CN107162930B - Fluorescence probe of superoxide anion and its preparation method and application, fibre-optical probe and preparation method thereof for identification - Google Patents
Fluorescence probe of superoxide anion and its preparation method and application, fibre-optical probe and preparation method thereof for identification Download PDFInfo
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Abstract
The present invention relates to a kind of fluorescence probe of superoxide anion and its preparation method and application, fibre-optical probes and preparation method thereof for identification, belong to fluorescent probe technique field.The fluorescence probe of superoxide anion for identification, with structure shown in formula I: in formula I, the condensed ring radical that Ar and Ar ' separately replaces selected from phenyl, quinolyl, isoquinolyl, condensed ring radical, the phenyl of substituent group substitution or substituent group, the alkyl that substituent group is 1~4 independently selected from hydroxyl or carbon atom number, R1The alkyl for being 1~4 for carbon atom number, R2For hydroxyl or hydrogen.Fluorescence probe has the sensitive fluorescent for superoxide anion in the present invention, can react with superoxide anion, and lead to fluorescent quenching, can quickly identify superoxide anion by detecting fluorescence, detection sensitivity is higher, the easy detection suitable for superoxide anion.
Description
Technical field
The present invention relates to a kind of fluorescence probes of superoxide anion and its preparation method and application, fibre-optical probe for identification
And preparation method thereof, belong to fluorescent probe technique field.
Background technique
Superoxide anion belongs to oxygen radical one kind, and the intracorporal oxygen radical of biology has its specific physiological function, also has
Certain pathogenic effects.The pathophysiological process of many diseases has superoxide anion mediation.Kidney is a high blood flow organ,
Taking the photograph only 25% oxygen in oxygen in kidney is required for renal tissue cells survival, remaining oxygen is used mainly for reabsorption, kidney
Tubule reabsorption is more, and oxygen consumption is about more.Under normal circumstances, the oxidation of the oxidation resistance of kidney and the oxygen radical constantly generated
Relative dynamic balance is kept between ability.Renal disease patient body Scavenging ability reduces, if oxygen radical generates
Abnormal increase causes renal tissue to damage, and kidney cell will hypoxic-ischemic.
Superoxide anion can cause the protein structures such as methionine, histidine, cysteine and function to change.Band single electron
Oxygen radical and biomembrane on polyunsaturated fatty acid effect so that between polyunsaturated fatty acid and protein ratio lose
Weighing apparatus, the fluid of cell membrane, permeability and mobility change, thus cause the damage of various kinds of cell film system.Lysosome
Membrane permeability increases, and will lead to the leakage of lysosomal enzyme, accelerates the dissolution of cell itself；Mitochondrial membrane energy loss hurts glomerular mesangium
Cell, renal tubular epithelial and permeability and mobility, which change, can cause oxidative phosphorylation obstacle.Glomerular capillary base
Counterdie and renal cells film, which are damaged, can cause glomerular filtration to increase, and albuminuria, blood urine occur；Reabsorption,
Operating and secretory functional disturbance, occur glycosuria, diuresis, urine collapse, the low sodium of low potassium and metabolic acidosis etc..
Schiff bases refer to a kind of compound containing imines or azomethine characteristic group (- RC=N-), on hybridized orbit
N atom there is lone pair electrons, the metallic ion coordination of Yi Yuyou unoccupied orbital, therefore it is the ligand of a kind of function admirable.First is sub-
Amine characteristic group (- RC=N-) is under superoxide anion effect, it may occur that oxidation scission of link changes compound structure, causes glimmering
The variation of optical property.Therefore, effective, quick, simple and easy detection is carried out to superoxide anion using such compound, for
Human lives and natural environment suffer from extremely important meaning.
Summary of the invention
The object of the present invention is to provide a kind of fluorescence probe of superoxide anion for identification, which, which has, is directed to super oxygen
The sensitive fluorescent of anion can act on superoxide anion, and lead to fluorescent quenching, can quickly be identified by detecting fluorescence
Superoxide anion, detection sensitivity are high.
The present invention also provides a kind of preparation method and applications of the fluorescence probe of above-mentioned superoxide anion for identification,
Fibre-optical probe and preparation method thereof.
In order to achieve the goal above, technical solution used by the fluorescence probe of superoxide anion for identification of the invention
It is:
The fluorescence probe of superoxide anion for identification has structure shown in formula I:
In formula I, Ar and Ar ' are fluorophor.Ar and Ar ' is separately selected from phenyl, quinolyl, isoquinolyl, thick
The condensed ring radical that the phenyl or substituent group that ring group, substituent group replace replace, substituent group independently selected from hydroxyl or carbon atom number be 1~
4 alkyl, R1The alkyl for being 1~4 for carbon atom number, R2For hydroxyl or hydrogen.
Preferably, the condensed ring radical is selected from naphthalene, anthryl, base or pyrenyl.
Preferably, Ar and Ar ' is independently selected from naphthalene, phenyl, pyrenyl or methyl substituted phenyl.
Preferably, Ar and Ar ' is fluorophor.
Technical solution used by the preparation method of the fluorescence probe of superoxide anion for identification of the invention are as follows:
The preparation method of the fluorescence probe of above-mentioned superoxide anion for identification, includes the following steps: in acidic catalyst
Catalytic action under, by formula II, III compound represented of formula reacted in solvent A to get；
In formula II, Ar is fluorophor.Ar is selected from the benzene that phenyl, quinolyl, isoquinolyl, condensed ring radical, substituent group replace
The condensed ring radical that base or substituent group replace, the alkyl that substituent group is 1~4 independently selected from hydroxyl or carbon atom number.
In formula III, Ar ' is fluorophor.Ar ' is selected from phenyl, quinolyl, isoquinolyl, condensed ring radical, substituent group and replaces
The condensed ring radical that phenyl or substituent group replace, the alkyl that substituent group is 1~4 independently selected from hydroxyl or carbon atom number, R1For carbon original
The alkyl that subnumber is 1~4, R2For hydroxyl or hydrogen.
The acidic catalyst is selected from formic acid, acetic acid, sulfuric acid, hydrochloric acid, SiO2-Al2O3、B2O3-Al2O3One of or it is more
Kind.
The solvent A is selected from one of benzene, toluene, ethyl alcohol, propyl alcohol, ether, tetrahydrofuran, chloroform or a variety of.
The equation of the reaction is as follows:
The molar ratio of the acidic catalyst and II compound of formula is 1:1~100.
The formula II, the molar ratio of III compound of formula are 1:0.3~2.7.
The additional amount of the solvent A are as follows: every gram of II compound of formula is corresponding to be added 5~100mL solvent A.
The temperature of the reaction is 55~85 DEG C, 4~15h of time.
After completion of the reaction, solvent is first evaporated, then concentrate solution, after mixture of ice and water cooling, collects precipitating, it is pure
Change to get.Purify the method that recrystallization or chromatography can be used.Recrystallizing solvent for use can be identical as solvent A, such as uses chlorine
Imitative, methanol, ethyl alcohol etc..
Technical solution used by modification fiber probe of the invention are as follows: using the glimmering of above-mentioned superoxide anion for identification
The fibre-optical probe of light probe modification.
The preparation method of above-mentioned fibre-optical probe, includes the following steps:
1) optical fiber of possibly tapered is subjected to surface hydroxylation processing, obtains hydroxylating conical fiber；
2) the resulting hydroxylating conical fiber of step 1), 3-aminopropyltriethoxysilane are added in alcohol compound
It impregnates, ammonium hydroxide is then added in the reaction system and continues to impregnate, it is dry, obtain pretreatment optical fiber；
3) will above-mentioned fluorescence probe, condensing agent and the resulting pretreatment optical fiber of step 2) be added in solvent B reaction to get.
Used optical fiber is quartz material.
In step 1), the optical fiber of the possibly tapered can be using the method preparation included the following steps: optical fiber first being used dense
Sulfuric acid impregnate 1~2h, then insert optical fibers into the mixed solution of hydrofluoric acid and ammonium fluoride impregnate to get.The mixed solution
Be be 30~50% by mass fraction hydrofluoric acid and mass fraction be 15~30% ammonium chloride solution according to volume ratio be 75
~85:15~25 are mixed to get.
It can be using the method successively impregnated in piranha solution, hydrofluoric acid, piranha solution by the light of possibly tapered
Fibre carries out surface hydroxylation processing.The piranha solution is by H2O2What solution and the concentrated sulfuric acid were mixed to get.Preferably, H2O2
The mass fraction of solution is 30%.The mass fraction of the concentrated sulfuric acid is 98.3%.H2O2The volume ratio of solution and the concentrated sulfuric acid is 3:7.
When the optical fiber of possibly tapered is carried out surface hydroxylation processing, the mass fraction of the hydrofluoric acid used is 30~50%.
After carrying out surface hydroxylation processing to the optical fiber of possibly tapered, successively cleaned using water and ethyl alcohol.
In step 2), the alcohol compound is methanol, ethyl alcohol, propyl alcohol or butanol.
In step 2), the time impregnated in alcohol compound is 10~30min, is soaked after ammonium hydroxide is added in the reaction system
The time of bubble is 1h~3h.NH in ammonium hydroxide3Mass fraction be 25%~28%.Ammonium hydroxide can provide alkaline condition and promote water
Solution.The ammonium hydroxide of addition and the volume ratio of alcohol compound are 1~3:7~9.
In step 3), the solvent B is selected from one of methanol, ethyl alcohol, chloroform, methylene chloride, acetone, water or a variety of.
In step 3), the condensing agent is selected from EDC (1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate)
+ NHS (N- hydroxy thiosuccinimide)；Or one of DCC (dicyclohexylcarbodiimide) or a variety of.
In step 3), the temperature of the reaction is room temperature, and the time is 8~16h.
Technical program of the present invention also lies in: application of the above-mentioned fluorescence probe in terms of identifying or detecting superoxide anion.
Beneficial effects of the present invention:
Fluorescence probe has the sensitive fluorescent for superoxide anion in the present invention, can react with superoxide anion, and
Lead to fluorescent quenching, by detect fluorescence can quickly identify superoxide anion, detection sensitivity is higher, be suitable for super oxygen yin from
The easy detection of son.Meanwhile the fluorescence probe can also be used for preparing superoxide anion detection fluorescent optical sensor.
The fluorescence probe and fibre-optical probe of superoxide anion for identification in the present invention, can quickly identify the super oxygen in solution
Anion, sensitivity is higher, the easy detection suitable for superoxide anion.
The preparation process of fluorescence probe and fibre-optical probe is simple in the present invention, easy to operate, is suitable for large-scale industry metaplasia
It produces and applies.
Detailed description of the invention
Fig. 1 is the infrared spectrogram for being fluorescence probe in embodiment 1；
Fig. 2 is fluorescence probe in embodiment 1 to various concentration ultra-oxygen anion free radical (from top to bottom, superoxide anion
The concentration of free radical is respectively as follows: 0 μm of ol/L, 2 μm of ol/L, 4 μm of ol/L, 6 μm of ol/L, 8 μm of ol/L, 10 μm of ol/L, 15 μm of ol/L,
20 μm of ol/L, 25 μm of ol/L) fluorescence spectrum identify figure；
Fig. 3 is the ultraviolet irradiation image of the fibre-optical probe in embodiment 1.
Specific embodiment
Below in conjunction with specific embodiment, further description of the technical solution of the present invention.
Each hydrofluoric acid used in the examples and ammonium fluoride mixed solution are the hydrofluoric acid and matter by mass fraction for 40%
The ammonium fluoride solution that amount score is 25% is what 8:2 was mixed to get according to volume；The optical fiber of possibly tapered is being subjected to hydroxyl
The mass fraction of the hydrofluoric acid used during change is 40%；Piranha solution is the H for being 30% by mass fraction2O2Solution
The concentrated sulfuric acid for being 98.3% with mass fraction is what 3:7 was mixed to get according to volume ratio；NH in used ammonium hydroxide3Matter
Measuring score is 25%；The material of used optical fiber is quartz.
Embodiment 1
The fluorescence probe of the superoxide anion for identification of the present embodiment, structural formula are as follows:
The preparation method of above-mentioned fluorescence probe, comprising the following steps:
It takes 0.5g p-aminobenzoic acid to be dissolved in 15ml dehydrated alcohol, is added drop-wise to the vanillic aldehyde containing 0.65g with dropping funel
In 25ml dehydrated alcohol, 0.5ml glacial acetic acid is added as catalyst, 60 DEG C of return stirring 12h, steaming most of solvent has Huang
Color solid is precipitated, and using being filtered after mixture of ice and water cooling, is then washed with dehydrated alcohol, then tied again with dehydrated alcohol
Crystalline substance to get；Reaction equation is as follows:
The fibre-optical probe of the present embodiment is prepared using the above-mentioned fluorescence probe of superoxide anion for identification, preparation method
Include the following steps:
1) optical fiber is first impregnated into 1h with the concentrated sulfuric acid, is then inserted perpendicularly into hydrofluoric acid and ammonium fluoride mixed solution and impregnates, obtains
To the optical fiber of possibly tapered；
2) optical fiber of possibly tapered is successively impregnated in piranha solution, hydrofluoric acid solution, piranha solution, then according to
It is secondary to be cleaned with water and ethyl alcohol, obtain hydroxylating conical fiber；
3) resulting hydroxylating conical fiber, 3-aminopropyltriethoxysilane (APTEOS) are added in ethanol solution
20min is impregnated, ammonium hydroxide (volume ratio of ammonium hydroxide and ethyl alcohol is 2:8) is then added in the reaction system, then impregnate 1.5h, takes out light
Fibre, it is dry in baking oven, obtain pretreatment optical fiber；
4) by above-mentioned fluorescence probe, pretreatment optical fiber, EDC+NHS be added methanol in, room temperature reaction 8h to get.
Application of the fluorescence probe of the present embodiment in terms of identifying or detecting superoxide anion.
The fluorescence probe of the present embodiment is subjected to examination of infrared spectrum, resulting infrared spectrogram is tested and sees Fig. 1.By Fig. 1
It is found that~1628cm-1Neighbouring infrared vibration peak shows that there are schiff base structures in fluorescent probe molecule structure.
It is detected using fluorescence spectrum of the fluorescence method to the fluorescence probe of the present embodiment: by the fluorescence probe of the present embodiment
It is configured to the solution of 10 μm of ol/L, pyrogallol is then added and generates superoxide anion, when ultra-oxygen anion free radical in solution
Concentration (unit: μm ol/L) it is different when, fluorescence probe identifies the fluorescence spectrum of ultra-oxygen anion free radical as shown in Figure 2.
From figure 2 it can be seen that the fluorescence intensity of solution significantly increases with the increase of superoxide anion concentration.
The test of superoxide anion microscopic imaging fluorescence is carried out to the fibre-optical probe of the present embodiment, test result is shown in Fig. 3.It is connecing
Bright green fluorescence is showed before touching superoxide anion, after contact, fluorescence disappears.
Embodiment 2
The fluorescence probe of the superoxide anion for identification of the present embodiment, structural formula are as follows:
The preparation method of above-mentioned fluorescence probe, comprising the following steps:
It takes 0.5g 8- amino -3- quinoline carboxylic acid to be dissolved in 15ml toluene, is added drop-wise to the hydroxyl of 8- containing 0.17g-with dropping funel
In the 20ml toluene of 4- methoxy-2-naphthaldehyde, 0.5ml glacial acetic acid is added as catalyst, 85 DEG C of return stirring 15h steam
Most of solvent has yellow solid precipitation out, using being filtered after mixture of ice and water cooling, is then washed with a small amount of dehydrated alcohol
Wash, then with dehydrated alcohol recrystallize to get；Reaction equation is as follows:
The fibre-optical probe of the present embodiment is prepared using the above-mentioned fluorescence probe of superoxide anion for identification, preparation method
Include the following steps:
1) optical fiber is first impregnated into 2h with the concentrated sulfuric acid, is then inserted perpendicularly into hydrofluoric acid and ammonium fluoride mixed solution and impregnates, obtains
To the optical fiber of possibly tapered；
2) optical fiber of possibly tapered is successively impregnated in piranha solution, hydrofluoric acid solution, piranha solution, then according to
It is secondary to be cleaned with water and ethyl alcohol, obtain hydroxylating conical fiber；
3) resulting hydroxylating conical fiber, 3-aminopropyltriethoxysilane (APTEOS) are added in ethanol solution
10min is impregnated, ammonium hydroxide (volume ratio of ammonium hydroxide and ethyl alcohol is 2:8) is then added in the reaction system, then impregnate 1h, takes out light
Fibre, it is dry in baking oven, obtain pretreatment optical fiber；
4) by above-mentioned fluorescence probe, pretreatment optical fiber, DCC be added methanol in, room temperature reaction 12h to get.
Application of the fluorescence probe of the present embodiment in terms of identifying or detecting superoxide anion.
Embodiment 3
The fluorescence probe of the superoxide anion for identification of the present embodiment, structural formula are as follows:
The preparation method of above-mentioned fluorescence probe, comprising the following steps:
It takes 2.5g 10- hydroxyl -8- methoxyl group anthracene -2- formaldehyde to be dissolved in 20ml benzene, is added drop-wise to 9- containing 3.1g with dropping funel
In the 150mL benzene of -3 formic acid of amino, 0.5ml glacial acetic acid is added as catalyst, 85 DEG C of return stirring 4h steam major part
Solvent has solid precipitation, using mixture of ice and water it is cooling after filtered, then washed with a small amount of dehydrated alcohol, then with no water beetle
Alcohol recrystallization to get；Reaction equation is as follows:
The fibre-optical probe of the present embodiment is prepared using the above-mentioned fluorescence probe of superoxide anion for identification, preparation method
Include the following steps:
1) optical fiber is first impregnated into 1.5h with the concentrated sulfuric acid, is then inserted perpendicularly into hydrofluoric acid and ammonium fluoride mixed solution and impregnates,
Obtain the optical fiber of possibly tapered；
2) optical fiber of possibly tapered is successively impregnated in piranha solution, hydrofluoric acid solution, piranha solution, then according to
It is secondary to be cleaned with water and ethyl alcohol, obtain hydroxylating conical fiber；
3) resulting hydroxylating conical fiber, 3-aminopropyltriethoxysilane (APTEOS) are added in ethanol solution
30min is impregnated, ammonium hydroxide (volume ratio of ammonium hydroxide and ethyl alcohol is 2:8) is then added in the reaction system, then impregnate 2.5h, takes out light
Fibre, it is dry in baking oven, obtain pretreatment optical fiber；
4) by above-mentioned fluorescence probe, pretreatment optical fiber, DCC be added methanol in, room temperature reaction 12h to get.
Application of the fluorescence probe of the present embodiment in terms of identifying or detecting superoxide anion.
Embodiment 4
The fluorescence probe of the superoxide anion for identification of the present embodiment, structural formula are as follows:
The preparation method of above-mentioned fluorescence probe, comprising the following steps:
It takes 2.6g 6- amino 2- pyrene formic acid to be dissolved in 15ml dehydrated alcohol, is added drop-wise to the methyl of 4- containing 1.7g -3 with dropping funel
In the 100ml dehydrated alcohol of methoxyl group -5- hydroxy benzaldehyde, 0.2g B is added2O3-Al2O3As catalyst, 75 DEG C of reflux
12h is stirred, steaming most of solvent has solid precipitation, using being filtered after mixture of ice and water cooling, then with a small amount of anhydrous
Ethanol washing, then with dehydrated alcohol recrystallize to get；Reaction equation is as follows:
The fibre-optical probe of the present embodiment is prepared using the above-mentioned fluorescence probe of superoxide anion for identification, preparation method
With embodiment 1.
Application of the fluorescence probe of the present embodiment in terms of identifying or detecting superoxide anion.
Embodiment 5
The fluorescence probe of the superoxide anion for identification of the present embodiment, structural formula are as follows:
The preparation method of above-mentioned fluorescence probe, comprising the following steps:
It takes -2 pyrene formaldehyde of 6 methoxyl group -9- hydroxyl of 2.8g to be dissolved in 15ml dehydrated alcohol, is added drop-wise to dropping funel containing 2.0g
In the 50ml dehydrated alcohol of (6- amino -7- hydroxyl) naphthyl methyl ketone, 0.2g SiO is added2-Al2O3As catalyst, 85 DEG C
Return stirring 12h, steaming most of solvent has solid precipitation, using being filtered after mixture of ice and water cooling, then with a small amount of
Dehydrated alcohol washing, then with dehydrated alcohol recrystallize to get；Reaction equation is as follows:
The fibre-optical probe of the present embodiment is prepared using the above-mentioned fluorescence probe of superoxide anion for identification, preparation method
With embodiment 1.
Application of the fluorescence probe of the present embodiment in terms of identifying or detecting superoxide anion.
Embodiment 6
The fluorescence probe of the superoxide anion for identification of the present embodiment, structural formula are as follows:
The preparation method of above-mentioned fluorescence probe, comprising the following steps:
It takes 2.5g (6- amino -9- hydroxyl) anthrylmethyl ketone to be dissolved in 15ml dehydrated alcohol, is added drop-wise to dropping funel containing 6g
In the 100ml dehydrated alcohol of -2 formaldehyde of 5- hydroxyl -12- methoxyl group, 0.4mL formic acid (mass fraction 98%) conduct is added
Catalyst, 85 DEG C of return stirring 12h, steaming most of solvent has solid precipitation, is filtered after being cooled down using mixture of ice and water,
Then washed with a small amount of dehydrated alcohol, then with dehydrated alcohol recrystallize to get；Reaction equation is as follows:
The fibre-optical probe of the present embodiment is prepared using the above-mentioned fluorescence probe of superoxide anion for identification, preparation method
With embodiment 1.
Application of the fluorescence probe of the present embodiment in terms of identifying or detecting superoxide anion.
Embodiment 7
The fluorescence probe of the superoxide anion for identification of the present embodiment, structural formula are as follows:
The preparation method of above-mentioned fluorescence probe, comprising the following steps:
It takes -4 methyl benzoic acid of 0.3g 3- amino to be dissolved in 30ml anhydrous methanol, is added drop-wise to the hydroxyl of 2- containing 1.0g with dropping funel
In the 100ml anhydrous methanol of -3 formaldehyde of -6 methoxy quinoline of base, 0.1mL sulfuric acid (mass fraction 98%) is added as catalysis
Agent, 85 DEG C of return stirring 12h, steaming most of solvent has yellow solid precipitation, is filtered after being cooled down using mixture of ice and water,
Then washed with a small amount of dehydrated alcohol, then with dehydrated alcohol recrystallize to get；Reaction equation is as follows:
The fibre-optical probe of the present embodiment is prepared using the above-mentioned fluorescence probe of superoxide anion for identification, preparation method
With embodiment 1.
Application of the fluorescence probe of the present embodiment in terms of identifying or detecting superoxide anion.
Embodiment 8
The fluorescence probe of the superoxide anion for identification of the present embodiment, structural formula are as follows:
The preparation method of above-mentioned fluorescence probe, comprising the following steps:
It takes -4 methyl benzoic acid of 0.3g 3- amino to be dissolved in 30ml dehydrated alcohol, is added drop-wise to dropping funel containing 6 first of 1.0g
In the 100ml dehydrated alcohol of -3 formaldehyde of phenoxyl quinoline, 0.5ml glacial acetic acid is added as catalyst, 85 DEG C of return stirring 12h,
Steaming most of solvent has yellow solid precipitation, using being filtered after mixture of ice and water cooling, then with a small amount of dehydrated alcohol
Washing, then with dehydrated alcohol recrystallize to get；Reaction equation is as follows:
The fibre-optical probe of the present embodiment is prepared using the above-mentioned fluorescence probe of superoxide anion for identification, preparation method
With embodiment 1.
Application of the fluorescence probe of the present embodiment in terms of identifying or detecting superoxide anion.
Claims (7)
1. the fibre-optical probe of the fluorescence probe modification of superoxide anion for identification, it is characterised in that: by what is included the following steps
Method is made:
1) optical fiber of possibly tapered is subjected to surface hydroxylation processing, obtains hydroxylating conical fiber；
2) the resulting hydroxylating conical fiber of step 1), 3-aminopropyltriethoxysilane are added in alcohol compound and are soaked
Then ammonium hydroxide is added in the reaction system and continues to impregnate for bubble, dry, obtains pretreatment optical fiber；The alcohol compound is first
Alcohol, ethyl alcohol, propyl alcohol or butanol；
3) will fluorescence probe, condensing agent and the resulting pretreatment optical fiber of step 2) be added in solvent B reaction to get；The solution B
Selected from one of methanol, ethyl alcohol, chloroform, methylene chloride, acetone, water or a variety of；The condensing agent is selected from 1- ethyl-(3- bis-
Dimethylaminopropyl) in phosphinylidyne diimmonium salt hydrochlorate, N- hydroxy thiosuccinimide or dicyclohexylcarbodiimide one
Kind is a variety of；
The fluorescence probe has structure shown in formula I:
2. the fibre-optical probe that the fluorescence probe of superoxide anion for identification according to claim 1 is modified, feature exist
In: the fluorescence probe is made by the method included the following steps: under the catalytic action of acidic catalyst, by formula II, formula III
Compound represented reacted in solvent A to get；
3. the fibre-optical probe that the fluorescence probe of superoxide anion for identification according to claim 2 is modified, feature exist
In: the acidic catalyst is selected from formic acid, acetic acid, sulfuric acid, hydrochloric acid, SiO2-Al2O3、B2O3-Al2O3One of or it is a variety of.
4. the fibre-optical probe that the fluorescence probe of superoxide anion for identification according to claim 2 is modified, feature exist
In: the temperature of the reaction is 55~85 DEG C, and the time is 4~15h.
5. the preparation method of fibre-optical probe as described in claim 1, characterized by the following steps:
1) optical fiber of possibly tapered is subjected to surface hydroxylation processing, obtains hydroxylating conical fiber；
2) the resulting hydroxylating conical fiber of step 1), 3-aminopropyltriethoxysilane are added in alcohol compound and are soaked
Then ammonium hydroxide is added in the reaction system and continues to impregnate for bubble, dry, obtains pretreatment optical fiber；The alcohol compound is first
Alcohol, ethyl alcohol, propyl alcohol or butanol；
3) fluorescence probe described in claim 1, condensing agent and the resulting pretreatment optical fiber of step 2) are added anti-in solvent B
It should be to get；The solution B is selected from one of methanol, ethyl alcohol, chloroform, methylene chloride, acetone, water or a variety of；The condensing agent
Selected from 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, N- hydroxy thiosuccinimide or two hexamethylenes
One of base carbodiimide is a variety of.
6. the preparation method of fibre-optical probe according to claim 5, it is characterised in that: in step 2), in alcohol compound
The time of middle immersion is 10~30min, and it is 1h~3h that the time impregnated after ammonium hydroxide is added in the reaction system.
7. the diagnosing and treating side of fibre-optical probe as described in claim 1 non-disease in terms of identifying or detecting superoxide anion
The application of method.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2701854A1 (en) * | 1976-01-19 | 1977-07-21 | Dow Chemical Co | HYPOLIPIDAEMIC P-BENZYLAMINOBENZOES ACIDS AND AGENTS CONTAINING THEM |
| CN105085726A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst for olefin polymerization |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106383101A (en) * | 2016-08-31 | 2017-02-08 | 清华大学 | Fluorescence detection method and fluorescence probe chip of mercury ions based on "off-on-off" mode |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2701854A1 (en) * | 1976-01-19 | 1977-07-21 | Dow Chemical Co | HYPOLIPIDAEMIC P-BENZYLAMINOBENZOES ACIDS AND AGENTS CONTAINING THEM |
| CN105085726A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst for olefin polymerization |
Non-Patent Citations (6)
| Title |
|---|
| Indirect determination of superoxide anion radical in the plant of red sage based on vanillin-8-aminoquinoline with fluorescence;Bo Tang 等;《Analytica Chimica Acta》;20040123;第502卷(第1期);第126页2.2第1段和图解1 * |
| Indirect determination of superoxide anion radical in the plant of red sage based on vanillin-8-aminoquinoline with fluorescence;Bo Tang 等;《Analytica Chimica Acta》;20040123;第502卷(第1期);第126页图解1 * |
| Preparative synthesis of {[4-hydroxy(alkyloyloxy, aryloyloxy)-3-methoxy (ethoxy)phenyl]methylene}(4-carboxyphenyl)amines;Dikusar,E.A. 等;《Russian Journal of Organic Chemistry》;20060228;第42卷(第2期);第206页右栏第1段 * |
| Synthesis, characterization and electrical conductivity of new poly (azomethine ester)s from hydroxy acids;Ravikumar,L. 等;《Materials Chemistry and Physics》;20090615;第115卷(第2-3期);第633页左栏2.2第三段化合物2 * |
| Synthesis, Crystal Structure, DFT Studies and Evaluation of the Antioxidant Activity of 3,4-Dimethoxybenzenamine Schiff Bases;Ahmad Nazif Aziz 等;《Molecules》;20140619;第19卷(第6期);第8416页图解1和第8418页表2 * |
| 荧光猝灭法测定超氧阴离子自由基的研究;蒲法章 等;《分析科学学报》;20091031;第25卷(第5期);第575页1原理 * |
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