CN103951840B - A kind of preparation method and application for detecting salicylic fluorescence sense film - Google Patents
A kind of preparation method and application for detecting salicylic fluorescence sense film Download PDFInfo
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- CN103951840B CN103951840B CN201410214863.9A CN201410214863A CN103951840B CN 103951840 B CN103951840 B CN 103951840B CN 201410214863 A CN201410214863 A CN 201410214863A CN 103951840 B CN103951840 B CN 103951840B
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Abstract
A kind of preparation method and application for detecting salicylic fluorescence sense film, it relates to preparation and the application of fluorescence sense film.It is intended to solve the technical problem that existing detection salicylic molecular engram film preparation process is complicated.This fluorescence sense film be with polymer as substrate, phthalic acid ester as plasticizer and template molecule, with 4 (N ' methyl piperazine base) the 1,8 naphthalimide derivative M1 thin film as fluorescent molecular probe.Preparation method: polymer, phthalic acid ester and M1 are dissolved in solvent, then solution is spread in slide surface, obtain sensing membrane after solvent volatilization.Application: sample to be tested is dissolved in buffer solution as sample to be tested, optical fiber fluorescence is detected the optical fiber head fluorescence sense film cladding of device, detection sample to be tested and the fluorescence intensity of blank sample, if Fluorescence Increasing, then containing salicylic acid in sample to be tested, detection by quantitative utilizes standard curve method.Can be used for salicylic detection in water, beverage and medicine.
Description
Technical field
The present invention relates to fluorescence sense film and preparation thereof and application.
Background technology
Salicylic acid is a kind of important Organic Chemicals being applied to the aspects such as medicine, spice, dyestuff and pesticide, due to it
Preferably " exfoliation, unclogging " ability, high safety, the zest low to skin, makes it a kind of new standby
Favorite skin-protection product.Additionally, it is mainly used as preparing the medical material of aspirin antibiotic medicine.But the bigcatkin willow of excess
Acid may result in the generation of some side effect, such as skin pruritus, allergy, serious tinnitus, dizziness and other situations, therefore
Set up the most quickly salicylic acid content detection method significant.
The salicylic method of conventional detection has headspace liquid-phase microextraction, spectral technique, high performance liquid chromatography, capillary electrophoresis
Method, fluorescence immunoassay and electrochemical techniques etc..But these methods have some shortcomings to a certain extent, such as selectivity
Low, time-consuming, medicine is prepared complicated, to need costliness instrument, the experiment condition of accurate control and spends high.Relative to upper
The method stated, utilizes the method for Fibre Optical Sensor to have simply, and low cost, response time is short, disturbs the advantages such as little.Utilize
Needing to be prepared as probe substance fluorescence sense film in the method for Fibre Optical Sensor, fluorescence sense film has highly sensitive, selects
Property is good, does not pollute system to be measured and the advantage such as reusable, by the extensive concern of scientists.
Meng etc. are at the 132-145 page article " optimizing surface trace delivered of the 231st phases in 2013 of " Chemical Engineering journal "
Layer PVDF membrane salicylic acid in the Selective Separation aspirin " disclose and a kind of salicylic acid is had high selection
Property molecular engram film (MIM), this film use methacrylic acid (MAA), acrylamide (AM), 4-vinylpyridine (4-VP)
For function monomer, poly-(vinylidene fluoride) (PVDF) is template, and benzophenone is that light trigger synthesis obtains, and prepares
Film needs with apparatus,Soxhlet's eluted template and unnecessary initiator in the mixed solvent of methanol/acetic acid (9:1).Although the party
Blotting membrane prepared by method can realize salicylic detection, but detection method exists the shortcoming that blotting membrane preparation process is complicated.
Summary of the invention
The present invention is to solve the technical problem that existing detection salicylic molecular engram film preparation process is complicated, and provide one
Plant the preparation method and application for detecting salicylic fluorescence sense film.
It is to spread out with 4-(N '-methyl-piperazinyl group)-1,8-naphthalimide that the one of the present invention is used for detecting salicylic fluorescence sense film
Biology is fluorescent molecular probe, and this 4-(N '-methyl-piperazinyl group)-1, the molecular structural formula formula of 8-naphthalimide derivative is such as
Under:
In formula: R1、R2It is the alkyl of C12～C20.
It is above-mentioned that to be used for detecting salicylic fluorescence sense film be to be divided by 4-(N '-methyl-piperazinyl group)-1,8-naphthalimide derivative
It is dispersed in the addition of and the polymeric film of phthalic acid ester formed.
In above-mentioned fluorescence sense film, with polymer as substrate, phthalic acid ester as plasticizer and template molecule, with 4-(N '-
Methyl-piperazinyl group)-1,8-naphthalimide derivative is fluorescent molecular probe.
Above-mentioned is as follows for detecting the preparation method of salicylic fluorescence sense film:
One, 50～150mg polymer, 100～300mg phthalic acid ester are weighed, 0.5～1.5mg4-(N '-methyl-
Piperazinyl)-1,8-naphthalimide derivative, they are all dissolved in 5mL solvent, obtain solution；
Two, solution prepared by step one being spread in slide surface, volatilization naturally under room temperature, then by slide surface
Film strips down, and obtains for detecting salicylic fluorescence sense film.
Utilize and above-mentioned salicylic acid is carried out the method for qualitative detection according to the following steps for detecting salicylic fluorescence sense film
Carry out:
One, testing sample is joined in the buffer solution that pH value is 2.0～5.0, mix homogeneously, obtain sample to be tested, then
By this buffer solution as blank sample；
Two, blank sample and sample to be tested are separately added in the sample cell of optical fiber fluorescence detection device, then will be with detection bigcatkin willow
The optical fiber head that the fluorescence sense film cladding of acid is got up is put in sample cell, excites with ultraviolet source, detects the glimmering of blank sample
Light intensity value A0Fluorescence intensity level A with sample to be tested1；
Three, fluorescence intensity level and A are compared1If, A1Compare A0Improve more than 20%, then judge in sample to be tested containing water
Poplar acid.
Utilize and above-mentioned salicylic acid is carried out the method for detection by quantitative according to the following steps for detecting salicylic fluorescence sense film
Carry out:
One, by salicylic concentration from low to high, salicylic acid is joined in the buffer solution that pH value is 2.0～5.0, mixed
Close uniformly, obtain multiple standard specimen, then testing sample is joined in this buffer solution, obtain sample to be tested；
Two, standard specimen, testing sample are separately added in the sample cell of optical fiber fluorescence detection device, then with detecting bigcatkin willow
The optical fiber head that the fluorescence sense film cladding of acid is got up is put in sample cell, excites with ultraviolet source, detects multiple standard specimen
Fluorescence intensity level, mark for vertical with fluorescence intensity level, be denoted as figure with salicylic concentration for horizontal, obtain standard work song
Line；The fluorescence intensity level A of detection sample to be tested1；
Three, according to fluorescence intensity level A1, from standard curve, find salicylic content, complete salicylic acid detection by quantitative.
The sensing membrane of the present invention with single selective Fluorescence Increasing identification salicylic acid, can use the method detection bigcatkin willow of the present invention
Acid, not by other related compound such as ascorbic acid, PABA ethyl ester, nicotiamide, acamol, sugar
The impact of essence, aspirin, m-hydroxybenzoic acid, theophylline, P-hydroxybenzoic acid etc., has high selectivity.With
Britton-Robinson etc. are as buffer solution, and the solvent of buffer solution is water.Owing to testing in water, easy to use.
In the range of pH value is 2.0～5.0, sensing membrane is used for salicylic detection by Fluorescence Increasing.The linearity test of the method
Scope is 2.3 × 10-6Mol/L～1.0 × 10-3Mol/L, detection is limited to 2.3 × 10-6mol/L.Be alternately added salicylic acid and
Blank solution, sensing membrane fluorescence intensity generation reversibility changes.It is applied to this sensing membrane detect in the actual medicine of aspirin
Salicylic acid, the response rate is between 99.0%～102.0%.In a word, the inventive method be a kind of easy and simple to handle, highly sensitive,
Response time is short, reusable, the fluorescence sense film detection method of good stability.
Advantage of the present invention is as follows:
1. the present invention establishes a kind of with 4-(N '-methyl-piperazinyl group)-1, and 8-naphthalimide derivative M1 is luciferase assay reagent,
Polymer is substrate, and phthalic acid ester is the preparation method of the new fluorescence sense film of plasticizer and template molecule, simplifies
The preparation process of sensing membrane.
2. the present invention utilizes optical fiber fluorescence to detect device, intercepts the fluorescence sense film of suitable size, is coated on optical fiber head
Portion, is placed in the optical fiber handled well in the liquid to be measured containing sample, ultraviolet excitation, and fluorescence intensity based on sensing membrane is with water
The change of poplar acid concentration, establishes a kind of new salicylic acid quantitative detecting method.
3. the present invention is in weak acid buffer solution, and compared with a series of related compounds, low concentration salicylic acid makes fluorescence pass
The Fluorescence Increasing of sense film single selective.
4. the present invention to salicylic identification not by related compound such as ascorbic acid, PABA ethyl ester, nicotiamide,
The impact that acamol, saccharin, aspirin, m-hydroxybenzoic acid, theophylline, P-hydroxybenzoic acid coexist,
There is high selectivity.
5. the invention provides a kind of easy and simple to handle, response time (＜ 30s), high selectivity, high sensitivity and low inspection rapidly
The salicylic method of rising limit detection by quantitative.
6. present invention can apply to salicylic detection in actual sample, such as lake water, beverage, aspirin, flutter heat breath
Bitterly, salicylic detection by quantitative in benzocaine etc..
Accompanying drawing explanation
Fig. 1 be embodiment 1 test 1 in fluorescence intensity with the graph of relation of the change of pH value.
Fig. 2 be embodiment 1 test 2 in the analogue compounds change in fluorescence figure to sensing membrane.
Fig. 3 be embodiment 1 test 3 in other analogue compounds and the salicylic acid change in fluorescence figure of sensing membrane when competing.
Fig. 4 is in the test 6 of embodiment 1, fluorescence intensity and Determination of Salicylic Acid graph of a relation.
Detailed description of the invention
Detailed description of the invention one: the one of present embodiment be used for detecting salicylic fluorescence sense film be with 4-(N '-methyl-
Piperazinyl)-1,8-naphthalimide derivative is fluorescent molecular probe, this 4-(N '-methyl-piperazinyl group)-1, and 8-naphthalimide derives
The molecular structural formula formula of thing is as follows:
In formula: R1、R2It is the alkyl of C12～C20.
Detailed description of the invention two: present embodiment is used for detecting salicylic fluorescence sense unlike detailed description of the invention one
Film is to be dispersed in the polymeric film that with the addition of phthalic acid ester by 4-(N '-methyl-piperazinyl group)-1,8-naphthalimide derivative
Formed.
In present embodiment with polymer as substrate, with phthalic acid ester as plasticizer and template molecule, with 4-(N '-methyl
-piperazinyl)-1,8-naphthalimide derivative is fluorescent molecular probe.
The thickness of thin film is 0.1 μm～20 μm；
Detailed description of the invention three: the polymer described unlike detailed description of the invention two of present embodiment be polrvinyl chloride,
Polymethyl methacrylate or polyvinyl acetate.Other is identical with detailed description of the invention two.
Detailed description of the invention four: present embodiment phthalic acid ester described in unlike detailed description of the invention two or three is
Dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate or adjacent benzene two
Formic acid diamyl ester；Other is identical with detailed description of the invention two or three.
Detailed description of the invention five: present embodiment is used for detecting salicylic unlike one of detailed description of the invention one to four
In fluorescence sense film, phthalic acid ester is (1.6～3.0) with the mass ratio of polymer: 1；Polymer and 4-(N '-methyl-
Piperazinyl) mass ratio of-1,8-naphthalimide derivative is (30～300): 1.One of other and detailed description of the invention one to four
Identical.
Detailed description of the invention six: being used for described in detailed description of the invention one detects the preparation method of salicylic fluorescence sense film and press
Following steps are carried out:
One, polymer, phthalic acid ester are taken, 4-(N '-methyl-piperazinyl group)-1,8-naphthalimide derivative, they are the most molten
Solution, in solvent, obtains solution；
Two, solution prepared by step one being spread in slide surface, volatilization naturally under room temperature, then by slide surface
Film strips down, and obtains for detecting salicylic fluorescence sense film.
Detailed description of the invention seven: present embodiment is used for detecting salicylic fluorescence sense unlike detailed description of the invention six
The preparation method of film is as follows:
One, 50～150mg polymer, 100～300mg phthalic acid ester are weighed, 0.5～1.5mg4-(N '-methyl-
Piperazinyl)-1,8-naphthalimide derivative, they are all dissolved in 5mL solvent, obtain solution；
Two, solution prepared by step one being spread in slide surface, volatilization naturally under room temperature, then by slide surface
Film strips down, and obtains for detecting salicylic fluorescence sense film.
Detailed description of the invention eight: present embodiment is the polymer described in step one unlike detailed description of the invention six or seven
For polrvinyl chloride, polymethyl methacrylate or polyvinyl acetate；Other are identical with detailed description of the invention six or seven.
Detailed description of the invention nine: present embodiment is the neighbour described in step one unlike one of detailed description of the invention six to eight
Phthalic acid ester is dimethyl phthalate, diethyl phthalate, dipropyl phthalate, phthalic acid two
Butyl ester or diamyl phthalate；Other are identical with one of detailed description of the invention six to eight.
The addition of the phthalic acid ester described in step one can be effectively improved the pliability of sensing membrane, simultaneously because adjacent benzene two
Formic acid esters can be automatically migrated in solution from sensing membrane, it is to avoid eluting mould in conventional molecular imprinted polymer preparation process
The step of plate molecule, thus simplify the preparation of fluorescence sense film.
Detailed description of the invention ten: present embodiment molten described in step one unlike one of detailed description of the invention six to nine
Agent is Ketohexamethylene, hexamethylene or acetone；Other are identical with one of detailed description of the invention six to nine.
Detailed description of the invention 11: present embodiment is unlike one of detailed description of the invention six to ten described in step one
Dissolving is to use water-bath, ultrasonic or microwave treatment mode to promote to dissolve；Other are identical with one of detailed description of the invention six to ten.
Detailed description of the invention 12: utilize described in detailed description of the invention one for detecting salicylic fluorescence sense film to bigcatkin willow
Acid carries out the method for qualitative detection and sequentially includes the following steps:
One, testing sample is joined in the buffer solution that pH value is 2.0～5.0, mix homogeneously, obtain sample to be tested, then
By this buffer solution as blank sample；
Two, blank sample and sample to be tested are separately added in the sample cell of optical fiber fluorescence detection device, then will be with detection bigcatkin willow
The optical fiber head that the fluorescence sense film cladding of acid is got up is put in sample cell, excites with ultraviolet source, detects the glimmering of blank sample
Light intensity value A0Fluorescence intensity level A with sample to be tested1；
Three, fluorescence intensity level and A are compared1If, A1Compare A0Improve more than 20%, then judge in sample to be tested containing water
Poplar acid.
Detailed description of the invention 13；Buffer solution in present embodiment step one unlike detailed description of the invention 12 is
Britton-Robinson buffer solution, glycine-HCI buffer solution, disodium hydrogen phosphate-citric acid solution or Fructus Citri Limoniae
Acid-sodium hydroxide-hydrochloric acid buffer solution.Other are identical with detailed description of the invention 12.
Detailed description of the invention 14: utilize described in detailed description of the invention one to four for detecting salicylic fluorescence sense film pair
Salicylic acid carries out the method for detection by quantitative and sequentially includes the following steps:
One, by salicylic concentration from low to high, salicylic acid is joined in the buffer solution that pH value is 2.0～5.0, mixed
Close uniformly, obtain multiple standard specimen, then testing sample is joined in this buffer solution, obtain sample to be tested；
Two, standard specimen, testing sample are separately added in the sample cell of optical fiber fluorescence detection device, then with detecting bigcatkin willow
The optical fiber head that the fluorescence sense film cladding of acid is got up is put in sample cell, excites with ultraviolet source, detects multiple standard specimen
Fluorescence intensity level, mark for vertical with fluorescence intensity level, be denoted as figure with salicylic concentration for horizontal, obtain standard work song
Line；The fluorescence intensity level A of detection sample to be tested1；
Three, according to fluorescence intensity level A1, from standard curve, find salicylic content, complete salicylic acid detection by quantitative.
Beneficial effects of the present invention is verified by following example:
Embodiment 1: the preparation method being used for detecting salicylic fluorescence sense film of the present embodiment is as follows:
One, 68.0mg polrvinyl chloride, 200mg dibutyl phthalate are weighed, 1.0mg 1,3-bis-(4-(N '-methyl-
Piperazinyl)-N-octadecyl-1,8-naphthalimide) base benzene, use immersion method they to be all dissolved in 5mL Ketohexamethylene,
To solution；Wherein 1,3-bis-(4-(N '-methyl-piperazinyl group)-N-octadecyl-1,8-naphthalimide) structural formula of base benzene is as follows:
Two, solution prepared by step one being spread in slide surface, under room temperature, Ketohexamethylene volatilizees naturally, then by microscope slide
The film on surface strips down, and obtains for detecting salicylic fluorescence sense film.
Fluorescence sense film thickness prepared by the present embodiment is 0.2 μm.
The fluorescence sense film prepared by the present embodiment 1 is used for following test.
Test 1: intercept the sensing membrane of the embodiment 1 of suitable size, is coated on the optical fiber head of optical fiber fluorescence detection device
Portion, immerses in the sample cell of ultra-pure water and salicylic acid solution that concentration is 1mmol/L respectively by optical fiber head portion, with HCl or
NaOH solution regulation pH value, excites with ultraviolet source, measures the change with pH value of the sensing membrane fluorescence intensity.Obtain
Fluorescence intensity with the change of pH value relation curve as it is shown in figure 1, wherein a be in ultra-pure water fluorescence intensity with pH value
The relation curve of change, b be in the salicylic acid solution that concentration is 1mmol/L fluorescence intensity with the pass of the change of pH value
It is curve, the curve that two fluorescence intensities of comparison diagram 1 change with pH value, it is known that, it is 2.0～5.0 scopes at pH value
In, salicylic acid solution makes sensing membrane fluorescence be obviously enhanced.Showing, it is 2.0～5.0 models that sensing membrane can be used in pH value
Enclose interior salicylic detection.
Test 2: intercept the sensing membrane of the embodiment 1 of suitable size, is coated on the optical fiber head of optical fiber fluorescence detection device
Portion, optical fiber head portion is immersed respectively concentration be 1mmol/L different compounds (ascorbic acid, PABA ethyl ester,
Nicotiamide, acamol, saccharin, aspirin, m-hydroxybenzoic acid, theophylline, P-hydroxybenzoic acid and water
Poplar acid) water (0.1mol/L Britton-Robinson, pH=3.0) solution sample cell in, measure its fluorescence spectrum, read
Fluorescence intensity level, is vertical mark by fluorescence intensity, and abscissa represents classes of compounds, draws glimmering to sensing membrane of analogue compounds
Light variation diagram is as in figure 2 it is shown, the horizontal work mark 1-11 of Fig. 2 represents respectively: 1: blank；2: ascorbic acid；3: nicotiamide；
4: aspirin；5: ethylaminobenzoate；6: P-hydroxybenzoic acid；7: theophylline；8: acetylaminobenzene
Phenol；9: saccharin；10: m-hydroxybenzoic acid；11: salicylic acid.Figure it is seen that only salicylic acid causes sensing membrane
Fluorescence is obviously enhanced, and the aqueous solution of other compound is inconspicuous on the impact of sensing membrane fluorescence spectrum.Show, this enforcement
The fluorescence sense film of example can detect salicylic acid by single selective in different compound solutions.
Test 3: intercept the sensing membrane of the embodiment 1 of suitable size, be coated on optical fiber head, the optical fiber that will process
Head immerse respectively salicylic acid (1mmol/L) and from different compounds (ascorbic acid, PABA ethyl ester, nicotiamide,
Acamol, saccharin, aspirin, m-hydroxybenzoic acid, theophylline, P-hydroxybenzoic acid) water (0.1 that coexists
Mol/L Britton-Robinson, pH=3.0) solution sample cell in, measure its fluorescence spectrum, read fluorescence intensity level,
Being vertical mark by fluorescence intensity, abscissa represents classes of compounds, draws sensing membrane when other analogue compounds are competed with salicylic acid
Change in fluorescence figure as it is shown on figure 3, Fig. 3 horizontal work mark 1-11 represent respectively: 1: salicylic acid；2: aspirin+bigcatkin willow
Acid；3: ethylaminobenzoate+salicylic acid；4: nicotiamide+salicylic acid；5: acamol+salicylic acid；6: sugar
Essence+salicylic acid；7: m-hydroxybenzoic acid+salicylic acid；8: P-hydroxybenzoic acid+salicylic acid；9: ascorbic acid+salicylic acid；10:
Theophylline+salicylic acid.From figure 3, it can be seen that the most inconspicuous interference of the existence of other compounds is containing salicylic acid in salicylic acid solution
The fluorescent emission of sensing membrane in solution, its fluorescence intensity is similar to when only existing salicylic acid.Showing, sensing membrane is to salicylic
Fluoroscopic examination is not coexisted by other compound to be affected.
Test 4: intercept the sensing membrane of the embodiment 1 of suitable size, be coated on optical fiber head, the optical fiber that will process
Head immerse respectively salicylic acid (1mmol/L) and from different compounds (ascorbic acid, PABA ethyl ester, nicotiamide,
Acamol, saccharin, aspirin, m-hydroxybenzoic acid, theophylline, P-hydroxybenzoic acid) water (0.1 that coexists
Mol/L disodium hydrogen phosphate-citric acid, pH=3.0) solution sample cell in, concentration is 1mmol/L, measures its fluorescence
Spectrum.The fluorescent emission of sensing membrane in the existence of other compounds the most inconspicuous interference salicylic acid solution in salicylic acid solution, its
Fluorescence intensity is similar to when only existing salicylic acid.Show what salicylic fluoroscopic examination was not coexisted by sensing membrane by different compounds
Impact.
Test 5: intercept the sensing membrane of the embodiment 1 of suitable size, be coated on optical fiber head, the optical fiber that will process
Head immerse respectively salicylic acid (1mmol/L) and from different compounds (ascorbic acid, PABA ethyl ester, nicotiamide,
Acamol, saccharin, aspirin, m-hydroxybenzoic acid, theophylline, P-hydroxybenzoic acid) water (0.1 that coexists
Mol/L citric acid-sodium hydroxide-hydrochloric acid, pH=3.0) solution sample cell in, concentration is 1mmol/L, measures it glimmering
Light spectrum.Find, the fluorescence of sensing membrane in the existence of other compounds the most inconspicuous interference salicylic acid solution in salicylic acid solution
Launching, its fluorescence intensity is similar to when only existing salicylic acid.Show that sensing membrane is not subject to different chemical combination to salicylic fluoroscopic examination
The impact that thing coexists.
Test 6: intercept the sensing membrane of the embodiment 1 of suitable size, be coated on optical fiber head, the optical fiber that will process
Head immerses in the sample cell of blank water (0.1mol/L Britton-Robinson, pH=3.0) solution, is then gradually added into not
The salicylic acid solution (0.1mol/L Britton-Robinson, pH=3.0, [salicylic acid]=10mM) of same volume, measures it glimmering
Light intensity.Mark for vertical with fluorescence intensity, make plot with salicylic concentration for horizontal, the fluorescence intensity obtained and salicylic acid
Concentration relationship figure as shown in Figure 4, figure 4, it is seen that along with salicylic addition, sensing membrane fluorescence intensity gradually increases
Add, maximum emission wavelength generation blue shift, move to 490nm from 505nm.When Determination of Salicylic Acid is 2.3 × 10-6～1.0 × 10-3
In the range of mol/L, the fluorescence intensity of sensing membrane and Determination of Salicylic Acid present good linear relationship (R2=0.9937), its line
Property regression equation is y=20.96x+16.29；Blank sample is carried out 20 parallel assays, and by 3 σ/K, (σ is zero standard
Deviation, K is the slope of regression equation), calculate detection and be limited to 2.3 × 10-6mol/L.Show that the sensing membrane of the present embodiment can
With highly sensitive detection salicylic acid.
Test 7: intercept the sensing membrane of the embodiment 1 of suitable size, be coated on optical fiber head, the optical fiber that will process
Head alternately immerses blank water (0.1mol/L Britton-Robinson, pH=3.0) solution and salicylic acid (0.1mol/L
Britton-Robinson, pH=3.0, [salicylic acid]=1mmol/L) solution sample cell in, the fluorescence measuring sensing membrane is strong
Degree.Alternately sensing membrane is immersed blank and salicylic acid solution, circulate obtain for 5 times fluorescence intensity be respectively 17.1,35.6,17.4,
34.5、18.1、35.4、16.7、35.3、18.4、35.8.Response time is less than 30s.Show the sensing membrane of the present embodiment
Salicylic identification is had favorable reproducibility, the advantage that reversible and response time is short.
Test 8: intercept the sensing membrane of the embodiment 1 of suitable size, be coated on optical fiber head, the optical fiber that will process
Head immerses in the sample cell of 1mmol/L salicylic acid (0.1mol/L Britton-Robinson, pH=3.0) solution, every
30min measures the fluorescence intensity of sensing membrane, obtain fluorescence intensity be respectively 34.1,34.3,34.1,34.2,34.1,34.0,
34.3、34.3、34.1、34.4、34.2、34.4、34.3、34.2、34.2、34.3、34.5、34.1、34.0、34.5、
34.2、34.1、34.1、34.2；Calculating relative standard deviation is 0.41%.Show the sensing membrane stability of the present embodiment relatively
Good.
Test 9: the dry sensing membrane putting preservation embodiment 1, every 10 days, intercepts the sensing membrane of suitable size, Jiang Qibao
It is overlying on optical fiber head, the optical fiber head portion processed is immersed respectively the sample cell of the salicylic acid solution of ultra-pure water and 1mmol/L
In, measure the change with the holding time of the sensing membrane fluorescence intensity.Sensing membrane fluorescence intensity in ultra-pure water is respectively 17.2,
17.5,17.6,16.7,17.9,17.3,16.9,16.5,17.4；Sensing membrane fluorescence intensity in salicylic acid solution is respectively
It is 35.2,34.8,34.7,35.5,35.3,35.5,34.9,34.8,35.0.Preserve sensing membrane after 3 months, sensing membrane
Fluorescence response salicylic acid is stable.Show that the sensing membrane of the present embodiment is long for service life.
Test 10: the fluorescence sense film of embodiment 1 preparation, for the detection aqueous solution (0.1mol/L containing aspirin medicine
Britton-Robinson, pH=3.0) in salicylic acid content, specifically comprise the following steps that
One, by salicylic concentration from low to high, salicylic acid is joined 0.1mol/L Britton-Robinson buffer solution
In, pH=3.0, mix homogeneously, obtain multiple standard specimen, then press variable concentrations to be measured is added containing aspirin medicine
In this buffer solution, obtain five samples to be tested；
Two, standard specimen, testing sample are separately added in the sample cell of optical fiber fluorescence detection device, then with detecting bigcatkin willow
The optical fiber head that the fluorescence sense film cladding of acid is got up is put in sample cell, excites with ultraviolet source, detects multiple standard specimen
Fluorescence intensity level, mark for vertical with fluorescence intensity level, be denoted as figure with salicylic concentration for horizontal, obtain standard work song
Line；On curve, fluorescence intensity is linear with salicylic acid content, and the equation of linear regression of standard working curve is y=
24.965x+14.914, linearly dependent coefficient R2It is 0.997；The fluorescence intensity level of five samples to be tested of detection；
Three, according to the fluorescence intensity level of sample to be tested, from standard curve, find salicylic content, complete salicylic acid quantitative
Detection.
Under these experimental conditions, aspirin medicine adds the salicylic acid of known quantity, measure its fluorescence intensity, in conjunction with
Standard curve method measures salicylic content, calculates the salicylic response rate and is respectively 99.0%, and 99.6%, 101.2%,
101.7%, 100.3%.Show that the sensing membrane of the present embodiment may be used for detecting salicylic content in aspirin medicine,
And the most accurately.
Test 11: the fluorescence sense film of embodiment 1 preparation, for the detection aqueous solution (0.1mol/L containing acetaminophen medicine
Britton-Robinson, pH=3.0) in salicylic acid content, specifically comprise the following steps that
One, by salicylic concentration from low to high, salicylic acid is joined 0.1mol/L Britton-Robinson buffer solution
In, pH=3.0, mix homogeneously, obtain multiple standard specimen, then press variable concentrations to be measured is added containing acetaminophen medicine
In this buffer solution, obtain five samples to be tested；
Two, standard specimen, testing sample are separately added in the sample cell of optical fiber fluorescence detection device, then with detecting bigcatkin willow
The optical fiber head that the fluorescence sense film cladding of acid is got up is put in sample cell, excites with ultraviolet source, detects multiple standard specimen
Fluorescence intensity level, mark for vertical with fluorescence intensity level, be denoted as figure with salicylic concentration for horizontal, obtain standard work song
Line；Fluorescence intensity is linear with salicylic acid content, and the equation of linear regression of standard working curve is y=20.965x+
13.924, linearly dependent coefficient R2It is 0.990；The fluorescence intensity level of five samples to be tested of detection；
Three, according to the fluorescence intensity level of sample to be tested, from standard curve, find salicylic content, complete salicylic acid quantitative
Detection.
Under these experimental conditions, acetaminophen medicine adds the salicylic acid of known quantity, measure its fluorescence intensity, in conjunction with
Standard curve method measures salicylic content, calculates the salicylic response rate and is respectively 99.2%, and 99.1%, 99.2%, 100.7%,
101.3%.Show that the sensing membrane of the present embodiment may be used for detecting salicylic content in acetaminophen medicine, and ratio is calibrated
Really.
Test 12: the fluorescence sense film of embodiment 1 preparation, for the detection aqueous solution (0.1mol/L containing benzocaine medicine
Britton-Robinson, pH=3.0) in salicylic acid content, specifically comprise the following steps that
One, by salicylic concentration from low to high, salicylic acid is joined 0.1mol/L Britton-Robinson buffer solution
In, pH=3.0, mix homogeneously, obtain multiple standard specimen, then by variable concentrations, benzocaine medicine to be measured is joined
In this buffer solution, obtain five samples to be tested；
Two, standard specimen, testing sample are separately added in the sample cell of optical fiber fluorescence detection device, then with detecting bigcatkin willow
The optical fiber head that the fluorescence sense film cladding of acid is got up is put in sample cell, excites with ultraviolet source, detects multiple standard specimen
Fluorescence intensity level, mark for vertical with fluorescence intensity level, be denoted as figure with salicylic concentration for horizontal, obtain standard work song
Line；On this curve, fluorescence intensity is linear with salicylic acid content, and equation of linear regression is y=22.965x+11.944,
Linearly dependent coefficient R2It is 0.993；The fluorescence intensity level of five samples to be tested of detection；
Three, according to the fluorescence intensity level of sample to be tested, from standard curve, find salicylic content, complete salicylic acid quantitative
Detection.
Under these experimental conditions, benzocaine medicine adds the salicylic acid of known quantity, measure its fluorescence intensity, in conjunction with
Standard curve method measures salicylic content, calculates the salicylic response rate and is respectively 99.1%, and 98.6%, 100.2%, 99.7%,
99.3%.Show that the sensing membrane of the present embodiment may be used for detecting salicylic content in acetaminophen medicine, and the most accurate.
Test 13: the fluorescence sense film of embodiment 1 preparation, for the detection aqueous solution (0.1mol/L containing soda pop
Britton-Robinson, pH=3.0) in salicylic acid content, specifically comprise the following steps that
One, by salicylic concentration from low to high, salicylic acid is joined 0.1mol/L Britton-Robinson buffer solution
In, pH=3.0, mix homogeneously, obtain multiple standard specimen, then by variable concentrations, soda pop to be measured is joined this
In buffer solution, obtain five samples to be tested；
Two, standard specimen, testing sample are separately added in the sample cell of optical fiber fluorescence detection device, then with detecting bigcatkin willow
The optical fiber head that the fluorescence sense film cladding of acid is got up is put in sample cell, excites with ultraviolet source, detects multiple standard specimen
Fluorescence intensity level, mark for vertical with fluorescence intensity level, be denoted as figure with salicylic concentration for horizontal, obtain standard work song
Line；On this curve, fluorescence intensity is linear with salicylic acid content, and equation of linear regression is y=21.965x+15.514,
Linearly dependent coefficient R2It is 0.987；The fluorescence intensity level of five samples to be tested of detection；
Three, according to the fluorescence intensity level of sample to be tested, from standard curve, find salicylic content, complete salicylic acid quantitative
Detection.
Under these experimental conditions, soda pop adds the salicylic acid of known quantity, measure its fluorescence intensity, combined standard
Curve method measures salicylic content, calculates the salicylic response rate and is respectively 98.3%, and 99.7%, 99.2%, 98.7%,
99.3%.Show that the sensing membrane of the present embodiment may be used for detecting salicylic content in soda pop, and the most accurate.
Test 14: the fluorescence sense film of embodiment 1 preparation, for the detection aqueous solution (0.1mol/L containing lake water
Britton-Robinson, pH=3.0) in salicylic acid content, specifically comprise the following steps that
One, by salicylic concentration from low to high, salicylic acid is joined 0.1mol/L Britton-Robinson buffer solution
In, pH=3.0, mix homogeneously, obtain multiple standard specimen, then by variable concentrations, lake water to be measured is joined this buffering
In solution, obtain five samples to be tested；
Two, standard specimen, testing sample are separately added in the sample cell of optical fiber fluorescence detection device, then with detecting bigcatkin willow
The optical fiber head that the fluorescence sense film cladding of acid is got up is put in sample cell, excites with ultraviolet source, detects multiple standard specimen
Fluorescence intensity level, mark for vertical with fluorescence intensity level, be denoted as figure with salicylic concentration for horizontal, obtain standard work song
Line；On this curve, fluorescence intensity is linear with salicylic acid content, and equation of linear regression is y=19.965x+13.914,
Linearly dependent coefficient R2It is 0.991；The fluorescence intensity level of five samples to be tested of detection；
Three, according to the fluorescence intensity level of sample to be tested, from standard curve, find salicylic content, complete salicylic acid quantitative
Detection.
Under these experimental conditions, lake water adds the salicylic acid of known quantity, measure its fluorescence intensity, combined standard curve
Method measures salicylic content, calculates the salicylic response rate and is respectively 99.1%, and 99.6%, 100.2%, 100.7%, 99.3%.
Show that the sensing membrane of the present embodiment may be used for detecting salicylic content in soda pop, and the most accurate.
Embodiment 2: the preparation method being used for detecting salicylic fluorescence sense film of the present embodiment is as follows:
One, 68.0mg polymethyl methacrylate, 200mg dibutyl phthalate are weighed, 1.0mg 1,3-bis-(4-(N '-
Methyl-piperazinyl group)-N-octadecyl-1,8-naphthalimide) base benzene, use immersion method that they are all dissolved in 5mL Ketohexamethylene
In, obtain solution；
Two, solution prepared by step one being spread in slide surface, under room temperature, Ketohexamethylene volatilizees naturally, then by microscope slide
The film on surface strips down, and obtains for detecting salicylic fluorescence sense film.
Embodiment 3: the preparation method being used for detecting salicylic fluorescence sense film of the present embodiment is as follows:
One, 68.0mg polyvinyl acetate, 200mg dibutyl phthalate are weighed, and 1.0mg 1,3-bis-(4-(N '-first
Base-piperazinyl)-N-cetyl-1,8-naphthalimide) base benzene, use immersion method they to be all dissolved in 5mL Ketohexamethylene,
Obtain solution；Wherein 1,3-bis-(4-(N '-methyl-piperazinyl group)-N-cetyl-1,8-naphthalimide) structural formula of base benzene is as follows:
Two, solution prepared by step one being spread in slide surface, under room temperature, Ketohexamethylene volatilizees naturally, then by microscope slide
The film on surface strips down, and obtains for detecting salicylic fluorescence sense film.
Embodiment 4: the preparation method being used for detecting salicylic fluorescence sense film of the present embodiment is as follows:
One, 68.0mg polrvinyl chloride, 200mg dimethyl phthalate are weighed, 1.0mg 1,3-bis-(4-(N '-methyl-
Piperazinyl)-N-eicosyl-1,8-naphthalimide) base benzene, use immersion method they to be all dissolved in 5mL Ketohexamethylene,
To solution；Wherein 1,3-bis-(4-(N '-methyl-piperazinyl group)-N-eicosyl-1,8-naphthalimide) structural formula of base benzene is as follows:
Two, solution prepared by step one being spread in slide surface, under room temperature, Ketohexamethylene volatilizees naturally, then by microscope slide
The film on surface strips down, and obtains for detecting salicylic fluorescence sense film.
Claims (6)
1. for detecting the preparation method of salicylic fluorescence sense film, it is characterised in that the method sequentially includes the following steps:
One, polymer, phthalic acid ester are taken, 4-(N '-methyl-piperazinyl group)-1,8-naphthalimide derivative, they are the most molten
Solution, in solvent, obtains solution；Wherein the molecular structural formula formula of 4-(N '-methyl-piperazinyl group)-1,8-naphthalimide derivative is
In formula: R1、R2It is the alkyl of C12～C20；
Two, solution prepared by step one being spread in slide surface, volatilization naturally under room temperature, then by slide surface
Film strips down, and obtains for detecting salicylic fluorescence sense film.
Preparation method for detecting salicylic fluorescence sense film the most according to claim 1, it is characterised in that the party
Method sequentially includes the following steps:
One, 50～150mg polymer, 100～300mg phthalic acid ester, 0.5～1.5mg4-(N '-methyl-piperazine are weighed
Piperazine base)-1,8-naphthalimide derivative, they are all dissolved in 5mL solvent, obtain solution；Wherein 4-(N '-methyl-piperazine
Piperazine base) the molecular structural formula formula of-1,8-naphthalimide derivative is
In formula: R1、R2It is the alkyl of C12～C20；
Two, solution prepared by step one being spread in slide surface, volatilization naturally under room temperature, then by slide surface
Film strips down, and obtains for detecting salicylic fluorescence sense film.
Preparation method for detecting salicylic fluorescence sense film the most according to claim 1 and 2, it is characterised in that
Solvent described in step one is Ketohexamethylene, hexamethylene or acetone.
Preparation method for detecting salicylic fluorescence sense film the most according to claim 1 and 2, it is characterised in that
Described dissolving is to use water-bath, ultrasonic or microwave treatment mode to promote to dissolve.
5. utilize the side that for detecting salicylic fluorescence sense film, salicylic acid is carried out qualitative detection prepared by claim 1
Method, it is characterised in that the method sequentially includes the following steps:
One, testing sample is joined in the buffer solution that pH value is 2.0～5.0, mix homogeneously, obtain sample to be tested, then
By this buffer solution as blank sample；
Two, blank sample and sample to be tested are separately added in the sample cell of optical fiber fluorescence detection device, then will be with detection bigcatkin willow
The optical fiber head that the fluorescence sense film cladding of acid is got up is put in sample cell, excites with ultraviolet source, detects the glimmering of blank sample
Light intensity value A0Fluorescence intensity level A with sample to be tested1；
Three, fluorescence intensity level A is compared0And A1If, A1Compare A0Improve more than 20%, then judge sample to be tested contains
Salicylic acid.
6. utilize the side that for detecting salicylic fluorescence sense film, salicylic acid is carried out detection by quantitative prepared by claim 1
Method, it is characterised in that the method sequentially includes the following steps:
One, by salicylic concentration from low to high, salicylic acid is joined in the buffer solution that pH value is 2.0～5.0, mixed
Close uniformly, obtain multiple standard specimen, then sample to be measured is joined in this buffer solution, obtain sample to be tested；
Two, standard specimen, testing sample are separately added in the sample cell of optical fiber fluorescence detection device, then with detecting bigcatkin willow
The optical fiber head that the fluorescence sense film cladding of acid is got up is put in sample cell, excites with ultraviolet source, detects multiple standard specimen
Fluorescence intensity level, mark for vertical with fluorescence intensity level, be denoted as figure with salicylic concentration for horizontal, obtain standard work song
Line；The fluorescence intensity level A of detection sample to be tested1；
Three, according to fluorescence intensity level A1, from standard curve, find salicylic content, complete salicylic acid detection by quantitative.
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