CN106478892A - One kind can ratio test hypochlorous polymer fluorescent Sensors ＆ Application - Google Patents
One kind can ratio test hypochlorous polymer fluorescent Sensors ＆ Application Download PDFInfo
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Abstract
The invention discloses one kind can ratio test hypochlorous polymer fluorescent Sensors ＆ Application, this fluorescent optical sensor is with poly glycol monomethyl ether chain-transferring agent（PEG‑TTC）, styrene（St）, a kind of new ratio fluorescent sensor that 4 bromine 1,8 naphthoyl dianhydride and allyl isosulfocyanate are prepared for raw material.This fluorescent optical sensor can enable to hypochlorous high selectivity and the detection of high sensitivity rapid rates in pure water solution.Compared to existing detection technique of fluorescence, the fluorescent optical sensor that the present invention obtains has to hypochlorous acid high selectivity ratio quick response, low cytotoxicity, excellent water dispersible, and input cost is relatively low, the advantages of synthetic route is simple, is suitable to amplify synthesis and production application, has huge application prospect in technical fields such as analytical chemistry, life sciences and environmental sciences.
Description
Technical field
The present invention relates to a kind of fluorescent optical sensor that can be used for hypochlorous acid detection and application, it particularly relates to can ratio
Detect hypochlorous polymer fluorescent Sensors ＆ Application, belong to chemical material preparation and analysis detection field.
Background technology
Active oxygen species (ROS) are to be widely present in a kind of very important species in biological cell, and it is in biological cell
In signal transduction, differentiation, migration and cellular immunization in all play very important effect.But ROS is owned by common spy
Both activity in vivo was higher, content is relatively low, skewness for property, and how to go to explore their functions in vivo becomes
Particularly important.Endogenic hypochlorous acid（HOCl）As the important a member in ROS, it is hydrogen peroxide（H2O2）Exist with chloride ion
The lower reaction of the catalysis of myeloperoxidase (MPO) (MPO) obtains.Additionally, HOCl by multiple biological in nature with antibacterial killer's
Identity is used for system of defense.As a kind of efficient weapon that sterilizes, its mechanism be due to antibacterial lack decomposing H OCl enzyme and must
So it is subject to HOCl strong oxidizing property, highly active effect, lead to bacterial death.In human body, HOCl is also very important, normally
The HCOl of level is extremely important for the maintenance of health.But can lead to as follows in human body during the ANOMALOUS VARIATIONS of HOCl level
Disease：As arthritis, arteriosclerosiss etc..At present, HOCl is applied to the surface treatment of some food compositions and life is used
The disinfecting of water, these process can remain a certain amount of HOCl unavoidably, long-term takes in the water containing HOCl or food, to people
The digestive system of body also can have a negative impact.And hypochlorous acid because strong oxidizing property and Bleachability so that the life containing HOCl
Inconvenience can be brought with water to daily life.
At present, the hypochlorous method of detection having grown up is a lot, but mainly based on small molecule sensor.So
And, it is related to small molecule sensor, just can not ignore defect specific to it, be that small molecule sensor great majority have pure first
Work in machine solvent or mixed solvent, because the bio-toxicity of organic solvent limits its applicability；Next to that little point
Sub- sensor can lead to assemble because π-π each other interacts in water, further limit applicability.This also leads
This kind of sensor is caused to reduce in the feasibility of actually detected middle utilization.Therefore, invention is a kind of simple, inexpensive, excellent water-soluble
Property, bio-toxicity is low and efficient Fast Detection Technique has considerable realistic meaning and application prospect.In recent years, gather
Compound fluorescent optical sensor is because its excellent water solublity, low cytotoxicity, organic solvent-free residual, designability are strong, high sensitivity,
The advantages of high selectivity, of increased attention, show extremely in research fields such as chemistry, medical science and environmental sciences
Wide application prospect.
Content of the invention
It is an object of the invention to provide one kind can ratio test hypochlorous polymer fluorescent Sensors ＆ Application, this is glimmering
Optical sensor is with poly glycol monomethyl ether chain-transferring agent（PEG-TTC）, styrene（St）, 4- bromo- 1,8- naphthoyl dianhydride and different sulfur
Cyanic acid allyl ester is prepared for raw material.Applied research shows, this fluorescent optical sensor is capable of to hypochlorous highly sensitive further
Degree, the rapid rates detection of high selectivity.
The purpose of the present invention is accomplished by：
One kind can ratio test hypochlorous polymer fluorescent sensor, by amphipathic graft copolymer in water self assembly and
Become, the structural formula of described amphipathic graft copolymer is：
In formula, n/x/y is 90 ~ 10：20~5：1, R is C6-C20One of alkyl.
A kind of can ratio test hypochlorous polymer fluorescent sensor preparation, comprise the following steps：
（1）By a certain amount of 4-（2- aminoethyl）Morpholine and 4- bromo- 1,8- naphthoyl dianhydride are dissolved in Ethylene glycol methyl ether, are placed in
N2Protection and lucifuge under conditions of, be rapidly heated to 110 ~ 130 DEG C stir 4 hours, then plus a certain amount of distillation water precipitation, sucking filtration
Obtain required product, vacuum drying, obtain product 1；
（2）Take a certain amount of product 1 to be dissolved in ethylenediamine, mixed solution is placed in lucifuge and N270 ~ 90 DEG C under conditions of protection
Stirring 4 hours, reaction terminates rear rotary evaporation and removes major part（85~95%）Ethylene glycol methyl ether, crosses post purified product, vacuum
It is dried, obtain product 2；
（3）A certain amount of product 2 and allyl isosulfocyanate are dissolved in ethanol and methylene chloride volume than for 1：1 mixing is molten
In liquid, it is placed in N2Under conditions of protection and lucifuge, 20 ~ 30 DEG C are stirred 4 hours, and reaction terminates rear sucking filtration, and vacuum drying obtains product
3；
（4）By poly glycol monomethyl ether chain-transferring agent（PEG-TTC, molecular weight is 5000）, styrene, product 3 and azo two different
Butyronitrile is dissolved in the N of 0.5 ~ 2 mL, N- dimethylformamide（DMF）In, holding poly glycol monomethyl ether chain transfer agent concentration is
0.01 ~ 0.1 mol/L, under condition of ice bath, evacuation-inflated with nitrogen circulates three times, is then rapidly heated little to 80 ~ 100 DEG C of reactions 4
When, reaction is precipitated with ether after terminating, sucking filtration, and vacuum drying obtains product 4；
（5）Take step（2）The product 4 of synthesis is made into certain density oxolane (THF) solution, then takes with 0.1 ~ 0.4 mL
Solution constant volume to 1 mL, under rapid stirring the water of 10 mL is slowly added in above-mentioned solution, is added dropwise to complete it
Continue stirring 10 ~ 30 min afterwards, THF be then removed under reduced pressure at room temperature, constant volume to 10 mL obtains required fluorescent optical sensor,
I.e. one kind can ratio test hypochlorous polymer fluorescent sensor.
According to the polymer fluorescent sensor of above-mentioned preparation method preparation, described step（1）In, 4-（2- aminoethyl）Morpholine
1,8- naphthoyl dianhydride mol ratio bromo- with 4- is 1 ~ 2:1；Described step（2）In, concentration in ethylenediamine for the product 1 is 0.1 ~ 1
mol/L；Described step（3）In,NThe rubbing of-(aminoethyl morpholine) -4- aminoethyl -1,8- naphthoyl dianhydride and allyl isosulfocyanate
That ratio is 1:1~2；KeepNConcentration in mixed solution for-(the aminoethyl morpholine) -4- aminoethyl -1,8- naphthoyl dianhydride be 0.01 ~
0.1 mol/l；Described step（4）In, poly glycol monomethyl ether chain-transferring agent（PEG-TTC）, styrene, product 1 and azo two
Isopropyl cyanide mol ratio is 3.5:660~688:12~40:1；Described step（5）In, concentration in oxolane for the product 2 be 0.5 ~
3 mg/mL.
According to the fluorescent optical sensor of above-mentioned preparation method preparation, its specific course of reaction is as follows：
In formula, n/x/y is 90 ~ 10:20~5:1, R is C6-C20One of alkyl.
The invention provides one kind can ratio test hypochlorous polymer fluorescent sensor in ratio test hypochlorous acid
Application.
The present invention is with poly glycol monomethyl ether chain-transferring agent（PEG-TTC）, styrene（St）, 4- bromo- 1,8- naphthoyl dianhydride
With allyl isosulfocyanate to prepare for raw material required for polymer fluorescent sensor, this polymer fluorescent sensor pH
After buffer solution dilution for 5, in the presence of having HOCl, can occur significantly with the increase of HOCl concentration at 444 nm
Enhancement of Fluorescence, and at 551 nm, the increase with HOCl concentration assumes obvious fluorescence decline phenomenon, and then show
Significantly ratio test effect.And the increase with hypochlorous acid concentration it is seen that under light solution be gradually changed into from bright green
Colourless, and under ultraviolet light, solution gradually becomes bright blue-fluorescence by bright green fluorescence.Show obvious colorimetric
Effect.And this fluorescent optical sensor has obvious high selectivity quick response to hypochlorous detection, and Gao Ling can be reached
The effect of sensitivity detection.Compared to some detection techniques existing, the fluorescence chemical sensor cost input in the present invention is less,
Synthetic route is simple, convenient post-treatment, directly hypochlorous acid can be realized with quick specific recognition, especially in physiology such as lysosomes
Environment pH is that the application of 5 about biological internal milieu has extremely important meaning.
Sum it up, the invention provides one kind can ratio test hypochlorous polymer fluorescent sensor and its application,
The preparation of this polymer fluorescent sensor is simple, and sensitivity is high, is expected to be used widely in biomaterial scientific domain.
Brief description
Fig. 1 is the grain-size graph of the polymer fluorescent sensor of preparation.
Fig. 2 is the polymer fluorescent sensor of preparation to hypochlorous identification schematic diagram.
When Fig. 3 is different HOCl concentration, the fluorescence emission spectrum variation diagram of polymer fluorescent sensor（Excitation wavelength：420
nm）, [HOCl]=0（a）, 1.0 × 10-7mol/l（b）, 2.0×10-7mol/l（c）, 3.0×10-7mol/l（d）, 6
×10-7mol/l（e）, 1.0 × 10-6mol/l（f）, 1.5×10-6mol/l（g）, 2×10-6mol/l（h）, 3.0 × 10-6
mol/l（i）.
Fig. 4 is that polymer fluorescent sensor is worth corresponding matched curve with the fluorescence intensity change of HOCl concentration change and is somebody's turn to do
Functional arrangement corresponding to curve.
Fig. 5 is the selectivity correction data figure of this polymer fluorescent sensor ratio fluorescent intensity of various ion pairs, adds
The concentration of ion afterwards is 5.0 × 10-5Mol/l, hypochlorous acid concentration is 1.0 × 10-6Mol/L, I444And I551For each ion
With 420nm as excitation wavelength, 444 nm and 551 nm are transmitted wave strong point to fluorescent optical sensor before and after adding with peroxide
Fluorescence intensity change value.
Fig. 6 is the interference correction data figure of the ratio fluorescent intensity of various ion pair polymerization thing fluorescent optical sensors, adds
The concentration of various ions afterwards is 5.0 × 10-5Mol/l, hypochlorous acid concentration is 1.0 × 10-6Mol/L, I444And I551For each
With 420nm as excitation wavelength, 444 nm and 551 nm are transmitted wave to fluorescent optical sensor before and after ion and peroxide addition
The fluorescence intensity change value of strong point.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment is described in further detail to the present invention.
Embodiment 1：A kind of can the hypochlorous fluorescent optical sensor of ratio test preparation, below concrete steps：
（1）By bromo- for 4- 1,8- naphthoyl dianhydride（10 mmol）And 4-（2- aminoethyl）Morpholine（10 mmol）It is dissolved in ethylene glycol first
Base ether（10 mL）In, it is placed in N2Under conditions of protection and lucifuge, it is rapidly heated and stirs 4 hours to 120 DEG C, reaction is straight after terminating
Connect the distillation water precipitation being added to 40 mL, sucking filtration obtains required product, vacuum drying, obtain product 1；
（2）Take step（1）The product 1 of synthesis（3 mmol）It is dissolved in the ethylenediamine of 10 mL, mixed solution is placed in lucifuge and N2
80 DEG C of stirring 4 h under conditions of protection, reaction terminates rear rotary evaporation and removes major part（85~95%）Ethylene glycol methyl ether, crosses post
Purified product, vacuum drying, obtain product 2；
（3）By step（2）The product 2 of synthesis（0.82 mmol）It is dissolved in ethanol（8 mL）With dichloromethane（6 mL）Mixing
In solution, allyl isosulfocyanate（0.90 mmol）It is dissolved in the dichloromethane of 2 mL, be placed in N2Protection and the ice bath bar of lucifuge
Under part, by the dichloromethane solution dissolved with allyl isosulfocyanate be slowly dropped to dissolved withN- (aminoethyl morpholine) -4- aminoethyl -
In the mixed solution of 1,8- naphthoyl dianhydride, after being added dropwise to complete, 25 DEG C are stirred 4 hours, and reaction terminates rear sucking filtration, and vacuum drying obtains
Product 3, yield is 68%；
（4）Take step（3）The product 3 of synthesis（0.2 mmol）, with PEG-TTC（0.02 mmol）, styrene（3.8 mmol）With
Azodiisobutyronitrile (0.0057 mmol) is dissolved in the DMF of 1 mL together, evacuation and inflated with nitrogen circulation three under condition of ice bath
Secondary.It is warming up to 90 DEG C of reaction 4 h, reaction is precipitated with 15 mL ether after terminating, centrifugation, vacuum drying obtains greenish yellow solid and produces
Thing 4；
（5）Take step（4）The product 4 of synthesis is formulated as oxolane (THF) solution that concentration is 2 mg/mL, then takes 0.2
The solution constant volume of mL, to 1 mL, under rapid stirring the water of 10 mL is slowly added in above-mentioned solution, is added dropwise to complete
Continue stirring 30 min afterwards, then utilize room temperature decompression method to remove THF, constant volume to 10 mL obtains required fluorescence sense
Device, that is, one kind can ratio test hypochlorous polymer fluorescent sensor.This polymer fluorescent sensor is with the shape of nanoparticle
Formula exists, and its particle size data is as shown in Figure 1.
Embodiment 2：A kind of can the hypochlorous fluorescent optical sensor of ratio test preparation, below concrete steps：
（1）By bromo- for 4- 1,8- naphthoyl dianhydride（10 mmol）And 4-（2- aminoethyl）Morpholine（10 mmol）It is dissolved in ethylene glycol first
Base ether（10 mL）In, it is placed in N2Under conditions of protection and lucifuge, it is rapidly heated and stirs 4 hours to 120 DEG C, reaction is straight after terminating
Connect the distillation water precipitation being added to 40 mL, sucking filtration obtains required product, vacuum drying, obtain product 1；
（2）Take step（1）The product 1 of synthesis（3 mmol）It is dissolved in the ethylenediamine of 10 mL, mixed solution is placed in lucifuge and N2
80 DEG C of stirring 4 h under conditions of protection, reaction terminates rear rotary evaporation and removes major part（85~95%）Ethylene glycol methyl ether, crosses post
Purified product, vacuum drying, obtain product 2；
（3）By step（2）The product 2 of synthesis（0.82 mmol）It is dissolved in ethanol（8 mL）With dichloromethane（6 mL）Mixing
In solution, allyl isosulfocyanate（0.82 mmol）It is dissolved in the dichloromethane of 2 mL, be placed in N2Protection and the ice bath bar of lucifuge
Under part, by the dichloromethane solution dissolved with allyl isosulfocyanate be slowly dropped to dissolved withN- (aminoethyl morpholine) -4- aminoethyl -
In the mixed solution of 1,8- naphthoyl dianhydride, after being added dropwise to complete, 25 DEG C are stirred 4 hours, and reaction terminates rear sucking filtration, and vacuum drying obtains
Product 3；
（4）Take step（3）The product 3 of synthesis（0.4 mmol）, with PEG-TTC（0.02 mmol）, styrene（3.6 mmol）With
Azodiisobutyronitrile (0.0057 mmol) is dissolved in the DMF of 1 mL together, evacuation and inflated with nitrogen circulation three under condition of ice bath
Secondary.It is warming up to 90 DEG C of reaction 4 h, reaction is precipitated with 15 mL ether after terminating, centrifugation, vacuum drying obtains greenish yellow solid and produces
Thing 4；
（5）Take step（4）The product 4 of synthesis is formulated as oxolane (THF) solution that concentration is 2 mg/mL, then takes 0.2
The solution constant volume of mL, to 1 mL, under rapid stirring the water of 10 mL is slowly added in above-mentioned solution, is added dropwise to complete
Continue stirring 30 min afterwards, then utilize room temperature decompression method to remove THF, constant volume to 10 mL obtains required fluorescence sense
Device, that is, one kind can ratio test hypochlorous polymer fluorescent sensor.This polymer fluorescent sensor is with the shape of nanoparticle
Formula exists, and its particle size data is as shown in Figure 1.
Embodiment 3：A kind of can the hypochlorous fluorescent optical sensor of ratio test preparation, below concrete steps：
（1）By bromo- for 4- 1,8- naphthoyl dianhydride（10 mmol）And 4-（2- aminoethyl）Morpholine（10 mmol）It is dissolved in ethylene glycol first
Base ether（10 mL）In, it is placed in N2Under conditions of protection and lucifuge, it is rapidly heated and stirs 4 hours to 120 DEG C, reaction is straight after terminating
Connect the distillation water precipitation being added to 40 mL, sucking filtration obtains required product, vacuum drying, obtain product 1；
（2）Take step（1）The product 1 of synthesis（3 mmol）It is dissolved in the ethylenediamine of 10 mL, mixed solution is placed in lucifuge and N2
80 DEG C of stirring 4 h under conditions of protection, reaction terminates rear rotary evaporation and removes major part（85~95%）Ethylene glycol methyl ether, crosses post
Purified product, vacuum drying, obtain product 2；
（3）By step（2）The product 2 of synthesis（0.82 mmol）It is dissolved in ethanol（8 mL）With dichloromethane（6 mL）Mixing
In solution, allyl isosulfocyanate（1.07 mmol）It is dissolved in the dichloromethane of 2 mL, be placed in N2Protection and the ice bath bar of lucifuge
Under part, by the dichloromethane solution dissolved with allyl isosulfocyanate be slowly dropped to dissolved withN- (aminoethyl morpholine) -4- aminoethyl -
In the mixed solution of 1,8- naphthoyl dianhydride, after being added dropwise to complete, 25 DEG C are stirred 4 hours, and reaction terminates rear sucking filtration, and vacuum drying obtains
Product 3；
（4）Take step（3）The product 3 of synthesis（0.1 mmol）, with PEG-TTC（0.02 mmol）, styrene（3.9 mmol）With
Azodiisobutyronitrile (0.0057 mmol) is dissolved in the DMF of 1 mL together, evacuation and inflated with nitrogen circulation three under condition of ice bath
Secondary.It is warming up to 90 DEG C of reaction 5 h, reaction is precipitated with 15 mL ether after terminating, centrifugation, vacuum drying obtains greenish yellow solid and produces
Thing 4；
（5）Take step（4）The product 4 of synthesis is formulated as oxolane (THF) solution that concentration is 2 mg/mL, then takes 0.2
The solution constant volume of mL, to 1 mL, under rapid stirring the water of 10 mL is slowly added in above-mentioned solution, is added dropwise to complete
Continue stirring 30 min afterwards, then utilize room temperature decompression method to remove THF, constant volume to 10 mL obtains required fluorescence sense
Device, that is, one kind can ratio test hypochlorous polymer fluorescent sensor.This polymer fluorescent sensor is with the shape of nanoparticle
Formula exists, and its particle size data is as shown in Figure 1.
Embodiment 4：Hypochlorous test experience.
Take 95 mL sample bottles, be separately added into fluorescent optical sensor solution 0.3 mL of gained in embodiment 1（This polymer
The concentration of fluorescent optical sensor original solution is 0.02 mg/mL）, the pH sequentially adding 2.7 mL is 5 buffer solution solution, stirring
After 3min respectively by concentration be [HOCl]=0（a）, 1.0 × 10-4mol/L（b）, 2.0 × 10-4mol/L（c）, 3.0 ×
10-4mol/L（d）, 6 × 10-4mol/L（e）, 1.0 × 10-3mol/L（f）, 1.5 × 10-3mol/L（g）, 2 × 10-3mol/L
（h）, 3.0 × 10-3mol/ L（i）3 l hypochlorite solution add 9 sample bottles in, after stirring 1 min under room temperature, with
420nm is excitation wavelength, measures the fluorescence emission spectrum of each sample respectively, obtains the fluorescence emission spectrum variation diagram of 9 samples,
See Fig. 3.Measurement result shows：This polymer fluorescent sensor fluorescence intensity at 444 nm is with hypochlorous acid concentration gradually
Increase and gradually rise, and the fluorescence intensity at 551 nm is decreased obviously.Strong according to fluorescence at 444 nm in Fig. 3 and 551 nm
Degree rate of change value and the variation relation of concentration can make more satisfactory function curve diagram and this curve after corresponding matching
Corresponding functional arrangement（Y=a+b*x, a=0.0460, b=0.0012, R2=0.9972）, see Fig. 4.
Embodiment 5：The comparison and detection experiment of other ions and peroxide impact.
Take 14 5 mL sample bottles, be respectively charged into polymer fluorescent sensor solution 0.3 mL of gained in embodiment 1（Should
Fluorescent optical sensor concentration is 0.02 mg/mL）, the pH then sequentially adding 2.7 mL is 5 buffer solution, after stirring 3 min
Respectively by concentration be 5.0 × 10-2The NO of mol/L2 -、SO3 2-、SO4 2-、NO3 -、HPO4 2-、H2PO4 -、NO•（Selenite）、
HO•（Hydroxyl base free radical）、t-BuO•（Tert-butyl peroxide free radical）、1O2（Singlet oxygen）、H2O2（Hydrogen peroxide）、TBHP
（Tertbutanol peroxide）Solution and concentration are 1.0 × 10-3The HClO solution of mol/L respectively takes 3 L to add in addition front 13 sample bottles
In, No. 14 samples are blank sample.Then measure fluorescence data under 420 nm wavelength excite for 14 samples respectively, obtain
Ratio fluorescent changing value at 444 nm and 551 nm wavelength transmittings, result is shown in Fig. 5.Measurement result shows：Except hypochlorous acid
Outward, other above-mentioned various ions and peroxide be not obvious to the ratio fluorescent intensity of prepared polymer fluorescent sensor
Impact.
Embodiment 6：The comparison and detection experiment of impact when other ions and peroxide coexist.
Take 14 5 mL sample bottles, be respectively charged into the polymer fluorescent sensor solution 0.3mL of gained in embodiment 1（Should
Polymer fluorescent sensor concentration is 0.02 mg/mL）, the pH then sequentially adding 2.7 mL is 5 buffer solution, stirs 3
After min, No. 1 is blank sample, and remaining sample bottle sequentially adds 1.0 × 10-3HClO solution 3 L of mol/L, continues stirring 1
Min, then respectively by the concentration of 3 L be 5.0 × 10-2The NO of mol/L2 -、SO3 2-、SO4 2-、NO3 -、HPO4 2-、H2PO4 -、NO•（Sub-
Nitro free radical）、HO•（Hydroxyl base free radical）、t-BuO•（Tert-butyl peroxide free radical）、1O2（Singlet oxygen）、H2O2（Cross
Hydrogen oxide）、TBHP（Tertbutanol peroxide）It is added in No. 3 to No. 14 sample bottles.Then 14 are measured respectively after stirring 5 min
Fluorescence data under 420 nm excite for wavelength for the individual sample, obtains the fluorescence at 444 nm and 551 nm wavelength transmittings
Rate of change value, result is shown in Fig. 6.Measurement result shows：In addition to hypochlorous acid, other above-mentioned various ions and peroxide are to institute
The ratio fluorescent intensity of the polymer fluorescent sensor of preparation has not significant impact.
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, the present invention spirit and
In scope of the claims, to any modifications and changes done by the present invention, both fall within protection scope of the present invention.
Claims (3)
1. one kind can ratio test hypochlorous polymer fluorescent sensor it is characterised in that being existed by amphipathic graft copolymer
In water, self assembly forms, and the structural formula of described amphipathic graft copolymer is：
In formula, n/x/y is 90 ~ 10：20~5：1, R is C6-C20One of alkyl.
2. one kind can ratio test hypochlorous polymer fluorescent sensor it is characterised in that being that to be synthesized by step real
Existing：
（1）By 4-（2- aminoethyl）Morpholine and 4- bromo- 1,8- naphthoyl dianhydride are according to mole than for 2 ~ 1：1 is dissolved in ethylene glycol first
In base ether, it is rapidly heated and stirs 4 hours to 110 ~ 130 DEG C, be then added to distill water precipitation, sucking filtration obtains required product, vacuum
It is dried, obtain product 1；
（2）Take product 1 to be dissolved in ethylenediamine, mixed solution is placed in 70 ~ 90 DEG C and stirs 4 hours, reaction terminates rear rotary evaporation
Remove most of ethylenediamine, cross post purified product, vacuum drying, obtain product 2；
（3）Product 2 and allyl isosulfocyanate are 1 according to mol ratio:1 ~ 2 is dissolved in ethanol and methylene chloride volume than for 1：
In 1 mixed solution, 20 ~ 30 DEG C are stirred 2 ~ 7 hours, and reaction terminates rear sucking filtration, and vacuum drying obtains product 3；
（4）By poly glycol monomethyl ether chain-transferring agent（Molecular weight is 5000）, styrene, product 3 and azodiisobutyronitrile according to
Mol ratio is 3.5：660~688：12~40：1 N being dissolved in 1 mL, N- dimethylformamide（DMF）In, take out true under condition of ice bath
Sky-inflated with nitrogen circulates three times, is then rapidly heated and reacts 4 hours to 80 ~ 100 DEG C, and reaction is precipitated with ether after terminating, sucking filtration,
Vacuum drying, obtains product 4, i.e. amphipathic graft copolymer described in claim 1；
（5）Take step（4）The product 4 of synthesis is formulated as oxolane (THF) solution, is then obtained required using self-assembling technique
Fluorescent optical sensor, that is, one kind can ratio test hypochlorous polymer fluorescent sensor.
3. polymer fluorescent sensor the answering in ratio test hypochlorous acid of preparation method preparation according to claim 2
With.
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| 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 |
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| CN103435730A (en) * | 2013-07-30 | 2013-12-11 | 湖南科技大学 | Water-dispersible fluorescent polymer nano particle with copper ion and negative sulfur ion identification function, and preparation method and application of water-dispersible fluorescent polymer nano particle |
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| 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 |
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