CN102702546B - 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
- Publication number
- CN102702546B CN102702546B CN 201210143615 CN201210143615A CN102702546B CN 102702546 B CN102702546 B CN 102702546B CN 201210143615 CN201210143615 CN 201210143615 CN 201210143615 A CN201210143615 A CN 201210143615A CN 102702546 B CN102702546 B CN 102702546B
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- polymer gel
- preparation
- fluorescence sense
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
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 cholesterol 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 hydrogen atom in ammonia, and be the odor polluting source of a quasi-representative.Investigation is found, all can produce the amine composition in the industrial production of many industries and vegeto-animal decay process, stack field, rubbish container, water drain etc. such as chemical plant, pharmaceutical factory, tannery, packing house, hennery and fishery products, the generating source that can regard the amine repugnant substance as, and organic amine also plays very important effect in industrial production.
In the middle of numerous organic amines, methyl amphetamine (being commonly called as methamphetamine) is violated drugs international, domestic strict control, it is also one of present most popular Drug abuse, the central nervous system of grievous injury human body not only after suction, and habituation is very big, then causes a series of social concerns.Because the methamphetamine raw materials is cheap, synthetic technology is simple, and only China in 2008 has just captured 6.15 tons.But capturing of these drugs is mainly to complete under help by drug law enforcement criminal policeman's personal experience or police dog, and therefore not hard to imagine still have a large amount of methamphetamines to flow to society.At present the detection method for methamphetamine mainly contains the gas chromatography-mass spectrography technology, high performance liquid chromatography, and immunological technique, these methods are mainly to detect for liquid phase, can not be in real time, fast drugs are detected.In view of above present situation, the exploitation for methyl amphetamine fast and efficiently the detection technique tool be of great significance.
In numerous detection techniques, fluorescent method has advantages of that response is quick, simple to operate, highly sensitive, selectivity 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 by the method for spin coating, have realized the selectivity of gas phase methyl amphetamine is detected.
At first the seminar at contriver place prepares film forming with derivatives of porphyrin and the doping of poly-fluorenes of metal-complexing, due to transfer transport effect strong between metal ion and porphyrin, film fluorescence is by quencher, but when methyl amphetamine is introduced, specific combination due to itself and metal 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 investigation chemical sensor performance quality of sensitivity, response speed and recovery, limited greatly its application in real drugs fighting work.Therefore, the sensing material of development with good autonomous dress characteristic satisfies real demand tool and is of great significance.Such desirable 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 effectively is assembled into these sensing materials the regular nanometer network structure such as nanofiber and remains so far a very challenging research field.
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 cholesterol polymer gel fluorescence sense film is provided.
Another technical problem to be solved by this invention is as adopting aforesaid method that a kind of new purposes that provides of De perylene diimide cholesterol polymer gel fluorescence sense film is provided.
Solving the problems of the technologies described above the technical scheme that adopts is that the method is comprised of following step:
1, activation substrate
Be 30% hydrogen peroxide with massfraction be that 98% sulfuric acid is to mix at 1: 3 by volume with massfraction, be mixed with washing lotion; With distilled water, washing with alcohol activation substrate, dry up in rear submergence washing lotion heating washing lotion to 80～100 ℃, activate 1～2 hour, naturally cool to room temperature, with second distillation water washing activation substrate, wash the washing lotion of remained on surface off, dry up with blower, make the activation substrate.
2, preparationⅠcompound
Be under the argon gas condition of 0.6～0.8mL/s at flow velocity, drip mass percentage concentration in the mixture of glycol amine and methylene dichloride and be in 5% cholesterol chloro-formic ester dichloromethane solution, 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 as follows:
Formula I
In formula, the value of n is 2 or 3 or 4 or 6 or 12.
3, preparation formula II compound
Perylene acid anhydride, 12－aminolauric acid are joined in N-Methyl pyrrolidone; the mol ratio of 1 hour perylene acid anhydride of 60～65 ℃ of stirring reactions and 12－aminolauric acid, N-Methyl pyrrolidone is 1:1.2:5～25 under nitrogen protection; filtering the solid that obtains after reaction finishes is 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, its reaction equation is as follows:
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, refluxes 12 hours under nitrogen protection, and reaction is cooling after finishing; underpressure distillation is removed methyl-sulphoxide and is obtained formula III compound, and its reaction equation is as follows:
The formula III
5, preparation formula IV polymkeric substance
Flask 60 ℃ of stirrings under the argon gas condition of formula III compound will be filled; remove residual thionyl chloride; be cooled to 0 ℃; again formula I compound and N-Methyl pyrrolidone are joined in flask; the mol ratio of III compound and formula I compound, N-Methyl pyrrolidone is 1:1:5～20; 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 centrifugation obtains is used methanol wash, in 50 ℃ of dryings of vacuum drying oven; get the IV polymkeric substance, its reaction equation is as follows:
6, Bei perylene diimide cholesterol polymer gel fluorescence sense film processed
Formula IV compound is dissolved in 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, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Is in perylene acid anhydride, 12－aminolauric acid join N-Methyl pyrrolidone in preparation formula II compound step 3 of the present invention; the optimum mole ratio of 1 hour perylene acid anhydride of 60～65 ℃ of stirring reactions and 12－aminolauric acid, N-Methyl pyrrolidone is 1:1.2:10 under nitrogen protection; filtering the solid that obtains after reaction finishes is 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; flask 60 ℃ of stirrings under the argon gas condition of formula III compound will be filled; remove residual thionyl chloride; be cooled to 0 ℃; again formula I compound and N-Methyl pyrrolidone are joined in flask; 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; refluxed 1 hour; the question response temperature is reduced to 60 ℃, and the solid matter that centrifugation obtains is used methanol wash; in 50 ℃ of dryings of vacuum drying oven, get the IV polymkeric substance.
In Bei perylene diimide cholesterol polymer gel fluorescence sense film step 6 processed of the present invention, formula IV compound is dissolved in 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, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
In Bei perylene diimide cholesterol polymer gel fluorescence sense film step 6 processed of the present invention, formula IV compound is dissolved in 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, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Adopt the inventive method to prepare the purposes of De perylene diimide cholesterol polymer gel fluorescence sense film in methamphetamine analogue N-Methylphenethylamine detects, its using method is as follows:
Perylene diimide cholesterol polymer gel fluorescence sense film is positioned over does not contain that in N-Methylphenethylamine steam air, 3 minutes ， are positioned over perylene diimide cholesterol polymer gel fluorescence sense film in luminoscope, record its fluorescent emission intensity I
0Zai is positioned in the air that contains N-Methylphenethylamine steam 3 minutes Jiang perylene diimide cholesterol polymer gel fluorescence sense film, then perylene diimide cholesterol polymer gel fluorescence sense film is positioned in luminoscope, luminoscope demonstrates its fluorescent emission intensity I to be weakened, and shows to detect to contain N-Methylphenethylamine gas in air.
The present invention combines the cholesterol fragment Yu perylene diimide, self-assembly characteristic by cholesterol, design a class supramolecule jelling agent, gathering behavior by the regulation and control cholesterol makes it form the nanometer packaging assembly in solution, 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 this fluorescence sense film can be arranged on the detecting instrument that utilizes the fluorescence principle to detect N-Methylphenethylamine gas and use, directly detect with fluorescent instrument after also this fluorescence sense film can being experienced N-Methylphenethylamine gas.
Description of drawings
Fig. 1 is the fluorescence emission spectrogram of fluorescence sense film under different N-Methylphenethylamine vapour pressure of embodiment 1 preparation
Fig. 2 is the atomic force microscopy of the fluorescence sense film of embodiment 1 preparation.
Embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Embodiment 1
The preparation method of this Shi Shi Li perylene diimide cholesterol polymer gel fluorescence sense film is comprised of following step:
1, activation substrate
Be 30% hydrogen peroxide with massfraction be that 98% sulfuric acid is to mix at 1: 3 by volume with massfraction, be mixed with washing lotion; With distilled water, washing with alcohol activation substrate, dry up in rear submergence washing lotion heating washing lotion to 80～100 ℃, activate 1～2 hour, naturally cool to room temperature, with second distillation water washing activation substrate, wash the washing lotion of remained on surface off, dry up with blower, make the activation substrate.
2, preparationⅠcompound
Be under the argon gas condition of 0.6～0.8mL/s at flow velocity, add the 6.3g diethanolamine to mix in the three-necked flask that fills the 12g methylene dichloride, drip wherein the 50mL mass concentration again and be 5% cholesterol chloro-formic ester dichloromethane solution, the mol ratio of diethanolamine 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 as follows: in formula, the value of n is 2.
Formula I
3, preparation formula II compound
Getting the mol ratio that 5g perylene acid anhydride, 5.73g 12－aminolauric acid join perylene acid anhydride and 12－aminolauric acid in the 6g N-Methyl pyrrolidone, N-Methyl pyrrolidone is 1:1.2:10; 60～65 ℃ were stirred 1 hour under nitrogen protection; reaction is filtered after finishing; 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
Formula II compound 2.3g is joined in the there-necked flask that fills the 50mL thionyl chloride; the mol ratio of II compound and thionyl chloride is 1:30; refluxed 12 hours under nitrogen protection; cool to room temperature after question response finishes; methyl-sulphoxide is removed in underpressure distillation; the 2.5g formula III compound that obtains, its reaction equation is as follows:
The formula III
5, preparation formula IV polymkeric substance
Modus ponens III compound 2.5g is contained in flask; pass into fast lower 60 ℃ of stirrings at argon gas; remove residual thionyl chloride; be cooled to 0 ℃; again 3g formula I compound and 30mL N-Methyl pyrrolidone are joined in flask and mix; the mol ratio of III compound and formula I compound, N-Methyl pyrrolidone is 1:1:15; stirred 1 hour under 100 ℃ of nitrogen protections; refluxed 1 hour; temperature of reaction is reduced to 60 ℃, the solid matter that centrifugation obtains, solid matter methanol wash; 50 ℃ of dryings, get the IV polymkeric substance in vacuum drying oven.
6, Bei perylene diimide cholesterol polymer gel fluorescence sense film processed
Formula IV compound is dissolved in 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 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, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Embodiment 2
The preparation method of this Shi Shi Li perylene diimide cholesterol polymer gel fluorescence sense film is comprised of following step:
In preparationⅠcompound step 2, flow velocity is under the argon gas condition of 0.6～0.8mL/s, adds the 8.6g dipropanolamine in the three-necked flask that fills the 12g methylene dichloride, and the mol ratio of dipropanolamine and methylene dichloride is 1: 2.5; Drip wherein mass percentage concentration again and be 5% cholesterol chloro-formic ester dichloromethane solution 50mL, other steps of this step are identical with embodiment 1, are prepared into 1.0g formula I compound, and in formula, the value of n is 3.
Other steps are identical with embodiment 1, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Embodiment 3
The preparation method of this Shi Shi Li perylene diimide cholesterol polymer gel fluorescence sense film is comprised of following step:
In preparationⅠcompound step 2, flow velocity is under the argon gas condition of 0.6～0.8mL/s, adds 11.2g two butanolamines in the three-necked flask that fills the 12g methylene dichloride, and the mol ratio of two butanolamines and methylene dichloride is 1: 2.5; Drip wherein mass percentage concentration again and be 5% cholesterol chloro-formic ester dichloromethane solution 50mL, other steps of this step are identical with embodiment 1, are prepared into 1.0g formula I compound, and in formula, the value of n is 4.
Other steps are identical with embodiment 1, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Embodiment 4
The preparation method of this Shi Shi Li perylene diimide cholesterol polymer gel fluorescence sense film is by being comprised of following step:
In preparationⅠcompound step 2, be under the argon gas condition of 0.6～0.8mL/s at flow velocity, add 18.0g two hexanol amine in the three-necked flask that fills the 12g methylene dichloride, the mass ratio of two hexanol amine and methylene dichloride is 1: 2.5; Drip wherein mass percentage concentration again and be 5% cholesterol chloro-formic ester dichloromethane solution 50mL, other steps of this step are identical with embodiment 1, preparation accepted way of doing sth I compound, and in formula, the value of n is 6.
Other steps are identical with embodiment 1, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Embodiment 5
The preparation method of the present embodiment Zhong perylene diimide cholesterol polymer gel fluorescence sense film is comprised of following step:
In preparationⅠcompound step 2, be under the argon gas condition of 0.6～0.8mL/s at flow velocity, add 38.4g two-12-hydramine in the three-necked flask that fills the 12g methylene dichloride, the mol ratio of two-12-hydramine and methylene dichloride is 1: 2.5; Drip wherein mass percentage concentration again and be 5% cholesterol chloro-formic ester dichloromethane solution 50mL, other steps of this step are identical with embodiment 1, preparation accepted way of doing sth I compound, and in formula, the value of n is 12.
Other steps are identical with embodiment 1, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Embodiment 6
In the step 2 of embodiment 1～5, be under the argon gas condition of 0.6～0.8mL/s at flow velocity, add glycol amine to mix in the three-necked flask that fills the 4.8g methylene dichloride, 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, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Embodiment 7
In the step 2 of embodiment 1～5, be under the argon gas condition of 0.6～0.8mL/s at flow velocity, add glycol amine to mix in the three-necked flask that fills the 48g methylene dichloride, 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 corresponding embodiment, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Embodiment 8
In the preparation formula IV compound step 5 of embodiment 1～5, flask 60 ℃ of stirrings under the argon gas condition of 2.5g formula III compound will be filled, remove residual thionyl chloride, be cooled to 0 ℃, again formula I compound and 10mL N-Methyl pyrrolidone are joined in 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 corresponding embodiment, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Embodiment 9
In the preparation formula IV compound step 5 of embodiment 1～5, flask 60 ℃ of stirrings under the argon gas condition of 2.5g formula III compound will be filled, remove residual thionyl chloride, be cooled to 0 ℃, again formula I compound and 40mL N-Methyl pyrrolidone are joined in 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 corresponding embodiment, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Embodiment 10
In the step 6 of the Bei perylene diimide cholesterol polymer gel fluorescence sense film processed of embodiment 1～9, formula IV compound is dissolved in 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, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Embodiment 11
In the step 6 of the Bei perylene diimide cholesterol polymer gel fluorescence sense film processed of embodiment 1～9, formula IV compound is dissolved in 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, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
Embodiment 12
The purposes of embodiment 1 preparation De perylene diimide cholesterol polymer gel fluorescence sense film in methamphetamine analogue N-Methylphenethylamine detects, its using method is as follows:
Do not contain with adopting the embodiment of the present invention 1 preparation De perylene diimide cholesterol polymer gel fluorescence sense film that perylene diimide cholesterol polymer gel fluorescence sense film is positioned over that in N-Methylphenethylamine steam air, 3 minutes are positioned over perylene diimide cholesterol polymer gel fluorescence sense film in luminoscope, record its fluorescent emission intensity I0.Zai is positioned in the air that contains N-Methylphenethylamine steam 3 minutes Jiang perylene diimide cholesterol polymer gel fluorescence sense film, then perylene diimide cholesterol polymer gel fluorescence sense film is positioned in luminoscope, luminoscope demonstrates its fluorescent emission intensity I to be weakened, and shows to detect to contain N-Methylphenethylamine gas in air.
In order to verify beneficial effect of the present invention, the contriver adopts the embodiment of the present invention 1 preparation De perylene diimide cholesterol polymer gel fluorescence sense film to carry out a large amount of laboratory study tests, and various test situation are as follows:
Laboratory apparatus: FLS920 type single photon counting time resolution fluorescence spectral instrument, produced by Britain Edinburgh instrument company.
1,, the detection sensitivity test of perylene diimide cholesterol polymer gel fluorescence sense film to N-Methylphenethylamine steam
Adopt FLS920 type single photon counting time resolution fluorescence spectral instrument that the embodiment of the present invention 1 preparation De perylene diimide cholesterol 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 measuring is respectively 3,5,8,11,14ppb, result such as Fig. 1.As seen from Figure 1, prepared De perylene diimide cholesterol polymer gel fluorescence sense film has obvious fluorescence intensity to change when N-Methylphenethylamine vapour concentration only is 3ppb, and the Ming perylene diimide cholesterol polymer gel fluorescence sense film of Shuoing has very high detection sensitivity to N-Methylphenethylamine steam.
2,, perylene diimide cholesterol polymer gel fluorescence sense film is tested N-Methylphenethylamine steam response speed
Adopt FLS920 type single photon counting time resolution fluorescence spectral instrument that the embodiment of the present invention 1 Bei perylene diimide processed cholesterol 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 selected N-Methylphenethylamine steam is respectively 3,5,8,11,14ppb.The experiment discovery, prepared De perylene diimide cholesterol polymer gel fluorescence sense film has very fast response speed to N-Methylphenethylamine steam, reaches a second level.
3,, the Choice tests of perylene diimide cholesterol polymer gel fluorescence sense film
Adopt FLS920 type single photon counting time resolution fluorescence spectral instrument to measure the embodiment of the present invention 1 preparation De perylene diimide cholesterol polymer gel fluorescence sense film at N-Methylphenethylamine, 2,4,6 trotyls, 2,4-dinitrotoluene (DNT), 2,4, place the fluorescent emission intensity of 50 seconds in the 190ppm steam of 6-trinitrophenol, oil of mirbane, toluene, benzene, testing method is identical with embodiment 12.
Test result sees Table 1.
Table 1 perylene diimide cholesterol polymer gel fluorescence sense film in time fluorescence intensity in different organic steams
By as seen from Table 1, prepared De perylene diimide cholesterol polymer gel fluorescence sense film is 2,4,6-trotyl, 2, in the saturation steam of 4-dinitrotoluene (DNT), 2，4，6-trinitrophenol, oil of mirbane, toluene, benzene, fluorescence intensity is without considerable change, and what these organic solvents were described exists the detection of Dui perylene diimide cholesterol polymer gel fluorescence sense film noiseless; Perylene diimide cholesterol polymer gel fluorescence sense film is in the saturation steam of N-Methylphenethylamine, fluorescence intensity generation considerable change, storage period, the fluorescence intensity of longer perylene diimide cholesterol polymer gel fluorescence sense film was lower, and the Ming perylene diimide cholesterol polymer gel fluorescence sense film of Shuoing has good selective response to N-Methylphenethylamine steam.
Claims (6)
1. the preparation method of Yi Zhong perylene diimide cholesterol polymer gel fluorescence sense film is characterized in that the method is comprised of following step:
(1) activation substrate
Be 30% hydrogen peroxide with massfraction be that 98% sulfuric acid is to mix at 1: 3 by volume with massfraction, be mixed with washing lotion; With distilled water, washing with alcohol activation substrate, dry up in rear submergence washing lotion heating washing lotion to 80～100 ℃, activate 1～2 hour, naturally cool to room temperature, with second distillation water washing activation substrate, wash the washing lotion of remained on surface off, dry up with blower, make the activation substrate;
(2) preparationⅠcompound
Be under the argon gas condition of 0.6～0.8mL/s at flow velocity, drip mass percentage concentration in the mixture of glycol amine and methylene dichloride and be in 5% cholesterol chloro-formic ester dichloromethane solution, 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 as follows:
In formula, the value of n is 2 or 3 or 4 or 6 or 12;
(3) preparation formula II compound
Perylene acid anhydride, 12－aminolauric acid are joined in N-Methyl pyrrolidone; the mol ratio of 1 hour perylene acid anhydride of 60～65 ℃ of stirring reactions and 12－aminolauric acid, N-Methyl pyrrolidone is 1:1.2:5～25 under nitrogen protection; filtering the solid that obtains after reaction finishes is 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, its reaction equation is as follows:
(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, refluxes 12 hours under nitrogen protection, and reaction is cooling after finishing; underpressure distillation is removed methyl-sulphoxide and is obtained formula III compound, and its reaction equation is as follows:
(5) preparation formula IV polymkeric substance
Flask 60 ℃ of stirrings under the argon gas condition of formula III compound will be filled; remove residual thionyl chloride; be cooled to 0 ℃; again formula I compound and N-Methyl pyrrolidone are joined in flask; the mol ratio of III compound and formula I compound, N-Methyl pyrrolidone is 1:1:5～20; 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 centrifugation obtains is used methanol wash, in 50 ℃ of dryings of vacuum drying oven; get the IV polymkeric substance, its reaction equation is as follows:
(6) Bei perylene diimide processed cholesterol polymer gel fluorescence sense films
Formula IV compound is dissolved in 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, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
2. according to the preparation method of claim 1 Suo Shu De perylene diimide cholesterol polymer gel fluorescence sense film, it is characterized in that: in preparation formula II compound step (3), Jiang the perylene acid anhydride, 12－aminolauric acid joins in N-Methyl pyrrolidone, 60～65 ℃ of stirring reactions are 1 hour under nitrogen protection, perylene acid anhydride and 12－aminolauric acid, the mol ratio of N-Methyl pyrrolidone is 1:1.2:10, filter the solid that obtains after reaction finishes and using successively methyl alcohol, acetic acid, methyl alcohol, ether washs, 3000Pa in vacuum drying oven, 50～70 ℃ of dryings 4～6 hours, obtain formula II compound.
3. according to the preparation method of claim 1 Suo Shu De perylene diimide cholesterol polymer gel fluorescence sense film, it is characterized in that: in preparation formula IV polymkeric substance step (5), flask 60 ℃ of stirrings under the argon gas condition of formula III compound will be filled, remove residual thionyl chloride, be cooled to 0 ℃, again formula I compound and N-Methyl pyrrolidone are joined in flask, III compound and formula I compound, the mol ratio of N-Methyl pyrrolidone is 1:1:15, 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 centrifugation obtains, use methanol wash, in 50 ℃ of dryings of vacuum drying oven, get the IV polymkeric substance.
4. according to the preparation method of claim 1 Suo Shu De perylene diimide cholesterol polymer gel fluorescence sense film, it is characterized in that: in Zai Bei perylene diimide processed cholesterol polymer gel fluorescence sense film step (6), formula IV compound is dissolved in 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 200～280nm, room temperature was placed 1 hour, vacuum-drying, sealing is preserved, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
5. according to the preparation method of claim 1 Suo Shu De perylene diimide cholesterol polymer gel fluorescence sense film, it is characterized in that: in Zai Bei perylene diimide processed cholesterol polymer gel fluorescence sense film step (6), formula IV compound is dissolved in 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 250nm, room temperature was placed 1 hour, vacuum-drying, sealing is preserved, Bei Cheng perylene diimide cholesterol polymer gel fluorescence sense film processed.
6. according to the purposes of claim 1 Suo Shu De perylene diimide cholesterol polymer gel fluorescence sense film in methamphetamine analogue N-Methylphenethylamine detects.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210143615 CN102702546B (en) | 2012-05-10 | 2012-05-10 | Preparation method of perylene bisimide cholesterol polymer gel fluorescent sensing film, and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210143615 CN102702546B (en) | 2012-05-10 | 2012-05-10 | Preparation method of perylene bisimide cholesterol polymer gel fluorescent sensing film, and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102702546A CN102702546A (en) | 2012-10-03 |
| CN102702546B true CN102702546B (en) | 2013-11-06 |
Family
ID=46895623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210143615 Active CN102702546B (en) | 2012-05-10 | 2012-05-10 | Preparation method of perylene bisimide cholesterol polymer gel fluorescent sensing film, and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102702546B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106872435A (en) * | 2017-04-14 | 2017-06-20 | 重庆大学 | The protein bio luminescence imaging sensor of Ji Yu perylene diimide multiarm polymers |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN105254656B (en) * | 2015-11-30 | 2017-03-22 | 陕西师范大学 | Amphipathy BODIPY derivative and preparing method thereof |
| 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 |
| 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 |
| CN116731319A (en) * | 2023-06-15 | 2023-09-12 | 济南大学 | Perylene bisimide covalent organic polymer film 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 |
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 (4)
| Title |
|---|
| "Chemically assembled monolayers of fluorophores as chemical sensing materials";Ding LP et al.;《CHEMICAL SOCIETY REVIEWS》;20101231;第39卷(第11期);第4258－4273页 * |
| "以苝二酰胺为构筑块的超分子聚集体的研究进展";冯君茜等;《化学通报》;20080915(第9期);第650－658页 * |
| Ding LP et al.."Chemically assembled monolayers of fluorophores as chemical sensing materials".《CHEMICAL SOCIETY REVIEWS》.2010,第39卷(第11期),第4258－4273页. |
| 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》.2008,(第9期),第650－658页. |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106872435A (en) * | 2017-04-14 | 2017-06-20 | 重庆大学 | The protein bio luminescence imaging sensor of Ji Yu perylene diimide multiarm polymers |
| CN106872435B (en) * | 2017-04-14 | 2019-07-16 | 重庆大学 | Protein bio luminescence imaging sensor based on acid imide multiarm polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102702546A (en) | 2012-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102702546B (en) | Preparation method of perylene bisimide cholesterol polymer gel fluorescent sensing film, and application thereof | |
| CN101864029B (en) | Molecularly imprinted polymer and preparation method and application thereof | |
| CN102353661B (en) | Fluorescent sensor film preparation method based on perylene diimide cholesterol derivative | |
| Makarević et al. | Bis (amino acid) oxalyl amides as ambidextrous gelators of water and organic solvents: supramolecular gels with temperature dependent assembly/dissolution equilibrium | |
| CN101768238B (en) | Citrinin molecular engram material and preparation method as well as application thereof | |
| CN104892606A (en) | Preparation and application of fluorescent compound having sensing function on methamphetamine and methamphetamine analogues and preparation and application of fluorescent sensing thin film | |
| CN104910316B (en) | A kind of macromolecule colorimetric nano film material and preparation method thereof and it is used for Fe3+With the application of pyrophosphate context of detection | |
| CN103837523B (en) | A kind of method detecting orthene and test kit | |
| CN109406474A (en) | A kind of aggregation-induced emission-molecular engram fluorescent optical sensor preparation method and application detecting rhodamine B | |
| CN105085413B (en) | Tetrahydroquinazoline-2-schiff base compounds as well as synthesis method and application thereof | |
| Chichak et al. | Nanoscale borromeates | |
| CN107189012B (en) | The preparation method and product of phthalate molecularly imprinted polymer and application | |
| CN107698614A (en) | A kind of carborane diimide derivative and synthetic method and the sensor array based on it and preparation method and application | |
| CN101935400B (en) | Alkali metal-cucurbituril multilayer mesh organic framework polymer and synthetic method and application thereof | |
| CN104987346A (en) | Method for preparing fluorescence polyamino compound | |
| CN109364880A (en) | It is a kind of with circulation parsing function supermolecule organic framework materials and removal water body in organic dyestuff application | |
| CN107915655A (en) | A kind of organogel compound and preparation method and application | |
| Zhou et al. | A novel photo‐responsive organogel based on azobenzene | |
| CN107033331A (en) | A kind of fluorescence conjugated macromolecule of side-chain amino group protonation, preparation method and applications | |
| Dalapati et al. | Reusable anion detection kit: An aqueous medium anion detection | |
| CN102866226B (en) | Method for using pyrazosulfuron-ethyl molecularly imprinted polymer for analyzing sulfonylurea herbicide and application thereof | |
| Jang et al. | Supramolecular nanofiber formation of macrocyclic dendrimer | |
| CN106964323A (en) | A kind of novel C O containing imine linkage2Sorbing material and its preparation method and application | |
| Yu et al. | Hydroxytyrosol magnetic molecularly imprinted polymers as the sorbent for solid-phase extraction for selective recognition of hydroxytyrosol from Chinese olive leaves | |
| CN103626405B (en) | Single fluorescent conjugated polymer film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |