CN105778897B - PH sensitive fluorescence dyes and its preparation method and application - Google Patents
PH sensitive fluorescence dyes and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of pH sensitive fluorescence dyes and its preparation method and application, and containing two fluorophors to pH responses in the molecule of the pH sensitive fluorescence dyes, for the molecular structural formula of pH sensitive fluorescence dyes as shown in formula I, wherein M is selected from NH2Or COOH, R are selected from (CH2)nOr Ph, 2≤n≤4.PH sensitive fluorescence dyes link together naphthalimide derivative and derivatives of porphyrin by schiff base reaction and are prepared, when M is NH2When, by aliphatic dialdehydes or aromatic dialdehyde as connection bridge；When M is COOH, by acyclic straight diamides or terephthalate amine as connection bridge.The pH sensitive fluorescence dyes of the present invention can be used for making ratio fluorescent sensor.The pH sensitive fluorescence dyes high sensitivity, selectivity are good, high quantum production rate stable to light.
Description
Technical field
The invention belongs to fluorescent dye field, is related to a kind of pH sensitive fluorescence dyes and its preparation method and application, especially
It is related to reference pH sensitive fluorescence dyes and its preparation method and application in a kind of double fluorescent emissive molecules.
Background technology
Solution ph is the important chemical parameters of solution acid alkalinity, and the pH value of measurement and control solution is in chemistry, environment section
The fields such as, biochemistry, clinical chemistry, which all have, to have very important significance.The method of traditional measurement pH value be mainly pH test paper,
Various glass electrodes, metal-metallic oxide electrode and ISE etc., but the sensor response that conventional method makes
Time is long, stability is poor, is difficult to measure minor variations；PH test paper can only carry out observational measurement；Glass electrode pH sensors are present
The defects of impedance is high, cracky, and " alkaline error " be present in the case of high alkalinity.Simultaneously as measurement matrix volume itself
Greatly, the on-line checking of microenvironment and biological living is should not be used in, also should not be used in in-situ treatment analysis and the adverse circumstances of sample.
Compared with traditional detection method, fluorescence optical fiber pH chemical sensors have small volume, in light weight, anti-electromagnetism and nothing
Line electricity frequency interferences, the advantages that dynamic range is big, the response time is short, measurement accuracy is high, and microcell measurement can be carried out, remote surveyed
Measurement in amount and organism.Especially for the deficiency of glass electrode pH sensors, fluorescence optical fiber pH chemical sensors are limiting
Alkaline error, the equilibration time that shortens, widen dynamic range, enhancing signal stabilization and service life on have very big change
Enter.
Fluorescence optical fiber pH chemical sensors be by spectral analysis technique and optical fiber sensing technology with reference to and one kind for forming is new
The pH detection means of type.Because various optical hardwares are becoming cheap in recent years, traditional optics can be combined with fibre optics, be led to
Cross and modify stratification pH identification auroral poles films in optical fiber end, to prepare novel optical fiber chemical sensor.When tested component is with changing
When learning the reagent effect in pH identification auroral poles films, optical change (such as absorption, reflection, fluorescence, the scattering of auroral poles film will be caused
Deng), this change is collected by optical fiber and imports optical detection system, so as to obtain measurement signal.It is suitable wherein to find
Novel pH Sensitive carrier, the development for fluorescence optical fiber pH chemical sensors are very important.
Go deep into simultaneously with research, ratio fluorescent sensor is increasingly taken seriously, and one kind is to utilize fluorometric reagent energy
The change of two fluorescence intensities (difference excites or transmitted wave strong point) is produced to substrate, so as to abatement apparatus condition itself and the external world
Measurement error caused by environmental change；Another kind is to utilize two kinds of fluorometric reagents, i.e., changes sensitive sensitive agents and right to pH
PH changes insensitive reference reagent and realizes that ratio fluorescent measures.It is but this at present with dual wavelength, sensitive to pH glimmering
Light reagent is also seldom, and the fluorescent dye of ratio fluorescent sensor generally carries out the system of chemical pH identifications auroral poles film using copolymerization mode
It is standby so that the fluorescence intensity of different batches chemistry pH identification auroral poles films has differences, and being unsuitable for extensive, continuous reality should
With.Therefore, good, stable to light, high quantum production rate the pH sensitive fluorescence dyes of design synthesis high sensitivity, selectivity are applied to glimmering
Light ratio sensor is necessary.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided a kind of high sensitivity, selectivity it is good,
Stable to light, high quantum production rate pH sensitive fluorescence dyes, and a kind of preparation method of the pH sensitive fluorescence dyes is accordingly provided
And its application.
Specifically, an object of the present invention is to provide a kind of new double glimmering with naphthalimide and porphyrin fluorescence characteristic
Reference pH sensitive fluorescence dyes in light transmitting；The second purpose is to provide double fluorescent bases with naphthalimide and porphyrin fluorescence characteristic
The synthetic method of the intramolecular reference pH sensitive fluorescence dyes of group；The third purpose provides the application of the fluorescent dye.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of pH sensitive fluorescence dyes, two fluorescent bases to pH responses are contained in the molecule of the pH sensitive fluorescence dyes
Group, for the molecular structural formula of the pH sensitive fluorescence dyes as shown in formula I, wherein M is selected from-NH2Or-COOH, R are selected from-(CH2)n-
Or-Ph-, 2≤n≤4,
The inventive concept total as one, the present invention also provide a kind of preparation method of above-mentioned pH sensitive fluorescence dyes,
Naphthalimide derivative is connected by the pH sensitive fluorescence dyes by schiff base reaction with derivatives of porphyrin to be prepared；
When M is-NH2When, by aliphatic dialdehydes or aromatic dialdehyde as connection bridge；When M is-COOH, by acyclic straight two
Acid amides or terephthalate amine are as connection bridge.
In the preparation method of above-mentioned pH sensitive fluorescence dyes, it is preferred that the naphthalimide derivative be N- pi-allyls-
4- (N- aminoethanes) -1,8- naphthalimides, the derivatives of porphyrin are 5,10,15,20- tetra- (4- aminophenyls) -21H,
23H- porphyrins, the connection bridge is terephthalaldehyde.
In the preparation method of above-mentioned pH sensitive fluorescence dyes, it is preferred that the preparation method comprises the following steps：
(1) by the dissolving terephthalaldehyde in organic solvent, N- pi-allyls -4- (N- aminoethanes) -1,8- is added
Naphthalimide, after reacted, filtering, after gained filtrate is dried, obtain compound 1；
(2) compound 1 is dissolved in organic solvent, and dissolved with 5,10,15,20- tetra- (4- aminophenyls) -21H,
The organic solvent mixing of 23H- porphyrins, after reacted, obtains the solution containing compound 2；
(3) sodium borohydride is added into the solution containing compound 2, after reacted, filtering, after the filtrate is dried, is obtained
PH sensitive fluorescence dyes.
In the preparation method of above-mentioned pH sensitive fluorescence dyes, it is preferred that in the step (1), the terephthalaldehyde
With the mass ratio of N- pi-allyls -4- (N- aminoethanes) -1,8- naphthalimides for 0.08~0.1: 0.16~0.18 (preferably mole
Than for 1.1~1.5: 1), the time of the reaction is 12h~18h；In the step (2), the compound 1 and 5,10,15,
20- tetra- (4- aminophenyls) -21H, 23H- porphyrins, the mass ratio of sodium borohydride for 0.03~0.04: 0.05~0.06: 0.06~
0.07 (preferred molar ratio 1: 1: 2), the time of the reaction is 12h~18h；In the step (3), the time of the reaction
For 5min~10min.
In the preparation method of above-mentioned pH sensitive fluorescence dyes, it is preferred that the N- pi-allyls -4- (N- aminoethanes) -
The synthesis step of 1,8- naphthalimides is as follows：
(1 ') adds bromo- 1, the 8- naphthalene anhydrides of 4- and allyl amine in organic solvent, after reacted, cools down, filtering, obtains N-
The bromo- 1,8- naphthalimides of pi-allyl -4-；
(2 ') mix bromo- 1, the 8- naphthalimides of N- pi-allyls -4- with ethylenediamine, gained mixed solution and CuSO4·5H2O
After being flowed back in glycol monoethyl ether, add water to stand, filter, it is sub- to obtain N- pi-allyls -4- (N- aminoethanes) -1,8- naphthoyls
Amine；
And/or described 5,10,15,20- tetra- (4- aminophenyls) -21H, the synthesis step of 23H- porphyrins is as follows：
Lactic acid is added in nitrobenzene by (1 "), is heated to boiling, and is added dropwise under return stirring dissolved with p- nitrobenzaldehyde and pyrrole
The nitrobenzene solution coughed up, after reacting 1h~2h, it is cooled at 55 DEG C~65 DEG C and adds methanol, after stirring, filtering, obtains four (4-
Nitrobenzophenone) porphyrin；
Four (4- nitrobenzophenones) porphyrins are dissolved in concentrated hydrochloric acid by (2 "), then instill dissolved with SnCl2·2H2O concentrated hydrochloric acid is molten
Liquid, after reacting 2h~3h, reaction temperature is increased to 65 DEG C~70 DEG C and continues to react, is cooled down after reaction, obtains 5,10,15,20-
Four (4- aminophenyls) -21H, the hydrochloride of 23H- porphyrins；
5,10,15,20- tetra- (4- aminophenyls) -21H, the hydrochloride of 23H- porphyrins are dispersed in water by (3 "), add alkali soluble
Liquid regulation pH is 8.0~10.0, after drying, obtains 5,10,15,20- tetra- (4- aminophenyls) -21H, 23H- porphyrins.
In the preparation method of above-mentioned pH sensitive fluorescence dyes, it is preferred that the N- pi-allyls -4- (N- aminoethanes) -
The synthesis condition of 1,8- naphthalimides is as follows：In the step (1 '), the mass ratio of bromo- 1, the 8- naphthalene anhydrides of the 4- and allyl amine
For 2.8~3.2: 0.8~1.0, the reaction time is 1h~2h；In the step (2 '), the N- pi-allyls -4- bromo- 1,
The mass ratio of 8- naphthalimides and ethylenediamine is 0.4~0.6: 0.3~0.4, the CuSO4·5H2O quality be 0.1g~
0.2g, the time of the backflow is 2h~3h；
And/or described 5,10,15,20- tetra- (4- aminophenyls) -21H, the synthesis condition of 23H- porphyrins is as follows：The step
Suddenly in (1 "), the lactic acid, total p- nitrobenzaldehyde, the mass ratio of total pyrroles are 8.0~9.0: 4.0~5.0: 1.5~2.5,
It is added dropwise and is no longer than 20min dissolved with the time of p- nitrobenzaldehyde and the nitrobenzene solution of pyrroles, adds after methanol the time stirred
For 30min~50min；In the step (2 "), the SnCl2·2H2The mass ratio of O and four (4- nitrobenzophenones) porphyrins is 4.0
~5.0: 1.0~2.0, it is added dropwise dissolved with SnCl2·2H2The time of O concentrated hydrochloric acid solution is no more than 20min, described to continue what is reacted
Time is 20min~50min；In step (3 "), the aqueous slkali is concentrated ammonia liquor.
The technical concept total as one, the present invention also provide a kind of above-mentioned pH sensitive fluorescence dyes or above-mentioned preparation
Application of the pH sensitive fluorescence dyes in ratio fluorescent sensor made from method.
In above-mentioned application, it is preferred that the application comprises the following steps：
(a) silanised glass slides are made；
(b) pH sensitive fluorescence dyes are dissolved in DMF, then sequentially add acrylamide, methyl-prop
Olefin(e) acid hydroxyl ethyl ester, crosslinking agent triethoxy trimethyl acrylic ester, benzoin ethyl ether and benzophenone, fully dissolving；
(c) the final resulting solution of step (b) is taken to drip in the silanised glass slides that on polyfluortetraethylene plate, step (a) is obtained
It is placed on thereon, then after with ultra violet lamp, finally washing, drying, the slide of the thin layer of film containing auroral poles is made, i.e., with interior reference
Ratio fluorescent sensor.
Compared with prior art, the advantage of the invention is that：
1st, TAPP groups and AAEAN gene expressions go out good pH responses, TAPP in pH sensitive fluorescence dyes of the invention
Group changes obvious with pH value in an acidic solution, does not change substantially with pH value in alkaline solution, and AAEAN groups exactly phase
Instead, so as to realizing intramolecular reference each other.The ratio of fluorescence intensity can more accurately reflect pH change as measurement signal,
Measurement error caused by avoiding the fluctuation of excitation source, the transmission change of optical fiber, light scattering of sample etc., improves the reliable of measurement
Property.
2nd, pH sensitive fluorescence dyes of the invention introduce end group double bond in AAEAN groups, can be used for fluorescent dye point
Polymerization of the son on the slide that silanization treatment is crossed, it can load on slide or optical fiber and chemical pH identifications auroral poles film is made,
The preparation for ratio fluorescent sensor is realized, effectively prevents the loss of fluorescence carrier, extends the service life of sensor, extensively
Measure for pH in chemistry and biological field.
3rd, the wide scope pH measure that pH sensitive fluorescence dyes of the invention can be used in solution, it can eliminate and common join each other
Two kinds of fluorometric reagent error in dipping phenomenons of ratio, and common inorganic ions and organic matter not interference measurement.PH sensitive fluorescences contaminate
Expect the ratio fluorescent sensor prepared, the response time is short, and reappearance and invertibity are good.
Brief description of the drawings
Fig. 1 is the synthetic route chart of AAEAN in the embodiment of the present invention 1.
Fig. 2 is the synthetic route chart of TAPP in the embodiment of the present invention 1.
Fig. 3 is the synthetic route chart of pH sensitive fluorescence dyes AAEAN-TAPP in the embodiment of the present invention 1.
Fig. 4 is the mass spectrogram of pH sensitive fluorescence dyes AAEAN-TAPP in the embodiment of the present invention 1.
Fig. 5 is response diagram of the pH sensitive fluorescence dyes in different pH in the embodiment of the present invention 1.
Fig. 6 is the fluorescence intensity of pH sensitive fluorescence dyes and the linear relationship chart of pH value in the embodiment of the present invention 3.
Embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Raw material and instrument employed in following examples are commercially available.
The invention provides a kind of pH sensitive fluorescence dyes, the luminescent dye molecule contains two can be to the glimmering of pH responses
Light group, having the characteristic of naphthalimide and Porphyrin Molecule parent, (naphthalimide is that a kind of property is stable, quantum yield is high, property
The excellent fluorescent material of energy, porphyrin are a kind of compounds with rigid structure), it is used as and is connected by the use of aliphatic dialdehydes or aromatic dialdehyde
Connect bridge to link together naphthalimide and Porphyrin Molecule parent by schiff base reaction, under the pH sensitive fluorescence dyes have
Structural formula shown in formula (I), wherein M=-NH2, R=- (CH2)n- or-Ph-, 2≤n≤4.In addition, the sensitive double fluorescent bases of the pH
In group's luminescent dye molecule structure, M groups can also be-COOH, now can be by acyclic straight diamides or terephthalate amine
Class forms the sensitive double fluorophor fluorescent dyes of pH as connection bridge connection derivatives of porphyrin and naphthalimide derivative.
Below with naphthalimide derivative N- pi-allyls -4- (N- aminoethanes) -1,8- naphthalimides and derivatives of porphyrin
5,10,15,20- tetra- (4- aminophenyls) -21H, pH sensitive fluorescence dyes, but not limited to this are prepared exemplified by 23H- porphyrins.
Embodiment 1
A kind of pH sensitive fluorescence dyes of the invention, containing two to pH responses in the molecule of the pH sensitive fluorescence dyes
Fluorophor, pH sensitive fluorescence dyes have the structural formula shown in formula I, and wherein M is-NH2, R is-Ph-.
A kind of preparation method of the pH sensitive fluorescence dyes of above-mentioned the present embodiment, with naphthalimide derivative N- pi-allyls-
4- (N- aminoethanes) -1,8- naphthalimides (being abbreviated as AAEAN) and (the 4- aminobenzenes of derivatives of porphyrin 5,10,15,20- tetra-
Base) -21H, 23H- porphyrins (being abbreviated as TAPP) preparation pH sensitive fluorescence dyes (being abbreviated as AAEAN-TAPP), including following step
Suddenly：
1st, the conjunction of naphthalimide derivative N- pi-allyls -4- (N- aminoethanes) -1,8- naphthalimides (being abbreviated as AAEAN)
Into synthetic route is as shown in figure 1, comprise the following steps：
(1 ') takes bromo- 1, the 8- naphthalene anhydrides of 3g4- and 0.9272g allyl amines in ethanol, after back flow reaction 2h, by reactant
Cooling, filtering, gained solid are washed and dried with ethanol, obtain (the letter of bromo- 1, the 8- naphthalimides of light yellow solid N- pi-allyls -4-
It is written as ABN), 142 DEG C~144 DEG C of fusing point；
(2 ') regard compound ABN obtained by step (1 ') as reactant, take 0.5gABN, 0.36g ethylenediamine and
0.2gCuSO4·5H2O is added in 20ml glycol monoethyl ethers, fully dissolving, and flow back 2h, after cooling, adds substantial amounts of water,
Stand overnight.Then filter, yellow solid AAEAN is obtained after gained solid distilled water flushing and drying.160~162 DEG C of fusing point.
2nd, derivatives of porphyrin 5,10,15,20- tetra- (4- aminophenyls) -21H, the synthesis of 23H- porphyrins (being abbreviated as TAPP),
Synthetic route is as shown in Fig. 2 comprise the following steps：
8.4g lactic acid is added in 25ml nitrobenzene by (1 "), is heated to boiling, molten in being added dropwise in 20min under return stirring
There are the p- nitrobenzaldehydes of 4.1978g and the nitrobenzene solution of 1.845g pyrroles, and continue to react 2h, be subsequently cooled at 60 DEG C
Methanol is added, stirs 30min, stands 8h, is filtered, gained solid is washed colourless to eluate with methanol, isolates solid, 60 DEG C
Lower vacuum drying, obtain brilliant violet color four (4- nitrobenzophenones) porphyrin crystals (being abbreviated as TNPP)；
The TNPP1.06g that step (1 ") obtains is dissolved in concentrated hydrochloric acid (mass fraction 36%~38%) by (2 "), at room temperature
The SnCl dissolved with 4.64g is instilled in 10min2·2H2O concentrated hydrochloric acid solutions, 2.5h is reacted, temperature is then risen to 65 DEG C~70 DEG C
Continue to react 30min, ice-water bath cooling, isolate bottle green TAPP HCl, solids.
The TAPP HCl, solids that step (2 ") obtains are scattered in 200ml deionized waters by (3 "), with concentrated ammonia liquor (quality
Fraction 25%~28%) pH=9 is neutralized to, centrifuge, obtained solid becomes brown purple after the lower 60 DEG C of dryings of vacuum.With
Chloroform is solvent, is extracted with Soxhlet extractor, after gained extract recovery chloroform, obtains brilliant violet color TAPP crystal.Fusing point (m.p.)
121 DEG C~123 DEG C, MS (ESI): M+675.3。
3rd, the synthesis of pH sensitive fluorescence dyes, synthetic route is as shown in figure 3, comprise the following steps：
(1) 0.0911g dissolving terephthalaldehyde is weighed in 40ml ethanol, adds 0.1612g N- pi-allyls -4-
(N- aminoethanes) -1,8- naphthalimides (AAEAN) stirring and dissolving, reacts 12h at normal temperatures, the product mistake that then will be obtained
Filter, takes filtrate rotary evaporation, and solid matter compound 1 i.e. shown in Fig. 3 is obtained after being evaporated.
(2) the solid matter 0.0346g for taking step (1) to obtain is dissolved in a small amount of ethanol, is then added to 20ml dissolvings
In the DMF for there are (4- aminophenyls) porphyrins of 0.0568g tetra- (TAPP), stirring at normal temperature reaction 12h, Fig. 3 is obtained
Shown in compound 2.
(3) weigh 0.0637g sodium borohydrides to be added in the solution containing compound 2 of step (2) reaction gained, stirring is anti-
5min is answered, 1ml distilled water is added, filtering, filtrate rotation is evaporated, takes out solid, cross post purifying, obtain containing double fluorophors
PH sensitive fluorescence dyes (AAEAN-TAPP), i.e., compound 3 shown in Fig. 3.
It is room temperature when reaction temperature is not particularly illustrated in above operating procedure.
Above-mentioned AAEAN-TAPP products manufactured in the present embodiment are C69H58N11O2, the mass spectrogram of product is as shown in figure 4, MS
(ESI)：M+1072.4767.The pH sensitive fluorescence dyes have response to pH value, and Fig. 5 shows the pH sensitive fluorescence dyes in pH
Response when respectively 1,4,7,11 to pH value.PH sensitive fluorescence dyes AAEAN-TAPP is dissolved in N, N- dimethyl formyls
In amine, in excitation wavelength lambdaexDuring=407nm, the pH sensitive fluorescence dyes are to have stronger light at 515nm and 655nm in wavelength
Emission peak.
Embodiment 2
A kind of application of pH sensitive fluorescence dyes of the invention in ratio fluorescent sensor, is made using above-described embodiment 1
Standby pH sensitive fluorescence dyes, comprise the following steps：
A, slide silanization：Common slide (diameter 13mm) is immersed in chromic acid lotion and soaks 30min, and is washed with distillation
Only, then it is sequentially placed into the hydrofluoric acid solution that percentage by volume is 3% and the hydrogenperoxide steam generator that percentage by volume is 10%
Each immersion 20min, and, the slide that is pre-processed clean with distilled water flushing.The Acetic acid-sodium acetate that 2ml pH are 3.6 is delayed
Fliud flushing (0.2mol l-1) and 8ml distilled water be mixed to get mixed liquor, by 0.2ml 3- (trimethoxy silane base) methacrylic acid
Propyl ester is added in above-mentioned mixed liquor, is sufficiently stirred, and becomes uniform emulsion.The slide of pretreatment is immersed into uniformly breast
2h in shape liquid, finally clean with distilled water flushing, drying at room temperature, obtain the slide of silanization.
B, pH sensitive fluorescence dyes (AAEAN-TAPP) 2mg of Example 1 is dissolved in 0.20ml N,N-dimethylformamides
In, then sequentially add 200mg acrylamides, 0.60ml hydroxyethyl methacrylates, 0.15ml crosslinking agent triethoxy front threes
Base acrylate, 45mg benzoin ethyl ethers, 30mg benzophenone, fully dissolving.
C, the final resulting solution 0.15ml drops of step b are taken in the silane that on clean polyfluortetraethylene plate, step a is obtained
The slide of change is placed on thereon, then irradiates 3h with uviol lamp (wavelength 254nm), finally with distilled water flushing, drying at room temperature, is made
The slide of the thin layer of film containing auroral poles, i.e. the ratio fluorescent sensor with interior reference.
Embodiment 3：Ratio fluorescent sensor determines for pH value of solution
The measurement of fluorescence is on the Perking-Elmer LS55 luminoscopes with computer digital animation software systems
Carry out, light source is 150W xenon lamps, and detector is R928F photomultipliers.Ratio fluorescent sensor prepared by embodiment 2 loads
Flow cell top, one with auroral poles film thin layer is face-down, auroral poles film is contacted with sample solution.One both arms optical fiber is (straight
Footpath 8mm, length 1m) end is connected on luminoscope, and other end insertion flow cell is simultaneously close to surface of glass slide.The spoke that excitation source is sent
Penetrate to be transferred in flow cell by one end of both arms optical fiber and irradiate surface of glass slide, excite the fluorescent material in auroral poles film thin layer, send out
The fluorescence penetrated is transmitted back to detector by the other end, is measured.Peristaltic pump is with 1.4mlmin-1Speed sample is inputted
Flow cell, sample solution are the B-R buffer solutions of different pH value.Fixed excitation wavelength 407nm, excitation-emission slit is 5nm, is surveyed
The fluorescence intensity of pH sensitive fluorescence dyes in auroral poles film is measured, has strong absworption peak at 515nm and 655nm two, is pH quick respectively
Feel the emission peak of AAEAN fluorophors and TAPP fluorophors in luminescent dye molecule.PH sensitivities are glimmering at various ph values for record
Two fluorescence intensity F in photoinitiator dyeAAEANWith FTAPP, to represent both ratio with α：
In formula (1), FTAPP0It is the fluorescence intensity when TAPP is protonated completely, i.e., in pH ＜ 0.5 cushioning liquid
Fluorescence intensity, FAAEAN0The fluorescence intensity when the complete deprotonations of AAEAN, i.e., it is glimmering in pH ＞ 11.0 cushioning liquid
Luminous intensity.Fluorescence carrier AAEAN and TAPP and both ratio ccs and pH relation are as shown in Figure 6.It is 1.0~5.0 Hes in pH
Between 5.0~9.5, good linear relationship is presented in α and pH.According to the protonation and deprotonation of two fluorophors, work as TAPP
Fluorescence intensity when protonating completely, calculates both ratio ccs.Using pH as abscissa, α is ordinate, with SigmaPlot softwares
Draw, can obtain the curve that sensor responds to pH, as shown in fig. 6, be 1.0~5.0 in pH and pH is in the range of 5.0~9.5,
Good linear relationship is presented in α and pH, and curve representation formula is respectively as shown in formula (2) and formula (3).
α=30.5000-12.6226pH+1.3961pH2(R=0.9970, pH 1.0~5.0) (2)
α=3.2843-0.3269pH (R=0.9960, pH 5.0~9.5) (3)
It is in 4.0 cushioning liquid, to sensitive membrane (the i.e. light on sensor in pH value to investigate the stability of sensor
Pole film) carry out test up to more than 6h.Excitation wavelength is set as 407nm, determines AAEAN in AAEAN-TAPP molecules respectively
The fluorescence intensity of fluorophor and TAPP fluorophors, time interval 30min, determine 13 times, two fluorophors it is relative
Standard deviation is AAEAN fluorophors 0.73% respectively, TAPP fluorophors 0.69%.Sensitive membrane is shown after placing one month
Preferable stability.
In addition, the selectivity of sensor is also investigated.The interfering material of various concentrations is added to pH value as 6.5
Cushioning liquid in, determine the fluorescence intensity of two fluorogens respectively, fluorescence intensity change value is as shown in table 1.In common nothing
In the presence of machine thing and possible organic matter, fluorescence intensity relative changing value can meet to use needs within ± 5.0%.
The fluorescence intensity of sensitive membrane in the presence of the disturbance thing of table 1
Wherein, Δ FAAEAN=FAAEAN2–FAAEAN1, FAAEAN1And FAAEAN2It is that AAEAN fluorophors are not present when pH is 6.5
With the fluorescence intensity level that each interfering material be present；
ΔFTAPP=FTAPP2–FTAPP1, FTAPP1And FTAPP2It is TAPP fluorophors when pH is 6.5 the absence and presence of each
The fluorescence intensity level of interfering material.
Embodiment 4：Ratio fluorescent sensor determines for waste water sample pH
Water sample is different waste water, river, lake water and the running water of pH value, water sample is passed through into flow cell, by embodiment 3
Continuous mode carries out fluorescence intensity measurement, the pH value of water sample is determined with calibration curve method, its result with pH glass electrodes with being surveyed
As a result consistent, table 2 compared for the measurement result of two methods.
The ratio fluorescent sensor of table 2 and the Comparative result of glass electrode measure water sample pH value
| Sample | pHa | pHb | Deviation |
| Waste water | 3.54 | 3.59 | -0.05 |
| River | 7.76 | 7.72 | 0.04 |
| Lake water | 7.72 | 7.74 | -0.02 |
| Running water | 7.40 | 7.44 | -0.04 |
In table 1, pHaFor the measured value (average value of measurement result three times) of ratio fluorescent sensor；pHbFor glass electrode
Measured value.
Above example is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned reality
Apply example.All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It is noted that led for this technology
For the those of ordinary skill in domain, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of pH sensitive fluorescence dyes, it is characterised in that rung in the molecule of the pH sensitive fluorescence dyes containing two to pH
The fluorophor answered, the molecular structural formula of the pH sensitive fluorescence dyes are shown below,
A kind of 2. preparation method of pH sensitive fluorescence dyes as claimed in claim 1, it is characterised in that the pH sensitive fluorescences
Naphthalimide derivative is connected and is prepared by dyestuff by schiff base reaction with derivatives of porphyrin, is made by aromatic dialdehyde
To connect bridge.
3. the preparation method of pH sensitive fluorescence dyes according to claim 2, it is characterised in that the naphthalimide derives
Thing is N- pi-allyls -4- (N- aminoethanes) -1,8- naphthalimides, and the derivatives of porphyrin is 5,10,15,20- tetra- (4- amino
Phenyl) -21H, 23H- porphyrins, the connection bridge is terephthalaldehyde.
4. the preparation method of pH sensitive fluorescence dyes according to claim 3, it is characterised in that the preparation method includes
Following steps：
(1) by the dissolving terephthalaldehyde in organic solvent, N- pi-allyls -4- (N- aminoethanes) -1,8- naphthoyls are added
Imines, after reacted, filtering, after gained filtrate is dried, obtain compound 1；
(2) compound 1 is dissolved in organic solvent, and dissolved with 5,10,15,20- tetra- (4- aminophenyls) -21H, 23H- porphins
The organic solvent mixing of quinoline, after reacted, obtains the solution containing compound 2；
(3) sodium borohydride is added into the solution containing compound 2, after reacted, filtering, after the filtrate is dried, it is quick to obtain pH
Feel fluorescent dye.
5. the preparation method of pH sensitive fluorescence dyes according to claim 4, it is characterised in that in the step (1), institute
State the mass ratio of terephthalaldehyde and N- pi-allyls -4- (N- aminoethanes) -1,8- naphthalimides for 0.08~0.1: 0.16~
0.18, the time of the reaction is 12h~18h；In the step (2), (the 4- amino of compound 1 and 5,10,15,20- tetra-
Phenyl) -21H, 23H- porphyrins, the mass ratio of sodium borohydride are 0.03~0.04: 0.05~0.06: 0.06~0.07, described anti-
The time answered is 12h~18h；In the step (3), the time of the reaction is 5min~10min.
6. the preparation method of the pH sensitive fluorescence dyes according to any one of claim 3~5, it is characterised in that described
The synthesis step of N- pi-allyls -4- (N- aminoethanes) -1,8- naphthalimides is as follows：
(1 ') adds bromo- 1, the 8- naphthalene anhydrides of 4- and allyl amine in organic solvent, after reacted, cools down, filtering, obtains N- allyls
The bromo- 1,8- naphthalimides of base -4-；
(2 ') mix bromo- 1, the 8- naphthalimides of N- pi-allyls -4- with ethylenediamine, gained mixed solution and CuSO4·5H2O is in second
After being flowed back in glycol monomethyl ether, add water to stand, filter, obtain N- pi-allyls -4- (N- aminoethanes) -1,8- naphthalimides；
And/or described 5,10,15,20- tetra- (4- aminophenyls) -21H, the synthesis step of 23H- porphyrins is as follows：
Lactic acid is added in nitrobenzene by (1 "), is heated to boiling, and is added dropwise under return stirring dissolved with p- nitrobenzaldehyde and pyrroles
Nitrobenzene solution, after reacting 1h~2h, it is cooled at 55 DEG C~65 DEG C and adds methanol, after stirring, filtering, obtains four (4- nitros
Phenyl) porphyrin；
Four (4- nitrobenzophenones) porphyrins are dissolved in concentrated hydrochloric acid by (2 "), then instill dissolved with SnCl2·2H2O concentrated hydrochloric acid solution,
After reacting 2h~3h, reaction temperature is increased to 65 DEG C~70 DEG C and continues to react, is cooled down after reaction, obtains 5,10,15,20- tetra-
(4- aminophenyls) -21H, the hydrochloride of 23H- porphyrins；
5,10,15,20- tetra- (4- aminophenyls) -21H, the hydrochloride of 23H- porphyrins are dispersed in water by (3 "), add aqueous slkali to adjust
It is 8.0~10.0 to save pH, after drying, obtains 5,10,15,20- tetra- (4- aminophenyls) -21H, 23H- porphyrins.
7. the preparation method of pH sensitive fluorescence dyes according to claim 6, it is characterised in that the N- pi-allyls -4-
The synthesis condition of (N- aminoethanes) -1,8- naphthalimides is as follows：In the step (1 '), bromo- 1, the 8- naphthalene anhydrides of the 4- and alkene
The mass ratio of propyl group amine is 2.8~3.2: 0.8~1.0, and the reaction time is 1h~2h；In the step (2 '), the N-
The mass ratio of bromo- 1, the 8- naphthalimides of pi-allyl -4- and ethylenediamine is 0.4~0.6: 0.3~0.4, the CuSO4·5H2O's
Quality is 0.1g~0.2g, and the time of the backflow is 2h~3h；
And/or described 5,10,15,20- tetra- (4- aminophenyls) -21H, the synthesis condition of 23H- porphyrins is as follows：The step
In (1 "), the lactic acid, total p- nitrobenzaldehyde, the mass ratio of total pyrroles are 8.0~9.0: 4.0~5.0: 1.5~2.5, drop
Solubilization has the time of p- nitrobenzaldehyde and the nitrobenzene solution of pyrroles to be no longer than 20min, adds after methanol the time stirred and is
30min~50min；In the step (2 "), the SnCl2·2H2The mass ratio of O and four (4- nitrobenzophenones) porphyrins be 4.0~
5.0: 1.0~2.0, it is added dropwise dissolved with SnCl2·2H2The time of O concentrated hydrochloric acid solution is no more than 20min, it is described continue reaction when
Between be 20min~50min；In step (3 "), the aqueous slkali is concentrated ammonia liquor.
A kind of 8. preparation method any one of pH sensitive fluorescence dyes as claimed in claim 1 or claim 2~7
Application of the obtained pH sensitive fluorescence dyes in ratio fluorescent sensor.
9. application according to claim 8, it is characterised in that the application comprises the following steps：
(a) silanised glass slides are made；
(b) pH sensitive fluorescence dyes are dissolved in DMF, then sequentially add acrylamide, methacrylic acid
Hydroxyl ethyl ester, crosslinking agent triethoxy trimethyl acrylic ester, benzoin ethyl ether and benzophenone, fully dissolving；
(c) the final resulting solution of step (b) is taken to drip on polyfluortetraethylene plate, the silanised glass slides that step (a) is obtained are placed on
Thereon, then with ultra violet lamp, after finally washing, drying, the slide of the thin layer of film containing auroral poles, the i.e. fluorescence with interior reference is made
Ratio sensor.
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