CN103833944A - Amphiphilic polymer nano particle for detecting mercury ion and preparation method and application thereof - Google Patents
Amphiphilic polymer nano particle for detecting mercury ion and preparation method and application thereof Download PDFInfo
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- CN103833944A CN103833944A CN201410061992.9A CN201410061992A CN103833944A CN 103833944 A CN103833944 A CN 103833944A CN 201410061992 A CN201410061992 A CN 201410061992A CN 103833944 A CN103833944 A CN 103833944A
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Abstract
The invention discloses an amphiphilic polymer nano particle for detecting mercury ions and a preparation method and an application of the amphiphilic polymer nano particle. The amphiphilic polymer nano particle is prepared by reprecipitating a prepared amphipathy rhodamine B grafted copolymer into water by using a simple reprecipitation method under an ultrasonic condition. The prepared amphipathy rhodamine B grafted copolymer is prepared by grafting ethidene diamine sulfo-lactam rhodamine B into an amphiphilic polymer polyoxyethylene-b-poly(styrene-co-p-chlorine alpha-methylstyrene) through methylation. The amphiphilic polymer nano particle has good dispersity and small size in water, and can achieve fluorescence and colorimetric change detection on mercury ions in water with high sensitivity and high selectivity. Compared with the prior art, the amphiphilic polymer nano particle can achieve rapid detection on micro mercury ions in a pure water medium, is simple in synthesis route, convenient to use and small in use amount, is applicable to amplification synthesis and practical production application, and has a wide application prospect in the field of biologic and environment detection.
Description
Technical field
The present invention relates to material preparation and biological and environment ion detection technique field, specifically, relate to amphipathic nature polyalcohol nanoparticle having fluorescence and colorimetric variation detection mercury ion function and preparation method thereof, and this amphipathic nature polyalcohol nanoparticle application to mercury ion detecting in water.
Background technology
Mercury is a kind of heavy metal element of severe toxicity, is extensively present in environment, is distributed in each corner, the whole world.Hg simple substance and Hg
2+entering after environment, can be converted into methyl mercury by water microorganisms, it is enrichment in vivo, and be finally absorbed by the body through food chain, arrive after human body, can destroy people's central nervous system, make people produce serious feeling sick, vomit, suffer from abdominal pain, and bring severe renal functional lesion, cause tremendous influence to people's health.Therefore, for residual detection, the monitoring of food safety etc. of mercury ion in the selectivity rapid detection of mercury ion especially environmental pollutant, for environmental science, medical science and biological study have extremely important effect.
Current, detecting the common method of mercury ion has atomic absorption/emission spectrometry, dithizone colorimetry, inductively coupled plasma mass spectrometry method and electrochemical method.But these method costs are higher, testing process is cumbersome, and needs more complicated plant and instrument.Therefore, invention is directly simple, and the detection technique of high efficiency, low cost has very important realistic meaning and application prospect undoubtedly.In recent years, change to detect the chemical sensor method of metal ion by fluorescence or colorimetric because there is simple and quick, highly sensitive, highly selective, do not destroy sample and the advantage such as can identify in water, receive increasing concern, become the focus in ion detection and Study of recognition.The chemical sensor based on mercury ion of having reported at present concentrates on organic molecule field mostly.But most small molecules sensors do not possess water-soluble, be unfavorable for the metal ion detection application in water and coenocorrelation; And possess water miscible small molecules sensor, in water, quantum yield is lower mostly, and therefore detection sensitivity is not high; In addition, organic molecule system often has bio-toxicity, and easily produces self aggregation and cause detection system unstable.Therefore, developing a kind of can simple, the highly sensitive sensor of rapid detection mercury ion be a huge challenge in water.
The present invention adopts quadrol thio lactam rhodamine B is grafted to and on amphipathic multipolymer, forms amphipathic rhodamine B graft copolymer, then its redeposition is formed to amphipathic nature polyalcohol nanoparticle mercury ion to measuring ability in water.That the amphipathic nature polyalcohol nanoparticle of preparing for the method has is synthetic convenient, Stability Analysis of Structures, particle diameter are little, need not use the features such as other tensio-active agent and dispersion agent.Produce specific complexing action by the probe group on mercury ion and nanoparticle, the spirane structure of induction probe group is opened, thereby there is color reaction and produce fluorescent signal, can realize the highly sensitive to mercury ion in water and the rapid detection of highly selective.
Summary of the invention
The object of the present invention is to provide a kind of amphipathic nature polyalcohol nanoparticle, preparation method and application thereof with mercury ion detecting function.The strategy that it adopts functional polymer crosslinking technology to combine with redeposition method, obtain the amphipathic fluorescent polymer nanoparticle that particle dia is about 20nm, further application shows, this amphipathic nature polyalcohol nanoparticle can be realized highly sensitive, the highly selective measuring ability to mercury ion in water.
For achieving the above object, technical scheme of the present invention is: a kind of amphipathic nature polyalcohol nanoparticle with mercury ion detecting function, be prepared from water by amphipathic rhodamine B graft copolymer redeposition under ultrasonic condition, the structural formula of described amphipathic rhodamine B graft copolymer is:
In formula, a/b/x is 16:8:1 ~ 7:3.5:1.
Its preparation method comprises: the tetrahydrofuran solution of amphipathic rhodamine B graft copolymer is joined fast just in ultrasonic water, after ultrasonic 10 minutes, again the tetrahydrofuran (THF) in solution is removed by the method for normal temperature rotary evaporation, constant volume obtains required amphipathic nature polyalcohol nano-particle solution, and particle dia is about 20nm.
The synthetic route of described amphipathic rhodamine B graft copolymer is:
The preparation method of described amphipathic rhodamine B graft copolymer comprises the following steps:
(1) solvent dimethyl formamide, polyoxyethylene macromolecular chain transfering reagent, vinylbenzene, p-chloromethyl styrene and Diisopropyl azodicarboxylate are placed in to reaction flask, inflated with nitrogen at low temperatures-vacuumize three times repeatedly, sealing, the lower reaction of oil bath 90 degree 4 hours, product precipitates in sherwood oil and ether mixed solvent, then dissolves with methylene dichloride, in triplicate, remove unreacted monomer and small molecular weight impurity, vacuum-drying, obtain amphipathic multipolymer polyoxyethylene-
b-poly-(vinylbenzene-
co-p-chloromethyl styrene), its structural formula is as follows:
In formula, a/b/x is 16:8:1 ~ 7:3.5:1,
The structural formula of described polyoxyethylene macromolecular chain transfering reagent is as follows:
In formula, a is 112;
(2) will contain amphipathic multipolymer polyoxyethylene-
b-poly-(vinylbenzene-
co-p-chloromethyl styrene) tetrahydrofuran solution join in the tetrahydrofuran solution that contains quadrol thio lactam rhodamine B and diisopropylethylamine; under nitrogen protection, under room temperature, lucifuge is reacted 24 hours; product precipitates in the mixed solvent of sherwood oil, ether and ethanol; dissolve with tetrahydrofuran (THF) again; in triplicate; remove unreacted quadrol thio lactam rhodamine B and other small molecular weight impurity, vacuum-drying, obtains amphipathic rhodamine B graft copolymer.
In step (1), the mol ratio of polyoxyethylene macromolecular chain transfering reagent, hydrophobic monomer, p-chloromethyl styrene and Diisopropyl azodicarboxylate is 3.5:1400:140:1 ~ 3.5:1400:420:1.
In step (1), the volume proportion of described sherwood oil and ether mixed solvent is: sherwood oil: ether=1:1.
In step (2), wherein amphipathic multipolymer polyoxyethylene-
b-poly-(vinylbenzene-
co-p-chloromethyl styrene), the mol ratio of quadrol thio lactam rhodamine B and diisopropylethylamine is 1:20:60.
In step (2), the volume proportion of the mixed solvent of sherwood oil, ether and ethanol is: sherwood oil: ether: ethanol=5:5:1.
In step (2), the preparation method of described quadrol thio lactam rhodamine B is: under the condition of lucifuge, 3.0g rhodamine B is dissolved in 130ml methyl alcohol, at N
2under protection, add fast 7.5g quadrol, be warming up to 85
oc reaction 24 hours.Then rotary evaporation is removed most of methyl alcohol, in large water gaging, precipitates, and filters, and throw out vacuum-drying obtains incarnadine powder, is quadrol lactamize rhodamine B; 1.0g quadrol lactamize rhodamine B and 1.6g lawesson reagent are dissolved in the refining toluene of 250ml, at N
2under protection, be warming up to backflow, react 6 hours, then remove solvent, sherwood oil and the ethyl acetate mixed solvent of mixture take volume ratio as 3:1 is developping agent, the quadrol thio lactam rhodamine B that utilizes column chromatography to separate requiredly.
Amphipathic nature polyalcohol nanoparticle provided by the present invention can be used for the detection of water mercury ion, its method is generally that this amphipathic nature polyalcohol nanoparticle is mixed with to certain density aqueous dispersions, controlling pH value is 6 ~ 8, can detect the mercury ion in water by the variation that detects its Absorption and fluorescence.Concentration can determine according to test condition and Change of absorption degree, and for amphipathic nature polyalcohol nanoparticle of the present invention, can be made into polymer concentration is 0.1g/L ~ 0.5g/L, and conventional testing method is 0.2g/L ~ 0.4g/L.The detection of mercury ion is to realize by detecting the variation of described dispersion liquid Absorption and fluorescence with identification.Concrete test can adopt absorption or fluorescent emission working curve to detect existence and the change in concentration of mercury ion.
The present invention adopts rhodamine B derivative is grafted on amphipathic multipolymer, and then redeposition under ultrasonic condition detects the required amphipathic nature polyalcohol nanoparticle of mercury ion to form.In water, produce specific complexing action by the sulfuration rhodamine group on mercury ion and particle, the spirane structure of induction probe group is opened, nanoparticle generation color reaction and fluorescence intensity are strengthened gradually, thereby realize the highly sensitive to mercury ion in water, identification and the detection of highly selective.Compared with prior art, amphipathic nature polyalcohol nanoparticle synthetic route in the present invention is simple, convenient post-treatment, Stability Analysis of Structures, particle diameter compared with little, consumption is few, can directly carry out highly sensitive and specific recognition, be applicable to amplifying and synthesize and production application the mercury ion in water.
Accompanying drawing explanation
Fig. 1 is the size distribution figure that amphipathic nature polyalcohol nanoparticle laser particle size analyzer records.
Fig. 2 is the variation diagram that adds the absorption spectrum of different concns mercury ion in the prepared amphipathic nature polyalcohol nanoparticle of the embodiment aqueous solution (0.4g/L).Ion concentration of mercury is by 0 ~ 2.4 × 10
-4mol/L.
Fig. 3 is the variation diagram that adds the fluorescence emission spectrum of different concns mercury ion in the prepared amphipathic nature polyalcohol nanoparticle of the embodiment aqueous solution (0.4g/L).Excitation wavelength is 520nm, and ion concentration of mercury is by 0 ~ 2.4 × 10
-4mol/L.
Fig. 4 adds various positively charged ions (concentration is 4 × 10 in the prepared amphipathic nature polyalcohol nanoparticle of the embodiment aqueous solution (0.4g/L)
-5the variation diagram of fluorescence emission spectrum mol/L).Excitation wavelength is 520nm.
Fig. 5 adds mercury ion simultaneously (concentration is 4 × 10 with other positively charged ion in the prepared amphipathic nature polyalcohol nanoparticle of the embodiment aqueous solution (0.4g/L)
-5mol/L) fluorescence intensity comparison diagram.(wherein excitation wavelength is 520nm, and emission wavelength is 594nm, 0=Hg
2+; 1=Hg
2++ Cu
2+; 2=Hg
2++ Ca
2+; 3=Hg
2++ Mg
2+; 4=Hg
2++ Co
2+; 5=Hg
2++ Ni
2+; 6=Hg
2++ Zn
2+; 7=Hg
2++ Fe
2+; 8=Hg
2++ Pb
2+; 9=Hg
2++ Mn
2+; 10=Hg
2++ K
+; 11=Hg
2++ Na
+).
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail, but the present invention is not limited thereto.
Embodiment 1:
(1) amphipathic multipolymer polyoxyethylene-
b-poly-(vinylbenzene-
co-p-chloromethyl styrene) [referred to as PEO-b-P (St-co-VBC)] synthetic: by 0.50g(0.1mmol) polyoxyethylene macromolecular chain transfering reagent, 4.16g(40mmol) vinylbenzene, 1.22g(2mmol) p-chloromethyl styrene and 4.69mg(0.028mmol) Diisopropyl azodicarboxylate (AIBN) and 5ml dimethyl formamide DMF be placed in reaction flask, inflated with nitrogen at low temperatures-vacuumize three times repeatedly, sealing, the lower reaction of oil bath 90 degree 4 hours.Product precipitates in the mixed solvent that sherwood oil and ether volume ratio are 1:1, then dissolves with methylene dichloride, in triplicate, removes unreacted monomer and small molecular weight impurity, and vacuum-drying, obtains required product.
(2) amphipathic rhodamine B graft copolymer is synthetic: the amphipathic copolymer p EO-b-P (St-co-VBC) of the above-mentioned preparation of 200mg is dissolved in after the tetrahydrofuran (THF) (THF) of 10ml; join in tetrahydrofuran (THF) (THF) solution (5ml) that contains 146mg quadrol thio lactam rhodamine B (SRhB) and 113mg diisopropylethylamine (DIEA), under nitrogen protection, under room temperature, lucifuge is reacted 24 hours.Product is at sherwood oil, precipitation in the mixed solvent (three's volume ratio is 5:5:1) of ether and ethanol, dissolve with THF again, in triplicate, remove unreacted quadrol thio lactam rhodamine B (SRhB) and other small molecular weight impurity, vacuum-drying, obtains the amphipathic rhodamine B graft copolymer of required product.
(3) there is the preparation of the amphipathic nature polyalcohol nanoparticle of mercury ion detecting function: the THF solution that the amphipathic rhodamine B graft copolymer of above-mentioned preparation is made into 8mg/ml, getting 0.5ml solution joins fast just in ultrasonic 10ml water, ultrasonic 10 minutes (ultrasonic power is 100W), then the THF in solution is removed by the method for normal temperature rotary evaporation, after constant volume, obtain required amphipathic nature polyalcohol nano-particle solution, concentration is 0.4g/L.
Embodiment 2: size and the distribution of the amphipathic nature polyalcohol nanoparticle of preparation in test implementation example 1.
The instrument of concrete test is Malvern Nano-ZS90 laser particle size analyzer, test concentrations is (0.4g/L), and probe temperature is 25oC, shown in result Fig. 1, result shows that the particle diameter of prepared amphipathic nature polyalcohol nanoparticle sample is in 20nm left and right, and the monodispersity of particle is better.
Embodiment 3: the test experience of mercury ion.
(1) getting 12 5ml sample bottles, add respectively the concentration of gained in embodiment 1 for the amphipathic nature polyalcohol nanoparticle 3ml of (0.4g/L), is then that the mercury ion aqueous solution 3ul of 0 ~ 0.24 mol/L adds respectively in 12 sample bottles by concentration.Under normal temperature, stir after 3 minutes the absorption spectrum of these samples of sequentially determining and fluorescence emission spectrum (excitation wavelength is 520nm).Result is as Fig. 2 and Fig. 3.Measurement result shows: the absorption intensity of this amphipathic nature polyalcohol nanoparticle and fluorescence intensity strengthen gradually along with the increase of ion concentration of mercury, and in the time of ion concentration of mercury >5 μ mol/l, the fluorescence intensity of amphipathic nature polyalcohol nanoparticle is significantly increased.
(2) get 12 5ml sample bottles, add respectively gained in embodiment 1 the concentration amphipathic nature polyalcohol nanoparticle 3ml that is (0.4g/L), be then 4 × 10 by concentration
-2the mercury ion of mol/L and other 11 kinds of common metal ion (Mg
2+, Cu
2+, Pb
2+, Ca
2+, Zn
2+, Co
2+, Mn
2+, Fe
2+, Ni
2+, K
+, Na
+) aqueous solution 3ul add respectively in 12 sample bottles.Under normal temperature, stir after 3 minutes, the fluorescence emission spectrum of these samples of sequentially determining (excitation wavelength is 520nm), obtains the variation diagram of 12 fluorescent emmission spectrum.See Fig. 4.Measurement result shows: in numerous common metal ion, this amphipathic nature polyalcohol nanoparticle only has higher selectivity to mercury ion.
(3) get 12 5ml sample bottles, be numbered 0 ~ 11, add respectively gained in embodiment 1 the concentration amphipathic nature polyalcohol nanoparticle 3ml that is (0.4g/L).Be 4 × 10 by concentration
-2the mercury ion aqueous solution 3ul of mol/L adds in No. 0 sample bottle, is 4 × 10 by concentration simultaneously
-2the mercury ion aqueous solution 3ul of mol/L and other metal ion species (Mg
2+, Cu
2+, Pb
2+, Ca
2+, Zn
2+, Co
2+, Mn
2+, Fe
2+, Ni
2+, K
+, Na
+) aqueous solution 3ul add in other 11 sample bottles simultaneously.Under normal temperature, stir after 3 minutes, the fluorescence emission spectrum of these samples of sequentially determining (excitation wavelength is 520nm), obtains the comparison diagram of the fluorescent emission relative intensity of 12 samples.See Fig. 5.Measurement result shows: this amphipathic nature polyalcohol nanoparticle has stronger anti-other Cation Interferences ability to the detection of mercury ion.
Above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change that the present invention is made, all fall into protection scope of the present invention.
Claims (10)
1. an amphipathic nature polyalcohol nanoparticle that detects mercury ion, is characterized in that, is prepared from water by amphipathic rhodamine B graft copolymer redeposition under ultrasonic condition, and the structural formula of described amphipathic rhodamine B graft copolymer is:
In formula, a/b/x is 16:8:1 ~ 7:3.5:1.
2. the preparation method of the amphipathic nature polyalcohol nanoparticle of a detection mercury ion as claimed in claim 1 in right, it is characterized in that, step comprises: the tetrahydrofuran solution of amphipathic rhodamine B graft copolymer is joined fast just in ultrasonic water, after ultrasonic 10 minutes, the tetrahydrofuran (THF) in solution is removed by the method for normal temperature rotary evaporation, constant volume obtains required amphipathic nature polyalcohol nano-particle solution again.
3. the preparation method of the amphipathic nature polyalcohol nanoparticle of detection mercury ion according to claim 2, is characterized in that, the preparation method of described amphipathic rhodamine B graft copolymer comprises the following steps:
(1) solvent dimethyl formamide, polyoxyethylene macromolecular chain transfering reagent, vinylbenzene, p-chloromethyl styrene and Diisopropyl azodicarboxylate are placed in to reaction flask, inflated with nitrogen at low temperatures-vacuumize three times repeatedly, sealing, the lower reaction of oil bath 90 degree 4 hours, product precipitates in sherwood oil and ether mixed solvent, then dissolves with methylene dichloride, in triplicate, remove unreacted monomer and small molecular weight impurity, vacuum-drying, obtain amphipathic multipolymer polyoxyethylene-
b-poly-(vinylbenzene-
co-p-chloromethyl styrene), its structural formula is as follows:
In formula, a/b/x is 16:8:1 ~ 7:3.5:1,
The structural formula of described polyoxyethylene macromolecular chain transfering reagent is as follows:
In formula, a is 112;
(2) will contain amphipathic multipolymer polyoxyethylene-
b-poly-(vinylbenzene-
co-p-chloromethyl styrene) tetrahydrofuran solution join in the tetrahydrofuran solution that contains quadrol thio lactam rhodamine B and diisopropylethylamine; under nitrogen protection, under room temperature, lucifuge is reacted 24 hours; product precipitates in the mixed solvent of sherwood oil, ether and ethanol; dissolve with tetrahydrofuran (THF) again; in triplicate; remove unreacted quadrol thio lactam rhodamine B and other small molecular weight impurity, vacuum-drying, obtains amphipathic rhodamine B graft copolymer.
4. the preparation method of the amphipathic nature polyalcohol nanoparticle of detection mercury ion according to claim 3, it is characterized in that, in step (1), the mol ratio of polyoxyethylene macromolecular chain transfering reagent, hydrophobic monomer, p-chloromethyl styrene and Diisopropyl azodicarboxylate is 3.5:1400:140:1 ~ 3.5:1400:420:1.
5. the preparation method of the amphipathic nature polyalcohol nanoparticle of detection mercury ion according to claim 3, is characterized in that, in step (1), the volume proportion of described sherwood oil and ether mixed solvent is sherwood oil: ether=1:1.
6. the preparation method of the amphipathic nature polyalcohol nanoparticle of detection mercury ion according to claim 3, is characterized in that, in step (2), and wherein amphipathic multipolymer polyoxyethylene-
b-poly-(vinylbenzene-
co-p-chloromethyl styrene), the mol ratio of quadrol thio lactam rhodamine B and diisopropylethylamine is 1:20:60.
7. the preparation method of the amphipathic nature polyalcohol nanoparticle of detection mercury ion according to claim 3, is characterized in that, in step (2), the volume proportion of the mixed solvent of sherwood oil, ether and ethanol is: sherwood oil: ether: ethanol=5:5:1.
8. the preparation method of the amphipathic nature polyalcohol nanoparticle of detection mercury ion according to claim 3, it is characterized in that, in step (2), the preparation method of described quadrol thio lactam rhodamine B is: under the condition of lucifuge, 3.0g rhodamine B is dissolved in 130ml methyl alcohol, at N
2under protection, add fast 7.5g quadrol, be warming up to 85
oc reaction 24 hours;
Then rotary evaporation is removed most of methyl alcohol, in large water gaging, precipitates, and filters, and throw out vacuum-drying obtains incarnadine powder, is quadrol lactamize rhodamine B; 1.0g quadrol lactamize rhodamine B and 1.6g lawesson reagent are dissolved in the refining toluene of 250ml, at N
2under protection, be warming up to backflow, react 6 hours, then remove solvent, sherwood oil and the ethyl acetate mixed solvent of mixture take volume ratio as 3:1 is developping agent, the quadrol thio lactam rhodamine B that utilizes column chromatography to separate requiredly.
9. amphipathic nature polyalcohol nanoparticle as claimed in claim 1 application aspect mercury ion in detection water.
10. amphipathic nature polyalcohol nanoparticle according to claim 8, detecting the application aspect mercury ion in water, is characterized in that, the detection of mercury ion is to realize by the enhancing of observation solution colour/Change of absorption and fluorescence with identification.
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Cited By (5)
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| CN104910316A (en) * | 2015-05-26 | 2015-09-16 | 郑州大学 | High-polymer colorimetric nano thin-film material and preparation method and application thereof in detecting Fe<3+> and pyrophosphate |
| CN106008796A (en) * | 2016-05-30 | 2016-10-12 | 金宝丽科技（苏州）有限公司 | Production method of mercury ion probe sheet |
| CN107389636A (en) * | 2017-07-13 | 2017-11-24 | 湖南科技大学 | A kind of preparation and application of the water soluble fluorescence sensor that endogenous glutathione can be detected in cancer cell |
| CN109575915A (en) * | 2018-12-17 | 2019-04-05 | 鲁东大学 | A kind of method of amphiphilic polymer modified AuNPs colorimetric detection organic mercury |
| CN114437713A (en) * | 2022-01-11 | 2022-05-06 | 江苏大学 | Temperature response type polymer fluorescent probe, preparation method thereof and application of temperature response type polymer fluorescent probe in detection of gold ions |
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| CN104910316A (en) * | 2015-05-26 | 2015-09-16 | 郑州大学 | High-polymer colorimetric nano thin-film material and preparation method and application thereof in detecting Fe<3+> and pyrophosphate |
| CN106008796A (en) * | 2016-05-30 | 2016-10-12 | 金宝丽科技（苏州）有限公司 | Production method of mercury ion probe sheet |
| CN106008796B (en) * | 2016-05-30 | 2018-01-02 | 金宝丽科技（苏州）有限公司 | A kind of preparation method of mercury ion probe sheet material |
| CN107389636A (en) * | 2017-07-13 | 2017-11-24 | 湖南科技大学 | A kind of preparation and application of the water soluble fluorescence sensor that endogenous glutathione can be detected in cancer cell |
| CN107389636B (en) * | 2017-07-13 | 2019-09-10 | 湖南科技大学 | A kind of preparation and application of the fluorescent optical sensor of detectable endogenous glutathione |
| CN109575915A (en) * | 2018-12-17 | 2019-04-05 | 鲁东大学 | A kind of method of amphiphilic polymer modified AuNPs colorimetric detection organic mercury |
| CN109575915B (en) * | 2018-12-17 | 2021-08-24 | 鲁东大学 | Method for colorimetric detection of organic mercury by using amphiphilic polymer modified AuNPs |
| CN114437713A (en) * | 2022-01-11 | 2022-05-06 | 江苏大学 | Temperature response type polymer fluorescent probe, preparation method thereof and application of temperature response type polymer fluorescent probe in detection of gold ions |
| CN114437713B (en) * | 2022-01-11 | 2023-09-22 | 江苏大学 | Temperature response type polymer fluorescent probe, preparation method thereof and application of temperature response type polymer fluorescent probe in detection of gold ions |
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