reduced pressure, and saturation NaHCO is added3Solution (20mL) is by CH2Cl2(3 × 20mL, point
3 progress, each 20m) extraction, organic phase is collected, through anhydrous MgSO4After drying, solvent is removed under reduced pressure and obtains crude product, it is thick to produce
Product pass through silica gel column chromatography separating-purifying (petrol ether/ethyl acetate=10:1), obtain midbody compound 2, yield 88%.
It takes compound 2 (1.0 mmol), 2- formylpyridine (2.1mmol), in 50 milliliters of flasks in 10 milliliters of ethyl alcohol,
Nitrogen protection, be heated to reflux under conditions of react 12h, depressurized after sodium borohydride (2.1mmol) reduction 12h is added
Remove ethyl alcohol
, saturation NaHCO is added3Solution (20mL) is by CH2Cl2(3 × 20 mL) extraction, collects organic phase, through anhydrous
MgSO4After drying, solvent is removed under reduced pressure and obtains crude product, crude product passes through silica gel column chromatography separating-purifying (petroleum ether/acetic acid second
Ester=5:1), obtain target product 3, yield 91%.
The characterization result of target product 3
1) infrared spectrum measurement:
With pellet technique in 400 ~ 4000cm–1750 Fourier's infrared light of U.S. Nicolet magna is used in range
Spectrometer measurement.The main infrared absorption peak of gained compound are as follows: 3358,2976,1604,1522,1473,1391,
946, 671 cm-1.
2) nuclear magnetic resonance hydrogen spectruming determining:
It is solvent with deuterated chloroform, tetramethylsilane is internal standard, with Bruker400 nuclear magnetic resonance chemical analyser measurement hydrogen spectrum.
The nuclear magnetic resonance spectroscopy of gained compound are as follows:
8.84(s, 1H), 7.93 (d, J = 1.7 Hz, 1H), 7.82(d, J = 1.7 Hz, 2H), 7.66–
7.53(m, 4H), 7.47–7.32(m, 4H), 7.29 (s, 1H), 7.22(d, J = 1.4 Hz, 1H), 7.10
(d, J = 8.0, 2H), 7.01–6.92(m, 4H), 6.77(d, J = 8.0, 1.1 Hz, 2H), 6.64(d, J =
7.5, 1.2 Hz, 2H), 5.38(s, 4H), 4.82(s, 4H), 2.89(s, 2H).
3) carbon-13 nmr spectra measures:
It is solvent with deuterated chloroform, tetramethylsilane is internal standard, with Bruker400 nuclear magnetic resonance chemical analyser measurement carbon spectrum.
The carbon-13 nmr spectra of gained compound are as follows: 162,158,153,150,148,145,139,136,132,129,
128, 128, 125, 123, 121, 119, 117, 38.
4) determination of elemental analysis:
Elemental analysis PE company of the U.S., PE2400-II elemental analyser measurement: the elemental analysis value of gained compound
Are as follows: C, 76.62; H, 5.26; N, 11.00; S, 10.02.(theoretical value: C, 73.67; H, 5.23; N, 11.01;
S, 10.09).
5) mass spectroscopy:
Mass spectrum is measured with Bruker Compass DataAnalysis mass spectrograph: the mass spectrum of gained compound are as follows: 635.89
[M]+(theoretical value: 635.84).
Target product 3 is in detection Fe3+In application
Iron ion detection reagent (target product 3) is configured to 3.0 × 10-5The DMSO solution of mmol/L.To containing respectively
There is (Li+, Na+, K+, Ag+, Mg2+, Ca2+, Ba2+, Pb2+, Zn2+, Co2+, Cd2+, Hg2+, Ni2+, Cu2+, Mn2 +, Cr3+, Al3+And Fe3+Deng) DMSO solution be test object.The result shows that: Fe is being added3+When ion, detection reagent
Fluorescent quenching, and the fluorescence of detection reagent is almost unchanged when other ions are added.In experiment, 3 mL iron ion detection reagents is taken to add
Enter into cuvette, be then added to the metal ion containing different kinds and concentrations and uniformly mix, measures the fluorescence of each group solution
Data.Its detection limit must be measured up to 4.60 × 10 through fluorescence titration and the Fitting Calculation-7M.Iron ion of the invention detects examination
Agent can qualitatively and quantitatively detect iron ion (III).
Claims (3)
1. a kind of iron ion detection reagent, which is characterized in that the structure of the iron ion detection reagent is as follows:
。
2. iron ion detection reagent preparation method as described in claim 1, it is characterised in that synthesize the iron ion inspection in two steps
Test agent；
Step 1: Anhydrous potassium carbonate is alkali using anhydrous acetonitrile as solvent, 2,9- dibromo methylacridines and near amino thiophenols are adding
12h is reacted under conditions of heat reflux, the purified processing of reaction product obtains compound 2；The structural formula of compound 2 is as follows:
；
Step 2: using ethyl alcohol as solvent, compound 2 and 2- formylpyridine is anti-under conditions of nitrogen protection, being heated to reflux
12h is answered, sodium borohydride reduction 12h is added, the purified processing of reaction product obtains the iron ion detection reagent.
3. iron ion detection reagent as described in claim 1 is in detection Fe3+In application.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005043124A2 (en) * | 2003-10-30 | 2005-05-12 | Georgetown University | Chiral 1,8-diarylnaphthalenes, methods of making them, and their use as sensors |
| CN103923017A (en) * | 2014-03-13 | 2014-07-16 | 华南师范大学 | Didansyl histidine and application thereof |
| CN105917234A (en) * | 2014-01-17 | 2016-08-31 | 梅托珍尼克斯株式会社 | Iron(II) ion detection agent and detection method using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005043124A2 (en) * | 2003-10-30 | 2005-05-12 | Georgetown University | Chiral 1,8-diarylnaphthalenes, methods of making them, and their use as sensors |
| CN105917234A (en) * | 2014-01-17 | 2016-08-31 | 梅托珍尼克斯株式会社 | Iron(II) ion detection agent and detection method using same |
| CN103923017A (en) * | 2014-03-13 | 2014-07-16 | 华南师范大学 | Didansyl histidine and application thereof |
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