CN102702546A - Preparation method of perylene bisimide cholesterol polymer gel fluorescent sensing film, and application thereof - Google Patents
Preparation method of perylene bisimide cholesterol polymer gel fluorescent sensing film, and application thereof Download PDFInfo
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- CN102702546A CN102702546A CN2012101436150A CN201210143615A CN102702546A CN 102702546 A CN102702546 A CN 102702546A CN 2012101436150 A CN2012101436150 A CN 2012101436150A CN 201210143615 A CN201210143615 A CN 201210143615A CN 102702546 A CN102702546 A CN 102702546A
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Abstract
The invention relates to a preparation method of perylene bisimide cholesterol polymer gel fluorescent sensing film. The preparation method comprises the following steps: activating a substrate, preparing compound of formula I, preparing compound of formula II, preparing monomer of formula III, preparing polymer of formula IV, and preparing the perylene bisimide cholesterol polymer gel fluorescent sensing film. The method provided by the invention is simple in operation and mild in reaction conditions; the fluorescent sensing film prepared by the method has the advantages of good stability, long service life and high sensitivity; the fluorescent sensing film can be used for detecting sensing film containing amphetamin chloride analogue that is N-methylphenethylamine gas, also can be mounted on detection instruments for detecting the N-methylphenethylamine gas according to the fluorescence principle, and also can be affected by the N-methylphenethylamine gas and then detected directly by fluorescence instruments.
Description
Technical field
The invention belongs to polymer fluorescent sense film material technology field, be specifically related to for organic amine Min Gan De perylene diimide SUV polymer gel fluorescence sense film.
Background technology
Organic amine is the organic derivative of ammonia, formed by the alkyl or aryl replacement by the one or more of the Wasserstoffatoms in the ammonia, and be the odor pollution source of a quasi-representative.Investigation is found; All can produce the amine composition in the industrial production of many industries and the vegeto-animal decay process; For example chemical plant, pharmaceutical factory, tannery, packing house, hennery and fishery products yard, rubbish container, water drain etc.; The generation source that can regard the amine repugnant substance as, and organic amine also plays important effect in industrial production.
In the middle of numerous organic amines, methyl amphetamine (being commonly called as methamphetamine) is the violated drugs of international, domestic strict control; It also is one of present most popular Drug abuse; The cns of heavy damage human body not only after the suction, and habituation property is very big, causes a series of social concerns then.Because it is cheap that methamphetamine prepares cost of material, synthetic technology is simple, and only China in 2008 has just captured 6.15 tons.But capturing of these drugs mainly is to accomplish down by drug law enforcement criminal policeman's personal experience or the help of police dog, and therefore not hard to imagine still have a large amount of methamphetamines to flow to society.At present the detection method to methamphetamine mainly contains the gas chromatography-mass spectrography technology, and HPLC, immunological technique, these methods mainly are to detect to liquid phase, can not be in real time, fast drugs are detected.In view of above present situation, exploitation to methyl amphetamine fast and efficiently detection technique have crucial meaning.
In numerous detection techniques, fluorescent method has the advantage that response is quick, simple to operate, highly sensitive, selectivity is good, meets the detection demand of present methyl amphetamine.Cheng and co-worker thereof have synthesized a kind of turn-on type organic amine fluorescent optical sensor through the method for spin coating, have realized the selectivity of gas phase methyl amphetamine is detected.
The seminar at contriver place at first with the derivatives of porphyrin of metal-complexing with gather the fluorenes preparation film forming of mixing; Because intensive transfer transport effect between metals ion and the porphyrin; Film fluorescence is by quencher, but when methyl amphetamine is introduced, owing to the specific combination of itself and metals ion; Quenching process is blocked, and film fluorescence recovers.But this sense film does not possess the characteristics of nano-sensor high-specific surface area; Not very outstanding on the index of these several investigation chemical sensor performance quality of sensitivity, response speed and recovery, limited its application in real drugs fighting work greatly.Therefore, the sensing material of development with good autonomous dress characteristic satisfies real demand and has crucial meaning.The ideal said material should satisfy following characteristics: be easy to synthesize, assembling characteristic is good and be widely used.Yet the methamphetamine sensing material of design synthesizing new also remains a challenging research field of ten minutes with regular nanometer network structures such as these sensing material assembling becoming nanofibers effectively so far.
Summary of the invention
A technical problem to be solved by this invention is to overcome the existing shortcoming of above-mentioned preparation fluorescence sense film preparation method, and the preparation method of a kind of easy and simple to handle, fluorescence sense film good stability that reaction conditions is gentle, prepared, long service life, highly sensitive De perylene diimide SUV polymer gel fluorescence sense film is provided.
Another technical problem to be solved by this invention is to adopting a kind of new purposes that provides of method for preparing De perylene diimide SUV polymer gel fluorescence sense film.
Solving the problems of the technologies described above the technical scheme that is adopted is that this method is made up of following step:
1, activation substrate
Be 30% ydrogen peroxide 50 with massfraction with massfraction be that 98% sulfuric acid is to mix at 1: 3 by volume, be mixed with washing lotion; With zero(ppm) water, washing with alcohol activation substrate, dry up in the submergence washing lotion of back heating washing lotion to 80～100 ℃; Activation 1～2 hour naturally cools to room temperature, with second distillation water washing activation substrate; Wash the washing lotion of remained on surface off, use drier, process the activation substrate.
2, preparation
At flow velocity is under the argon gas condition of 0.6～0.8mL/s, in the mixture of glycol amine and methylene dichloride, drips mass percentage concentration and is in 5% the SUV chloro-formic ester dichloromethane solution, and the mol ratio of glycol amine and methylene dichloride is 1: 1～10; 0 ℃ of stirring reaction 2 hours; Filter washing, drying; The compound of preparation accepted way of doing sth I, its reaction equation is following:
Formula I
The value of n is 2 or 3 or 4 or 6 or 12 in the formula.
3, preparation formula II compound
Perylene acid anhydride, 12 are joined in the N-Methyl pyrrolidone; The mol ratio of 60～65 ℃ of stirring reaction 1 hour perylene acid anhydrides and 12, N-Methyl pyrrolidone is 1:1.2:5～25 under nitrogen protection, and reaction finishes the solid that after-filtration obtains is washing with methyl alcohol, acetic acid, methyl alcohol, ether successively, and 3000Pa, 50～70 ℃ of dryings are 4～6 hours in vacuum drying oven; Obtain formula II compound, its reaction equation is following:
4, preparation formula III monomer
The formula II
Formula II compound is joined in the there-necked flask that fills thionyl chloride; The mol ratio of II compound and thionyl chloride is 1:30, and nitrogen protection refluxed 12 hours, reaction finished postcooling; Underpressure distillation is removed methyl-sulphoxide and is obtained formula III compound, and its reaction equation is following:
The formula III
5, preparation formula IV polymkeric substance
With the flask that fills formula III compound 60 ℃ of stirrings under the argon gas condition, remove residual thionyl chloride, be cooled to 0 ℃; Formula I compound and N-Methyl pyrrolidone are joined in the flask, the mol ratio of III compound and formula I compound, N-Methyl pyrrolidone is 1:1:5～20 again, and 100 ℃ of stirring reactions are 1 hour under nitrogen protection; Refluxed 1 hour, the question response temperature is reduced to 60 ℃, the solid matter that spinning obtains; Use methanol wash; In 50 ℃ of dryings of vacuum drying oven, get the IV polymkeric substance, its reaction equation is following:
6, Zhi Bei perylene diimide SUV polymer gel fluorescence sense film
Formula IV compound is dissolved in the N-Methyl pyrrolidone; Be mixed with mass percent and be 0.05%～0.4% storing solution, storing solution evenly is spun on the activation substrate, film forming thickness is 150～300nm; Room temperature was placed 1 hour; Vacuum-drying, sealing is preserved, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
Joins perylene acid anhydride, 12 in the N-Methyl pyrrolidone in preparation formula II compound step 3 of the present invention; The optimum mole ratio of 60～65 ℃ of stirring reaction 1 hour ， perylene acid anhydrides and 12, N-Methyl pyrrolidone is 1:1.2:10 under nitrogen protection, and reaction finishes the solid that after-filtration obtains and washing with methyl alcohol, acetic acid, methyl alcohol, ether successively; 3000Pa, 50～70 ℃ of dryings are 4～6 hours in vacuum drying oven, obtain formula II compound.
In preparation formula IV polymkeric substance step 5 of the present invention,, remove residual thionyl chloride with the flask that fills formula III compound 60 ℃ of stirrings under the argon gas condition; Be cooled to 0 ℃, formula I compound and N-Methyl pyrrolidone joined in the flask again, the optimum mole ratio of III compound and formula I compound, N-Methyl pyrrolidone is 1:1:15; 100 ℃ of stirring reactions are 1 hour under nitrogen protection, reflux 1 hour, and the question response temperature is reduced to 60 ℃; The solid matter that spinning obtains; Use methanol wash,, get the IV polymkeric substance in 50 ℃ of dryings of vacuum drying oven.
In Zhi Bei perylene diimide SUV polymer gel fluorescence sense film step 6 of the present invention, formula IV compound is dissolved in the N-Methyl pyrrolidone, be mixed with mass percent and be 0.05%～0.4% storing solution; Storing solution evenly is spun on the activation substrate; Film forming thickness is preferably 200～280nm, and room temperature was placed 1 hour, vacuum-drying; Sealing is preserved, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
In Zhi Bei perylene diimide SUV polymer gel fluorescence sense film step 6 of the present invention, formula IV compound is dissolved in the N-Methyl pyrrolidone, be mixed with mass percent and be 0.05%～0.4% storing solution; Storing solution evenly is spun on the activation substrate; Film forming thickness the best is 250nm, and room temperature was placed 1 hour, vacuum-drying; Sealing is preserved, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
Adopt the inventive method to prepare the purposes of De perylene diimide SUV polymer gel fluorescence sense film in methamphetamine analogue N-Methylphenethylamine detects, its method of use is following:
Perylene diimide SUV polymer gel fluorescence sense film is positioned over do not contain that 3 minutes ， are positioned over perylene diimide SUV polymer gel fluorescence sense film in the luminoscope in the N-Methylphenethylamine steam air, write down its fluorescent emission intensity I
0Zai was positioned over perylene diimide SUV polymer gel fluorescence sense film in the air that contains N-Methylphenethylamine steam 3 minutes; Then perylene diimide SUV polymer gel fluorescence sense film is positioned in the luminoscope; Luminoscope demonstrates its fluorescent emission intensity I to be weakened, and shows to detect to contain N-Methylphenethylamine gas in the air.
The present invention combines the SUV fragment Yu perylene diimide; Self-assembly characteristic by SUV; Design one type of supramolecule jelling agent; Gathering behavior through the regulation and control SUV makes it in solution, form the nanometer packaging assembly, and it is transferred to the organic amine senser element that the substrate surface preparation has the 1-dimention nano packaging assembly.The present invention is easy and simple to handle, reaction conditions is gentle; Prepared fluorescence sense film good stability, long service life, highly sensitive; Can be used for detecting the sensing diaphragm that contains methamphetamine analogue N-Methylphenethylamine gas; Also can this fluorescence sense film be installed on the detecting instrument that utilizes the fluorescence principle to detect N-Methylphenethylamine gas and use, directly detect after also can this fluorescence sense film being experienced N-Methylphenethylamine gas with fluorescent instrument.
Description of drawings
Fig. 1 is the fluorescence emission spectrogram of fluorescence sense film under different N-Methylphenethylamine vp of embodiment 1 preparation
Fig. 2 is the AFM photo of the fluorescence sense film of embodiment 1 preparation.
Embodiment
To further explain of the present invention, but the invention is not restricted to these embodiment below in conjunction with accompanying drawing and embodiment.
Embodiment 1
The preparation method that this reality is executed routine perylene diimide SUV polymer gel fluorescence sense film is made up of following step:
1, activation substrate
Be 30% ydrogen peroxide 50 with massfraction with massfraction be that 98% sulfuric acid is to mix at 1: 3 by volume, be mixed with washing lotion; With zero(ppm) water, washing with alcohol activation substrate, dry up in the submergence washing lotion of back heating washing lotion to 80～100 ℃; Activation 1～2 hour naturally cools to room temperature, with second distillation water washing activation substrate; Wash the washing lotion of remained on surface off, use drier, process the activation substrate.
2, preparation
At flow velocity is under the argon gas condition of 0.6～0.8mL/s; In the three-necked flask that fills the 12g methylene dichloride, adding the 6.3g diethylolamine mixes; Be 5% SUV chloro-formic ester dichloromethane solution to Dropwise 5 0mL mass concentration wherein again, the mol ratio of diethylolamine and methylene dichloride is 1: 2.5; 0 ℃ of stirring reaction 2 hours filters, washing, and drying obtains 1.2g formula I compound, and its reaction equation is following: the value of n is 2 in the formula.
Formula I
3, preparation formula II compound
Getting the mol ratio that 5g perylene acid anhydride, 5.73g 12 join perylene acid anhydride and 12 in the 6g N-Methyl pyrrolidone, N-Methyl pyrrolidone is 1:1.2:10, and 60～65 ℃ were stirred 1 hour under nitrogen protection, and reaction finishes after-filtration; Obtain the garnet solid; The garnet solid matter is washed with methyl alcohol, acetic acid, methyl alcohol, ether successively, 3000Pa, 50～70 ℃ of dryings are 4～6 hours in vacuum drying oven, obtain 8g formula II compound again.
The formula II
4, preparation formula III compound
2.3g joins in the there-necked flask that fills the 50mL thionyl chloride with formula II compound; The mol ratio of II compound and thionyl chloride is 1:30; Nitrogen protection refluxed 12 hours, question response finished postcooling to room temperature, and methyl-sulphoxide is removed in underpressure distillation; The 2.5g formula III compound that obtains, its reaction equation is following:
The formula III
5, preparation formula IV polymkeric substance
Modus ponens III compound 2.5g is contained in the flask, and residual thionyl chloride is removed in 60 ℃ of stirrings under argon gas feeds fast; Be cooled to 0 ℃, 3g formula I compound and 30mL N-Methyl pyrrolidone joined in the flask mix again, the mol ratio of III compound and formula I compound, N-Methyl pyrrolidone is 1:1:15; Under 100 ℃ of nitrogen protections, stirred 1 hour, refluxed 1 hour, temperature of reaction is reduced to 60 ℃; The solid matter that spinning obtains; Solid matter is used methanol wash, and 50 ℃ of dryings in vacuum drying oven get the IV polymkeric substance.
6, Zhi Bei perylene diimide SUV polymer gel fluorescence sense film
Formula IV compound is dissolved in the N-Methyl pyrrolidone, is mixed with mass percent and is 0.05%～0.4% storing solution, storing solution evenly is spun on the activation substrate; Film forming thickness is 250nm; Room temperature was placed 1 hour, and 3000Pa pressure, 50 ℃ of dryings are 24 hours in vacuum drying oven, take out; Sealing is preserved, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
Embodiment 2
The preparation method that this reality is executed routine perylene diimide SUV polymer gel fluorescence sense film is made up of following step:
In preparation step 2, flow velocity is under the argon gas condition of 0.6～0.8mL/s, in the three-necked flask that fills the 12g methylene dichloride, adds the 8.6g dipropanolamine, and the mol ratio of dipropanolamine and methylene dichloride is 1: 2.5; Be 5% SUV chloro-formic ester dichloromethane solution 50mL to wherein dripping mass percentage concentration again, other steps of this step are identical with embodiment 1, are prepared into 1.0g formula I compound, and the value of n is 3 in the formula.
Other steps are identical with embodiment 1, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
Embodiment 3
The preparation method that this reality is executed routine perylene diimide SUV polymer gel fluorescence sense film is made up of following step:
In preparation step 2, flow velocity is under the argon gas condition of 0.6～0.8mL/s, in the three-necked flask that fills the 12g methylene dichloride, adds 11.2g two butanolamines, and the mol ratio of two butanolamines and methylene dichloride is 1: 2.5; Be 5% SUV chloro-formic ester dichloromethane solution 50mL to wherein dripping mass percentage concentration again, other steps of this step are identical with embodiment 1, are prepared into 1.0g formula I compound, and the value of n is 4 in the formula.
Other steps are identical with embodiment 1, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
Embodiment 4
This reality is executed the preparation method of routine perylene diimide SUV polymer gel fluorescence sense film by being made up of following step:
In preparation step 2, be under the argon gas condition of 0.6～0.8mL/s at flow velocity, in the three-necked flask that fills the 12g methylene dichloride, add 18.0g two hexanol amine, the mass ratio of two hexanol amine and methylene dichloride is 1: 2.5; Be 5% SUV chloro-formic ester dichloromethane solution 50mL to wherein dripping mass percentage concentration again, other steps of this step are identical with embodiment 1, preparation accepted way of doing sth I compound, and the value of n is 6 in the formula.
Other steps are identical with embodiment 1, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
The preparation method of perylene diimide SUV polymer gel fluorescence sense film is made up of following step in the present embodiment:
In preparation step 2, be under the argon gas condition of 0.6～0.8mL/s at flow velocity, in the three-necked flask that fills the 12g methylene dichloride, add 38.4g two-12-hydramine, the mol ratio of two-12-hydramine and methylene dichloride is 1: 2.5; Be 5% SUV chloro-formic ester dichloromethane solution 50mL to wherein dripping mass percentage concentration again, other steps of this step are identical with embodiment 1, preparation accepted way of doing sth I compound, and the value of n is 12 in the formula.
Other steps are identical with embodiment 1, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
Embodiment 6
In the step 2 of embodiment 1～5; At flow velocity is under the argon gas condition of 0.6～0.8mL/s, in the three-necked flask that fills the 4.8g methylene dichloride, adds glycol amine and mixes, and the mol ratio of glycol amine and methylene dichloride is 1: 1; Other steps of this step are identical with embodiment 1, preparation accepted way of doing sth I compound.
Other steps are identical with embodiment 1, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
Embodiment 7
In the step 2 of embodiment 1～5; At flow velocity is under the argon gas condition of 0.6～0.8mL/s, in the three-necked flask that fills the 48g methylene dichloride, adds glycol amine and mixes, and the mol ratio of glycol amine and methylene dichloride is 1: 10; Other steps of this step are identical with embodiment 1, preparation accepted way of doing sth I compound.
Other steps are identical with respective embodiments, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
Embodiment 8
In the preparation formula IV compound step 5 of embodiment 1～5; With the flask that fills 2.5g formula III compound 60 ℃ of stirrings under the argon gas condition, remove residual thionyl chloride, be cooled to 0 ℃; Again formula I compound and 10mL N-Methyl pyrrolidone are joined in the flask; The mol ratio of III compound and formula I compound, N-Methyl pyrrolidone is 1:1:5, and other steps of this step are identical with embodiment 1, preparation accepted way of doing sth IV compound.
Other steps are identical with respective embodiments, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
Embodiment 9
In the preparation formula IV compound step 5 of embodiment 1～5; With the flask that fills 2.5g formula III compound 60 ℃ of stirrings under the argon gas condition, remove residual thionyl chloride, be cooled to 0 ℃; Again formula I compound and 40mL N-Methyl pyrrolidone are joined in the flask; The mol ratio of III compound and formula I compound, N-Methyl pyrrolidone is 1:1:20, and other steps of this step are identical with embodiment 1, preparation accepted way of doing sth IV compound.
Other steps are identical with respective embodiments, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
In the step 6 of the Zhi of embodiment 1～9 Bei perylene diimide SUV polymer gel fluorescence sense film, formula IV compound is dissolved in the N-Methyl pyrrolidone, be mixed with mass percent and be 0.05%～0.4% storing solution; Storing solution evenly is spun on the activation substrate; Film forming thickness is 150nm, and room temperature was placed 1 hour, vacuum-drying; Sealing is preserved, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
In the step 6 of the Zhi of embodiment 1～9 Bei perylene diimide SUV polymer gel fluorescence sense film, formula IV compound is dissolved in the N-Methyl pyrrolidone, be mixed with mass percent and be 0.05%～0.4% storing solution; Storing solution evenly is spun on the activation substrate; Film forming thickness is 300nm, and room temperature was placed 1 hour, vacuum-drying; Sealing is preserved, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
Embodiment 12
The purposes of embodiment 1 preparation De perylene diimide SUV polymer gel fluorescence sense film in methamphetamine analogue N-Methylphenethylamine detects, its method of use is following:
Do not contain with adopting the embodiment of the invention 1 preparation De perylene diimide SUV polymer gel fluorescence sense film that perylene diimide SUV polymer gel fluorescence sense film is positioned over that 3 minutes are positioned over perylene diimide SUV polymer gel fluorescence sense film in the luminoscope in the N-Methylphenethylamine steam air, write down its fluorescent emission intensity I0.Zai was positioned over perylene diimide SUV polymer gel fluorescence sense film in the air that contains N-Methylphenethylamine steam 3 minutes; Then perylene diimide SUV polymer gel fluorescence sense film is positioned in the luminoscope; Luminoscope demonstrates its fluorescent emission intensity I to be weakened, and shows to detect to contain N-Methylphenethylamine gas in the air.
In order to verify beneficial effect of the present invention, the contriver adopts the embodiment of the invention 1 preparation De perylene diimide SUV polymer gel fluorescence sense film to carry out a large amount of laboratory study tests, and various test situation are following:
Laboratory apparatus: FLS920 type single photon counting time resolution fluorescence spectral appearance, produce by Britain Edinburgh instrument company.
1 、, perylene diimide SUV polymer gel fluorescence sense film is to the detection sensitivity test of N-Methylphenethylamine steam
Adopt FLS920 type single photon counting time resolution fluorescence spectral appearance that the embodiment of the invention 1 preparation De perylene diimide SUV polymer gel fluorescence sense film is measured the detection sensitivity of N-Methylphenethylamine steam; Testing method is identical with embodiment 12; The N-Methylphenethylamine vapour concentration of being measured is respectively 3,5,8,11,14ppb, result such as Fig. 1.Visible by Fig. 1; Prepared De perylene diimide SUV polymer gel fluorescence sense film has tangible fluorescence intensity to change when N-Methylphenethylamine vapour concentration is merely 3ppb, and the Ming perylene diimide SUV polymer gel fluorescence sense film of Shuoing has very high detection sensitivity to N-Methylphenethylamine steam.
2 、, perylene diimide SUV polymer gel fluorescence sense film is tested N-Methylphenethylamine steam response speed
Adopt FLS920 type single photon counting time resolution fluorescence spectral appearance that the embodiment of the invention 1 Zhi Bei perylene diimide SUV polymer gel fluorescence sense film is measured the detection speed of N-Methylphenethylamine steam, testing method is identical with embodiment 12.The mensuration concentration of the N-Methylphenethylamine steam of selecting for use is respectively 3,5,8,11,14ppb.Experiment finds that prepared De perylene diimide SUV polymer gel fluorescence sense film has very fast response speed to N-Methylphenethylamine steam, reaches a second level.
3 、, the selectivity of perylene diimide SUV polymer gel fluorescence sense film test
Adopt FLS920 type single photon counting time resolution fluorescence spectral appearance to measure the embodiment of the invention 1 preparation De perylene diimide SUV polymer gel fluorescence sense film at N-Methylphenethylamine, 2; 4; 6 trotyls, 2,4-DNT, 2,4; Place 50 seconds fluorescent emission intensity in the 190ppm steam of 6-trinitrophenol, oil of mirbane, toluene, benzene, testing method is identical with embodiment 12.
Test result is seen table 1.
Table 1 perylene diimide SUV polymer gel fluorescence sense film in time fluorescence intensity in different organic steams
Visible by table 1, prepared De perylene diimide SUV polymer gel fluorescence sense film is 2,4; 6-trotyl, 2; In the saturation steam of 4-DNT, 2, oil of mirbane, toluene, benzene; Fluorescence intensity does not have considerable change, and what these organic solvents were described exists the detection of Dui perylene diimide SUV polymer gel fluorescence sense film noiseless; Perylene diimide SUV polymer gel fluorescence sense film is in the saturation steam of N-Methylphenethylamine; Fluorescence intensity generation considerable change; Storage period, the fluorescence intensity of long more perylene diimide SUV polymer gel fluorescence sense film was low more, and the Ming perylene diimide SUV polymer gel fluorescence sense film of Shuoing has good selective response to N-Methylphenethylamine steam.
Claims (6)
1. the preparation method of a perylene diimide SUV polymer gel fluorescence sense film is characterized in that this method is made up of following step:
(1) activation substrate
Be 30% ydrogen peroxide 50 with massfraction with massfraction be that 98% sulfuric acid is to mix at 1: 3 by volume, be mixed with washing lotion; With zero(ppm) water, washing with alcohol activation substrate, dry up in the submergence washing lotion of back heating washing lotion to 80～100 ℃; Activation 1～2 hour naturally cools to room temperature, with second distillation water washing activation substrate; Wash the washing lotion of remained on surface off, use drier, process the activation substrate;
(2) preparation
At flow velocity is under the argon gas condition of 0.6～0.8mL/s, in the mixture of glycol amine and methylene dichloride, drips mass percentage concentration and is in 5% the SUV chloro-formic ester dichloromethane solution, and the mol ratio of glycol amine and methylene dichloride is 1: 1～10; 0 ℃ of stirring reaction 2 hours; Filter washing, drying; The compound of preparation accepted way of doing sth I, its reaction equation is following:
Formula I
The value of n is 2 or 3 or 4 or 6 or 12 in the formula;
(3) preparation formula II compound
Perylene acid anhydride, 12 are joined in the N-Methyl pyrrolidone; The mol ratio of 60～65 ℃ of stirring reaction 1 hour perylene acid anhydrides and 12, N-Methyl pyrrolidone is 1:1.2:5～25 under nitrogen protection, and reaction finishes the solid that after-filtration obtains is washing with methyl alcohol, acetic acid, methyl alcohol, ether successively, and 3000Pa, 50～70 ℃ of dryings are 4～6 hours in vacuum drying oven; Obtain formula II compound, its reaction equation is following:
The formula II
(4) preparation formula III monomer
Formula II compound is joined in the there-necked flask that fills thionyl chloride; The mol ratio of II compound and thionyl chloride is 1:30, and nitrogen protection refluxed 12 hours, reaction finished postcooling; Underpressure distillation is removed methyl-sulphoxide and is obtained formula III compound, and its reaction equation is following:
The formula III
(5) preparation formula IV polymkeric substance
With the flask that fills formula III compound 60 ℃ of stirrings under the argon gas condition, remove residual thionyl chloride, be cooled to 0 ℃; Formula I compound and N-Methyl pyrrolidone are joined in the flask, the mol ratio of III compound and formula I compound, N-Methyl pyrrolidone is 1:1:5～20 again, and 100 ℃ of stirring reactions are 1 hour under nitrogen protection; Refluxed 1 hour, the question response temperature is reduced to 60 ℃, the solid matter that spinning obtains; Use methanol wash; In 50 ℃ of dryings of vacuum drying oven, get the IV polymkeric substance, its reaction equation is following:
(6) Zhi Bei perylene diimide SUV polymer gel fluorescence sense films
Formula IV compound is dissolved in the N-Methyl pyrrolidone; Be mixed with mass percent and be 0.05%～0.4% storing solution, storing solution evenly is spun on the activation substrate, film forming thickness is 150～300nm; Room temperature was placed 1 hour; Vacuum-drying, sealing is preserved, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
2. according to the preparation method of claim 1 Suo Shu De perylene diimide SUV polymer gel fluorescence sense film; It is characterized in that: joins perylene acid anhydride, 12 aminoundecane-earboxylic acids in the N-Methyl pyrrolidone in preparation formula II compound step (3); The mol ratio of 60～65 ℃ of stirring reaction 1 hour ， perylene acid anhydrides and 12, N-Methyl pyrrolidone is 1:1.2:10 under nitrogen protection, and reaction finishes the solid that after-filtration obtains and washing with methyl alcohol, acetic acid, methyl alcohol, ether successively; 3000Pa, 50～70 ℃ of dryings are 4～6 hours in vacuum drying oven, obtain formula II compound.
3. according to the preparation method of claim 1 Suo Shu De perylene diimide SUV polymer gel fluorescence sense film, it is characterized in that: in preparation formula IV polymkeric substance step (5), the flask that fills formula III compound 60 ℃ of stirrings under the argon gas condition; Remove residual thionyl chloride, be cooled to 0 ℃, again formula I compound and N-Methyl pyrrolidone are joined in the flask; The mol ratio of III compound and formula I compound, N-Methyl pyrrolidone is 1:1:15; 100 ℃ of stirring reactions are 1 hour under nitrogen protection, reflux 1 hour, and the question response temperature is reduced to 60 ℃; The solid matter that spinning obtains; Use methanol wash,, get the IV polymkeric substance in 50 ℃ of dryings of vacuum drying oven.
4. according to the preparation method of claim 1 Suo Shu De perylene diimide SUV polymer gel fluorescence sense film; It is characterized in that: in the Zai Zhi Bei perylene diimide SUV polymer gel fluorescence sense film step (6), formula IV compound is dissolved in the N-Methyl pyrrolidone, is mixed with mass percent and is 0.05%～0.4% storing solution; Storing solution evenly is spun on the activation substrate; Film forming thickness is 200～280nm, and room temperature was placed 1 hour, vacuum-drying; Sealing is preserved, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
5. according to the preparation method of claim 1 Suo Shu De perylene diimide SUV polymer gel fluorescence sense film; It is characterized in that: in the Zai Zhi Bei perylene diimide SUV polymer gel fluorescence sense film step (6), formula IV compound is dissolved in the N-Methyl pyrrolidone, is mixed with mass percent and is 0.05%～0.4% storing solution; Storing solution evenly is spun on the activation substrate; Film forming thickness is 250nm, and room temperature was placed 1 hour, vacuum-drying; Sealing is preserved, Zhi Bei Cheng perylene diimide SUV polymer gel fluorescence sense film.
6. the purposes of claim 1 perylene diimide SUV polymer gel fluorescence sense film in methamphetamine analogue N-Methylphenethylamine detects.
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Cited By (7)
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|---|---|---|---|---|
| CN104892606A (en) * | 2015-05-15 | 2015-09-09 | 陕西师范大学 | Preparation and application of fluorescent compound having sensing function on methamphetamine and methamphetamine analogues and preparation and application of fluorescent sensing thin film |
| CN104964955A (en) * | 2015-05-26 | 2015-10-07 | 广西师范学院 | Production method and application of fluorescence gel film for detecting mercury ions |
| CN105254656A (en) * | 2015-11-30 | 2016-01-20 | 陕西师范大学 | Amphipathy BODIPY derivative and preparing method thereof |
| CN105548098A (en) * | 2015-12-03 | 2016-05-04 | 中国科学院上海微系统与信息技术研究所 | Fluorescent probe and detection method for detection of methamphetamine or/and ketamine |
| CN114874279A (en) * | 2022-06-14 | 2022-08-09 | 中国药科大学 | Steroid-perylene diimide compound, preparation method and preparation and application of fluorescent film thereof |
| CN116589757A (en) * | 2023-07-17 | 2023-08-15 | 苏州驳凡熹科技有限公司 | Degradable film fluorescence sensor and preparation method and application thereof |
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| CN106872435B (en) * | 2017-04-14 | 2019-07-16 | 重庆大学 | Protein bio luminescence imaging sensor based on acid imide multiarm polymers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4978625A (en) * | 1987-10-19 | 1990-12-18 | Becton, Dickinson And Company | Fluorescence immunoassay using water insoluble dyes |
| CN102353661A (en) * | 2011-06-29 | 2012-02-15 | 陕西师范大学 | Fluorescent sensor film preparation method based on perylene diimide cholesterol derivative |
-
2012
- 2012-05-10 CN CN 201210143615 patent/CN102702546B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4978625A (en) * | 1987-10-19 | 1990-12-18 | Becton, Dickinson And Company | Fluorescence immunoassay using water insoluble dyes |
| CN102353661A (en) * | 2011-06-29 | 2012-02-15 | 陕西师范大学 | Fluorescent sensor film preparation method based on perylene diimide cholesterol derivative |
Non-Patent Citations (3)
| Title |
|---|
| 《化学通报》 20080915 冯君茜等 "以苝二酰胺为构筑块的超分子聚集体的研究进展" 第650－658页 1－6 , 第9期 * |
| DING LP ET AL.: ""Chemically assembled monolayers of fluorophores as chemical sensing materials"", 《CHEMICAL SOCIETY REVIEWS》 * |
| 冯君茜等: ""以苝二酰胺为构筑块的超分子聚集体的研究进展"", 《化学通报》 * |
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| CN104892606B (en) * | 2015-05-15 | 2017-01-25 | 陕西师范大学 | Preparation and application of fluorescent compound having sensing function on methamphetamine and methamphetamine analogues and preparation and application of fluorescent sensing thin film |
| CN104964955A (en) * | 2015-05-26 | 2015-10-07 | 广西师范学院 | Production method and application of fluorescence gel film for detecting mercury ions |
| CN104964955B (en) * | 2015-05-26 | 2017-08-11 | 广西师范学院 | A kind of preparation method and application for being used to detect the fluorescence gel film of mercury ion |
| CN105254656A (en) * | 2015-11-30 | 2016-01-20 | 陕西师范大学 | Amphipathy BODIPY derivative and preparing method thereof |
| CN105254656B (en) * | 2015-11-30 | 2017-03-22 | 陕西师范大学 | Amphipathy BODIPY derivative and preparing method thereof |
| CN105548098A (en) * | 2015-12-03 | 2016-05-04 | 中国科学院上海微系统与信息技术研究所 | Fluorescent probe and detection method for detection of methamphetamine or/and ketamine |
| CN105548098B (en) * | 2015-12-03 | 2018-07-13 | 中国科学院上海微系统与信息技术研究所 | A kind of fluorescence probe and detection method detecting crystal methamphetamine or/and ketamine |
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| CN116731319A (en) * | 2023-06-15 | 2023-09-12 | 济南大学 | Perylene bisimide covalent organic polymer film and preparation method and application thereof |
| CN116589757A (en) * | 2023-07-17 | 2023-08-15 | 苏州驳凡熹科技有限公司 | Degradable film fluorescence sensor and preparation method and application thereof |
| CN116589757B (en) * | 2023-07-17 | 2023-09-22 | 苏州驳凡熹科技有限公司 | Degradable film fluorescence sensor and preparation method and application thereof |
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