CN103232842B - A kind of fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material and rapid examination test paper - Google Patents
A kind of fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material and rapid examination test paper Download PDFInfo
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Abstract
The present invention relates to a kind of fluorescent probe and rapid examination test paper of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material, based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material, that there is the compound shown in (I) formula: wherein, Z is carbon or nitrogen, and R is hydrogen, C1 ~ C4 alkyl, C1 ~ C4 alkoxyl group, halogen, nitro or C1 ~ C4 ester group.The invention still further relates to a kind of fluorescent probe of sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material and the preparation method of rapid examination test paper.The fluorescent probe selectivity and the sensitivity that the present invention is based on the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material are higher, stable chemical nature, conveniently preserve use for a long time, the detection realizing sulfurous acid hydrogen radical ion of energy rapid sensitive, preparation process is simple, and raw material is easy to get, and is easy to apply; Rapid examination test paper preparation method is simple, is convenient to family and individual's use.
Description
Technical field
The present invention relates to a kind of fluorescent probe based on aggregation inducing Fluorescence Increasing material sulfurous acid hydrogen radical ion and rapid examination test paper, belong to the technical field of fluorescence organic compound.
Background technology
Hydrosulphite is a kind of common foodstuff additive, be widely used in food, vegetables and medicine anti-oxidant, anticorrosion.But excessive sulfurous acid hydrogen radical ion can cause the anaphylaxis that eater is serious, as allergic asthma etc.So there are strict requirement in many countries to the sulfurous acid hydrogen radical ion content in food, medicine in the world.In China, this content requirement is lower than 0.05mg/kg.The Quantitative detection of sulfurous acid hydrogen radical ion and fast qualitative are detected and is very necessary and there is sizable practical value.
Pyridine (benzene) isothiazolinone is a kind of common heterocyclic molecular, early has people to report about biological activitys such as the anti-platelet aggregations that its derivative has, but the luminescent properties of its derivative someone finds so far.The present invention has found pyridine (benzene) and the AIE(aggregation inducing Fluorescence Increasing that has of isothiazolinone derivatives unexpectedly) the characteristics of luminescence, and the fluorescent probe of a kind of sulfurous acid hydrogen radical ion that utilized its feature to prepare and quick detection test paper.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of fluorescent probe based on aggregation inducing Fluorescence Increasing material sulfurous acid hydrogen radical ion and rapid examination test paper.
Term illustrates:
THF/HEPES (v/v, 1/999) solution: refer to tetrahydrofuran (THF) (THF): 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) damping fluid=1:999, volume ratio, the solution of composition; 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) damping fluid is the aqueous solution of 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES), and concentration is 20mmol/L.
Technical scheme of the present invention is as follows:
Based on a fluorescent probe for the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material, be that there is the compound shown in (I) formula:
Wherein, Z is carbon or nitrogen, and R is hydrogen, C1 ~ C4 alkyl, C1 ~ C4 alkoxyl group, halogen, nitro or C1 ~ C4 ester group.
According to the present invention, preferably, described C1 ~ C4 alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, or tertiary butyl;
Preferably, described C1 ~ C4 alkoxyl group is 4-methoxyl group or 3,4,5-trimethoxy;
Preferably, described halogen is fluorine, chlorine or bromine;
Preferably, described C1 ~ C4 ester group is 2-group-4 ethyl formate.
The preparation method of the fluorescent probe of the above-mentioned sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material of the present invention is as follows:
(1) sulfo-nicotinic acid or thiosalicylic acid joined in solvent dissolve, add thionyl chloride, back flow reaction 1 ~ 3 hour reaction solution; Described sulfo-nicotinic acid or thiosalicylic acid: the mass volume ratio of solvent is 1:(40 ~ 60) g/ml, described thionyl chloride: the volume ratio of solvent is 1:(40 ~ 60);
(2) solvent in reaction solution and remaining thionyl chloride are removed in distillation, then be dissolved into in the solvent of step (1) same volume lysate, by amine solvent in solvent and water amine aqueous solution, amine aqueous solution is added drop-wise in lysate and reacts 10 ~ 20h; The add-on of described amine controls 80 ~ 110% of sulfo-nicotinic acid in step (1) or thiosalicylic acid molar weight;
Described amine has the general formula shown in (II) formula, and wherein R is hydrogen, C1 ~ C4 alkyl, C1 ~ C4 alkoxyl group, halogen, nitro or C1 ~ C4 ester group;
(3) adjust pH to 6 ~ 8, then suction filtration removing solid; Filtrate solvent extraction, anhydrous sodium sulfate drying, petrol ether/ethyl acetate crosses silica gel chromatographic column, to obtain final product;
Solvent described in step (1) ~ (3) is methylene dichloride, chloroform, tetracol phenixin, 1,2-ethylene dichloride, acetonitrile, DMF (DMF) or dimethyl sulfoxide (DMSO) (DMSO).
According to the present invention, preferably, the sulfo-nicotinic acid described in step (1) or thiosalicylic acid: the mass volume ratio of solvent is 1:50g/ml, thionyl chloride: the volume ratio of solvent is 1:50.
According to the present invention, preferably, the add-on of the amine described in step (2) is identical with the add-on of sulfo-nicotinic acid in step (1) or thiosalicylic acid; It is ice bath environment that amine aqueous solution is added drop-wise to temperature of reaction condition in lysate; Described C1 ~ C4 alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, or tertiary butyl, and described C1 ~ C4 alkoxyl group is 4-methoxyl group or 3,4,5-trimethoxy, and described C1 ~ C4 ester group is 2-group-4 ethyl formate.
According to the present invention, preferably, the volume ratio of the petrol ether/ethyl acetate described in step (3) is 1:1, and in described silica gel chromatographic column, silica gel specification is 300 ~ 400 orders.
The present invention is based on the reaction formula related in the preparation method of the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material as follows:
Wherein, Z is carbon or nitrogen, and R is hydrogen, C1 ~ C4 alkyl, C1 ~ C4 alkoxyl group, halogen, nitro or C1 ~ C4 ester group.
The fluorescent probe that the present invention is based on the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material prepares the rapid examination test paper of sulfurous acid hydrogen radical ion, and step is as follows:
(i) the fluorescent probe methylene dichloride of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material is dissolved;
(ii) filter paper is dipped in step solution (i), then takes out, be drying to obtain under room temperature.
According to the present invention, preferably, step (i) in based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material: the mass volume ratio of methylene dichloride is 1:(30 ~ 40) g/ml.
Step (ii) middle object of soaking is that the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material is fully immersed in filter paper.
The present invention is based on the qualitative detection that the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material and rapid examination test paper can be applicable to sulfurous acid hydrogen radical ion remaining in food and medicine, not only rapid sensitive, and easy to use.
The fluorescent probe that the present invention is based on the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material can carry out detection by quantitative to sulfurous acid hydrogen radical ion by wiring solution-forming.
The invention has the beneficial effects as follows:
1, the fluorescent probe selectivity and the sensitivity that the present invention is based on the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material are higher, the detection realizing sulfurous acid hydrogen radical ion of energy rapid sensitive.
2, the preparation process that the present invention is based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material is simple, and raw material is easy to get, and is easy to apply.
3, the rapid examination test paper preparation method of sulfurous acid hydrogen radical ion of the present invention is simple, is convenient to family and individual's use.
4, the present invention is based on the stable chemical nature of the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material, conveniently preserve use for a long time.
Accompanying drawing explanation
Fig. 1 is dissolved in the fluorescence emission spectrogram in THF/HEPES (v/v, the 1/999) solution of different water-content based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material in detection example 1 of the present invention; Excitation wavelength is 350nm, and slit width is 5nm/5nm.
Fig. 2 is the fluorescent emission intensity change picture be dissolved in based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material in detection example 1 of the present invention in THF/HEPES (v/v, the 1/999) solution of different water-content.
Fig. 3 to be dissolved in THF/HEPES (v/v, 1/999) solution based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material in detection example 2 of the present invention and to add HSO
3 -, F
-, Cl
-, Br
-, I
-, ClO
3 -, ClO
4 -, NO
3 -, SO
4 2-, CO
3 2-, PO
4 3-, Ac
-, HCO
3 -, HSO
4 -. carry out fluorometric investigation respectively, the fluorescence emission spectrogram obtained; Fluorescent probe concentration based on the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material is 10
-4mol/L, the concentration of each ion is 20 × 10
-4mol/L, excitation wavelength is 350nm, and slit width is 10nm/10nm.
Fig. 4 is based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material and the AIE effect of quick detection test paper and Detection results figure in detection example 3 of the present invention; wherein Fig. 4-1 is the fluorescence phenomenon be dissolved in based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material in THF, Fig. 4-2 is dissolved in THF/HEPES (v/v based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material, 1/999) fluorescence phenomenon in solution, Fig. 4-3 is dissolved in THF/HEPES (v/v based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material, 1/999) fluorescence phenomenon of sulfurous acid hydrogen radical ion is added in solution, Fig. 4-4 is colour-change under the quick detection test paper ultraviolet lamp (365nm) prepared based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material, Fig. 4-5 is that the quick detection test paper prepared based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material to be stained with after sulfurous acid hydrogen radical ion solution colour-change under ultraviolet lamp (365nm), Fig. 4-6 is that the quick detection test paper prepared based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material to be stained with after sulfurous acid hydrogen radical ion solution colour-change under daylight.
Fig. 5 is after the quick detection test paper prepared based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material in detection example 4 of the present invention drips different anions solution, the colour-change of observing under ultraviolet lamp (365nm).
Fig. 6 is after the quick detection test paper prepared based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material in detection example 4 of the present invention drips different anions solution, the colour-change of observed under daylight.
Fig. 7 is titration curve and working curve diagram in detection example 5 of the present invention, and wherein, A is titration curve, and B is working curve.
Embodiment
Below by specific embodiment, the present invention will be further described, but be not limited thereto.
Raw materials usedly in embodiment and detection example be this area conventional reagent, commercial products; Equipment used is this area conventional equipment.Wherein: sulfo-nicotinic acid, thiosalicylic acid, uncommon to like that (Shanghai) changes into industrial development company limited on sale for ladder; Aniline, Jin Jin happy Industrial Co., Ltd. in Shanghai is on sale; 4-anisidine, Shanghai Hu Feng Chemical Co., Ltd. is on sale; Para-fluoroaniline, Chengdu Ai Keda chemical reagent company limited is on sale; 3,4,5-trimethoxy-aniline, Shanghai Rui Teng Chemical Co., Ltd. is on sale; 2-Methyl anthranilate, hundred is on sale along (Beijing) chemical Science and Technology Ltd..
The fluorescent probe of embodiment 1, a kind of sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material, preparation process is as follows:
(1) add 3.10g sulfo-nicotinic acid in single port bottle, add methylene dichloride 150ml and dissolve, add 3ml thionyl chloride, back flow reaction 2 hours;
(2) solvent in distillation removal reaction solution and remaining thionyl chloride, dissolve to obtain lysate with methylene dichloride 150ml; By 1.67g(1.8mmol) aniline to be dissolved in 20ml methylene dichloride and to add 3ml water and obtain amine aqueous solution, and amine aqueous solution is reacted 20h by being added drop-wise in lysate under constant pressure funnel ice bath;
(3) add in 100ml water, 5g salt of wormwood and the acid generated, then suction filtration removing solid, filtrate dichloromethane extraction, dried over sodium sulfate is spent the night, and petrol ether/ethyl acetate (1:1) is crossed silica gel chromatographic column and be get final product.
The structural formula of the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material prepared by the present embodiment is as follows:
2-phenylpyridine isothiazolinone (CAS:104857-27-4.): white crystal, mp137-138 ° of C, yield 43%.
1HNMR(300MHz,CDCl
3)δ8.81(dd,1H,J=1.5,4.8Hz),8.40(d,1H,J=8.1Hz),7.70(d,2H,J=7.5Hz),7.50(t,2H,J=7.8Hz),7.44(t,1H,J=3.9Hz),7.36(t,1H,J=7.5Hz)。
13CNMR(75MHz,CDCl
3)δ162.5,161.9,154.0,136.7,135.3,129.5,127.5,124.9,121.0。HRMScalcdforC
12h
8n
2oS [(M+H)
+], 229.0391; Found, 229.0425(high resolution mass spec, molecular ion peak 229.0425).
The fluorescent probe of embodiment 2, a kind of sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material, preparation process with embodiment 1, unlike in step (2) by 2.21g(1.8mmol) 4-anisidine to be dissolved in 20ml methylene dichloride and to add 3ml water and obtain amine aqueous solution.
The structural formula of the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material prepared by the present embodiment is as follows:
2-(4-methoxyl group) phenylpyridine isothiazolinone (CAS:104857-29-6): yellow needle-like crystals, yield 40%, mp169-171 ° of C.
1HNMR(300MHz,CDCl
3)δ8.80(d,1H,J=3.3Hz),8.34(dd,1H,J=1.2,7.8Hz),7.58-7.53(m,2H),7.40(dd,1H,J=4.6,7.8Hz),7.02-6.97(m,2H),3.85(s,3H)。
13CNMR(100MHz,CDCl
3)δ162.7,162.0,159.0,153.9,135.2,129.0,121.0,119.6,114.7,55.6。HRMScalcdforC
13h
10n
2o
2s [(M+H)
+], 259.0497; Found, 259.0536(high resolution mass spec, molecular ion peak 259.0536).
The fluorescent probe of embodiment 3, a kind of sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material, preparation process with embodiment 1, unlike in step (2) by 2.00g(1.8mmol) para-fluoroaniline to be dissolved in 20ml methylene dichloride and to add 3ml water and obtain amine aqueous solution.
The structural formula of the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material prepared by the present embodiment is as follows:
2-(4-fluorine) phenylpyridine isothiazolinone (CAS:158093-65-3): white needle-like crystals, mp188-190 ° of C, yield 33%.
1HNMR(300MHz,CDCl
3)δ8.83(dd,1H,J=1.2,4.8Hz),8.36(dd,1H,J=1.2,7.8Hz),7.68-7.63(m,2H),7.42(dd,1H,J=4.8,7.8),7.21-7.16(m,2H)。
13CNMR(100MHz,CDCl
3)δ162.7(d,J
C-F=12Hz),161.8,160.3,154.1,135.4,133.0,132.4(d,J
C-F=2.9Hz),127.1(d,J
C-F=8.5Hz),121.1,119.5,116.5(d,J
C-F=23Hz)。HRMScalcdforC
12h
7fN
2oS [(M+H)
+], 247.0297; Found, 247.0334(high resolution mass spec, molecular ion peak 247.0334).
The fluorescent probe of embodiment 4, a kind of sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material, preparation process, with embodiment 1, changes 3.10g sulfo-nicotinic acid into 3.08g thiosalicylic acid unlike in step (1).
The structural formula of the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material prepared by the present embodiment is as follows:
2-phenyl BIT (CAS:2527-03-9): white crystal, mp142-143.5 ° of C, yield 31%.
1HNMR(400MHz,CDCl
3)δ8.11(d,1H,J=7.8Hz),7.73-7.70(m,2H),7.69-7.65(m,1H),7.59(d,1H,J=8.0Hz),7.52-7.43(m,3H),7.32(t,1H,J=7.4Hz)。
13cNMR (75MHz, CDCl
3) δ 164.1,139.9,137.3,132.3,129.4,127.2,127.0,125.8,124.9,124.6,120.1.HRMScalcdforC
13h
9n
2oS [(M+H)
+], 228.0438; Found, 228.0472(high resolution mass spec, molecular ion peak 228.0472).
The fluorescent probe of embodiment 5, a kind of sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material, preparation process is with embodiment 4, unlike in step (2) by 3.29g(1.8mmol) 3,4,5-trimethoxy-anilines to be dissolved in 20ml methylene dichloride and to add 3ml water and obtain amine aqueous solution.
The structural formula of the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material prepared by the present embodiment is as follows:
2-(3,4,5-trimethoxy) phenylpyridine isothiazolinone (CAS:158093-76-6): yellow powder, mp120-121 ° of C, yield 38%.
1HNMR(300MHz,CDCl
3)δ8.82(dd,1H,J=1.5,4.8Hz),8.35(dd,1H,J=1.5,7.8Hz),7.42(dd,1H,J=4.8,7.8Hz),6.91(s,2H),3.90(s,6H),3.88(s,3H)。
13CNMR(75MHz,CDCl
3)δ162.6,161.9,154.1,153.6,137.6,135.2,131.9,121.1,119.7,103.1,61.0,56.3。HRMScalcdforC
15h
14n
2o
4s [(M+H)
+], 319.0708; Found, 319.0708(high resolution mass spec, molecular ion peak 319.0708).
The fluorescent probe of embodiment 6, a kind of sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material, preparation process with embodiment 4, unlike in step (2) by 2.97g(1.8mmol) 2-Methyl anthranilate to be dissolved in 20ml methylene dichloride and to add 3ml water and obtain amine aqueous solution.
The structural formula of the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material prepared by the present embodiment is as follows:
2-(2-methyl benzoate base) pyrido isothiazolinone (CAS:158093-88-0.): white powder, mp142-143.5 ° of C, yield 31%.
1HNMR(300MHz,CDCl
3)δ8.94(dd,1H,J=1.8,4.8Hz),8.38(dd,1H,J=1.8,7.8Hz),7.98(dd,1H,J=1.5,7.8Hz),7.80(td,1H,J=15.3,7.8Hz),7.63(m,3H),3.64(s,3H)。
13CNMR(75MHz,CDCl
3)δ165.0,162.7,161.9,154.6,135.2,134.5,133.6,131.0,129.7,129.4,129.1,121.7,117.9,52.3。HRMScalcdforC
15h
12n
2o
3s [(M+H)
+], 301.0602; Found, 301.0602(high resolution mass spec, molecular ion peak 301.0602).
Detection example 1,
In this detection example, checking the present invention is based on fluorescent characteristic and aggregation-induced emission (AIE) effect of the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material.
The fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material embodiment 1 prepared is dissolved in THF/HEPES (v/v, the 1/999) solution of different water-content, is made into 10
-4the solution of mol/L, ultrasonic vibration 2min, then tests AIE effect.Find that assemble, fluorescence intensity strengthens greatly after water-content raises.
As shown in Figure 1 and Figure 2, prove that there is higher fluorescence quantum efficiency, there is good AIE effect simultaneously.
Detection example 2,
In this detection example, checking the present invention is based on the ion selectivity of the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material.
The fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material embodiment 1 prepared is dissolved in THF/HEPES (v/v, 1/999) solution, is made into 10
-4the solution of mol/L, ultrasonic vibration 2min, is then added dropwise to the contrast negatively charged ion of 20 times of concentration, finds to only have sulfurous acid hydrogen radical ion can make probe solution generation fluorescent quenching, proves that probe has good ion selectivity, as shown in Figure 3.
Detection example 3,
In this detection example, checking the present invention is based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material and the AIE effect of quick detection test paper and Detection results.
The fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material embodiment 1 prepared is dissolved in unstressed configuration phenomenon in THF, as shown in Fig. 4-1; Be dissolved in THF/HEPES (v/v, 1/999) solution and clustering phenomena occur simultaneously Fluorescence Increasing is as shown in the Fig. 4-2; After being dissolved in THF/HEPES (v/v, 1/999) solution, add sulfurous acid hydrogen radical ion, its colour changed into yellow, as shown in Fig. 4-3; The fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material embodiment 1 prepared is prepared into quick detection test paper.Quick detection test paper sends blue light, as shown in Fig. 4-4 under ultraviolet lamp (365nm); There is fluorescent quenching after being stained with sulfurous acid hydrogen radical ion solution in quick detection test paper, under ultraviolet lamp (365nm), blue light disappears, as illustrated in figures 4-5; After quick detection test paper is stained with sulfurous acid hydrogen radical ion solution, under daylight, be observed visually flavescence, as Figure 4-Figure 6.
Detection example 4,
This detection example investigates the ion selectivity of the quick detection test paper prepared based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material.Quick detection test paper being dripped concentration is 10
-3the different anions solution of mol/L, observes colour-change under ultraviolet lamp (365nm), as shown in Figure 5.Investigate F respectively
-, Cl
-, Br
-, I
-, ClO
3 -, ClO
4 -, NO
3 -, SO
4 2-, CO
3 2-, PO
4 3-, Ac
-, HCO
3 -, HSO
4 -, and HSO
3 -, except HSO
3 -outward, the quick detection test paper dripping other solions is blueness under ultraviolet lamp (365nm), drips HSO
3 -the quick detection test paper of solution is blue under ultraviolet lamp (365nm) to disappear.Quick detection test paper is dripped above-mentioned anion solutions, observed under daylight colour-change, as shown in Figure 6; Except HSO
3 -, drip the quick detection test paper of other solions in the sunlight without colour-change outward, drip HSO
3 -the quick detection test paper displaing yellow in the sunlight of solution.
Detection example 5,
This detection example is investigated based on the titration curve of the fluorescent probe solution of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material and working curve.The fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material is added to be configured to concentration in THF/HEPES (v/v, 1/999) solution be 10
-5the solution of mol/L, joins in cuvette by above-mentioned for 1ml solution, and the water sample to be measured at every turn getting 10 μ L joins in cuvette, mixes, and measure fluorescence intensity curves, excitation wavelength is 350nm, and slit width is 10nm/10nm.
The fluorescent emission intensity choosing 467nm makes working curve, and as shown in Figure 6, wherein A is titration curve, and B is working curve.
Linear relationship is Y=-0.00984+0.08871X, R=0.99573, Y=1-I/I
0, X=C (concentration), detection limit=0.39 μm ol/L.
Claims (2)
1. utilize the fluorescent probe based on the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material to prepare a method for sulfurous acid hydrogen radical ion rapid examination test paper, step is as follows:
(i) the fluorescent probe methylene dichloride of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material is dissolved;
The structural formula of the fluorescent probe of the described sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material is as follows:
(ii) filter paper is dipped in step solution (i), then takes out, be drying to obtain under room temperature.
2. the method for sulfurous acid hydrogen radical ion rapid examination test paper is prepared in utilization according to claim 1 based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material, it is characterized in that, step (i) in based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing Fluorescence Increasing material: the mass volume ratio of methylene dichloride is 1:(30 ~ 40) g/ml.
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| CN104610955B (en) * | 2014-05-16 | 2018-10-30 | 中南大学 | A kind of Ratio-type detects the synthesis and application of fluorine ion and inferior sulfate radical fluorescent molecular probe simultaneously |
| CN104262287B (en) * | 2014-09-02 | 2016-06-08 | 苏州罗兰生物科技有限公司 | The preparations and applicatio of a kind of inferior sulfate radical ratio fluorescent probe |
| CN107860758A (en) * | 2017-12-15 | 2018-03-30 | 中国科学院上海微系统与信息技术研究所 | A kind of method for detecting primary amine |
| CN113372282B (en) * | 2021-07-01 | 2023-03-24 | 齐齐哈尔大学 | Fluorescent probe for detecting bisulfite ions in real time and preparation method and application thereof |
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2013
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| US5733921A (en) * | 1995-05-31 | 1998-03-31 | Warner-Lambert Company | Isothiazolone compounds |
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