CN109060733A

CN109060733A - iron ion molecular fluorescence sensor and preparation method thereof

Info

Publication number: CN109060733A
Application number: CN201810379715.0A
Authority: CN
Inventors: 戴宇; 赵建永; 张文昕
Original assignee: Suzhou Shoutong Technology Development Co ltd; Institute of Biophysics of CAS
Current assignee: Suzhou Shoutong Technology Development Co ltd; Institute of Biophysics of CAS
Priority date: 2018-04-25
Filing date: 2018-04-25
Publication date: 2018-12-21
Anticipated expiration: 2038-04-25
Also published as: CN109060733B

Abstract

The present invention provides iron ion molecular fluorescence sensors and preparation method thereof.The iron ion molecular fluorescence sensor it include transparent resin basal layer；Test layer is arranged on a side surface of transparent resin basal layer, and test layer includes the first gel base and the Fe that is scattered in the first gel base³⁺Molecular fluorescence compound；Light shield layer is arranged on the surface of separate transparent resin basal layer side of test layer, and light shield layer includes the second gel base, the opacifying fillers and oxidant that are dispersed in the second gel base；Wherein, Fe³⁺The structure of molecular fluorescence compound is shown in Formulas I, and Polym is amidized large hydrophilic molecular polymeric groups.Iron ion molecular fluorescence sensor provided by the invention can quickly detect the total concentration of ferrous ion and ferric ion in testing liquid, and the advantages that had both measurement efficiency height, high sensitivity, good accuracy.

Description

Iron ion molecular fluorescence sensor and preparation method thereof

Technical field

The present invention relates to organic syntheses and element analysis technology field, in particular to a kind of iron ion molecular fluorescence Sensor and preparation method thereof.

Background technique

Iron is one of internal the most abundant microelement, it is the important of composition hemoglobin, myoglobins and a variety of enzymes Ingredient takes part in the processes such as oxygen intake, oxygen metabolism, electronics transfer.If lacking iron in vivo, the synthesis of hemoglobin can be influenced, Can make the activity of the enzymes such as cytochrome c, ribonucleotide reductase, succinate dehydrogenase reduces, so as to cause serious body Dysfunction.Fe in human body³⁺The change of content is related to many diseases, as iron deficiency will lead to anaemia, cancer, diabetes and organ Dysfunction etc., and Fe supply then can by Fenton's reaction generate Cells Induced by Reactive Oxygen Species Alzheimer's disease, Huntington's disease and Parkinson's disease etc..Therefore, the content of iron ion in environment and human body is quick and precisely detected for the strong of Environmental security and the mankind Health has a very important significance.

Currently, detection micro Fe³⁺Analytical technology there are many kinds of, including atomic absorption spectrography (AAS), plasma emissioning light Spectrum, plasma mass, electrochemical process, titration etc..These methods are needed mostly using expensive large-scale instrument, and operation is multiple It is miscellaneous, portability difference and unsuitable on line real-time monitoring.The equipment as needed for fluorescence analysis is simple, and have fast response time, High sensitivity, it is easy to operate the advantages that, therefore using fluorescence probe come qualitative and quantitative detect Fe³⁺Have become research hotspot.

In recent years, about Fe³⁺The existing a small amount of report of the research of fluorescence probe.Wherein most is using rhodamine as fluorescent base The iron ion fluorescence probe of group, such as Chinese patent CN107011351A, CN 105884788A, Synthesis and evaluation of a novel rhodamine B-based'off-on'fluorescent chemosensor for the selective determination of Fe³⁺Ions, Sensors and Actuators B:Chemicals, 2017,242,921-931.The testing principle of rhodamine fluorescence probe are as follows: by causing acyl in itself with Action of Metal Ions Open loop occurs for amine Spirocyclic structure, and so as to cause ultravioletvisible absorption and fluorescence spectrum to change, it is different to be finally reached detection The purpose of concentration of metal ions.

However, since rhodamine can participate in ion coupling reaction, excitation wavelength and launch wavelength can because detection from Son variation and change, cause the rhodamine base fluorescent optical sensor of a variety of different ions that cannot use the same excitation and launch wavelength It is detected.And the Fe of above-mentioned report³⁺Fluorescent optical sensor excitation wave is about 560nm, and transmitted wave is about 580nm, stoke This (Stockes) displacement only has 20nm or so, and ordinary optical light splitting eyeglass is difficult to an exciting light and fluorescence distinguishes, thus shadow Testing result is rung, the general light spectrum detecting apparatus high using spectral resolution carries out fluorescence signal acquisition, detection difficulty and cost It can greatly increase.

In addition to problem above, contains ferrous ion and ferric ion in existing some liquid environments simultaneously, detecting When generally require detection ferrous ion and ferric ion total concentration.However current Fe³⁺Molecular fluorescence sensor Ferrous ion therein can not be detected, and some spectrophotometry are all based on greatly the detection of total iron content in solution First by Fe³⁺Fe is reduced into reducing agent hydroxylamine hydrochloride²⁺, after 10min stablizes, then to Fe²⁺It is measured, time-consuming, sensitivity It is low.

Based on the above reasons, provide it is a kind of being able to detect ferrous ion and ferric ion total concentration, and can be fast Speed detection, the more sensitive iron ion fluorescent optical sensor of measurement be very it is necessary to.

Summary of the invention

The main purpose of the present invention is to provide a kind of iron ion molecular fluorescence sensors and preparation method thereof, existing to solve There is the Fe in technology³⁺Molecular fluorescence sensor can not measure quickly, sensitivity not enough and can not detect simultaneously ferrous ion and The problem of ferric ion total concentration.

To achieve the goals above, according to an aspect of the invention, there is provided a kind of iron ion molecular fluorescence sensor, It includes transparent resin basal layer；Test layer is arranged on a side surface of transparent resin basal layer, and test layer includes first solidifying Gum base materials and the Fe being scattered in the first gel base³⁺Molecular fluorescence compound；The separate transparent of test layer is arranged in light shield layer The opacifying fillers that on the surface of resin base layer side, light shield layer includes the second gel base, is dispersed in the second gel base And oxidant；Wherein, Fe³⁺Molecular fluorescence compound has structure shown in Formulas I:

In Formulas I, Polym is amidized large hydrophilic molecular polymeric groups.

Further, Polym is the residue of the residue of aminocellulose dehydrogenation formation, amino maltodextrin dehydrogenation formation Or the residue that amino polyvinylpyrrolidone dehydrogenation is formed；It is preferred that aminocellulose is amino ethyl cellulose, amino ethoxy One of cellulose, amino hydroxypropyl cellulose and aminocarbonyloxymethyl cellulose are a variety of.

Further, oxidant is one of potassium permanganate, ceric sulfate and sodium bismuthate or a variety of.

Further, opacifying fillers are carbon black.

Further, the first gel base and the second gel base are respectively selected from D4 hydrogel, D6 hydrogel, acryloyl Amine-one of acrylonitrile copolymer and polyvinyl alcohol is a variety of.

Further, the material of transparent resin basal layer is one of PET, PMMA, PC, PVC, PS, PP and ABS or more Kind.

According to another aspect of the present invention, a kind of preparation method of iron ion molecular fluorescence sensor is additionally provided, is wrapped Include following steps: step L1 provides transparent resin basal layer；Step L2, by Fe³⁺Molecular fluorescence compound, the first gel base Gel rubber material and the first gel solvent mixing, obtained mixture is coated on a side surface of transparent resin basal layer, Test layer is formed after drying；Step L3, opacifying fillers, oxidant, the gel rubber material of the second gel base and the second gel is molten Obtained mixture is coated on a side surface of the separate transparent resin basal layer of test layer, is formed and hidden after dry by agent mixing Photosphere, and then obtain iron ion molecular fluorescence sensor；Wherein, Fe³⁺Molecular fluorescence compound has structure shown in Formulas I:

In Formulas I, Polym is amidized large hydrophilic molecular polymeric groups.

Further, Fe³⁺Molecular fluorescence compound is prepared by following methods:

Compound A and compound B is carried out condensation reaction, forms compound C by step S1；Compound A, compound B and change The structure for closing object C is as follows, and wherein the X in compound A is halogen:

Compound C is hydrolyzed reaction and obtains compound D by step S2；The structure of compound D is as follows:

Compound D and amidized large hydrophilic molecular polymer are carried out condensation amidation process, obtained by step S3 Fe³⁺Molecular fluorescence compound.

Further, amidized large hydrophilic molecular polymer is aminocellulose, amino maltodextrin or amino Polyvinylpyrrolidone；Preferably, before step S1, preparation method further includes the steps that prepare compound A comprising: it will 4- cyanobenzoic acid and the tert-butyl alcohol carry out esterification, obtain the 4- cyanobenzoic acid tert-butyl ester；By the 4- cyanobenzoic acid tert-butyl ester, Catalyst and methanol are mixed to form mixed system, and hydrogen is passed through into mixed system and carries out hydrogenation, obtains 4- amino methyl T-butyl perbenzoate E；Wherein catalyst is one of Raney nickel, palladium-carbon catalyst and Co catalysts or a variety of；By 4- ammonia Ylmethyl t-butyl perbenzoate E is reacted with compound F, obtains compound A；Wherein 4- aminomethyl benzoic acid tert-butyl ester E, Compound F has the following structure:

Wherein the X in compound F is halogen.

Further, step S1 includes: to mix compound A, compound B and acid binding agent with the first solvent, obtains first Mixture；First mixture is subjected to condensation reaction at a temperature of 80~100 DEG C, obtains the first product system；By the first product System is cooled and poured into water, and precipitating, as compound C is obtained by filtration；Preferably, the first solvent be N-Methyl pyrrolidone, One of DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, dimethyl acetamide and tetrahydrofuran are a variety of；Preferably, acid is tied up Agent is N, one of N- diisopropylethylamine, N,N-dimethylformamide, 4-dimethylaminopyridine and triethylamine or a variety of；It is excellent Selection of land, the molar ratio between compound A, compound B and acid binding agent are 1~6:1~5:1~15；Preferably, filtration step it Afterwards, step S1 further includes the steps that washing precipitating, and washing step includes: that precipitating is dissolved in chloroform, Xiang Qi Middle addition water is washed, and liquid separation obtains organic phase and water phase；Using the dry organic phase of anhydrous sodium sulfate, filters and evaporate, obtain To compound C.

Further, step S2 includes: that compound C, carbonyl removing reagent and the second solvent are mixed and reacted, and obtains the Two product systems；It uses volume ratio to dilute the second product system for the chloroform of 1:1/methanol mixed solution, then evaporates molten Agent obtains compound D；Preferably, carbonyl removing reagent is trifluoroacetic acid, the hydrochloric acid that volume ratio is 1:2 and ethyl acetate mix Reagent or silica gel；Preferably, the second solvent is methylene chloride and/or chloroform；Preferably, the molal quantity of compound C is de- for carbonyl Except the 1.8~2.0% of reagent molal quantity, preferably 1.9%.

Further, step S3 includes: by compound D, amidized large hydrophilic molecular polymer, dehydrating agent, carbonyl Activator is mixed and is reacted with third solvent, obtains third product system；Third product system is filtered, and to filtering gained Precipitating is washed, is dried, and Fe is obtained³⁺Molecular fluorescence compound；Preferably, the carbonization of dehydrating agent N, N- dicyclohexyl -1,3- Diimine, 1- (3- dimethylamino-propyl) one of -3- ethyl-carbodiimide hydrochloride and diisopropylcarbodiimide or more Kind；Preferably, carbonyl activation agent is n-hydroxysuccinimide and/or N- hydroxy thiosuccinimide；Preferably, third is molten Agent is N,N-dimethylformamide, N, one in N- diethylformamide, DMAC N,N' dimethyl acetamide and hexamethylphosphoramide Kind is a variety of；Preferably, the dosage of compound D is the 2~3% of the weight of amidized large hydrophilic molecular polymer；It is preferred that Ground, before by amidized large hydrophilic molecular mixed with polymers, step S3 further include: by amidized large hydrophilic molecular Polymer is suspended in aqueous sodium carbonate, and filtering is resuspended in DMF, is filtered, then washed with DMF, is obtained pretreated ammonia The large hydrophilic molecular polymer of base.

Further, the step of 4- cyanobenzoic acid and the tert-butyl alcohol being subjected to esterification include: by 4- cyanobenzoic acid, The 4th solvent of acylating reagent is mixed and is reacted, and obtains intermediary；After removing the solvent in intermediary, by it with esterification catalyst, The tert-butyl alcohol is mixed and is reacted, and obtains the 4th product system；The 4th product system is purified, the 4- cyanobenzoic acid tert-butyl ester is obtained；It is excellent Selection of land, acylating reagent are one of oxalyl chloride, thionyl chloride, phosphorus trichloride and phosphorus pentachloride or a variety of；Preferably, esterification is urged Agent is one of pyridine, N,N-dimethylformamide, 4-dimethylaminopyridine and triethylamine or a variety of；Preferably, 4- cyanogen Molar ratio between yl benzoic acid and acylating reagent is 2~3:3~5；Volume ratio between esterification catalyst and the tert-butyl alcohol is 1~ 1.1:1。

Further, in the step of preparing 4- aminomethyl benzoic acid tert-butyl ester E, the 4- cyanobenzoic acid tert-butyl ester and catalysis Weight ratio between agent is 10~20:1~3；Weight ratio between the 4- cyanobenzoic acid tert-butyl ester and methanol is 1~3:8~20； Preferably, after being passed through hydrogen, the pressure of reaction system is 0.8~1.2MPa.

Further, the step of 4- aminomethyl benzoic acid tert-butyl ester E being reacted with compound F includes: by 4- ammonia Ylmethyl t-butyl perbenzoate E, compound F are mixed and are reacted with the 5th solvent, obtain the 5th product system；Filter the 5th product Obtained precipitating is dried system, obtains compound A；Preferably, the 5th solvent is ethyl alcohol, methanol, propyl alcohol and isopropanol One of or it is a variety of；Preferably, the molar ratio between 4- aminomethyl benzoic acid tert-butyl ester E and compound F is 1:1.

Further, the first gel solvent and the second gel solvent are the mixed solvent of water and ethyl alcohol.

The present invention provides a kind of iron ion molecular fluorescence sensors comprising transparent resin basal layer, test layer and screening Photosphere, test layer are arranged on a side surface of transparent resin basal layer, and test layer includes the first gel base and is scattered in the Fe in one gel base³⁺Molecular fluorescence compound；The separate transparent resin basal layer side of test layer is arranged in light shield layer On surface, light shield layer includes the second gel base, the opacifying fillers and oxidant that are dispersed in the second gel base.

Firstly, contain oxidant in the light shield layer of the sensor provided by the invention, it is during atual detection, to be checked It surveys liquid and first passes through light shield layer into test layer, ferrous ion therein can be oxidized agent and be oxidized to ferric ion, The ferric ion concentration detected in test layer is the total concentration of ferrous ion and ferric ion in testing liquid actually. Meanwhile the opacifying fillers in light shield layer can also play the purpose of shielding ambient interference, so as to improve sensor Measurement accuracy.

Secondly, the Fe in above-mentioned test layer³⁺Molecular fluorescence compound, for fluorophor, is made it have with 1,8- naphthalene Asia amide Good photostability, exciting (449nm) and transmitting light (521nm) is wavelength visible, and Stokes shift is big (72nm), quantum yield are high.Meanwhile the Fe³⁺In molecular fluorescence compoundGroup (test group) is for Fe³⁺'s Sensitivity is higher, and pyridine nuclear nitrogen and 4- bit amino nitrogen can be with Fe³⁺Complexing occurs and forms ion complexation body, so as to Cause electronics transfer or energy transfer, makes the test agent in different Fe³⁺There is different fluorescence responses under concentration.Except this with Outside, the Fe³⁺Amidized large hydrophilic molecular polymeric groups in molecular fluorescence compound can play to fluorophor and The fixed function and good peptizaiton for testing group enable fluorophor and test group to better disperse and come, and Amidized large hydrophilic molecular polymeric groups itself provides micropore, make the Fe in sample to be tested³⁺It can be more fully Into and with test group more sufficiently faster contact so that Fe provided by the invention³⁺Molecular fluorescence compound has both Better test accuracy and sensitivity.

In short, the factor of aspects above enables iron ion molecular fluorescence sensor provided by the invention quickly to detect The total concentration of ferrous ion and ferric ion in testing liquid, and it is good to have had both measurement efficiency height, high sensitivity, accuracy The advantages that.

Detailed description of the invention

The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:

Fig. 1 shows the structural schematic diagram of iron ion molecular fluorescence sensor according to the present invention；

Fig. 2 shows the tert-butyl -4- amine picoline -1,8- naphthalimides that the embodiment of the present invention 1 is prepared The hydrogen nuclear magnetic resonance spectrogram of ylmethyl；

Fig. 3 shows the 4- amine picoline -1,8- naphthalimido methylbenzene that the embodiment of the present invention 1 is prepared The hydrogen nuclear magnetic resonance spectrogram of formic acid；

Fig. 4 shows in the embodiment of the present invention 1 iron ion fluorescent optical sensor obtained with iron ion (Fe³⁺:Fe²⁺=1: 1) concentration increases the variation diagram of fluorescence spectrum；

Fig. 5 shows in the embodiment of the present invention 1 iron ion fluorescent optical sensor obtained with iron ion (Fe³⁺:Fe²⁺=1: 1) concentration increases the variation diagram of fluorescence intensity；

Fig. 6 shows iron ion (Fe made from the embodiment of the present invention 1³⁺:Fe²⁺=1:1) fluorescent optical sensor is to iron ion Fluorescence selectivity identifies schematic diagram；

Fig. 7 shows iron ion (Fe made from the embodiment of the present invention 1³⁺:Fe²⁺=1:1) fluorescent optical sensor detection iron ion Anti-interference identify schematic diagram；

Fig. 8 shows in the embodiment of the present invention 1 iron ion fluorescent optical sensor obtained to containing various concentration ratio Fe³⁺With Fe²⁺The fluorescence intensity identification schematic diagram of iron ion mixed liquor [identical letter a expression is in least significant difference in not going together Method (LSD) is not significantly different (P < 0.05) under examining].

Wherein, the above drawings include the following reference numerals:

10, transparent resin basal layer；20, test layer；30, light shield layer.

Specific embodiment

It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.

The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally Apply for range claimed.

As described in background technology part, Fe in the prior art³⁺Molecular fluorescence sensor reversible can not measure, is quasi- Exactness is inadequate and can not detect the total concentration of ferrous ion and ferric ion simultaneously.

To solve the above-mentioned problems, the present invention provides a kind of iron ion molecular fluorescence sensors, as shown in Figure 1, it is wrapped Include transparent resin basal layer 10, test layer 20 and light shield layer 30；The side table of transparent resin basal layer 10 is arranged in test layer 20 On face, test layer 20 includes the first gel base and the Fe being scattered in the first gel base³⁺Molecular fluorescence compound；Light shield layer 30 are arranged on the surface of separate 10 side of transparent resin basal layer of test layer 20, light shield layer 30 include the second gel base, The opacifying fillers and oxidant being dispersed in the second gel base；Wherein, Fe³⁺Molecular fluorescence compound has structure shown in Formulas I:

In Formulas I, Polym is amidized large hydrophilic molecular polymeric groups.

In short, to be able to detect iron ion molecular fluorescence sensor provided by the invention to be measured for the factor of aspects above The total concentration of ferrous ion and ferric ion in liquid, and it is good etc. excellent to have had both measurement efficiency height, high sensitivity, accuracy Point.The sensor is to Fe³⁺Concentration linear response range be 4~1000 μm of ol/L, Monitoring lower-cut be 1.36 μm of ol/L.

Besides the above advantages, the non-gel base of decentralized medium used in test layer 20 and light shield layer 30 in the present invention Material can greatly simplify preparation section using gel base compared to other decentralized media, after coating only need to drying can be at Type is not necessarily to photocuring or thermal curing procedures, is also beneficial to the stability for preventing photo-thermal curing condition from influencing test machine.

It should be noted that in the above-mentioned Formulas I of the present invention(here referred to as functional group) and Molar ratio between Polym large hydrophilic molecular polymeric groups is not defined as 1:1, large hydrophilic molecular polymeric groups The load capacity of upper functional group is can be adjusted according to the amido functional group quantity in corresponding large hydrophilic molecular polymer Whole, only indicate between functional group and large hydrophilic molecular polymeric groups to be connected by way of chemical bond herein.

In a preferred embodiment, above-mentioned Polym include but is not limited to aminocellulose dehydrogenation formed residue, The residue that the residue or amino polyvinylpyrrolidone dehydrogenation that amino maltodextrin dehydrogenation is formed are formed.These residues are actually The group formed after amidized large hydrophilic molecular polymer removes amino hydrogen atom.It is preferred that aminocellulose is amino second One of base cellulose, amino hydroxyethyl cellulose, amino hydroxypropyl cellulose and aminocarbonyloxymethyl cellulose are a variety of.This A little macro-radicals all have good hydrophily, and can be formed between above-mentioned functional group it is stable be connected chemically, and For above-mentioned functional group dispersion performance more preferably, the carrier as functional group can further increase Fe³⁺Molecular fluorescence Close stability, sensitivity and the measurement accuracy of object.Moreover, these macro-radicals and final iron ion molecular fluorescence sensor In basal layer between have good adhesive property, be also beneficial to further increase the stability of product.

In a preferred embodiment, oxidant is one of potassium permanganate, ceric sulfate and sodium bismuthate or more Kind.These types of oxidant has stronger oxidability, can aoxidize ferrous ion more quickly.Sensor of the invention is used The content of micro iron ion in test liquid, the effect of oxidant is by the micro Fe in testing liquid²⁺It is oxidized to Fe^3+,Cause This, the additional amount of specific oxidant can be according to Fe in prepare liquid²⁺Substantially content be adjusted, this is those skilled in the art What member should be understood that.

In a preferred embodiment, opacifying fillers are carbon black.It can be improved light shield layer using above-mentioned opacifying fillers 30 shading performance, to advantageously reduce the interference for being further reduced light for fluorescence detection.In actually detected, second Weight ratio between gel base and opacifying fillers can be adjusted according to detection environment, this is that those skilled in the art answer Understand.In order to be further reduced light interference, there is another aspect formula light shield layer relatively high cohesive force to suggest this hair Weight ratio between bright second gel base and opacifying fillers is 3.2:1.

In a preferred embodiment, the first gel base and the second gel base are respectively selected from D4 hydrogel, D6 One of hydrogel, nitrile-acrylamide-acrylic acid lonitrile copolymer and polyvinyl alcohol are a variety of.Above-mentioned Fe provided by the invention³⁺Molecule There is better compatibility, test agent is more preferable in dispersibility wherein between fluorescent chemicals and these types of hydrogel.Except this with Outside, there is better adhesive property between these types of hydrogel and basal layer, be conducive to further increase iron ion molecular fluorescence The stability of sensor.In addition, sensor of the invention is used to test the content of micro iron ion in liquid, in test layer 20 Fe³⁺Weight ratio between molecular fluorescence compound and the first gel base can be according to Fe in prepare liquid³⁺And Fe²⁺Substantially contain Amount is adjusted, this is also that those skilled in the art should be understood that.

In a preferred embodiment, the material of transparent resin basal layer 10 include but is not limited to PET, PMMA, PC, One of PVC, PS, PP and ABS or a variety of.The transparency that these types of resin material has more preferably, is conducive to further increase The Stability and veracity of fluorescence detection.

Preferably, transparent resin basal layer 10 with a thickness of 75~125 μm, test layer 20 with a thickness of 100~200 μm, Light shield layer 30 with a thickness of 100~200 μm.

In Formulas I, Polym is amidized large hydrophilic molecular polymeric groups.

As it was noted above, either in aqueous solution or in human body fluid, utilizing iron ion made from the preparation method Molecular fluorescence sensor Fe in measurement sample³⁺Have many advantages, such as that measurement efficiency height, high sensitivity, accuracy are good when concentration, opens up Good analytical characteristics is shown, to Fe³⁺Concentration linear response range be 4~1000 μM, Monitoring lower-cut be 1.36 μM.Together When, which can also detect the total concentration of ferrous ion and ferric ion in testing liquid.

In a preferred embodiment, above-mentioned Fe³⁺Molecular fluorescence compound is prepared by following methods:

The present invention utilizes compound A and the condensation reaction of compound B, the hydrolysis of compound C, compound D and amino The reaction of the large hydrophilic molecular polymer of change has synthesized above-mentioned Fe with shorter route³⁺Molecular fluorescence compound, and the preparation Method process operation is simple, mild condition, is very suitable for industrializing large-scale application.

Preferably, above-mentioned amidized large hydrophilic molecular polymer is aminocellulose, amino maltodextrin or ammonia Base polyvinylpyrrolidone；More preferable aminocellulose is amino ethyl cellulose, amino hydroxyethyl cellulose, amino hydroxypropyl One of cellulose and aminocarbonyloxymethyl cellulose are a variety of.

Above compound A can select commercial product, in a preferred embodiment, before step S1, the system Preparation Method further includes the steps that prepare compound A comprising: 4- cyanobenzoic acid and the tert-butyl alcohol are subjected to esterification, obtained The 4- cyanobenzoic acid tert-butyl ester；By the 4- cyanobenzoic acid tert-butyl ester, catalyst (Raney nickel, palladium-carbon catalyst and Co catalysts One of or it is a variety of) and methanol be mixed to form mixed system, be passed through into mixed system hydrogen carry out hydrogenation, obtain 4- Aminomethyl benzoic acid tert-butyl ester E；4- aminomethyl benzoic acid tert-butyl ester E is reacted with compound F, obtains compound A； Wherein 4- aminomethyl benzoic acid tert-butyl ester E, compound F have the following structure:

Wherein the X in compound F is halogen.

Using above method prepare compound A, route is brief, simple process, cost is lower, yield is relatively high.

Concrete technology condition in above each synthesis step can be adjusted, specific as follows:

In a preferred embodiment, above-mentioned steps S1 includes: by compound A, compound B and acid binding agent and first Solvent mixing, obtains the first mixture；By the first mixture at 80~100 DEG C, more preferably carry out being condensed at a temperature of 90 DEG C anti- It answers, obtains the first product system；First product system is cooled and poured into water, precipitating, as compound C is obtained by filtration.

Preferably, the first solvent includes but is not limited to N-Methyl pyrrolidone, n,N-dimethylacetamide, dimethyl Asia One of sulfone, dimethyl acetamide and tetrahydrofuran are a variety of.

Preferably, above-mentioned acid binding agent is N-Methyl pyrrolidone, n,N-dimethylacetamide, dimethyl sulfoxide, dimethyl One of acetamide and tetrahydrofuran are a variety of.Using these types of acid binding agent, be conducive to further increase compound A and chemical combination Reaction efficiency between object B improves reaction conversion ratio.

Preferably, the molar ratio between compound A, compound B and acid binding agent is 1~6:1~5:1~15；Preferably, exist After filtration step, step S1 further includes the steps that washing precipitating, and washing step includes: that precipitating is dissolved in three chloromethanes In alkane, water is added thereto and is washed, liquid separation obtains organic phase and water phase；Using the dry organic phase of anhydrous sodium sulfate, filtering And evaporate, obtain compound C.

It is exemplified below: by the chloro- 1,8- naphthalimide ylmethyl (compound A) of tert-butyl -4-, 2- amine first Yl pyridines (compound B) and n,N-diisopropylethylamine are suspended in N-Methyl pyrrolidone (NMP) and heat 18 hours at 90 DEG C. Mixture is cooled and poured into water.Precipitating is obtained by filtration, is then dissolved in CHCl₃In and be washed with water, liquid separation.Organic layer is used Na₂SO₄It dries, filters and evaporates, obtain crude product, by 55~60 DEG C of hot methanol hot beating of crude product, filter and with 0~ 10 DEG C of cold methanol washing.50~55 DEG C of hot CHCl of obtained solid (solid after cold methanol washing)₃Recrystallization, obtains Huang Color crystallizes tert-butyl -4- amine picoline -1,8- naphthalimide ylmethyl (compound C).

In a preferred embodiment, above-mentioned steps S2 includes: that compound C, carbonyl removing reagent and second is molten Agent is mixed and is reacted, and obtains the second product system；Use volume ratio for the chloroform of 1:1/methanol mixed solution dilution second Then product system evaporates solvent, obtain compound D.Using the tertbutyloxycarbonyl of carbonyl removing reagent elimination reaction object C (BOC) group.Volume ratio is used to can be used as solvent cut back for chloroform/methanol mixed solution of 1:1, to remove Excessive carbonyl removes reagent.

Preferably, above-mentioned carbonyl removing reagent is trifluoroacetic acid, the hydrochloric acid that volume ratio is 1:2 and ethyl acetate mixing try Agent or silica gel.For reducing side reaction and simplifying the purpose of aftertreatment technology, more preferably removed using trifluoroacetic acid as carbonyl Reagent.

Preferably, the second solvent is methylene chloride and/or chloroform, wherein smaller, more environmentally friendly using methylene chloride toxicity.It is excellent Selection of land, the molal quantity of compound C are that carbonyl removes the 1.8~2.0% of reagent molal quantity, more preferably 1.9%.

It is exemplified below: trifluoroacetic acid (TFA) is added to tert-butyl -4- amine picoline -1,8- naphthalimide base CH where methyl benzoic acid ester (compound C)₂Cl₂In solution.Acquired solution is stirred at room temperature about 1 hour, until thin layer color Spectrum detection (TLC) shows that most of tert-butyl -4- amine picoline -1,8- naphthalimido methyl benzoic acid ester disappears. Then by the mixture CHCl of volume ratio 1:1₃: MeOH dilutes and evaporates solvent.Repeat 4 to 8 times to remove TFA, then Being placed in pump is completely dried it in upper 30 minutes, obtains yellow crystal 4- amine picoline -1,8-naphthalimide ylmethyl benzene Formic acid (compound D).

In a preferred embodiment, above-mentioned steps S3 includes: by compound D, amidized large hydrophilic molecular Polymer, dehydrating agent, carbonyl activation agent are mixed and are reacted with third solvent, obtain third product system；Third is filtered to produce Objects system, and filtering gained precipitating is washed, is dried, obtain Fe³⁺Molecular fluorescence compound.It can using carbonyl activation agent The carbonyl in activating compounds D is improved, cooperation dehydrating agent is conducive to improve the conversion ratio of reaction.Preferably, dehydrating agent N, N- Dicyclohexyl -1,3- carbodiimides (DCC), 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDCI) and One of diisopropylcarbodiimide (DIC) is a variety of；Preferably, carbonyl activation agent is n-hydroxysuccinimide (NHS) And/or N- hydroxy thiosuccinimide (Sulfo-NHS).

Preferably, third solvent is n,N-Dimethylformamide (DMF), N, N- diethylformamide (DEF), N, N- diformazan One of yl acetamide (DMAC) and hexamethylphosphoramide (HMPT) are a variety of；Preferably, the dosage of compound D is amino 2~3% (more preferably the weight ratio of the two is 13:500) of the weight of the large hydrophilic molecular polymer of change；Preferably, it is inciting somebody to action Before amidized large hydrophilic molecular mixed with polymers, step S3 further include: by amidized large hydrophilic molecular polymer It is suspended in aqueous sodium carbonate, filters, be resuspended in DMF, filter, then washed with DMF, obtain pretreated amidized Large hydrophilic molecular polymer.Amidized large hydrophilic molecular polymer can be washed using the step, and is removed therein Moisture.

It is exemplified below: large hydrophilic molecular polymer (such as amino ethyl cellulose) is suspended in aqueous sodium carbonate 30min, filtering, is resuspended in DMF 30 minutes, filters, is washed twice with DMF, to replace the water of retention.It then will washing Large hydrophilic molecular polymer afterwards is transferred to (to be changed containing 4- amine picoline -1,8- naphthalimido methyl benzoic acid Close object D), N is mixed in the anhydrous DMF of N- dicyclohexyl -1,3- carbodiimides (DCC) and n-hydroxysuccinimide (NHS) It closes, and mixed suspension is stirred at room temperature 20 hours.Then crude product is obtained by filtration, with DMF, water, HCl, water, NaOH, water, acetone, ether washing are finally dried in vacuo 16h, obtain yellow powder, as the Fe³⁺Molecular fluorescence compound.

In a preferred embodiment, include: by 4- cyanobenzoic acid and the step of tert-butyl alcohol progress esterification 4- cyanobenzoic acid, acylating reagent and the 4th solvent are mixed and reacted, intermediary is obtained；After removing the solvent in intermediary, It is mixed and reacted with esterification catalyst, t-butanol mixture, the 4th product system is obtained；The 4th product system is purified, is obtained To the 4- cyanobenzoic acid tert-butyl ester.Acylation reaction first is carried out with 4- cyanobenzoic acid using acylating reagent and forms intermediate product, so It can react to form the 4- cyanobenzoic acid tert-butyl ester with the tert-butyl alcohol under the action of esterification catalyst afterwards.Compared to acid with it is pure straight It is reversed to answer, the 4- cyanobenzoic acid tert-butyl ester is prepared using the route provided by the invention, feed stock conversion is higher.Preferably, acyl Change reagent is one of oxalyl chloride, thionyl chloride, phosphorus trichloride and phosphorus pentachloride or a variety of；Preferably, esterification catalyst is One of pyridine, N,N-dimethylformamide (DMF), 4-dimethylaminopyridine (DMAP) and triethylamine are a variety of.

Preferably, the molar ratio between 4- cyanobenzoic acid and acylating reagent is 2~3:3~5, more preferable 2:3；It will esterification The total weight of catalyst and the tert-butyl alcohol is denoted as n, the weight for removing the intermediary of solvent is denoted as m, m:n is 1~3:10~20, more Preferably 3:20；Volume ratio between esterification catalyst and the tert-butyl alcohol is 1~1.1:1, preferably 1:1.

It is exemplified below: 4- cyanobenzoic acid is dissolved in anhydrous CH₂Cl₂In, oxalyl chloride and dimethylformamide (DMF) is added. Gained mixture is stirred at room temperature 1 hour, until stopping generating gas.Remove solvent, gained residue pyridine/tertiary fourth Alcohol mixture is handled and is stirred at room temperature 6 hours.Solvent is evaporated under reduced pressure, and green residue is suspended in water, then uses Ethyl acetate extraction.Na is used after combined organic layer is washed₂SO₄It dries and evaporates.Crude product passes through ethyl acetate/petroleum ether After column purification, the white solid 4- cyanobenzoic acid tert-butyl ester is obtained.

In a preferred embodiment, in the step of preparing 4- aminomethyl benzoic acid tert-butyl ester E, 4- cyano benzene first Weight ratio between tert-butyl acrylate and catalyst is 10~20:1~3, more preferably 10:1；The 4- cyanobenzoic acid tert-butyl ester and first Weight ratio between alcohol is 1~3:8~20, more preferably 3:20；Preferably, after being passed through hydrogen, the pressure of reaction system is 0.8 ~1.2MPa, more preferable 1MPa.Using above-mentioned technique prepare 4- aminomethyl benzoic acid tert-butyl ester E, reaction it is more efficient, on One of Raney nickel, palladium-carbon catalyst and Co catalysts or a variety of can specifically be used by stating catalyst.

It is exemplified below: the 4- cyanobenzoic acid tert-butyl ester and Raney nickel is mixed in methyl alcohol, the hydrogen under the pressure of 1MPa Change 16 hours.Then solvent is removed under reduced pressure in Filtration of catalyst, obtain the white solid 4- aminomethyl benzoic acid tert-butyl ester.

In a preferred embodiment, step 4- aminomethyl benzoic acid tert-butyl ester E reacted with compound F Suddenly include: that 4- aminomethyl benzoic acid tert-butyl ester E, compound F are mixed and reacted with the 5th solvent, obtain the 5th product body System；The 5th product system is filtered, obtained precipitating is dried, obtains compound A.

Preferably, the 5th solvent is one of ethyl alcohol, methanol, propyl alcohol and isopropanol or a variety of；Preferably, 4- amino first Molar ratio between yl benzoic acid tert-butyl ester E and compound F is 1:1.

It is exemplified below: the chloro- 1,8- naphthalic anhydride of 4- and the 4- aminomethyl benzoic acid tert-butyl ester is put into ethyl alcohol and is formed Suspension.It is stirred at room temperature 16 hours.The precipitating being obtained by filtration, it is 8 hours dry at 50 DEG C, obtain white powder tert-butyl- The chloro- 1,8- naphthalimide ylmethyl of 4-.

Preferably, the first gel solvent and the second gel solvent are the mixed solvent of water and ethyl alcohol.For example volume ratio is 8 ~10 ethanol/water mixed solvent.

In short, iron ion fluorescent optical sensor provided by the invention has the advantage that

(1) Fe in sensor³⁺Molecular fluorescence compound has good photostability, excites (449nm) and transmitting light The advantages that (521nm) is wavelength visible, and Stokes shift is big (72nm), and quantum yield is high；

(2) the sensor energy selective enumeration method Fe designed by the present invention³⁺Variation, strong antijamming capability, and synthesis side Method is simple, and testing cost is low, reusable；

(3) light shield layer of sensor can be used to the color pair of veiling glare or sample in preferably removal environment in the present invention The interference of sample detection, while can also be filtered isolation to the macromolecular insoluble matter in sample, only allows solubility in sample Substance is contacted with test layer, improves detection accuracy；

(4) the first hydrogel in the present invention and the second hydrogel can allow Fe³⁺Molecular fluorescence compound and opacifying fillers It is evenly dispersed in substrate surface, further increases the homogeneity of sensor and stability.Also, the hydrogel can increase Adhesiveness enables test layer and light shield layer to be easily fixed together with basal layer very much, is not necessarily to the processes such as UV solidification, heat cure, Simplify fixed process；

(5) large hydrophilic molecular polymeric groups and the excellent isolation of light shield layer have also widened its application range, such as should Sensor can be applied in fields such as biological electrolyte fluorescence analysis, medicament high flux screening and environmental monitorings, wherein uncured Precursor substance (such as compound D) can be used for fluorescence probe, cell dyeing and fluorescence imaging field.

(6) iron ion fluorescent optical sensor of the invention is capable of detecting when ferrous ion and ferric ion in testing liquid Total concentration.

The preparation method of above-mentioned iron ion molecular fluorescence sensor is relatively simple, it is only necessary in transparent resin basal layer 10 The surface last time is coated with test layer 20 and light shield layer 30.Such as:

By Fe³⁺Molecular fluorescence compound is mixed with D4 hydrogel solution (D4 hydrogel is dissolved in second alcohol and water), and At least 18h is stirred at room temperature, keeps it evenly dispersed in hydrogel.Then the suspension is uniformly coated on transparent tree with scraper On aliphatic radical bottom 10, at least dry 30min.With at least carbon black of 18h, oxidant will be mixed and stirred for D6 hydrogel solution Suspension scraper is in Fe³⁺Continue even spread above fluorescent fiber element film, it is glimmering that the uniform iron ion of two layers of thickness can be obtained (upper layer is carbon black oxidizer layer, lower layer Fe to optical sensor³⁺Fluorescent fiber element layer)

Beneficial effects of the present invention are further illustrated by the following examples:

Embodiment 1

The synthesis of compound 1

4- cyanobenzoic acid (80g, 544mmol) is dissolved in anhydrous CH₂Cl₂In (1000mL).Addition oxalyl chloride (104mL, 816mmol) and dimethylformamide (DMF) 10mL.Resulting reaction mixture is stirred at room temperature 1 hour, until stopping Generate gas.Remove solvent.Gained residue is handled with 600mL pyridine/t-butanol mixture (1:1) and is stirred at room temperature 6 Hour.Solvent is evaporated under reduced pressure, and green residue is suspended in H₂In O.Aqueous suspension is extracted with ethyl acetate (3 × 500mL) It takes.By combined organic layer 10%KHSO₄(2 × 500mL), H₂O(500mL)NaHCO₃(500mL), H₂O (500mL) and salt Water (500mL) washing.By solvent Na₂SO₄It dries and evaporates.Crude product by using ethyl acetate/petroleum ether (1:4) column Chromatography purifying, obtains white solid 58g (yield 52%).

The synthesis of compound 2

The mixing in methanol (500mL) by the 4- cyanobenzoic acid tert-butyl ester (58g, 37mol) and Raney nickel (5.8g), in It is hydrogenated 16 hours under the pressure of 10kg.Then solvent is removed under reduced pressure in Filtration of catalyst, obtain white solid 47g (yield 80%).

The synthesis of compound 3

By the chloro- 1,8- naphthalic anhydride of 46.4g (200mmol) 4- and 41.4g (200mmol) 4- aminomethyl benzoic acid uncle Butyl ester, which is put into 250mLEtOH, forms suspension.It is stirred 16 hours at RT.The precipitating being obtained by filtration is small in 50 DEG C of dryings 8 When, obtain white powder 48g (yield 57%).

The synthesis of compound 4

By 24.33g (225mmol) 2- amine picoline and the chloro- 1,8- naphthalene diformazan of 31.3g (74.3mmol) tert-butyl -4- Imide methyl benzoic acid ester and 13mL (74.6mmol) n,N-diisopropylethylamine are suspended in 110mLN- methyl pyrrolidone (NMP) and at 90 DEG C it heats 18 hours.Mixture is cooled and poured into water (2L).Precipitating is obtained by filtration, is then dissolved in CHCl₃ It is washed in (800mL) and with water (5 × 800mL).Organic layer Na₂SO₄It dries, filters and evaporates, obtain 63.55g crude product. Residue is ground with hot methanol (600mL), filters and is washed with cold methanol (600mL).The hot CHCl of obtained solid₃It ties again Crystalline substance obtains yellow crystal 32.0g (yield 87%), tert-butyl -4- amine picoline -1,8-naphthalimide ylmethyl benzene first Acid esters, hydrogen nuclear magnetic resonance spectrogram are as shown in Figure 2.

The synthesis of compound 5

87.5mL (1.14mol) trifluoroacetic acid (TFA) is added to 10.68g (21.64mmol) tert-butyl -4- amine methyl Pyridine -1,8- naphthalimide ylmethyl is in CH₂Cl₂In the solution of (160mL).Acquired solution is stirred in room temperature It mixes about 1 hour, until thin-layer chromatography detection (TLC) shows most of tert-butyl -4- amine picoline -1,8- naphthalene diformazan imide Ylmethyl disappears.Then by the CHCl of mixture 1:1₃: MeOH (1.2L) dilutes and evaporates solvent.Repeat 6 Secondary to remove TFA, being subsequently placed in pump is completely dried it in upper 30 minutes, obtains yellow crystal 9.35g (yield 99%), 4- amine first Yl pyridines -1,8- naphthalimido methyl benzoic acid, hydrogen nuclear magnetic resonance spectrogram are as shown in Figure 3.

The synthesis of compound 6

Amino ethyl cellulose (5g) is suspended in 30min in 50mL2.5% aqueous sodium carbonate, filters, suspends again 30 minutes in 50mLDMF, filtering is washed twice with DMF, to replace the water of retention.Then the cellulose of washing is transferred to Containing 4- amine picoline -1,8- naphthalimido methyl benzoic acid (0.13g, 0.3mmol), N, dicyclohexyl -1 N-, 3- carbodiimides (DCC, 0.62g, 3mmol) and n-hydroxysuccinimide (NHS, 0.35g, 3mmol) are in anhydrous DMF It is mixed in the solution of (20mL), and mixed suspension is stirred at room temperature 20 hours.Then yellow fibers are obtained by filtration Cellulose fiber, with DMF (5 × 50mL), water (50mL), 0.2NHCl (2 × 50mL), water (50mL), 1.0NNaOH (2 × 50mL, 60 DEG C, 30min), water (10 × 50mL), acetone (2 × 50mL), ether (2 × 50mL) washing, be finally dried in vacuo 16h, obtain Huang Color powder 0.54g.

The production of iron ion fluorescent optical sensor

The 4- amine picoline -1,8-naphthalimide ylmethyl-benzamide cellulose 0.3g for taking 25 μm of sieves, with D4 hydrogel solution 4.7mL (D4 hydrogel 0.47g is dissolved in 3.807mL ethyl alcohol and 0.309mL water) mixing, and at room temperature At least 18h is stirred, keeps it evenly dispersed in hydrogel.Then the suspension is uniformly coated on the poly- of 100 μ m-thicks with scraper On ester (PET) diaphragm (light transmittance is more than or equal to 88%), at least dry 30min.With will be with D6 hydrogel solution 4.85mL (D6 hydrogel 0.475g is dissolved in 3.852mL ethyl alcohol and 0.428mL water) is mixed and stirred for at least carbon black of 18h (0.15g) Suspension scraper with oxidant potassium permanganate (0.1g) is in Fe³⁺Continue even spread above fluorescent fiber element film The uniform iron ion fluorescent optical sensor of two layers of thickness (upper layer is carbon black oxidizer layer, 150 μm of thickness, lower layer Fe³⁺Fluorescence Cellulose layer, 150 μm of thickness).

The fluorescence property of iron ion fluorescent optical sensor is tested

(1) iron ion fluorescent optical sensor is to various concentration iron ion (Fe³⁺:Fe²⁺=1:1) spectral signature

0.1622g iron chloride and 0.1268g frerrous chloride are dissolved in the Tris-HCl buffering of 0.05mol/LpH6.0 respectively In liquid, 1.0 × 10 are made with 100mL volumetric flask constant volume^-2The Fe of mol/L³⁺Standard solution and 1.0 × 10^-2The Fe of mol/L²⁺Standard Solution.Continue with the buffer to Fe obtained³⁺And Fe²⁺Titer is repeatedly diluted step by step in the ratio progress of 1:1, thus The titer of a series of different iron concentrations: 4 μm of ol/L, 8 μm of ol/L, 10 μm of ol/L, 40 μm of ol/L, 80 μ is arrived Mol/L, 100 μm of ol/L, 400 μm of ol/L, 800 μm of ol/L, 1000 μm of ol/L and 10000 μm of ol/L.By iron ion fluorescence sense Diagonally position is fixed in fluorescence cuvette device, is 650V, excitation wavelength and transmitted wave in the voltage of photomultiplier tube Length be respectively under conditions of 449nm and 521nm with fluorescence spectrophotometer measurement its in a series of above-mentioned different iron concentrations The variation of transmitting photocathode in titer.Fig. 4 is iron ion fluorescent optical sensor produced by the present invention with iron ion (Fe³⁺:Fe²⁺=1:1) concentration increase fluorescence spectrum variation diagram, it can be seen that iron ion fluorescent optical sensor is in Fe³⁺And Fe²⁺Deng Ratio shows strong fluorescent quenching in the case where coexisting.With the increase of iron concentration, the sensor is at 521nm Fluorescence intensity gradually decreases.Fig. 5 is iron ion fluorescent optical sensor produced by the present invention with iron ion (Fe³⁺:Fe²⁺=1:1) it is dense Degree increases the variation diagram of fluorescence intensity, can see from the figure as iron ion (Fe³⁺:Fe²⁺=1:1) concentration is in 4 μm of ol/L- When within the scope of 1000 μm of ol/L, fluorescence intensity and iron ion (Fe³⁺:Fe²⁺=1:1) concentration be in good linear relationship, The linear equation of fitting can be to iron ion (Fe³⁺:Fe²⁺=1:1) carry out quantitative detection.According to the mark of 3 times of 10 blank solutions The ratio of quasi- deviation and fit equation slope calculates iron ion (Fe³⁺:Fe²⁺=1:1) detection of concentration is limited to 1.36 μm of ol/L.

(2) spectral signature of the iron ion fluorescent optical sensor to 16 kinds of other heavy metal ion

By 16 metal ion species salt [NaCl, KCl, CH₃COOLi·2H₂O、Al(NO₃)₃、CaCl₂、MgCl₂·6H₂O、 ZnCl₂、CoCl₂·6H₂O、MnCl₂·4H₂O、CrCl₃·6H₂O、BaCl₂·2H₂O、NiCl₂·6H₂O、CuCl₂·2H₂O、 CdCl₂·2.5H₂O、Pb(NO₃)₂、HgCl₂] with the Tris-HCl buffer of 0.05mol/LpH6.0 accurately it is configured to respective concentration For the stock solution of 10mmol/L, be then diluted to concentration be 1000 μm of ol/L 16 kinds of ion titers it is spare.Also match simultaneously Set each metal ion respectively with iron ion (Fe³⁺:Fe²⁺=1:1) titer that coexists, so that single metal in every kind of titer Ion and iron ion (Fe³⁺:Fe²⁺=1:1) concentration be 1000 μm of ol/L.Fluorescence selectivity is tested as shown in fig. 6, by dense Degree is the Na of 1000 μm of ol/L⁺、K⁺、Li⁺、Al³⁺、Ca²⁺、Mg²⁺、Zn²⁺、Fe²⁺、Co²⁺、Mn²⁺、Cr³⁺、Ba²⁺、Ni²⁺、Cu² ⁺、Cd²⁺、Pb²⁺、Hg²⁺、Fe³⁺、Fe²⁺With iron ion (Fe³⁺:Fe²⁺=1:1) titer take respectively 2ml be added oblique cutting have iron ion In the cuvette of fluorescent optical sensor, after fluorescent stabilization, under 650V voltage with wavelength be 449nm excitation light detection its The variation of fluorescence intensity at 521nm.Fig. 6 is observed it is found that iron ion fluorescent optical sensor is to Fe³⁺、Fe²⁺With iron ion (Fe³⁺: Fe²⁺=1:1) there is apparent response effect, and fluorescence intensity is reduced to minimum, and the fluorescence intensity of three at 521nm Similar, this illustrates the sensor to Fe³⁺、Fe²⁺With iron ion (Fe³⁺:Fe²⁺=1:1) there is good selectivity.Cu is added²⁺ Afterwards, the fluorescence intensity of sensor also slightly reduces, but other equivalent metal ions do not have optrode film fluorescent emission intensity substantially It influences.In order to further study other common metal cations to iron ion (Fe³⁺:Fe²⁺=1:1) measurement interference effect, We conducted competitive assays, i.e., will contain 1000 μm of ol/L iron ion (Fe of other ions (concentration is 1000 μm of ol/L)³ ⁺:Fe²⁺=1:1) solution is added in the cuvette containing iron ion fluorescent optical sensor and is measured (result such as Fig. 7 white column Shown in figure).By competitive assay it is found that in addition to Cu²⁺、Fe³⁺And Fe²⁺, other ions and Fe³⁺Fluorescence when coexisting at 521nm Emissive porwer is without significant changes.From Fe³⁺And Fe²⁺Data it is found that the sensor to Fe³⁺And Fe²⁺There is good identification Property, and there is no difference to the recognition capability of the two.Therefore, in addition to Cu²⁺, other common metal cations and anion are (Bu Tong golden Belonging to cation is the addition in the form of chloride, nitrate or acetate) iron ion (Fe that will not interfere³⁺:Fe²⁺=1:1) Measurement.And work as Cu²⁺Concentration when being reduced to 100 μm of ol/L, to 1000 μm of ol/L iron ion (Fe³⁺:Fe²⁺=1:1) detection no longer It interferes.Therefore, this sensor is feasible for iron ion detection.

(3) iron ion fluorescent optical sensor to contain different proportion Fe³⁺And Fe²⁺Iron ion mixed liquor recognition capability

In order to further appreciate that the iron ion fluorescent optical sensor to Fe³⁺And Fe²⁺Recognition capability it is whether variant, configuration It is a series of to contain different proportion Fe³⁺And Fe²⁺Iron ion mixed liquor, the iron ion total concentration for keeping its final is 1000 μM. These processing include entirely Fe³⁺, Fe³⁺And Fe²⁺Concentration ratio be 5:1,4:1,3:1,2:1,1:1,1:2,1:3,1:4,1:5, And entirely Fe²⁺.Take the ferric ion solutions 2ml of various processing that the cuvette that oblique cutting has iron ion fluorescent optical sensor is added respectively In, after fluorescent stabilization, its fluorescence intensity at 521nm of the excitation light detection for being 449nm with wavelength under 650V voltage becomes Change, as a result as shown in Figure 8.As can be seen from FIG. 8, when iron ion total concentration is identical, the relative deviation of transmission light fluorescent value everywhere 4% hereinafter, and one-way analysis of variance show in the case where P < 0.05 difference of transmission photocathode everywhere Not significant, this illustrates the iron ion sensor for Fe³⁺And Fe²⁺Recognition capability it is the same, accurate detection can be used to containing not Same Fe³⁺And Fe²⁺The full iron concentration of concentration ratio.

Embodiment 2

The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 1, adjust The dosage of whole oxalyl chloride, makes the molar ratio 2:3 of 4- cyanobenzoic acid and oxalyl chloride, and the volume ratio between pyridine and the tert-butyl alcohol is 1.1:1.The yield of final compound 1 is 49%.

Embodiment 3

The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 1, adjust The dosage of whole oxalyl chloride makes the molar ratio 3:5 of 4- cyanobenzoic acid and oxalyl chloride.The yield of final compound 1 is 53%.

Embodiment 4

The technique of each step the difference is that only with embodiment 1 in the embodiment:, will in the synthesis process of compound 1 Oxalyl chloride replaces with thionyl chloride, and adjusts its dosage and make the molar ratio 3:2 of 4- cyanobenzoic acid and thionyl chloride,.By pyrrole Pyridine replaces with 4-dimethylaminopyridine, and adjusts its dosage and make volume ratio 1.2 between 4-dimethylaminopyridine and the tert-butyl alcohol: 1, the yield of final compound 1 is 45%.

Embodiment 5

The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 2, adjust The dosage of whole catalyst makes the weight ratio 20:3 between the 4- cyanobenzoic acid tert-butyl ester and Raney nickel, adjusts the use of methanol Amount, makes the weight ratio 1:8 between the 4- cyanobenzoic acid tert-butyl ester and methanol.The yield of compound 2 is 82%.

Embodiment 6

The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 2, adjust The dosage of whole catalyst makes the weight ratio 20:3 between the 4- cyanobenzoic acid tert-butyl ester and Raney nickel, adjusts the use of methanol Amount, makes the weight ratio 3:20 between the 4- cyanobenzoic acid tert-butyl ester and methanol.The yield of compound 2 is 84%.

Embodiment 7

The technique of each step the difference is that only with embodiment 1 in the embodiment:, will in the synthesis process of compound 2 Raney nickel replaces with palladium-carbon catalyst, and adjusts the dosage of catalyst, makes the 4- cyanobenzoic acid tert-butyl ester and palladium-carbon catalyst Between weight ratio be 15:1, adjust the dosage of methanol, make the weight ratio 1 between the 4- cyanobenzoic acid tert-butyl ester and methanol: 6.The yield of compound 2 is 74%.

Embodiment 8

The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 4, adjust The dosage of whole 2- amine picoline and n,N-diisopropylethylamine makes the chloro- 1,8-naphthalimide ylmethyl benzene of tert-butyl -4- Molar ratio between formic acid esters, 2- amine picoline and n,N-diisopropylethylamine is 1:1:1.The yield of compound 4 is 85%.

Embodiment 9

The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 4, adjust The dosage of whole 2- amine picoline and n,N-diisopropylethylamine makes the chloro- 1,8-naphthalimide ylmethyl benzene of tert-butyl -4- Molar ratio between formic acid esters, 2- amine picoline and n,N-diisopropylethylamine is 6:5:15.The yield of compound 4 is 82%.

Embodiment 10

The technique of each step the difference is that only with embodiment 1 in the embodiment:, will in the synthesis process of compound 4 N,N-diisopropylethylamine replaces with triethylamine, and adjusts the dosage of 2- amine picoline and triethylamine, keeps tert-butyl -4- chloro- Molar ratio between 1,8- naphthalimide ylmethyl, 2- amine picoline and triethylamine is 8:5:5.Compound 4 yield is 73%.

Embodiment 11

The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 5, adjust The dosage of whole trifluoroacetic acid makes tert-butyl -4- amine picoline -1,8-naphthalimide ylmethyl molal quantity It is the 1.8% of trifluoroacetic acid molal quantity.The yield of compound 5 is 97%.

Embodiment 12

The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 5, adjust The dosage of whole trifluoroacetic acid makes tert-butyl -4- amine picoline -1,8-naphthalimide ylmethyl molal quantity It is the 2.0% of trifluoroacetic acid molal quantity.The yield of compound 5 is 98%.

Embodiment 13

The technique of each step the difference is that only with embodiment 1 in the embodiment:, will in the synthesis process of compound 5 Trifluoroacetic acid replaces with volume ratio and is the hydrochloric acid and ethyl acetate mix reagent of 1:2, and adjusts its dosage, tert-butyl -4- amine first The molal quantity of yl pyridines -1,8- naphthalimide ylmethyl is the 3.0% of the mix reagent molal quantity.Compound 5 yield is 75%.

As can be seen from the above embodiments, iron ion molecular fluorescence sensor provided by the invention iron ion in measurement sample is dense It is good high to have many advantages, such as measurement efficiency height, high sensitivity, accuracy when spending, and be able to detect in liquid containing arbitrary proportion two The total concentration of valence iron ion and ferric ion.

The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims

1. a kind of iron ion molecular fluorescence sensor characterized by comprising

Transparent resin basal layer (10)；

Test layer (20) is arranged on a side surface of the transparent resin basal layer (10), and the test layer (20) includes the One gel base and the Fe being scattered in first gel base³⁺Molecular fluorescence compound；

Light shield layer (30) is arranged on the surface far from transparent resin basal layer (10) side of the test layer (20), The opacifying fillers and oxidant that the light shield layer (30) includes the second gel base, is dispersed in second gel base；

Wherein, the Fe³⁺Molecular fluorescence compound has structure shown in Formulas I:

In the Formulas I, Polym is amidized large hydrophilic molecular polymeric groups.

2. iron ion molecular fluorescence sensor according to claim 1, which is characterized in that the Polym is amino fibre The residue of residue, amino maltodextrin dehydrogenation formation that plain dehydrogenation is formed or amino polyvinylpyrrolidone dehydrogenation form residual Base；It is preferred that the aminocellulose is amino ethyl cellulose, amino hydroxyethyl cellulose, amino hydroxypropyl cellulose and amino One of carboxymethyl cellulose is a variety of.

3. iron ion molecular fluorescence sensor according to claim 1, which is characterized in that the oxidant is permanganic acid One of potassium, ceric sulfate and sodium bismuthate are a variety of.

4. iron ion molecular fluorescence sensor according to any one of claim 1 to 3, which is characterized in that the shading Filler is carbon black.

5. iron ion molecular fluorescence sensor according to claim 4, which is characterized in that first gel base and institute State the second gel base is respectively selected from D4 hydrogel, D6 hydrogel, nitrile-acrylamide-acrylic acid lonitrile copolymer and polyvinyl alcohol one Kind is a variety of.

6. iron ion molecular fluorescence sensor according to any one of claim 1 to 3, which is characterized in that described transparent The material of resin base layer (10) is one of PET, PMMA, PC, PVC, PS, PP and ABS or a variety of.

7. a kind of preparation method of iron ion molecular fluorescence sensor described in any one of claims 1 to 6, feature exist In the preparation method comprises the following steps:

Step L1 provides transparent resin basal layer；

Step L2, by Fe³⁺Molecular fluorescence compound, the gel rubber material of the first gel base and the mixing of the first gel solvent, will To mixture be coated on a side surface of the transparent resin basal layer, form test layer after dry；

Opacifying fillers, oxidant, the gel rubber material of the second gel base and the second gel solvent are mixed, will be obtained by step L3 Mixture be coated on the side surface far from the transparent resin basal layer of the test layer, form light shield layer after dry, And then obtain the iron ion molecular fluorescence sensor；

8. preparation method according to claim 7, which is characterized in that the Fe³⁺Molecular fluorescence compound is by following methods It is prepared:

Compound A and compound B is carried out condensation reaction, forms compound C by step S1；The compound A, the compound B And the structure of the compound C is as follows, wherein the X in the compound A is halogen:

The compound C is hydrolyzed reaction and obtains compound D by step S2；The structure of the compound D is as follows:

The compound D and amidized large hydrophilic molecular polymer are carried out condensation amidation process, obtain Fe by step S3³ ⁺Molecular fluorescence compound.

9. preparation method according to claim 8, which is characterized in that the amidized large hydrophilic molecular polymer is Aminocellulose, amino maltodextrin or amino polyvinylpyrrolidone；Preferably, before the step S1, the system Preparation Method further includes the steps that preparing the compound A comprising:

4- cyanobenzoic acid and the tert-butyl alcohol are subjected to esterification, obtain the 4- cyanobenzoic acid tert-butyl ester；

The 4- cyanobenzoic acid tert-butyl ester, catalyst and methanol are mixed to form mixed system, led into the mixed system Enter hydrogen and carry out hydrogenation, obtains 4- aminomethyl benzoic acid tert-butyl ester E；Wherein the catalyst is Raney nickel, palladium carbon One of catalyst and Co catalysts are a variety of；

The 4- aminomethyl benzoic acid tert-butyl ester E is reacted with compound F, obtains the compound A；The wherein 4- Aminomethyl benzoic acid tert-butyl ester E, the compound F have the following structure:

Wherein the X in the compound F is halogen.

10. preparation method according to claim 8 or claim 9, which is characterized in that the step S1 includes:

The compound A, the compound B and acid binding agent are mixed with the first solvent, obtain the first mixture；

First mixture is subjected to the condensation reaction at a temperature of 80~100 DEG C, obtains the first product system；

First product system is cooled and poured into water, precipitating is obtained by filtration, the as described compound C；

Preferably, first solvent is N-Methyl pyrrolidone, n,N-dimethylacetamide, dimethyl sulfoxide, dimethyl second One of amide and tetrahydrofuran are a variety of；

Preferably, the acid binding agent is n,N-diisopropylethylamine, n,N-Dimethylformamide, 4-dimethylaminopyridine and three second One of amine is a variety of；

Preferably, the molar ratio between the compound A, the compound B and the acid binding agent is 1~6:1~5:1~15；

Preferably, after filtration step, the step S1 further includes the steps that washing the precipitating, the purge step Suddenly include:

The precipitating is dissolved in chloroform, water is added thereto and is washed, liquid separation obtains organic phase and water phase；

Using the dry organic phase of anhydrous sodium sulfate, filters and evaporate, obtain the compound C.

11. the preparation method according to any one of claim 8 to 10, which is characterized in that the step S2 includes:

The compound C, carbonyl removing reagent and the second solvent are mixed and reacted, the second product system is obtained；

It uses volume ratio to dilute second product system for the chloroform of 1:1/methanol mixed solution, then evaporates solvent, Obtain the compound D；

Preferably, carbonyl removing reagent be trifluoroacetic acid, the hydrochloric acid that volume ratio is 1:2 and ethyl acetate mix reagent or Silica gel；

Preferably, second solvent is methylene chloride and/or chloroform；

Preferably, the molal quantity of the compound C is that the carbonyl removes the 1.8~2.0% of reagent molal quantity, preferably 1.9%.

12. the preparation method according to any one of claim 8 to 10, which is characterized in that the step S3 includes:

By the compound D, the amidized large hydrophilic molecular polymer, dehydrating agent, carbonyl activation agent and third solvent It mixes and is reacted, obtain third product system；

The third product system is filtered, and filtering gained precipitating is washed, is dried, obtains the Fe³⁺Molecular fluorescence Close object；

Preferably, the dehydrating agent is N, N- dicyclohexyl -1,3- carbodiimides, 1- (3- dimethylamino-propyl) -3- ethyl One of carbodiimide hydrochloride and diisopropylcarbodiimide are a variety of；

Preferably, the carbonyl activation agent is n-hydroxysuccinimide and/or N- hydroxy thiosuccinimide；

Preferably, the third solvent be n,N-Dimethylformamide, N, N- diethylformamide, n,N-dimethylacetamide and One of hexamethylphosphoramide is a variety of；

Preferably, the dosage of the compound D is the 2~3% of the weight of the amidized large hydrophilic molecular polymer；

Preferably, before by the amidized large hydrophilic molecular mixed with polymers, the step S3 further include: will be described Amidized large hydrophilic molecular polymer is suspended in aqueous sodium carbonate, and filtering is resuspended in DMF, is filtered, then use DMF washing, obtains the pretreated amidized large hydrophilic molecular polymer.

13. preparation method according to claim 9, which is characterized in that by the 4- cyanobenzoic acid and the tert-butyl alcohol Carry out esterification the step of include:

The 4- cyanobenzoic acid, the 4th solvent of acylating reagent are mixed and reacted, intermediary is obtained；

After removing the solvent in the intermediary, it is mixed and reacted with esterification catalyst, the tert-butyl alcohol, the 4th product body is obtained System；

The 4th product system is purified, the 4- cyanobenzoic acid tert-butyl ester is obtained；

Preferably, the acylating reagent is one of oxalyl chloride, thionyl chloride, phosphorus trichloride and phosphorus pentachloride or a variety of；

Preferably, the esterification catalyst is one in pyridine, n,N-Dimethylformamide, 4-dimethylaminopyridine and triethylamine Kind is a variety of；

Preferably, the molar ratio between the 4- cyanobenzoic acid and the acylating reagent is 2~3:3~5；The catalyzing esterification Volume ratio between agent and the tert-butyl alcohol is 1~1.1:1.

14. the preparation method according to claim 9 or 13, which is characterized in that prepare the 4- aminomethyl benzoic acid uncle In the step of butyl ester E, the weight ratio between the 4- cyanobenzoic acid tert-butyl ester and the catalyst is 10~20:1~3；Institute Stating the weight ratio between the 4- cyanobenzoic acid tert-butyl ester and the methanol is 1~3:8~20；Preferably, after being passed through the hydrogen, The pressure of reaction system is 0.8~1.2MPa.

15. the preparation method according to claim 9 or 13, which is characterized in that by the tertiary fourth of 4- aminomethyl benzoic acid The step of ester E is reacted with the compound F include:

The 4- aminomethyl benzoic acid tert-butyl ester E, the compound F are mixed and reacted with the 5th solvent, the 5th production is obtained Objects system；

The 5th product system is filtered, obtained precipitating is dried, obtains the compound A；

Preferably, the 5th solvent is one of ethyl alcohol, methanol, propyl alcohol and isopropanol or a variety of；

Preferably, the molar ratio between the 4- aminomethyl benzoic acid tert-butyl ester E and the compound F is 1:1.

16. preparation method according to claim 8, which is characterized in that first gel solvent and second gel Solvent is the mixed solvent of water and ethyl alcohol.