CN110408023A - A kind of fluorenyl fluorescent polymer and preparation method thereof - Google Patents

A kind of fluorenyl fluorescent polymer and preparation method thereof Download PDF

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Publication number
CN110408023A
CN110408023A CN201910301576.4A CN201910301576A CN110408023A CN 110408023 A CN110408023 A CN 110408023A CN 201910301576 A CN201910301576 A CN 201910301576A CN 110408023 A CN110408023 A CN 110408023A
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fluorenyl
polymer
fluorescent polymer
preparation
fluorescent
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宫琳丹
张博
范路安
郑文岐
杜松辉
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Harbin Engineering University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1425—Non-condensed systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Abstract

The present invention provides a kind of fluorenyl fluorescent polymer and preparation method thereof, include the following steps: step 1: with (9,9- bis- (6- bromine hexyl) -2, bis- fluorenes aldehyde of 7-) and (1S, 2S)-cyclohexanediamine is raw material, obtains intermediate polymer in the case where anhydrous LiCl is catalyst action；Step 2: resulting intermediate polymer dissolves in a solvent, and trimethylamine aqueous solution is added, obtains fluorenyl fluorescent polymer.The present invention provides a kind of fluorenyl fluorescent polymer and preparation method thereof, and detection iron ion handy and safe, easy to operate, the high result of selectivity be not by other ion interferences, and linear test scope is wider, the micro and trace detection especially suitable for iron ion；Sensitive, quick, the accurate detection for iron ion content in life entity and under various natural and artificial aqueous environment can be achieved in the present invention, and in medical treatment, industry, agricultural, building, the fields such as food have important application value and wide application prospect.

Description

A kind of fluorenyl fluorescent polymer and preparation method thereof
Technical field
The present invention relates to a kind of polymer and preparation method thereof more particularly to a kind of fluorenyl fluorescent polymer and its preparation sides Method belongs to metal ion detection field.
Background technique
Ferro element is the element on the earth containing flow control five, and rich reserves are widely used, and steel material accounts for the total metal in the world Yield 95%.Iron is also our body necessary elements, is one indispensable in humans and animals hemoglobin composition Point.It will lead to hypoferric anemia disease when human body lacks iron.However, intracellular excessive iron can induce and generate largely Active oxygen brings mortality to injure to cell, and iron ion can excessively cause serious intracerebral oxidation to damage in brain tissue, or even lead Cause epilepsy.
Have great importance to the detection of iron ion.The detection of traditional iron ion mainly have phenanthroline method (need using Sulfuric acid, ammonium hydroxide and glacial acetic acid), sulfosalicylic acid method (need to use ammonium hydroxide), and potassium rhodanide colorimetric method (need to use the concentrated sulfuric acid), process Cumbersome, operation difficulty is high, it is necessary to severe using corrosivity and penetrating odor solvent, test condition.And instrument test method is such as, member Element analysis, atom spectrum, the methods of plasma spectrum, required instrument is costly.
Summary of the invention
The purpose of the invention is to for a kind of handy and safe, easy to operate, the high fluorenyl fluorescent polymer of selectivity and Preparation method.
The object of the present invention is achieved like this:
A kind of fluorenyl fluorescent polymer, the structural formula of the fluorenyl fluorescent polymer are as follows:
A kind of preparation method of fluorenyl fluorescent polymer, includes the following steps:
Step 1: with (9,9- bis- (6- bromine hexyl) -2,7-, bis- fluorenes aldehyde) and (1S, 2S)-cyclohexanediamine for raw material, anhydrous LiCl is to obtain intermediate polymer under catalyst action；
Step 2: resulting intermediate polymer dissolves in a solvent, and trimethylamine aqueous solution is added, and obtains the polymerization of fluorenyl fluorescence Object.
The invention also includes features some in this way:
1. the molar ratio of (two fluorenes aldehyde of 9,9- bis- (6- bromine hexyl) -2,7-) and (1S, 2S)-cyclohexanediamine is 1 in step 1: 1~1:3；
2. the solvent in the step 1 is water removal DMF, reaction temperature environment is 100~120 DEG C of condensing refluxes, reaction Time be 8~for 24 hours；
3. the solvent in the step 2 is DMF solvent, the reaction time of the step 2 is 48~72 hours；
4. the reaction condition of described this method is N2Environment.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is detection reagent using the fluorenyl fluorescent polymer of the brand new of synthesis, is tested by Fluorescence Spectrometer Change response of the detection reagent to various ions.The specific response to iron ion may be implemented in the detection reagent.It is characterized in that fluorescence Excitation wavelength is 330 nanometers, and maximum emission wavelength is 425 nanometers.Its linear detection range is 0 μm of ol/L to 120 μ Mol/L, detection are limited to 0.802091 μm of ol/L；
The present invention provides a kind of fluorenyl fluorescent polymer and preparation method thereof, detection iron ion handy and safe, it is easy to operate, Selectivity is high, and as a result not by other ion interferences, linear test scope is wider, and the micro and trace especially suitable for iron ion is examined It surveys；
The present invention can be achieved in life entity and under various natural and artificial aqueous environment iron ion content it is sensitive, Quickly, it accurately detects, in medical treatment, industry, agricultural, building, the fields such as food have important application value and wide application Prospect.
Detailed description of the invention
Fig. 1 is the NMR spectrum figure of polymer II；
Fig. 2 is the infrared spectrogram of polymer II；
Fig. 3 is the NMR spectrum figure of polymer III；
Fig. 4 is the infrared spectrogram of polymer III；
Fig. 5 is the Fe of various concentration3+To the influence situation of polymer III fluorescent quenching degree；
Fig. 6 is the Fe that concentration is 1600 μm of ol/L3+、Hg2+、Cu2+、Ca2+、Ba2+、Co2+、Mg2+、Zn2+、Ni2+、Ag+、 K+、Na+To the fluorescent quenching percentage of prepared fluorenyl fluorescent polymer；
Fig. 7 is Cu2+、Hg2+Different metal ions (c=1600 μm of ol/L) after screening agent is added are to polymer III's Fluorescent quenching percentage schematic diagram；
Fig. 8 is the Fe that 120 μm of ol/L are added3+Afterwards under the conditions of different time polymer III fluorescence emission spectrogram of compound variation Situation；
Fig. 9 is the Fe that 1600 μm of ol/L are added3+Afterwards under the conditions of different time polymer III fluorescence emission spectrogram of compound variation Situation；
Figure 10 is the Fe of various concentration3+To the influence situation and Fe of polymer III fluorescent quenching degree3+Linear inspection Range out.
Specific embodiment
Present invention is further described in detail with specific embodiment with reference to the accompanying drawing.
The present invention is prepared for a kind of fluorenyl fluorescent polymer of brand new, which can be with iron ion specificity knot It closes, fluorescent quenching occurs.The present invention provides one kind can qualitative and quantitative judge iron ion detection method.The purpose of the present invention Following technical solution can be used to realize:
1. one kind passes through autofluorescence Characteristics Detection Fe3+Fluorenyl fluorescent polymer III, the structural formula of the polymer is such as Under:
A kind of preparation method route of above-mentioned fluorenyl fluorescent polymer is as follows:
2. a kind of preparation of fluorenyl fluorescent polymer
Step 1: being with compound I (two fluorenes aldehyde of 9,9- bis- (6- bromine hexyl) -2,7-) and (1S, 2S)-cyclohexanediamine first Raw material obtains polymer II under the catalytic action of anhydrous LiCl.
In some specific embodiment schemes: the molar ratio of first step compound of reaction I and cyclohexanediamine is 1:1~1: 3, solvent used is water removal DMF, reaction condition N2Environment, reaction temperature environment are 100~120 DEG C of condensing refluxes, reaction Time be 8~for 24 hours.
Step 2: resulting polymer II is dissolved in a solvent, trimethylamine aqueous solution is added, obtains polymer III.
In some specific embodiment schemes: the solvent for reacting used is DMF solvent system, reaction condition N2Ring Border, reaction time are 48~72 hours.
The structure of polymer II and III all pass through NMR spectrum (NMR) and fourier transform infrared spectroscopy (FT-IR) It is characterized.
3. polymer III is to Fe3+Detection
Conjugated polymer is because having the characteristics that molecular wire effect and fluorescent effect are widely used in gold as fluorescence probe Belong to ion detection field.But low-solubility limits conjugated polymer in the application of water solution system.Polymer III is a kind of fluorenes Base fluorescent polymer, because side chain ionizes, therefore dissolubility greatly increases.
Due to Fe3+Complex can be formed with the fluorenyl fluorescent polymer of ground state, lose the fluorenyl fluorescent polymer of excitation state Deexcitation can cause fluorescent quenching.Polymer III is exactly based on Fe3+Stronger Fluorescence quenching effect caused by it is realized pair Fe3Specific detection.
The present invention is prepared for a kind of fluorenyl fluorescent polymer III, is compared by observation and various concentration Fe is being added3+And not The degree of the polymer fluorescent Strength Changes is realized to metal ion during with type but concentration metal ion of the same race Specific detection.This method simple, detection sensitivity with sample handling characteristics compared with traditional metal ion inspection Height, selectivity is strong, linear test scope is wide and the advantages such as detection limit is low.
Embodiment 1
The preparation of fluorenyl fluorescent polymer III
0.0193g (35 μM) polymer I (two fluorenes aldehyde of 9,9- bis- (6- bromine hexyl) -2,7-) is added to the reaction of 100mL In bottle, it is that 1:2.5 feeds intake according to dialdehyde monomer and (1S, 2S)-(+)-cyclohexanediamine monomer mole ratio, weighs 0.0125g (0.11mmoL) (1S, 2S)-(+)-cyclohexanediamine, polymer solvent are water removal DMF15mL, and catalyst is 0.5g (0.0118moL) Anhydrous LiCl, reaction condition N2Environment, 110 DEG C of temperature condensing refluxes, time 12h.
After room temperature to be restored, reactant is slowly dropped in the ice water of 500mL and is precipitated, is centrifuged, dry, last deionization Water washs repeatedly for several times until supernatant is clarified, and vacuum drying 12h obtains brown powder 0.0145g at 40 DEG C, as polymerize Object II, yield 66%.
As shown in Figure 1, the 1H NMR spectra of polymer II, by low field to High-Field, the peak ownership of all kinds of Hydrogen Protons is as follows: 1H NMR (500MHz, DMSO, TMS, 20 DEG C, ppm): δ=8.20 (s, CH=N, 2H), 7.52-7.9 (m, Ph-H, 6H), 3.51-3.41(m,-CH2-Br,4H),2.01-0.31(m,-(CH2)6- Br, 20H), 1.60-1.21 (s, Cyh-H, 10H), point Analysis map shows successfully to synthesize dialdehyde monomer, and purity is higher, can be used for testing in next step.
As shown in Fig. 2, the FT-IR spectrogram of polymer II is in 3400cm-1The characteristic peak that place occurs belongs to phenyl ring hydrogen (Ph- H stretching vibration peak), 2929cm-1Belong to methylene (- CH2) asymmetric stretching vibration；2855cm-1And 619cm-1Place Characteristic peak be respectively belonging to methylene (- CH2) symmetrical stretching vibration and rocking vibration, 1630cm-1The C=N of appearance Stretching vibration peak show to have synthesized subject polymer II.
40mg (63.9 μM) second step product ion type chiral polymer II is dissolved in the DMAc solvent of 20mL, is added The trimethylamine aqueous solution of 15mL 30% is into the reaction eggplant bottle of 100mL, in room temperature N23d is reacted in environment.By what reaction was completed Liquid pressure-reducing is rotated to powdered, which is put into vacuum oven, and dry 2d, it is glimmering to obtain fluorenyl in 40 DEG C of environment Photopolymer III.
Polymer III's1Its chemical shift of H NMR spectra is unimodal in 3.00-3.20ppm appearance one, should be attributed to season Hydrogen Proton on ammonium salt integrates it to obtain 18 Hydrogen Protons, corresponding with structural formula, and analysis chart spectrum shows that the bromine on branch is former Son is substituted, and polymer III is successfully prepared.
As shown in figure 4, polymer III compared with polymer II structure, phenyl ring hydrogen (Ph-H) is flexible at 3402cm-1 Vibration peak, 2929cm-1And 751cm-1Alkyl vibration peak (the CH at place2-CH2) and 1640cm-1The imido grpup (C=N) at place vibrates Peak still exists, while polymer III is in 1208cm-1There is new vibration peak in place, is the feature of (C-N) in tertiary amine groups Peak, to determine that target product polymer III is successfully synthesized.
Embodiment 2
Fe3+Detection method
We are characterized and are analyzed to the fluorescence property of polymer III using LS55 model sepectrophotofluorometer, are sent out Wave-length coverage is penetrated in 330nm~625nm, reaction temperature is room temperature, using excitation wavelength lambdaex=330nm.
As shown in figure 5, polymer III is dissolved in the buffer solution that pH is 7, the sample that concentration is 10 μm of ol/L is made Then the different concentration such as 0,10,20,30,40,50,60,70,80,200,400,1000 and 1600 μm of ol/L are added in solution Fe3+Solution probes into the Fe of various concentration by sepectrophotofluorometer3+Influence of the solution to polymer III fluorescent quenching degree Situation.It can be seen from the figure that with Fe3+The increase of concentration, the fluorescent quenching effect of polymer III clearly, when by Fe3 +Concentration when increasing to 1600 μm of ol/L, the quenching percentage of polymer III is 83.23%, and quenching efficiency is very high.
As shown in fig. 6, being separately added into concentration of the same race (c=1600 μm of ol/L) Fe into sample solution3+、Hg2+、Cu2+、Ca2 +、 Ba2+、Co2+、Mg2+、Zn2+、Ni2+、Ag+、K+、Na+, different types of metal ion is probed into the fluorescent quenching of polymer III The size cases of degree.By comparing it can be found that the Fluorescence quenching effect of different metal ions is all different.Ca2+、Ba2+、Co2 +、 Mg2+、Ni2+、Na+、Zn2+、K+The quenching efficiency of this 8 metal ion species is relatively low, to the fluorescent quenching percentage of polymer III Than all within 30%；Hg2+、Cu2+、Ag+This 3 metal ion species is to polymer III fluorescent quenching percentage in 30% and 50% Between, the influence to the fluorescence intensity of polymer III is not especially big；Fe3+It is very bright to the Fluorescence-quenching of polymer III It is aobvious, it can tentatively obtain Fe3+It is exactly the metal ion that polymer III is capable of specific recognition.
Hg is additionally investigated2+、Cu2+、Ca2+、Ba2+、Co2+、Mg2+、Zn2+、Ni2+、Ag+、K+、Na+Polymer III is examined Survey Fe3+Interference effect, Ca is had found by Experimental Research2+、Ba2+、Co2+、Mg2+、Zn2+、Ni2+、Ag+、K+、Na+To polymer III detects Fe3+Noiseless effect, Cu2+And Hg2+Do not have under the conditions of respectively existing for the screening agent EDTA and L-cysteine yet Interference effect.
It is individually added into Cu2+Or Hg2+Fe can be detected to polymer III3+Weaker interference effect is generated, after screening agent is added Interference effect disappears.
As shown in fig. 7, being separately added into concentration of the same race (c=1600 μm of ol/L) Fe into sample solution3+、Hg2+、Cu2+、Ca2 +、 Ba2+、Co2+、Mg2+、Zn2+、Ni2+、Ag+、K+、Na+And Cu2+And Hg2+Screening agent after different metal ions to polymer The fluorescent quenching percentage schematic diagram of III, it can be seen that after screening agent EDTA and L-cysteine is added, in addition to Fe3+Except The fluorescent quenching percentage of all metal ions is all between 13% and 32%, only Fe3+Reach 80% or more, so as to Preferably to Fe3+Carry out specific recognition.
As shown in Fig. 8 Fig. 9, Fe is added in sample P3+, making its concentration is respectively 120 μm of ol/L and 1600 μm of ol/L, so It is detected according to the different time afterwards.The fluorescence intensity level at each of figure time point is passed through by the same sample The value for crossing 3 measurements takes average gained.Either concentration is 120 μm of ol/L or 1600 μm of ol/L, fluorescent polymer III To Fe3+Identification in 30min fluorescence just quench completely, illustrate within the scope of concentrations above, polymer III can achieve pair Fe3+The purpose of fast qualitative detection.
Shown in Figure 10, Fe is being recognized3+It is that polymer III is capable of under the metal ion of specific recognition, we continue Study Polymer Melts III is in identification Fe3+When fluorescent quenching the range of linearity and detection limit, the fluorescence intensity of each concentration point in figure Value is all that the value by the same sample by 3 measurements takes average gained, to (F0–F)/F0And Fe3+Concentration carried out linearly After fitting, following relational expression has been obtained:
(F0-F)/F0=0.00317 (± 0.00177) CFe3++0.14158(±0.00003)
By being obtained after linear fit, Fe3+Linear inspection range be 0 μm of ol L-1To 120 μm of ol L-1Between, and Degree of fitting R2=0.99596.According to LOD=3 σ/K, (LOD is detection limit, and K is the slope for drawing standard curve, and σ is blank sample The standard deviation of product), calculate to obtain Fe3+Detection be limited to 0.802091 μm of ol L-1。

Claims (7)

1. a kind of fluorenyl fluorescent polymer, which is characterized in that the structural formula of the fluorenyl fluorescent polymer are as follows:
2. a kind of preparation method of fluorenyl fluorescent polymer, characterized in that include the following steps:
Step 1: with (9,9- bis- (6- bromine hexyl) -2,7-, bis- fluorenes aldehyde) and (1S, 2S)-cyclohexanediamine for raw material, in anhydrous LiCl It is to obtain intermediate polymer under catalyst action；
Step 2: resulting intermediate polymer dissolves in a solvent, and trimethylamine aqueous solution is added, obtains fluorenyl fluorescent polymer.
3. the preparation method of fluorenyl fluorescent polymer according to claim 2, characterized in that (9,9- in the step 1 Two (6- bromine hexyl) -2,7-, two fluorenes aldehyde) it with the molar ratio of (1S, 2S)-cyclohexanediamine is 1:1~1:3.
4. the preparation method of fluorenyl fluorescent polymer according to claim 2 or 3, characterized in that used in the step 1 Solvent be water removal DMF, reaction temperature environment be 100~120 DEG C condensing reflux, the reaction time be 8~for 24 hours.
5. the preparation method of fluorenyl fluorescent polymer according to claim 2 or 3, characterized in that in the step 2 Solvent is DMF solvent, and the reaction time of the step 2 is 48~72 hours.
6. the preparation method of fluorenyl fluorescent polymer according to claim 4, characterized in that the solvent in the step 2 For DMF solvent, the reaction time of the step 2 is 48~72 hours.
7. the preparation method of fluorenyl fluorescent polymer according to claim 2, characterized in that the reaction item of described this method Part is N2Environment.
CN201910301576.4A 2019-04-16 2019-04-16 A kind of fluorenyl fluorescent polymer and preparation method thereof Pending CN110408023A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112029094A (en) * 2020-08-24 2020-12-04 哈尔滨工程大学 Ionic fluorenyl melamine hyperbranched conjugated polymer and preparation method and application thereof
CN112029075A (en) * 2020-08-24 2020-12-04 哈尔滨工程大学 Ionized fluorenyl pyridine conjugated polymer and preparation method and application thereof

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CN105295006A (en) * 2015-09-16 2016-02-03 南京邮电大学 Fluorenyl polymer-iridium complex soft salt and preparation and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112029094A (en) * 2020-08-24 2020-12-04 哈尔滨工程大学 Ionic fluorenyl melamine hyperbranched conjugated polymer and preparation method and application thereof
CN112029075A (en) * 2020-08-24 2020-12-04 哈尔滨工程大学 Ionized fluorenyl pyridine conjugated polymer and preparation method and application thereof

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Application publication date: 20191105