CN104087286A - Polymer pH fluorescent probe PRBH, and preparation method and application thereof - Google Patents
Polymer pH fluorescent probe PRBH, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polymer pH fluorescent probe PRBH, and a preparation method and an application thereof. A structural formula of the polymer pH fluorescent probe PRBH is shown as a formula (1). In the formula (1), x and y represent natural numbers; x is larger than or equal to 1 and smaller than or equal to 10; y is larger than or equal to 100 and smaller than or equal to 600; and z is larger than or equal to 100 and smaller than or equal to 600; and a molecular weight of a structure shown as the formula (1) ranges from 10,000 to 50,000. The polymer pH fluorescent probe PRBH provided by the invention has high applicability to a solvent and good anti-interference property, and is very sensitive to H<+>. A polymer film fluorescent sensor prepared from the polymer pH fluorescent probe PRBH is very sensitive to H<+>, and has the advantages of high applicability and good anti-interference property. Besides, the polymer film fluorescent sensor prevents the problem of non-uniformity, can overcome the phenomenon of non-uniform blending and phase separation in the prior art by controlling swelling property and solubility property of a copolymer in water by adjusting proportions of hydrophobic units to hydrophilic units.
Description
Technical field
The present invention relates to fluorescent probe technique field, relate in particular to a kind of polymer pH fluorescent probe PRBH and preparation method thereof and application.
Background technology
PH fluorescent probe can be used for detection and the research work in the fields such as biology, chemistry, environment, food.More for pH fluorescent probe relevant report at present, but most practicality that lack, wherein the problem of most critical is that solvent suitability is inadequate, and most application need to be carried out in 100% the aqueous solution, and most of pH fluorescent probe need to carry out work in the mixed solvent of organic solvent and water.Secondly, freedom from jamming is inadequate, and existing pH fluorescent probe is under certain condition to H
+have outside selective response, toward contact, some metal ions are had to certain weak reponse, can cause interference like this.These defects have caused the limitation of pH fluorescent probe in application aspect.
In prior art, macromolecule membrane fluorescent optical sensor often adopts embedding mode, by have fluorescence sense function small molecules embedding, be fixed in macromolecular material, but easily there is blend inequality or phenomenon of phase separation in this matrix material, causes the uneven detected result that affects of local material.In order to address this problem, small molecules fluorescent optical sensor is transformed into monomer directly in the present invention and other monomer copolymerizations obtain macromolecular material, it is macromolecule membrane fluorescent optical sensor, not only can avoid uneven problem, can also control swelling property and the solubility property of this macromolecule membrane fluorescent optical sensor in water by hydrophobic in adjusting multipolymer, hydrophilic unit ratio, thereby overcome the uneven phenomenon with being separated of blend in prior art.
Because applying polymer pH fluorescent probe PRBH on plastics counterdie, makes above-mentioned macromolecule membrane fluorescent optical sensor, therefore this macromolecule membrane fluorescent optical sensor is to H
+very responsive, also have advantages of that solvent suitability is strong and freedom from jamming is good.
As to above-mentioned a kind of improvement of preparing the method for macromolecule membrane fluorescent optical sensor, in step a, in above-mentioned mixed solvent, the volume ratio of acetone and sherwood oil is (8～12): 1.The volume ratio of acetone and sherwood oil is very large on the impact of the solubleness of polymer pH fluorescent probe PRBH, no matter the volume ratio of acetone and sherwood oil is to be less than 8:1, is still greater than 12:1, all can cause detrimentally affect to the solubleness of polymer pH fluorescent probe PRBH.
In addition, in the technical scheme of the present invention, all being not specifically noted, all can be by adopting the conventional means in this area realize the technical program.
Therefore, the invention has the beneficial effects as follows a kind of polymer pH fluorescent probe PRBH and preparation method thereof is provided, and adopt this polymer pH fluorescent probe PRBH to prepare macromolecule membrane fluorescent optical sensor; The solvent suitability of this polymer pH fluorescent probe PRBH is strong, and freedom from jamming is good, and to H
+very responsive, this macromolecule membrane fluorescent optical sensor is to H
+very responsive, also have advantages of that solvent suitability is strong and freedom from jamming is good, in addition, this macromolecule membrane fluorescent optical sensor not only can be avoided uneven problem, can also control its swelling property and solubility property in water by hydrophobic in adjusting multipolymer, hydrophilic unit ratio, thereby overcome the uneven phenomenon with being separated of blend in prior art.
Summary of the invention
The technical problem to be solved in the present invention is, for above-mentioned defects such as in prior art, pH fluorescent probe solvent suitability are inadequate, freedom from jamming is poor, provides that a kind of solvent suitability is strong, freedom from jamming good and to H
+highstrung polymer pH fluorescent probe PRBH, in addition, also provides preparation method and the application of this polymer pH fluorescent probe PRBH.
The technical solution adopted for the present invention to solve the technical problems is as follows:
A polymer pH fluorescent probe PRBH, is characterized in that, its structural formula is suc as formula shown in (1):
In formula (1), x and y are natural number, wherein, 1≤x≤10,100≤y≤300,100≤z≤600, and the span of the molecular weight of structure shown in formula (1) is (10000,50000).
In technical scheme of the present invention, the direct and electrophilic acryl of N atom in the polymer pH fluorescent probe PRBH of structure shown in above formula (1) on rhodamine volution is connected, and it is to H
+very responsive; When this polymer pH fluorescent probe PRBH molecule runs into H
+time, its bottom lactam nucleus is opened, and this polymer pH fluorescent probe PRBH molecule is by becoming hyperfluorescenceZeng Yongminggaoyingguang state without fluorescence state, and the required time of response is very short, in 10 seconds.
Because introduced electron-withdrawing group on polymer pH fluorescent probe PRBH rhodamine volution of the present invention, make the polarity of described polymer pH fluorescent probe PRBH molecule become large again, greatly promoted thus the solvent suitability of this polymer pH fluorescent probe PRBH.
In metal ion, this polymer pH fluorescent probe PRBH is only to Cu
2+more responsive, but it is to Cu
2+time of response longer, starting time approximately need be in about 4h, therefore Cu at short notice
2+can not this polymer pH fluorescent probe PRBH be produced and be disturbed, therefore polymer pH fluorescent probe PRBH of the present invention has good freedom from jamming.
The present invention also provides the preparation method of above-mentioned polymer pH fluorescent probe PRBH, and the synthetic route of this polymer pH fluorescent probe PRBH is as follows:
The present invention also provides the preparation method of polymer pH fluorescent probe PRBH according to said synthesis route, and this preparation method comprises following processing step:
(1) Mrh preparation;
(2) reactants dissolved: the Mrh0.255～0.345g that adds Hydroxyethyl acrylate 1.7～2.3g, n-butyl acrylate 1.02～1.38g, Diisopropyl azodicarboxylate 0.04～0.06g and prepared by step (1) in 25.5～34.5ml pimelinketone, stirs and makes above-mentioned reactants dissolved completely and obtain reactants dissolved liquid;
(3) building-up reactions: the reactants dissolved liquid being prepared by step (2) is placed in to protection of inert gas and reacts 5.6～10.4h at 76～84 ℃;
(4) product precipitating: after building-up reactions in step (3) is complete, the solution after building-up reactions is slowly poured in 200～600ml ethanol, be settled out incarnadine solid matter;
(5) product extracts: collect the incarnadine solid matter being settled out by step (4), after this incarnadine solid matter is extracted, is dried, obtain polymer pH fluorescent probe PRBH.
In the preparation method of above-mentioned polymer pH fluorescent probe PRBH, Diisopropyl azodicarboxylate is initiator, and this decomposition of initiator is even, only forms a kind of free radical in reaction process, without other side reaction, the quality and performance of this polymer pH fluorescent probe PRBH is had no adverse effects; In addition, the building-up reactions of above-mentioned polymer pH fluorescent probe PRBH requires very high to the consumption of Diisopropyl azodicarboxylate, under the condition of Hydroxyethyl acrylate 1.7～2.3g, n-butyl acrylate 1.02～1.38g and Mrh0.255～0.345g, if the consumption of Diisopropyl azodicarboxylate surpasses 0.06g, speed of response is too fast, be difficult to control whole reaction, if the consumption of Diisopropyl azodicarboxylate is lower than 0.04g, be difficult for causing this building-up reactions, building-up reactions can not normally be carried out, affect the performance of polymer P RBH.
In above-mentioned steps (3), the building-up reactions of reactants dissolved liquid under protection of inert gas is all higher to the requirement of temperature of reaction and time, if temperature is lower than 76 ℃ during reaction, the speed of this building-up reactions can be affected, and can cause reaction not exclusively; If when reaction, temperature surpassed 84 ℃, can hinder carrying out smoothly of this building-up reactions, and may also can cause some other side reaction, affect the purity of product; If the reaction times is less than 5.6h, can cause reaction not thorough, if the reaction times surpasses 10.4h, not only can cause the unnecessary waste of production time, more seriously may cause the generation of side reaction.
In above-mentioned steps (4), the solution after building-up reactions is slowly poured in 200～600ml ethanol, be settled out incarnadine solid matter, in this step, ethanol is precipitating agent, for precipitating the macromolecule product of solution after building-up reactions, i.e. polymer pH fluorescent probe PRBH.
In above-mentioned steps (5), adopt ethanol to carry out soxhlet extraction to incarnadine solid matter, and the time of soxhlet extraction is 8.4～15.6h, soxhlet extraction is good to the selectivity of polymer pH fluorescent probe PRBH, is conducive to improve the extraction purity of polymer pH fluorescent probe PRBH, and it is low to carry out soxhlet extraction power consumption, operating time is short, and solvent load is few, and it is simple to carry out the equipment of soxhlet extraction, easy and simple to handle, facilitated polymer pH fluorescent probe PRBH to extract carrying out smoothly of work.
In the preparation method of above-mentioned polymer pH fluorescent probe PRBH, the synthetic route of Mrh is as follows:
Preparation according to the Mrh of said synthesis route comprises the steps:
Steps A: adopt rhodamine B to prepare rhodamine B hydrazides;
Step B: add rhodamine B hydrazides that 2.28g obtains by steps A and the tetrahydrofuran (THF) of 3.6-4.4ml in reaction vessels, grind and be cooled to 0 ℃ after 4-8min and obtain rhodamine B hydrazides suspension;
Step C: 0.45-0.55ml acrylate chloride is dissolved in and obtains acrylate chloride suspension in 1.8-2.2ml tetrahydrofuran (THF);
Step D: the acrylate chloride suspension being prepared by step C is joined in the rhodamine B hydrazides suspension being prepared by step B and react 5-8h generation precipitation, this precipitation is Mrh;
Step e: after Mrh generates, the reaction suspension in filtration step D obtains Mrh, and this Mrh surface is cleaned to filtrate and become colorless, satisfactory Mrh obtained.
In the preparation process of above-mentioned Mrh, in step B and step C, all adopt tetrahydrofuran (THF) as the dispersion agent of rhodamine B hydrazides and acrylate chloride, to prepare rhodamine B hydrazides suspension and acrylate chloride suspension respectively, reduce rhodamine B hydrazides and acrylate chloride and completed required time of dispersion process and energy, can prevent sedimentation and the cohesion of solids in suspension particle, contribute to rhodamine B hydrazides suspension and acrylate chloride suspension to carry out next step reaction.
In above-mentioned steps B, adopt tetrahydrofuran (THF) to disperse to form stable rhodamine B hydrazides suspension to 2.28g rhodamine B hydrazides, now the consumption of tetrahydrofuran (THF) is had to requirement, if the consumption of tetrahydrofuran (THF) is less than 3.6ml, can cause rhodamine B hydrazides to disperse not thorough, in the rhodamine B hydrazides suspension that may cause forming, there is the solid particulate not disperseing, be unfavorable for follow-up reaction; If the consumption of tetrahydrofuran (THF) is greater than 4.4ml, can cause material wastage, affect preparation cost.
In addition, in reaction vessels, add after rhodamine B hydrazides and tetrahydrofuran (THF), need to grind, to strengthen the dispersion effect of tetrahydrofuran (THF); In rhodamine B hydrazides suspension preparation process and process of lapping, can produce heat, for preventing that this heat from producing detrimentally affect to subsequent reactions, need after grinding 4-8min, mixed solution be cooled to 0 ℃.
In step C, also adopt tetrahydrofuran (THF) to disperse 0.45-0.55ml acrylate chloride, same as above, now the consumption of tetrahydrofuran (THF) is had to requirement, if the consumption of tetrahydrofuran (THF) is less than 1.8ml, can cause acrylate chloride to disperse not thorough, in the acrylate chloride suspension that may cause forming, have the solid particulate not disperseing, be unfavorable for follow-up reaction; If the consumption of tetrahydrofuran (THF) is greater than 2.2ml, can cause material wastage, be unfavorable for minimizing of cost.
In step D, the acrylate chloride suspension preparing is joined in rhodamine B hydrazides suspension and reacted, now also there is to requirement in the reaction times, when the reaction times is during lower than 5h, can cause reaction not thorough, the one, affected the productive rate of Mrh, the 2nd, the rhodamine B hydrazides and the acrylate chloride that remain in reaction solution can exert an influence to the purity of Mrh, and then can have influence on solvent suitability and the interference free performance of Mrh.When the reaction times surpasses 8h, can cause the meaningless prolongation in reaction times, be unfavorable for the saving in reaction times.
As a kind of improvement to the preparation of above-mentioned Mrh, in above-mentioned steps E, adopt tetrahydrofuran (THF) that Mrh surface is cleaned to filtrate and become colorless.The precipitation surface being generated by step e remains red liquid, in order to wash this red liquid, therefore adopt tetrahydrofuran (THF) that Mrh surface is cleaned to filtrate and become colorless.
In addition, the present invention also provides and has adopted above-mentioned polymer pH fluorescent probe PRBH to prepare the method for macromolecule membrane fluorescent optical sensor, comprises following processing step:
Step a: above-mentioned polymer pH fluorescent probe PRBH being dissolved in and forming mass concentration in the mixed solvent of acetone and sherwood oil is 10% coating liquid;
Step b: the coating liquid being prepared by step a is spin-coated on plastics counterdie, obtains macromolecule membrane fluorescent optical sensor after liquid to be coated is dry on plastics counterdie.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the nuclear magnetic resonance hydrogen spectruming determining result of polymer pH fluorescent probe PRBH of the present invention;
Fig. 2 is that macromolecule membrane fluorescent optical sensor of the present invention immerses the fluorescence color intensity level after 5 minutes in the different pH aqueous solution, and wherein, excitaton source wavelength is 256nm.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment mono-:
A polymer pH fluorescent probe PRBH, its structural formula is suc as formula shown in (1):
In formula (1), x and y are natural number, wherein, 1≤x≤10,100≤y≤300,100≤z≤600, shown in formula (1), the span of the molecular weight of structure is (10000,50000), and the number-average molecular weight of structure shown in formula (1) is 34600, and molecular weight distributing index is 2.5.
By uv-absorbing analysis and GPC data, record, in the polymer pH fluorescent probe PRBH in formula (1), x=5, y=152, z=108.
The synthetic route of above-mentioned polymer pH fluorescent probe PRBH is as follows:
According to said synthesis route, the preparation method of this polymer pH fluorescent probe PRBH comprises following processing step:
(1) Mrh preparation;
The synthetic route of this Mrh is as follows:
And according to this synthetic route, the preparation of this Mrh comprises the steps:
Steps A: adopt rhodamine B to prepare rhodamine B hydrazides;
Step B: add rhodamine B hydrazides that 2.28g obtains by steps A and the tetrahydrofuran (THF) of 3.6ml in reaction vessels, grind and be cooled to 0 ℃ after 8min and obtain rhodamine B hydrazides suspension;
Step C: 0.45ml acrylate chloride is dissolved in and obtains acrylate chloride suspension in 1.8ml tetrahydrofuran (THF);
Step D: the acrylate chloride suspension being prepared by step C is joined in the rhodamine B hydrazides suspension being prepared by step B and react 5h generation precipitation, this precipitation is Mrh;
Step e: after Mrh generates, the reaction suspension in filtration step D obtains Mrh, and adopt tetrahydrofuran (THF) that this Mrh surface is cleaned to filtrate and become colorless, obtain satisfactory Mrh;
(2) reactants dissolved: the Mrh0.255g that adds Hydroxyethyl acrylate 1.7g, n-butyl acrylate 1.02g, Diisopropyl azodicarboxylate 0.04g and prepared by step (1) in 25.5ml pimelinketone, stirs and makes above-mentioned reactants dissolved completely and obtain reactants dissolved liquid;
(3) building-up reactions: the reactants dissolved liquid being prepared by step (2) is placed in to protection of inert gas and reacts 10.4h at 76 ℃;
(4) product precipitating: after building-up reactions in step (3) is complete, the solution after building-up reactions is slowly poured in 200ml ethanol, be settled out incarnadine solid matter;
(5) product extracts: collect the incarnadine solid matter being settled out by step (4), this incarnadine solid matter is carried out to Soxhlet and extract 8.4h, after being dried, obtain polymer pH fluorescent probe PRBH.
In addition, the present embodiment also provides a kind of macromolecule membrane fluorescent optical sensor, adopts above-mentioned polymer pH fluorescent probe PRBH to prepare this macromolecule membrane fluorescent optical sensor and comprises following processing step:
Step a: above-mentioned polymer pH fluorescent probe PRBH being dissolved in and forming mass concentration in the mixed solvent of acetone and sherwood oil is 10% coating liquid, and in this mixed solvent, the volume ratio of acetone and sherwood oil is 8:1;
Step b: the coating liquid being prepared by step a is spin-coated on plastics counterdie, obtains above-mentioned macromolecule membrane fluorescent optical sensor after liquid to be coated is dry on plastics counterdie.
Embodiment bis-:
The present embodiment and embodiment mono-are basic identical, and the difference of the two is the preparation method's of above-mentioned polymer pH fluorescent probe PRBH and macromolecule membrane fluorescent optical sensor difference, specific as follows:
The preparation method of above-mentioned polymer pH fluorescent probe PRBH comprises following processing step:
(1) Mrh preparation;
According to said synthesis route, the preparation of this Mrh comprises the steps:
Steps A: adopt rhodamine B to prepare rhodamine B hydrazides;
Step B: add rhodamine B hydrazides that 2.28g obtains by steps A and the tetrahydrofuran (THF) of 4ml in reaction vessels, grind and be cooled to 0 ℃ after 5min and obtain rhodamine B hydrazides suspension;
Step C: 0.5ml acrylate chloride is dissolved in and obtains acrylate chloride suspension in 2ml tetrahydrofuran (THF);
Step D: the acrylate chloride suspension being prepared by step C is joined in the rhodamine B hydrazides suspension being prepared by step B and react 6h generation precipitation, this precipitation is Mrh;
Step e: after Mrh generates, the reaction suspension in filtration step D obtains Mrh, and adopt tetrahydrofuran (THF) that this Mrh surface is cleaned to filtrate and become colorless, obtain satisfactory Mrh;
(2) reactants dissolved: the Mrh0.3g that adds Hydroxyethyl acrylate 2g, n-butyl acrylate 1.2g, Diisopropyl azodicarboxylate 0.05g and prepared by step (1) in 30ml pimelinketone, stirs and makes above-mentioned reactants dissolved completely and obtain reactants dissolved liquid;
(3) building-up reactions: the reactants dissolved liquid being prepared by step (2) is placed in to protection of inert gas and reacts 8h at 80 ℃;
(4) product precipitating: after building-up reactions in step (3) is complete, the solution after building-up reactions is slowly poured in 400ml ethanol, be settled out incarnadine solid matter;
(5) product extracts: collect the incarnadine solid matter being settled out by step (4), this incarnadine solid matter is carried out to Soxhlet and extract 12h, after being dried, obtain polymer pH fluorescent probe PRBH.
The preparation of above-mentioned macromolecule membrane fluorescent optical sensor comprises following processing step:
Step a: above-mentioned polymer pH fluorescent probe PRBH being dissolved in and forming mass concentration in the mixed solvent of acetone and sherwood oil is 10% coating liquid, and in this mixed solvent, the volume ratio of acetone and sherwood oil is 10:1;
Step b: the coating liquid being prepared by step a is spin-coated on plastics counterdie, obtains above-mentioned macromolecule membrane fluorescent optical sensor after liquid to be coated is dry on plastics counterdie.
Embodiment tri-:
The present embodiment and embodiment mono-are basic identical, and the difference of the two is the preparation method's of above-mentioned polymer pH fluorescent probe PRBH and macromolecule membrane fluorescent optical sensor difference, specific as follows:
The preparation method of above-mentioned polymer pH fluorescent probe PRBH comprises following processing step:
(1) Mrh preparation;
According to said synthesis route, the preparation of this Mrh comprises the steps:
Steps A: adopt rhodamine B to prepare rhodamine B hydrazides;
Step B: add rhodamine B hydrazides that 2.28g obtains by steps A and the tetrahydrofuran (THF) of 4.4ml in reaction vessels, grind and be cooled to 0 ℃ after 4min and obtain rhodamine B hydrazides suspension;
Step C: 0.55ml acrylate chloride is dissolved in and obtains acrylate chloride suspension in 2.2ml tetrahydrofuran (THF);
Step D: the acrylate chloride suspension being prepared by step C is joined in the rhodamine B hydrazides suspension being prepared by step B and react 8h generation precipitation, this precipitation is Mrh;
Step e: after Mrh generates, the reaction suspension in filtration step D obtains Mrh, and adopt tetrahydrofuran (THF) that this Mrh surface is cleaned to filtrate and become colorless, obtain satisfactory Mrh;
(2) reactants dissolved: the Mrh0.345g that adds Hydroxyethyl acrylate 2.3g, n-butyl acrylate 1.38g, Diisopropyl azodicarboxylate 0.06g and prepared by step (1) in 34.5ml pimelinketone, stirs and makes above-mentioned reactants dissolved completely and obtain reactants dissolved liquid;
(3) building-up reactions: the reactants dissolved liquid being prepared by step (2) is placed in to protection of inert gas and reacts 5.6h at 84 ℃;
(4) product precipitating: after building-up reactions in step (3) is complete, the solution after building-up reactions is slowly poured in 600ml ethanol, be settled out incarnadine solid matter;
(5) product extracts: collect the incarnadine solid matter being settled out by step (4), this incarnadine solid matter is carried out to Soxhlet and extract 15.6h, after being dried, obtain polymer pH fluorescent probe PRBH.
The preparation of above-mentioned macromolecule membrane fluorescent optical sensor comprises following processing step:
Step a: above-mentioned polymer pH fluorescent probe PRBH being dissolved in and forming mass concentration in the mixed solvent of acetone and sherwood oil is 10% coating liquid, and in this mixed solvent, the volume ratio of acetone and sherwood oil is 12:1;
Step b: the coating liquid being prepared by step a is spin-coated on plastics counterdie, obtains above-mentioned macromolecule membrane fluorescent optical sensor after liquid to be coated is dry on plastics counterdie.
Whether identical with above-mentioned formula (1) in order to verify the structure of the polymer pH fluorescent probe PRBH that embodiment mono-to embodiment tri-obtains, the polymer pH fluorescent probe PRBH that applicant obtains embodiment mono-to embodiment tri-has carried out nuclear magnetic resonance hydrogen spectruming determining, and concrete outcome is shown in shown in accompanying drawing 1.
Nuclear magnetic data in 1 is known with reference to the accompanying drawings, and the structure of the polymer pH fluorescent probe PRBH that embodiment mono-to embodiment tri-obtains is identical with the structure of embodiment in above-mentioned formula (1).
In addition, in order to detect macromolecule membrane fluorescent optical sensor that embodiment mono-to embodiment tri-obtains to H
+sensitivity and response interval, applicant soaks this macromolecule membrane fluorescent optical sensor in the different pH aqueous solution, excitaton source wavelength is 256nm, from accompanying drawing 2, this macromolecule membrane fluorescent optical sensor is to H
+response sensitivity very high, and to H
+response interval be 6-8, therefore the macromolecule membrane fluorescent optical sensor being obtained by embodiment mono-to embodiment tri-can be used as pH, be the meticulous pH fluorescent probe in 6-8 region.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (8)
1. a polymer pH fluorescent probe PRBH, is characterized in that, its structural formula is suc as formula shown in (1):
In formula (1), x and y are natural number, wherein, 1≤x≤10,100≤y≤300,100≤z≤600, and the span of the molecular weight of structure shown in formula (1) is (10000,50000).
2. a preparation method of polymer pH fluorescent probe PRBH claimed in claim 1, is characterized in that, the synthetic route of described polymer pH fluorescent probe PRBH is as follows:
3. the preparation method of polymer pH fluorescent probe PRBH according to claim 2, is characterized in that, comprises following processing step:
(1) Mrh preparation;
(2) reactants dissolved: the Mrh0.255～0.345g that adds Hydroxyethyl acrylate 1.7～2.3g, n-butyl acrylate 1.02～1.38g, Diisopropyl azodicarboxylate 0.04～0.06g and prepared by step (1) in 25.5～34.5ml pimelinketone, stirs and makes above-mentioned reactants dissolved completely and obtain reactants dissolved liquid;
(3) building-up reactions: the reactants dissolved liquid being prepared by step (2) is placed in to protection of inert gas and reacts 5.6～10.4h at 76～84 ℃;
(4) product precipitating: after building-up reactions in step (3) is complete, the solution after building-up reactions is slowly poured in 200～600ml ethanol, be settled out incarnadine solid matter;
(5) product extracts: collect the incarnadine solid matter being settled out by step (4), after described incarnadine solid matter is extracted, is dried, obtain described polymer pH fluorescent probe PRBH.
4. the preparation method of polymer pH fluorescent probe PRBH according to claim 3, is characterized in that, the synthetic route of described Mrh is as follows:
5. according to the preparation method of the polymer pH fluorescent probe PRBH described in claim 3 or 4, it is characterized in that, described Mrh preparation comprises the steps:
Steps A: adopt rhodamine B to prepare rhodamine B hydrazides;
Step B: add rhodamine B hydrazides that 2.28g obtains by steps A and the tetrahydrofuran (THF) of 3.6-4.4ml in reaction vessels, grind and be cooled to 0 ℃ after 4-8min and obtain rhodamine B hydrazides suspension;
Step C: 0.45-0.55ml acrylate chloride is dissolved in and obtains acrylate chloride suspension in 1.8-2.2ml tetrahydrofuran (THF);
Step D: the acrylate chloride suspension being prepared by step C is joined in the rhodamine B hydrazides suspension being prepared by step B and react 5-8h generation precipitation, described precipitation is Mrh;
Step e: after Mrh generates, the reaction suspension in filtration step D obtains described Mrh, and described Mrh surface is cleaned to filtrate and become colorless, satisfactory Mrh obtained.
6. the preparation method of polymer pH fluorescent probe PRBH according to claim 5, is characterized in that, in described step e, adopts tetrahydrofuran (THF) that described Mrh surface is cleaned to filtrate and become colorless.
7. adopt polymer pH fluorescent probe PRBH claimed in claim 1 to prepare a method for macromolecule membrane fluorescent optical sensor, it is characterized in that, comprise following processing step:
Step a: described polymer pH fluorescent probe PRBH being dissolved in and forming mass concentration in the mixed solvent of acetone and sherwood oil is 10% coating liquid;
Step b: the coating liquid being prepared by step a is spin-coated on plastics counterdie, obtains described macromolecule membrane fluorescent optical sensor after liquid to be coated is dry on plastics counterdie.
8. the method for preparing macromolecule membrane fluorescent optical sensor according to claim 7, is characterized in that, in step a, in described mixed solvent, the volume ratio of acetone and sherwood oil is (8～12): 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877669A (en) * | 2015-04-14 | 2015-09-02 | 温州生物材料与工程研究所 | Compound fluorescent micro-nano system and preparation method thereof based on one-pot process |
| CN106046246A (en) * | 2016-05-23 | 2016-10-26 | 苏州益可泰电子材料有限公司 | Heavy metal detection sensing material, and preparation method and application thereof |
| CN110229294A (en) * | 2019-06-19 | 2019-09-13 | 山东科建检测服务有限公司 | A kind of pH fluorescence chemical sensor and its synthetic method and application based on temperature sensitive type double-hydrophilic block polymer |
| CN110483682A (en) * | 2019-08-28 | 2019-11-22 | 济南大学 | Detect the high molecular fluorescent probe and the preparation method and application thereof of viscosity |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418215A (en) * | 2008-12-15 | 2009-04-29 | 苏州大学 | High molecule fluorescent detecting probe containing rhodamine gene and synthetic method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101418215A (en) * | 2008-12-15 | 2009-04-29 | 苏州大学 | High molecule fluorescent detecting probe containing rhodamine gene and synthetic method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877669A (en) * | 2015-04-14 | 2015-09-02 | 温州生物材料与工程研究所 | Compound fluorescent micro-nano system and preparation method thereof based on one-pot process |
| CN106046246A (en) * | 2016-05-23 | 2016-10-26 | 苏州益可泰电子材料有限公司 | Heavy metal detection sensing material, and preparation method and application thereof |
| CN110229294A (en) * | 2019-06-19 | 2019-09-13 | 山东科建检测服务有限公司 | A kind of pH fluorescence chemical sensor and its synthetic method and application based on temperature sensitive type double-hydrophilic block polymer |
| CN110229294B (en) * | 2019-06-19 | 2022-04-12 | 山东科建检测服务有限公司 | pH fluorescence chemical sensor based on temperature-sensitive type amphiphilic block polymer and synthesis method and application thereof |
| CN110483682A (en) * | 2019-08-28 | 2019-11-22 | 济南大学 | Detect the high molecular fluorescent probe and the preparation method and application thereof of viscosity |
| CN110483682B (en) * | 2019-08-28 | 2021-03-16 | 济南大学 | Polymer fluorescent probe for detecting viscosity and preparation method and application thereof |
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