CN103304509A - 7-(3-alkene butoxy)-3H-phenoxazine-3-ketone as well as preparation method and application thereof - Google Patents

7-(3-alkene butoxy)-3H-phenoxazine-3-ketone as well as preparation method and application thereof Download PDF

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CN103304509A
CN103304509A CN2013102347924A CN201310234792A CN103304509A CN 103304509 A CN103304509 A CN 103304509A CN 2013102347924 A CN2013102347924 A CN 2013102347924A CN 201310234792 A CN201310234792 A CN 201310234792A CN 103304509 A CN103304509 A CN 103304509A
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formula
ozone
storing solution
reagent storing
detection kit
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CN103304509B (en
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马会民
张阳阳
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Institute of Chemistry CAS
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Abstract

The invention discloses a detection reagent 7-(3-alkene butoxy)-3H-phenoxazine-3-ketone as well as a preparation method and an application thereof. The structural formula of the detection agent is as shown in the formula I. The preparation method of the compound as shown in the formula I provided by the invention comprises the following step of: in the presence of a basic catalyst, reacting the 7-hydroxyl phenoxazone sodium salt as shown in a formula II with 4-bromine-1-butene, thereby obtaining the compound as shown in the formula I. The invention discloses an ozone detection kit, wherein the kit composed of a reagent stock solution I and a reagent stock solution II, the reagent stock solution I is a phosphate buffer, and the reagent stock solution II is the solution of the compound as shown in the formula I. The ozone detection kit provided by the invention is an ozone detection device which is excellent in performance and convenient to use, and has great application foreground in the fields of quality, environment, biology and the like.

Description

7-(3-alkene butoxy)-3H-Phenazoxine-3-ketone and preparation method thereof and application
Technical field
The present invention relates to a kind of detection reagent 7-(3-alkene butoxy)-3H-Phenazoxine-3-ketone and preparation method thereof and application, be specifically related to its application in preparation ozone detection kit.
Background technology
The allotropic substance of ozone (zone) oxygen, at normal temperatures, it is a kind of blue gas that special odor is arranged.In the atmosphere, ozonosphere has the overwhelming majority ultraviolet ray that provide protection-its absorption sun discharges to tellurian, makes animals and plants exempt from the harm of this ray.On the other hand, when ozone concn is higher in the environment, be again a kind of environmental pollution gas, also be one of greenhouse gases, also human body cell constituted damage in the time of kill bacteria, by ultraviolet lamp, printer, all should note ventilating, avoid the too high toxic effect that causes of ozone concn.
Have the method that some detect ozone at present.Wherein, advantages such as fluorescent method is easy owing to having, sensitivity have caused people's attention recently.Yet there are drawbacks such as wavelength weak point, poor selectivity in the method for existing fluoroscopic examination ozone, and therefore, the development wavelength is long, selectivity good, detection ozone approach highly sensitive and easy and simple to handle, has important and practical meanings.
Summary of the invention
The purpose of this invention is to provide a kind of detection reagent 7-(3-alkene butoxy)-3H-Phenazoxine-3-ketone and preparation method thereof and application, 7-provided by the invention (3-alkene butoxy)-3H-Phenazoxine-3-ketone can be used for preparing the ozone detection kit.
7-provided by the invention (3-alkene butoxy)-3H-Phenazoxine-3-ketone, its structural formula be suc as formula shown in the I,
Figure BDA00003344318800011
The formula I.
The invention provides the preparation method of compound shown in the formula I, comprise the steps:
Under the condition that basic catalyst exists, the Phenazoxine ketone sodium salt of 7-hydroxyl shown in the formula II and 4-bromo-1-butylene react and namely get compound shown in the formula I;
Figure BDA00003344318800012
The formula II.
Among the above-mentioned preparation method, described basic catalyst can be organic bases and/or mineral alkali;
Described organic bases can be triethylamine and/or pyridine;
Described mineral alkali can be selected from salt of wormwood, sodium hydroxide, yellow soda ash and the sodium bicarbonate at least a.
Among the above-mentioned preparation method, the mol ratio of the Phenazoxine of 7-hydroxyl shown in formula II ketone sodium salt, 4-bromo-1-butylene and described basic catalyst can be 1:0.5～5:0.5～5, specifically can be 1:2:1.5.
Among the above-mentioned preparation method, the temperature of described reaction can be 0 ℃～60 ℃, and the time can be 1～24 hour, as reaction under 20 ℃ condition 12 hours;
The solvent of described reaction can be N, at least a in dinethylformamide, triethylamine, tetrahydrofuran (THF) and the acetonitrile.
The present invention also provides a kind of ozone detection kit, and it is made up of reagent storing solution I and reagent storing solution II;
Described reagent storing solution I is phosphate buffered saline buffer;
Described reagent storing solution II is the solution of compound shown in the formula I.
In the above-mentioned ozone detection kit, the pH value of described phosphate buffered saline buffer can be 6～9, as 6～7.4,6 or 7.4;
Phosphoric acid salt in the described phosphate buffered saline buffer is selected from Na 2HPO 4, NaH 2PO 4And KH 2PO 4In at least two kinds;
The concentration of described phosphate buffered saline buffer can be 0.01～0.5M, as 0.05M.
In the above-mentioned ozone detection kit, the solvent of described reagent storing solution II can be ethanol or dimethyl sulfoxide (DMSO);
The concentration of described reagent storing solution II can be 0.1～2mM, as 1mM.
In the above-mentioned ozone detection kit, the volume ratio of described reagent storing solution I and described reagent storing solution II can be 100:1～10, as 100:1.
The present invention has following advantage:
1) in the ozone detection kit of the present invention, reagent storing solution II is little band orange, and does not have fluorescence; With then can show red-purple behind the ozone reaction and send strong fluorescence.
When 2) using ozone detection kit of the present invention to carry out the ozone detection, speed of response is fast, can develop the color in 30～40 minutes.
3) ozone detection kit of the present invention is highly sensitive, and ozone concn can observe with the naked eye tangible red-purple and produce when 〉=5 μ M.
When 4) ozone detection kit of the present invention was carried out the ozone detection, the color reaction of generation only took place under the condition that ozone exists, and nitride, sulfide, heavy metal ion etc. do not produce interference in other common active oxygen species, the air.
When 5) ozone detection kit of the present invention is carried out the ozone detection, have long fluorescent emission wavelength (585nm), available fluorescent spectrometry detects, and limit of determination can reach 5.9nM, can be used for the detection of ozone content in the actual environment.
In sum, ozone detection kit of the present invention is a kind of excellent property, ozone test set easy to use, in quality, and environment, there is great application prospect in fields such as biology.
Description of drawings
Fig. 1 is the chemical equation of compound shown in the embodiment of the invention 1 preparation formula I.
Fig. 2 is the fluorescence spectrum of the ozone reaction of ozone detection kit of the present invention and different concns;
Fig. 3 is used for the fluorescence emission spectrum of various interference species reactions for ozone detection kit of the present invention;
Fig. 4 is ozoniferous gas sampling system in the air of ozone detection kit detection ultra violet lamp different time of the present invention;
Fig. 5 changes for ozoniferous fluorescence intensity in the air of ozone detection kit detection ultra violet lamp different time of the present invention.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Embodiment 1: 7-shown in the preparation formula I (3-alkene butoxy)-3H-Phenazoxine-3-ketone
Be prepared according to chemical reaction flow process figure shown in Figure 1.
In 7-hydroxyl Phenazoxine ketone sodium salt (235mg 1mmol) is dissolved in DMF(5mL), add 4-bromo-1-butylene (269mg, 2mmol), (210mg is 1.5mmol) in reaction solution, and 20 ℃ of reactions 12 hours for catalyzer carbonic acid potassium.Reaction finishes, and after cooling, the concentrating under reduced pressure solvent gets thick product, and (1:1 v/v) makes elutriant, and the column chromatography thick product of purifying obtains product 140mg with sherwood oil (b.p.60-90 ℃)/ethyl acetate.
The structural characterization data results of this product is as follows:
1H?NMR(300MHz,CDCl 3):δ=7.70(d,1H,J=9.0Hz),7.42(d,1H,J=9.9Hz),6.92-6.96(m,1H),6.81-6.86(m,2H),6.33(d,1H,J=2.1Hz),5.84-5.97(m,1H),5.14-5.24(m,2H),4.10-4.15(m,2H),2.57-2.64(m,2H).
13C?NMR(CDCl 3,75MHz,298K)δ186.3,163.0,149.8,145.7,145.5,134.7,134.2,133.5,131.6,128.4,117.7,114.0,106.7,100.6,68.2,33.3.
Ultimate analysis formula 1 (C 16H 13NO 3): calculated value C71.90, H4.90, N5.24%; Measured value: C71.52, H5.08, N5.10%.
As from the foregoing, this product structure is correct, is the 7-shown in the formula I (3-alkene butoxy)-3H-Phenazoxine-3-ketone.
Embodiment 2: the spectral quality of compound shown in the formula I and different concns ozone reaction
Take by weighing compound shown in the 2.67mg formula I, be made into the 10ml dimethyl sulphoxide solution as the mother liquor (1mM) of solvent.
The above-mentioned mother liquor of 100 μ L being added drop-wise in the 50mM phosphate buffer soln, adding the ozone solution of different concns then, is 7.4 with the phosphate buffer soln constant volume of 50mM to the pH of 10mL(phosphate buffer soln again, and wherein, phosphoric acid salt is Na 2HPO 4-NaH 2PO 4, the volume ratio of phosphate buffer soln and mother liquor is 100:1).Behind the reaction 30min, measure its fluorescence emission spectrum under 25 ℃.When fluorescence emission spectrum is measured with the 550nm de-excitation; The slit width that excites and launch is 10nm; Voltage 400V.
Fig. 2 is the fluorescence spectrum of compound shown in the formula I and 0～50 μ M ozone reaction.
As seen from Figure 2,7-shown in the formula I provided by the invention (3-alkene butoxy)-3H-Phenazoxine-3-ketone has following characteristics:
1) probe (being 7-(3-alkene butoxy)-3H-Phenazoxine-3-ketone) is colourless and does not have fluorescence in solution, but along with the adding of ozone, produces red-purple fluorescence behind this probe and the ozone reaction about the 585nm place;
2) fluorescence intensity increases with the increase of ozone concn;
When 3) using 7-(3-alkene butoxy)-3H-Phenazoxine of 10 μ M-3-ketone, the enhancing value of fluorescence intensity and the concentration of ozone are linear in 1～30 μ M scope.
Embodiment 3: compound shown in the formula I and other species response situation (selectivity research)
In the phosphate buffer soln that contains 10 μ M7-(3-alkene butoxy)-3H-Phenazoxine-3-ketone, add various materials respectively: hydrogen peroxide (100 μ M), hypochlorite (50 μ M), superoxide anion (100 μ M), singlet oxygen (100 μ M), hydroxyl radical free radical (100 μ M), nitric acid (250 μ M), sulfuric acid (250 μ M), lead ion (100nM), palladium ion (100nM), platinum ion (100nM), Sodium Nitrite (250 μ M), S-WAT (250 μ M), Sulfothiorine (250 μ M) and ozone (30 μ M).
Behind reaction 30min under 25 ℃, measure its fluorescence emission spectrum.When fluorescence emission spectrum is measured with the 550nm de-excitation; The slit width that excites and launch is 10nm; Voltage 400V.
Mixed 7-(3-alkene the butoxy)-3H-Phenazoxine-3-ketone mother liquor (1mM) that adds 100 μ L in the solution of above-mentioned various materials at 10ml, adding ozone again, to make its ultimate density be 30 μ M.
Experimental result shows to have only ozone can cause that 7-(3-alkene butoxy)-3H-Phenazoxine-3-ketone produces tangible optical signal response, prove that this reagent has the selectivity of height to ozone, and the mensuration of ozone is not disturbed in the existence of other species.
Fig. 3 is the fluorescence emission spectrum that 7-(3-alkene butoxy)-3H-Phenazoxine-3-ketone (10 μ M) obtains when mixing with various other materials.
Embodiment 4: the concentration of using the ozone of tetrabase box quantitative assay ultra violet lamp generation
1) gaseous sample sampling
According to device shown in Figure 4, air in ultra violet lamp 3,6 and 12 hours the airtight box is extracted 50mL with syringe, to contain the test tube sealing of the phosphate buffered saline buffer of 50mM with sealing cover, gas in the syringe is expelled to about 15 minutes in the phosphate buffered saline buffer of 50mM, adds 7-(3-alkene butoxy)-3H-Phenazoxine-3-reactive ketone and detect after 30 minutes.
2) making of working curve
The ozone that ozonizer produces feeds phosphate buffered saline buffer, and (pH is 6.0, and phosphoric acid salt wherein is Na 2HPO 4-NaH 2PO 4) in, its concentration can be measured (λ by ultra-violet absorption spectrum Max=258nm; ε=2900Lmol -1Cm -1), and prepare the standard inventory solution that ozone concn is 100 μ M accordingly.Then, take the ozone standard inventory solution of different volumes, placing the pH that contains certain volume is the sample bottle of 7.4 phosphate buffered saline buffer, and makes the ultimate density of ozone be followed successively by 1,3,6,9,12,15,18,21,24,27 and 30 μ M; Add 100 μ L reagent storing solution II [dimethyl sulphoxide solution of 7-(3-alkene butoxy)-3H-Phenazoxine-3-ketone] again, making its ultimate density is 10 μ M, shakes up (volume ratio of phosphate buffered saline buffer and reagent storing solution II is 100:1).Behind the reaction 30min, extract reaction solution in 1 centimetre of quartz colorimetric utensil, make excitation wavelength with 550nm, measure the fluorescence intensity at 585nm place, obtain series of standards fluorescence intensity of solution F, measure the fluorescence intensity F of corresponding reagent blank solution simultaneously 0
Concentration C (μ M) with ozone is X-coordinate, fluorescence intensity changing value Δ F(Δ F=F-F 0) be ordinate zou, the drawing curve, drawing corresponding equation of linear regression is △ F=66.3 * C (μ M)+22.6 (γ=0.998).
3) the ultra violet lamp different time produces the mensuration of ozone content
The gas of ultra violet lamp different time and the reaction of reagent storing solution II, measure the fluorescence intensity at 585nm place, be designated as F ', with F ' substitution above-mentioned steps 2) among gained equation of linear regression △ F=66.3 * C (μ M)+22.6 (γ=0.998), obtain the ultra violet lamp different time and produce ozone content.Repeated experiments three times, experimental result sees the following form shown in 1.
Table 1 ultra violet lamp different time produces the detected result of ozone content
Figure BDA00003344318800051
Fig. 5 changes for ozoniferous fluorescence intensity in the air of test kit detection ultra violet lamp different time.As shown in Figure 5, the ozone content that produces along with the increase ultra violet lamp air of time increases, and discharges more resorufin fluorophore, and fluorescence is enhanced.
It should be noted that at last: above-described embodiment is only enumerated so that 7-(3-alkene butoxy)-3H-Phenazoxine-3-ketone is fluorescent reagent, the concentration that contains 7-(3-alkene butoxy)-3H-Phenazoxine-3-ketone and phosphate buffered saline buffer in the reaction system is respectively 10 μ M, 50mM, the situation of reaction 30min.All the other fluorescent reagent concentration and the result in reaction times do not list one by one, yet it is not for limiting the present invention.Any those skilled in the art under the situation that does not break away from the spirit and scope of the present invention, should make various modifications and change.

Claims (10)

1. compound shown in the formula I,
The formula I.
2. the preparation method of compound shown in the formula I comprises the steps:
Under the condition that basic catalyst exists, the Phenazoxine ketone sodium salt of 7-hydroxyl shown in the formula II and 4-bromo-1-butylene react and namely get compound shown in the formula I;
Figure FDA00003344318700012
The formula II.
3. method according to claim 2, it is characterized in that: described basic catalyst is organic bases and/or mineral alkali;
Described organic bases is triethylamine and/or pyridine;
Described mineral alkali is selected from salt of wormwood, sodium hydroxide, yellow soda ash and the sodium bicarbonate at least a.
4. according to claim 2 or 3 described methods, it is characterized in that: the mol ratio of the Phenazoxine of 7-hydroxyl shown in formula II ketone sodium salt, 4-bromo-1-butylene and described basic catalyst is 1:0.5～5:0.5～5.
5. according to each described method among the claim 2-4, it is characterized in that: the temperature of described reaction is 0 ℃～60 ℃, and the time is 1～24 hour;
The solvent of described reaction is N, at least a in dinethylformamide, triethylamine, tetrahydrofuran (THF) and the acetonitrile.
6. the application of compound shown in the formula I in preparation ozone detection kit.
7. ozone detection kit, it is characterized in that: described test kit is made up of reagent storing solution I and reagent storing solution II:
Described reagent storing solution I is phosphate buffered saline buffer;
Described reagent storing solution II is the solution of compound shown in the formula I.
8. ozone detection kit according to claim 7, it is characterized in that: the pH value of described phosphate buffered saline buffer is 6～9;
Phosphoric acid salt in the described phosphate buffered saline buffer is selected from Na 2HPO 4, NaH 2PO 4And KH 2PO 4In at least two kinds;
The concentration of described phosphate buffered saline buffer is 0.01～0.5M.
9. according to claim 7 or 8 described ozone detection kit, it is characterized in that: the solvent of described reagent storing solution II is ethanol or dimethyl sulfoxide (DMSO);
The concentration of described reagent storing solution II is 0.1～2mM.
10. according to each described ozone detection kit among the claim 7-9, it is characterized in that: the volume ratio of described reagent storing solution I and reagent storing solution II is 100:1～10.
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Cited By (1)

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CN103592245A (en) * 2013-11-20 2014-02-19 陕西省计量科学研究院 Resorufin-2, 4-dinitrodiphenyl ether and application of resorufin- 2, 4-dinitrodiphenyl ether to detection of thiophenol

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Publication number Priority date Publication date Assignee Title
CN103592245A (en) * 2013-11-20 2014-02-19 陕西省计量科学研究院 Resorufin-2, 4-dinitrodiphenyl ether and application of resorufin- 2, 4-dinitrodiphenyl ether to detection of thiophenol
CN103592245B (en) * 2013-11-20 2015-10-28 陕西省计量科学研究院 Resorufin-2,4-dinitrodiphenyl ether and the application in detection benzenethiol thereof

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