CN103232842A - Bisulfate ion fluorescence probe base on aggregation and induction of fluorescence enhanced material and rapid examination test paper - Google Patents
Bisulfate ion fluorescence probe base on aggregation and induction of fluorescence enhanced material and rapid examination test paper Download PDFInfo
- Publication number
- CN103232842A CN103232842A CN2013101299478A CN201310129947A CN103232842A CN 103232842 A CN103232842 A CN 103232842A CN 2013101299478 A CN2013101299478 A CN 2013101299478A CN 201310129947 A CN201310129947 A CN 201310129947A CN 103232842 A CN103232842 A CN 103232842A
- Authority
- CN
- China
- Prior art keywords
- hydrogen radical
- radical ion
- sulfurous acid
- fluorescent probe
- strongthener
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WWKAFSOHULVYCS-UHFFFAOYSA-N COc(cc1)ccc1N1Sc2ncccc2C1=[U] Chemical compound COc(cc1)ccc1N1Sc2ncccc2C1=[U] WWKAFSOHULVYCS-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to a bisulfate ion fluorescence probe base on aggregation and induction of fluorescence enhanced material and rapid examination test paper, and the probe has the compound shown in the formula (I): wherein, Z is carbon or nitrogen, R is hydrogen, C1-C4 is alkyl, C1-C4 is alkyloxy, halogen, nitro or ester group. The invention also relates to preparation methods of the bisulfate ion fluorescence probe base on aggregation and induction of fluorescence enhanced material and the rapid examination test paper. The bisulfate ion fluorescence probe base on aggregation and induction of fluorescence enhanced material has higher sensitivity and selectivity, and stable chemical property, and can be stored for a long time, and can rapidly and sensitively detect bisulfate ions, and has the advantages of simple preparation step, easily available raw material and easy popularization and application; the rapid examination test paper has a simple preparation method and is convenient for household and personal usage.
Description
Technical field
The present invention relates to a kind of fluorescent probe and quick test test paper based on aggregation inducing fluorescence strongthener sulfurous acid hydrogen radical ion, belong to the technical field of fluorescence organic compound.
Background technology
Hydrosulphite is a kind of common foodstuff additive, is widely used in the anti-oxidant, anticorrosion of food, vegetables and medicine.But excessive sulfurous acid hydrogen radical ion can cause eater's severe anaphylactic reaction, as allergic asthma etc.So there is strict requirement in many countries to the sulfurous acid hydrogen radical ion content in food, the medicine in the world.In China, this content requirement is to be lower than 0.05mg/kg.Fast quantification detection and fast qualitative detection for sulfurous acid hydrogen radical ion are very necessary and have sizable practical value.
Pyridine (benzene) and isothiazolinone are a kind of common heterocycle molecules, and the biological activitys such as anti-platelet aggregation that have about its derivative early someone report, but the luminescent properties of its derivative so far the someone find.The present invention has found that unexpectedly the AIE(aggregation inducing fluorescence that pyridine (benzene) and isothiazolinone derivatives have strengthens) the characteristics of luminescence, and utilize its characteristics to prepare a kind of fluorescent probe and quick detection test paper of sulfurous acid hydrogen radical ion.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of fluorescent probe and quick test test paper based on aggregation inducing fluorescence strongthener sulfurous acid hydrogen radical ion.
The term explanation:
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:
A kind of fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing fluorescence strongthener is to have 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, preferred, 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 the 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 strongthener of the present invention is as follows:
(1) sulfo-nicotinic acid or thiosalicylic acid joined in the 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 and the remaining thionyl chloride in the reaction solution removed in distillation, be dissolved into again in the solvent with step (1) equal volume lysate, with amine solvent in solvent and water amine aqueous solution, amine aqueous solution is added drop-wise to reacts 10～20h in the lysate; The control of the add-on of described amine in step (1) sulfo-nicotinic acid or thiosalicylic acid molar weight 80～110%;
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, suction filtration is removed solid then; Filtrate is used solvent extraction, anhydrous sodium sulfate drying, and petrol ether/ethyl acetate is crossed silica gel chromatographic column, namely;
Solvent described in step (1)～(3) is methylene dichloride, chloroform, tetracol phenixin, 1,2-ethylene dichloride, acetonitrile, N, dinethylformamide (DMF) or dimethyl sulfoxide (DMSO) (DMSO).
According to the present invention, preferred, sulfo-nicotinic acid or the thiosalicylic acid described in the step (1): 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, preferred, the add-on of the amine described in the step (2) is identical with the add-on of the middle sulfo-nicotinic acid of step (1) or thiosalicylic acid; Amine aqueous solution is added drop-wise to that the temperature of reaction condition is the ice bath environment in the lysate; Described C1～C4 alkyl is methyl, ethyl, n-propyl, sec.-propyl, and normal-butyl, or tertiary butyl, described C1～C4 alkoxyl group are 4-methoxyl group or 3,4,5-trimethoxy, and described C1～C4 ester group is the 2-group-4 ethyl formate.
According to the present invention, preferred, the volume ratio of the petrol ether/ethyl acetate described in the step (3) is 1:1, and the silica gel specification is 300～400 orders in the described silica gel chromatographic column.
It is as follows to the present invention is based on the reaction formula that relates among the preparation method of fluorescent probe of sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener:
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 strongthener prepares the quick test test paper of sulfurous acid hydrogen radical ion, and step is as follows:
(i) will dissolve with methylene dichloride based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener;
(ii) filter paper is dipped in the solution of step (i), takes out then, be drying to obtain under the room temperature.
According to the present invention, preferred, in the step (i) based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener: the mass volume ratio of methylene dichloride is 1:(30～40) g/ml.
The purpose that step is soaked in (ii) is that the fluorescent probe based on the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener fully is immersed in the filter paper.
The present invention is based on the fluorescent probe of sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener and the qualitative detection that the quick test test paper can be applicable to sulfurous acid hydrogen radical ion remaining in the food and medicine, rapid sensitive not only, and also easy to use.
But the fluorescent probe wiring solution-forming that the present invention is based on the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener carries out detection by quantitative to sulfurous acid hydrogen radical ion.
The invention has the beneficial effects as follows:
1, it is higher to the present invention is based on fluorescent probe selectivity and the sensitivity of sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener, the detection of realization sulfurous acid hydrogen radical ion that can rapid sensitive.
2, it is simple to the present invention is based on the preparation process of fluorescent probe of sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener, and raw material is easy to get, and is easy to apply.
3, the quick test method for preparing test paper of sulfurous acid hydrogen radical ion of the present invention is simple, is convenient to family and individual's use.
4, it is stable to the present invention is based on the chemical property of fluorescent probe of sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener, makes things convenient for prolonged preservation to use.
Description of drawings
Fig. 1 detects in the example 1 fluorescence emission spectrogram in THF/HEPES (v/v, the 1/999) solution that fluorescent probe based on the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener is dissolved in different water-contents for the present invention; Excitation wavelength is 350nm, and slit width is 5nm/5nm.
Fig. 2 changes picture for the fluorescent emission intensity that the present invention detects in the example 1 in THF/HEPES (v/v, the 1/999) solution that the fluorescent probe that strengthens the sulfurous acid hydrogen radical ion of material based on aggregation inducing fluorescence is dissolved in different water-contents.
Fig. 3 is dissolved in THF/HEPES (v/v, the 1/999) solution and adds HSO for the present invention detects in the example 2 fluorescent probe that strengthens the sulfurous acid hydrogen radical ion of material based on aggregation inducing fluorescence
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 that obtains; The fluorescent probe concentration that strengthens the sulfurous acid hydrogen radical ion of material based on aggregation inducing fluorescence is 10
-4Mol/L, the concentration of each ion is 20 * 10
-4Mol/L, excitation wavelength is 350nm, slit width is 10nm/10nm.
Fig. 4 strengthens the fluorescent probe of the sulfurous acid hydrogen radical ion of expecting and AIE effect and the detection design sketch of quick detection test paper for the present invention detects in the example 3 based on aggregation inducing fluorescence; Wherein Fig. 4-1 is dissolved in fluorescence phenomenon among the THF for the fluorescent probe that strengthens the sulfurous acid hydrogen radical ion of material based on aggregation inducing fluorescence, Fig. 4-2 is dissolved in THF/HEPES (v/v for the fluorescent probe that strengthens the sulfurous acid hydrogen radical ion of material based on aggregation inducing fluorescence, 1/999) fluorescence phenomenon in the solution, Fig. 4-3 is dissolved in THF/HEPES (v/v for the fluorescent probe that strengthens the sulfurous acid hydrogen radical ion of material based on aggregation inducing fluorescence, 1/999) in the solution and add the fluorescence phenomenon of sulfurous acid hydrogen radical ion, Fig. 4-4 is based on colour-change under the quick detection test paper ultraviolet lamp (365nm) of the fluorescent probe preparation of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence enhancing material, Fig. 4-5 is stained with behind the sulfurous acid hydrogen radical ion solution ultraviolet lamp (365nm) colour-change down for the quick detection test paper of the fluorescent probe preparation of the sulfurous acid hydrogen radical ion that strengthens material based on aggregation inducing fluorescence, and Fig. 4-6 is stained with behind the sulfurous acid hydrogen radical ion solution colour-change under the daylight for the quick detection test paper of the fluorescent probe preparation of the sulfurous acid hydrogen radical ion that strengthens material based on aggregation inducing fluorescence.
After Fig. 5 drips different anions solution for the present invention detects in the example 4 quick detection test paper of fluorescent probe preparation that strengthens the sulfurous acid hydrogen radical ion of material based on aggregation inducing fluorescence, the colour-change that ultraviolet lamp (365nm) is observed down.
After Fig. 6 drips different anions solution for the present invention detects in the example 4 quick detection test paper of fluorescent probe preparation that strengthens the sulfurous acid hydrogen radical ion of material based on aggregation inducing fluorescence, the colour-change of observing under the daylight.
Fig. 7 detects titration curve and working curve diagram in the example 5 for the present invention, and wherein, A is titration curve, and B is working curve.
Embodiment
The present invention will be further described below by specific embodiment, but be not limited thereto.
The raw materials used conventional reagent in this area, the commercial product of being in embodiment and the detection example; Equipment used is this area conventional equipment.Wherein: sulfo-nicotinic acid, thiosalicylic acid, it is on sale that the uncommon love of ladder (Shanghai) changes into industrial development company limited; Aniline, Jin Jin happy Industrial Co., Ltd. in Shanghai is on sale; The 4-anisidine, Shanghai, Shanghai peaking worker company limited is on sale; Para-fluoroaniline, Chengdu Ai Keda chemical reagent company limited is on sale; 3,4,5-trimethoxy-aniline, the farsighted chemical industry company limited of rising in Shanghai is on sale; The 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 strongthener, preparation process is as follows:
(1) adds 3.10g sulfo-nicotinic acid in the single port bottle, add methylene dichloride 150ml dissolving, add the 3ml thionyl chloride, back flow reaction 2 hours;
(2) solvent and the remaining thionyl chloride in the reaction solution removed in distillation, with methylene dichloride 150ml dissolve lysate; With 1.67g(1.8mmol) aniline is dissolved in the 20ml methylene dichloride and adds 3ml water and get amine aqueous solution, and amine aqueous solution is reacted 20h by being added drop-wise under the constant pressure funnel ice bath in the lysate;
(3) add in 100ml water, the 5g salt of wormwood and the acid that generates, suction filtration is removed solid then, and filtrate is used dichloromethane extraction, and dried over sodium sulfate is spent the night, and petrol ether/ethyl acetate (1:1) is crossed silica gel chromatographic column namely.
The structural formula based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener of present embodiment preparation is as follows:
2-phenylpyridine and isothiazolinone (CAS:104857-27-4.): white crystal, mp137-138 ° of C, yield 43%.
1H?NMR(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)。
13C?NMR(75MHz,CDCl
3)δ162.5,161.9,154.0,136.7,135.3,129.5,127.5,124.9,121.0。HRMS calcd for C
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 strongthener, preparation process is with embodiment 1, and different is with 2.21g(1.8mmol in the step (2)) the 4-anisidine is dissolved in the 20ml methylene dichloride and adds 3ml water and get amine aqueous solution.
The structural formula based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener of present embodiment preparation is as follows:
2-(4-methoxyl group) phenylpyridine and isothiazolinone (CAS:104857-29-6): yellow needle-like crystal, yield 40%, mp169-171 ° of C.
1H?NMR(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)。
13C?NMR(100MHz,CDCl
3)δ162.7,162.0,159.0,153.9,135.2,129.0,121.0,119.6,114.7,55.6。HRMScalcd for C
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 strongthener, preparation process is with embodiment 1, and different is with 2.00g(1.8mmol in the step (2)) para-fluoroaniline is dissolved in the 20ml methylene dichloride and adds 3ml water and get amine aqueous solution.
The structural formula based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener of present embodiment preparation is as follows:
2-(4-fluorine) phenylpyridine and isothiazolinone (CAS:158093-65-3): white needle-like crystals, mp188-190 ° of C, yield 33%.
1H?NMR(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)。
13C?NMR(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)。HRMS calcd for C
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 strongthener, preparation process is with embodiment 1, and different is to change 3.10g sulfo-nicotinic acid into the 3.08g thiosalicylic acid in the step (1).
The structural formula based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener of present embodiment preparation is as follows:
2-phenyl benzisothiazole ketone (CAS:2527-03-9): white crystal, mp142-143.5 ° of C, yield 31%.
1H?NMR(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)。
13C NMR (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.HRMS calcd for C
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 strongthener, preparation process is with embodiment 4, different is with 3.29g(1.8mmol in the step (2)) 3,4, the 5-trimethoxy-aniline is dissolved in the 20ml methylene dichloride and adds 3ml water and gets amine aqueous solution.
The structural formula based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener of present embodiment preparation is as follows:
2-(3,4,5-trimethoxy) phenylpyridine and isothiazolinone (CAS:158093-76-6): yellow powder, mp120-121 ° of C, yield 38%.
1H?NMR(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)。
13C?NMR(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。HRMS calcd for C
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 strongthener, preparation process is with embodiment 4, and different is with 2.97g(1.8mmol in the step (2)) the 2-Methyl anthranilate is dissolved in the 20ml methylene dichloride and adds 3ml water and get amine aqueous solution.
The structural formula based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener of present embodiment preparation is as follows:
2-(2-methyl benzoate base) pyrido isothiazolinone (CAS:158093-88-0.): white powder, mp142-143.5 ° of C, yield 31%.
1H?NMR(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)。
13C?NMR(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。HRMS calcd for C
15H
12N
2O
3S[(M+H)
+], 301.0602; Found, 301.0602(high resolution mass spec, molecular ion peak 301.0602).
Detection example 1,
Verify fluorescent characteristic and aggregation inducing luminous (AIE) effect of the fluorescent probe of the sulfurous acid hydrogen radical ion that the present invention is based on aggregation inducing fluorescence strongthener in this detection example.
The fluorescent probe based on the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener of embodiment 1 preparation is dissolved in THF/HEPES (v/v, the 1/999) solution of different water-contents, is made into 10
-4The solution of mol/L, ultrasonic concussion 2min tests the AIE effect then.Find to assemble after water-content raises, fluorescence intensity strengthens greatly.
As shown in Figure 1 and Figure 2, prove to have higher fluorescence quantum efficiency, have good AIE effect simultaneously.
Detection example 2,
Verify the ion selectivity of the fluorescent probe of the sulfurous acid hydrogen radical ion that the present invention is based on aggregation inducing fluorescence strongthener in this detection example.
The fluorescent probe based on the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener of embodiment 1 preparation is dissolved in THF/HEPES (v/v, the 1/999) solution, is made into 10
-4The solution of mol/L, ultrasonic concussion 2min is added dropwise to the contrast negatively charged ion of 20 times of concentration then, finds to have only 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,
Verify the fluorescent probe of the sulfurous acid hydrogen radical ion that the present invention is based on aggregation inducing fluorescence strongthener and AIE effect and the detection effect of quick detection test paper in this detection example.
The fluorescent probe based on the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener of embodiment 1 preparation is dissolved in do not have fluorescence phenomenon among the THF, shown in Fig. 4-1; Be dissolved in and clustering phenomena fluorescence enhancing simultaneously take place in THF/HEPES (v/v, the 1/999) solution shown in 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 is shown in Fig. 4-3; The fluorescent probe based on the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener of embodiment 1 preparation is prepared into quick detection test paper.Quick detection test paper is sent blue light under ultraviolet lamp (365nm), shown in Fig. 4-4; Fluorescent quenching takes place after being stained with sulfurous acid hydrogen radical ion solution in quick detection test paper, and ultraviolet lamp (365nm) blue light down disappears, shown in Fig. 4-5; After quick detection test paper is stained with sulfurous acid hydrogen radical ion solution, under the daylight, be observed visually flavescence, shown in Fig. 4-6.
Detection example 4,
This detection case expedition is based on the ion selectivity of the quick detection test paper of the fluorescent probe preparation of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener.It is 10 that quick detection test paper is dripped concentration
-3The different anions solution of mol/L, ultraviolet lamp (365nm) are observed colour-change down, as shown in Figure 5.Investigated 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 that drips other solions is blueness under ultraviolet lamp (365nm), drips HSO
3 -The quick detection test paper of solution is in ultraviolet lamp (365nm) blue disappearance down.Quick detection test paper is dripped above-mentioned anion solutions, observe colour-change under the daylight, as shown in Figure 6; Except HSO
3 -Outward, the quick detection test paper that drips other solions does not have colour-change under daylight, drips HSO
3 -The quick detection test paper of solution is displaing yellow under daylight.
Detection example 5,
This detection case expedition is based on titration curve and the working curve of the fluorescent probe solution of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener.To add that to be configured to concentration in THF/HEPES (v/v, the 1/999) solution be 10 based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener
-5The solution of mol/L joins the above-mentioned solution of 1ml in the cuvette, and the water sample to be measured of at every turn getting 10 μ L joins in the cuvette, mixes, and measures fluorescence intensity curves, and excitation wavelength is 350nm, and slit width is 10nm/10nm.
The fluorescent emission intensity workmanship who chooses 467nm makes 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 μ mol/L.
Claims (9)
1. fluorescent probe based on the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener is to have 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.
2. the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing fluorescence strongthener according to claim 1 is characterized in that described C1～C4 alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, or tertiary butyl.
3. the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing fluorescence strongthener according to claim 1, it is characterized in that, described C1～C4 alkoxyl group is 4-methoxyl group or 3,4, the 5-trimethoxy, described halogen is fluorine, chlorine or bromine, and described C1～C4 ester group is the 2-group-4 ethyl formate.
4. the preparation method of the fluorescent probe of the described sulfurous acid hydrogen radical ion based on aggregation inducing fluorescence strongthener of a claim 1, step is as follows:
(1) sulfo-nicotinic acid or thiosalicylic acid joined in the 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 and the remaining thionyl chloride in the reaction solution removed in distillation, be dissolved into again in the solvent with step (1) equal volume lysate, with amine solvent in solvent and water amine aqueous solution, amine aqueous solution is added drop-wise to reacts 10～20h in the lysate; The control of the add-on of described amine in step (1) sulfo-nicotinic acid or thiosalicylic acid molar weight 80～110%;
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, suction filtration is removed solid then; Filtrate is used solvent extraction, anhydrous sodium sulfate drying, and petrol ether/ethyl acetate is crossed silica gel chromatographic column, namely;
Solvent described in step (1)～(3) is methylene dichloride, chloroform, tetracol phenixin, 1,2-ethylene dichloride, acetonitrile, N, dinethylformamide (DMF) or dimethyl sulfoxide (DMSO) (DMSO).
5. the preparation method of the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing fluorescence strongthener according to claim 4, it is characterized in that, sulfo-nicotinic acid or thiosalicylic acid described in the step (1): the mass volume ratio of solvent is 1:50g/ml, thionyl chloride: the volume ratio of solvent is 1:50.
6. the preparation method of the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing fluorescence strongthener according to claim 4, it is characterized in that the add-on of the amine described in the step (2) is identical with the add-on of the middle sulfo-nicotinic acid of step (1) or thiosalicylic acid; Amine aqueous solution is added drop-wise to that the temperature of reaction condition is the ice bath environment in the lysate, described C1～C4 alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, or tertiary butyl, described C1～C4 alkoxyl group is 4-methoxyl group or 3,4,5-trimethoxy, described C1～C4 ester group is the 2-group-4 ethyl formate.
7. the preparation method of the fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing fluorescence strongthener according to claim 4, it is characterized in that, the volume ratio of the petrol ether/ethyl acetate described in the step (3) is 1:1, and the silica gel specification is 300～400 orders in the described silica gel chromatographic column.
8. a fluorescent probe that utilizes the described sulfurous acid hydrogen radical ion based on aggregation inducing fluorescence strongthener of claim 1 prepares the method for sulfurous acid hydrogen radical ion quick test test paper, and step is as follows:
(i) will dissolve with methylene dichloride based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener;
(ii) filter paper is dipped in the solution of step (i), takes out then, be drying to obtain under the room temperature.
9. utilization according to claim 8 prepares the method for sulfurous acid hydrogen radical ion quick test test paper based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener, it is characterized in that, in the step (i) based on the fluorescent probe of the sulfurous acid hydrogen radical ion of aggregation inducing fluorescence strongthener: the mass volume ratio of methylene dichloride is 1:(30～40) g/ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310129947.8A CN103232842B (en) | 2013-04-15 | 2013-04-15 | A kind of fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material and rapid examination test paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310129947.8A CN103232842B (en) | 2013-04-15 | 2013-04-15 | A kind of fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material and rapid examination test paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103232842A true CN103232842A (en) | 2013-08-07 |
| CN103232842B CN103232842B (en) | 2015-11-18 |
Family
ID=48880914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310129947.8A Expired - Fee Related CN103232842B (en) | 2013-04-15 | 2013-04-15 | A kind of fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material and rapid examination test paper |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103232842B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262287A (en) * | 2014-09-02 | 2015-01-07 | 苏州罗兰生物科技有限公司 | Preparation and application of sulfite ratiometric fluorescent probe |
| CN104610955A (en) * | 2014-05-16 | 2015-05-13 | 中南大学 | Synthesis method and application of ratiometric fluorescent molecular probe for simultaneously detecting fluorine ion and sulfite radical |
| CN107860758A (en) * | 2017-12-15 | 2018-03-30 | 中国科学院上海微***与信息技术研究所 | A kind of method for detecting primary amine |
| CN113372282A (en) * | 2021-07-01 | 2021-09-10 | 齐齐哈尔大学 | Fluorescent probe for detecting bisulfite ions in real time and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3012039A (en) * | 1958-03-14 | 1961-12-05 | Ici Ltd | 2-p-chlorobenzyl-1, 2-benzisothiazolone |
| US4397858A (en) * | 1980-10-31 | 1983-08-09 | A. Nattermann & Cie Gmbh | Treatment of rheumatism and arteriosclerosis with n-halogenophenyl-benzisothiazoles |
| US5733921A (en) * | 1995-05-31 | 1998-03-31 | Warner-Lambert Company | Isothiazolone compounds |
| CN102659677A (en) * | 2012-04-28 | 2012-09-12 | 中南大学 | Fluorescent molecular probe for detecting sulfite ions through naked eyes and fluorescence ratio as well as synthesis and application thereof |
-
2013
- 2013-04-15 CN CN201310129947.8A patent/CN103232842B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3012039A (en) * | 1958-03-14 | 1961-12-05 | Ici Ltd | 2-p-chlorobenzyl-1, 2-benzisothiazolone |
| US4397858A (en) * | 1980-10-31 | 1983-08-09 | A. Nattermann & Cie Gmbh | Treatment of rheumatism and arteriosclerosis with n-halogenophenyl-benzisothiazoles |
| US5733921A (en) * | 1995-05-31 | 1998-03-31 | Warner-Lambert Company | Isothiazolone compounds |
| CN102659677A (en) * | 2012-04-28 | 2012-09-12 | 中南大学 | Fluorescent molecular probe for detecting sulfite ions through naked eyes and fluorescence ratio as well as synthesis and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| A. MONGE等: "Synthesis of 2-subsituted 3-oxoisothiazolo[5,4-b]pyridines", 《J. HETEROCYCL. CHEM.》, vol. 22, 31 December 1985 (1985-12-31), pages 1353 - 1356 * |
| SILVIYA D. FURDAS等: "Synthesis and biological testing of novel pyridoisothiazolones as histone acetyltransferase inhibitors", 《BIOORGANIC & MEDICINAL CHEMISTRY》, vol. 19, 2 February 2011 (2011-02-02), pages 3678 - 3689, XP028378033, DOI: doi:10.1016/j.bmc.2011.01.063 * |
| STEPHEN W. WRIGHT等: "Metabolism Resistant Isothiazolone Inhibitors of Cartilage Breakdown", 《BIOORGANIC & MEDICINAL CHEMISTRY》, vol. 3, 31 December 1995 (1995-12-31), pages 227 - 234 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610955A (en) * | 2014-05-16 | 2015-05-13 | 中南大学 | Synthesis method and application of ratiometric fluorescent molecular probe for simultaneously detecting fluorine ion and sulfite radical |
| 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 |
| CN104262287A (en) * | 2014-09-02 | 2015-01-07 | 苏州罗兰生物科技有限公司 | Preparation and application of sulfite ratiometric fluorescent probe |
| 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***与信息技术研究所 | A kind of method for detecting primary amine |
| CN113372282A (en) * | 2021-07-01 | 2021-09-10 | 齐齐哈尔大学 | Fluorescent probe for detecting bisulfite ions in real time and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103232842B (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | A new selective pyrazoline-based fluorescent chemosensor for Cu2+ in aqueous solution | |
| Park et al. | Signaling of water content in organic solvents by solvatochromism of a hydroxynaphthalimide-based merocyanine dye | |
| Kang et al. | A highly selective colorimetric and fluorescent turn-on chemosensor for Al3+ based on naphthalimide derivative | |
| CN102250134B (en) | Fluorescent probe for identifying fluorine ions and preparation method and use thereof | |
| CN107188876B (en) | It is a kind of for detecting the synthesis and application of the near infrared fluorescent probe of hydrogen polysulfide | |
| Ding et al. | Fluorescence quenching of a rhodamine derivative: selectively sensing Cu2+ in acidic aqueous media | |
| CN103232842B (en) | A kind of fluorescent probe of the sulfurous acid hydrogen radical ion based on aggregation inducing Fluorescence Increasing material and rapid examination test paper | |
| Pang et al. | A highly selective and sensitive coumarin derived fluorescent probe for detecting Hg2+ in 100% aqueous solutions | |
| CN105482812A (en) | Fluorescent probe reagent for concurrent selection and determination of multiple metal ions, and preparation and appliance | |
| CN104193706B (en) | A kind of based on not alkali and the preparation and detecting the application in mercury ion as acceptor molecule of the bilateral west of 1,5-diaminonaphthalene | |
| CN103804369B (en) | A kind of bore hole and ratio fluorescent detect the synthesis containing cryanide ion fluorescent molecular probe and application | |
| Lin et al. | Rational design, green synthesis of reaction-based dual-channel chemosensors for cyanide anion | |
| Teknikel et al. | Colorimetric and fluorometric pH sensor based on bis (methoxycarbonyl) ethenyl functionalized BODIPY | |
| Yan et al. | Synthesis and spectral analysis of fluorescent probes for Ce4+ and OCl− ions based on fluorescein Schiff base with amino or hydrazine structure: application in actual water samples and biological imaging | |
| WO2014115176A4 (en) | A novel aza bodipy compound for the selective detection of nitrite ions in water and a process for preparation thereof | |
| CN107417671A (en) | A kind of coumarin derivative of the substitution containing quinoline and preparation method thereof and the application on Ratio-type pH fluorescence probes | |
| CN103012372A (en) | Naphthalimide derivatives and applications thereof | |
| CN103387830A (en) | Chromium-ion ratio type fluorescence probe as well as preparation method and application thereof | |
| Chen et al. | Regulating donor-acceptor system toward highly efficient dual-state emission for sensitive response of nitroaromatic explosives | |
| Kim et al. | 2-{2-[4-(Dimethylamino) phenyl]-6-methyl-4H-pyran-4-ylidene} malononitrile: a colorimetric and fluorescent chemosensor for low pH values | |
| CN110627756B (en) | Colorimetric-fluorescent probe for detecting hypochlorite and preparation method and application thereof | |
| CN110627737B (en) | Water-soluble benzoxazole fluorescent probe for detecting zinc ions as well as preparation method and application thereof | |
| Li et al. | Two pH-responsive fluorescence probes based on indole derivatives | |
| CN105777758A (en) | Sliver ion fluorescence sensor molecule as well as synthesis and application thereof | |
| CN102627964B (en) | Water-soluble cationic conjugated microporous polymer phosphorescent probe and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151118 Termination date: 20190415 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |