CN102636468B - Polynaphthylene solution fluorescence chemical sensor and application thereof - Google Patents
Polynaphthylene solution fluorescence chemical sensor and application thereof Download PDFInfo
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Abstract
The invention provides fluorescent polynaphthylene. In a nitryl hydrocarbon alkyl system, lewis acid is taken as a catalytic oxidizer, and a naphthalene monomer is polymerized into no-sizing-state powdery polynaphthylene by adopting a one-step method. The polynaphthylene solution fluorescence chemical sensor provided by the invention has the advantages of simple operation, low preparation cost and easy industrial batch production. The polynaphthylene prepared by the invention has specific linear structure characteristic, and degree of polymerization is within the range from 3 to 29. The polynaphthylene disclosed by the invention is a blue fluorescent emitter, luminous power is far higher than that of a naphthalene monomer, and a Fe<3+> quenching fluorescent chemical sensor constructed by the polynaphthylene can realize sensing detection on Fe<3+> ion within the concentration range of 10<-6>-10<-3>mol/L; and meanwhile, the polynaphthylene has strong antijamming capability, alkali metal ions, alkali earth metal ions and transition metal ions such as Hg<2+>, Co<2+> and Pb<2+> have no substantial influence on detection of the polynaphthylene. The polynaphthylene polymer disclosed by the invention has a wide application prospect in the fields of chemical industry, sensing detection and analysis test.
Description
This case is dividing an application of following patented claim:
Application number: 201110102136.X;
The applying date: on April 22nd, 2011;
Denomination of invention: poly-naphthalene of fluorescence and preparation method thereof and application.
Technical field
The invention belongs to the analytical chemistry field, be specifically related to the purposes of luminiferous poly-naphthalene and synthetic method thereof and detection iron concentration.
Background technology
In the condensed-nuclei aromatics polymkeric substance, poly-naphthalene be study the earliest, one of the polymkeric substance of tool application prospect.The synthetic of poly-naphthalene can be traced back to the sixties in last century, and at that time, Japanese scientist Kovacic Peter is being used Lewis acid as FeCl
3(Kovacic P, Koch F W.Polymerization of benzene to p-Polyphenyl by ferric chloride.J.Org.Chem., 1963,28 (7): 1864-1867), MoCl
5(Kovacic P, Lange R M.Polymerization of benzene to p-polyphenyl by molybdenum pentachloride.J.Org.Chem., 1963,28 (4): 968-972), AlCl
3-CuCl
2(Kovacic P, Kyriakis A.Polymerization of benzene to p-Polyphenyl by aluminum chloride-cupric chloride.J.Am.Chem.Soc., 1963,85:454-458) etc. for catalytic oxidant, benzene is carried out to the oxidative dehydrogenation polycondensation and obtain on the basis of polyphenyl, take the lead in again using this method to pass through FeCl
3catalytic oxidation synthesized poly-naphthalene (Kovacic P, Koch F W.Coupling of naphthalene nuclei by lewis acid catalyst-oxidant.J.Org.Chem., 1965,30:3176-3181).But, the poly-naphthalene molecular weight so obtained is very low, can't be at last polymkeric substance truly.Be to have synthesized poly-naphthalene, it would be better to say that it is to have invented new technology prepared by two dinaphthalenes and three dinaphthalenes, because with regard to obtaining two dinaphthalenes and three dinaphthalenes, this synthetic method is compared and is had obvious advantage with three dinaphthalene preparation technologies with two dinaphthalenes that synthesis step at that time can reach at most 11 steps.The poly-naphthalene that people say now, it is no longer this low-molecular-weight oligomerisation naphthalene, its synthesizing mean is more variation also, as electrochemical method for synthesizing also is widely adopted (Hara S in recent years, Toshima N, Electrochemical polymerization of naphthalene using a composite electrolyte of aluminum chloride and copper (I) chloride.Chem.Lett., 1990,19:269-272; Huang Z M, Qu L T, Shi G Q, et al.Electrochemical polymerization of naphthalene in the electrolyte of boron trifluoride diethyl etherate containing trifluoroacetic acid and polyethylene Glycol oligomer.J.Electroanal.Chem., 2003,556:159-165).Can say, the research work of poly-naphthalene is after the silence that has experienced the seventies and eighties in last century, active again recently.Yet, though various different synthetic method all has its unique advantage, also have the problem of needing solution badly simultaneously.Although as simple to operate as lewis acid oxidative dehydrogenation condensation methods, be easy to suitability for industrialized production, also do not obtain the poly-naphthalene of certain high polymerization degree at present.Relative molecular weight is higher, poly-naphthalene that structure is determined although complex catalysis Grignard reagent intermediary method can obtain for nickel (II), and the synthetic method process is tediously long, and catalyzer is expensive.How the efficient poly-naphtho-that simply synthesizes certain degree of polymerization is widened it functional is a challenging job.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of poly-naphthalene and synthetic method thereof of emitting fluorescence is provided, the fluorescence chemical sensor of surveying used as ferric ion.
The present invention adopts chemical oxidization method in the nitroparaffins system, and the lewis acid of take aggregates into the Powdered poly-naphthalene of dark unformed shape by white flaky crystal state naphthalene monomer by single stage method as catalytic oxidant.This poly-naphthalene is a kind of polymkeric substance with height conjugated structure, is rich in the mobility electronics in its molecule, and this electronics very easily analyzes the matter effect with electrophilic, makes its fluorescent quenching, thereby sets up the ferric ion fluorescence chemical sensor.The concrete technical scheme that the present invention adopts is as follows:
A kind of fluorescence is gathered naphthalene, and its structural formula is as follows:
Wherein, m and n are integer, and m+n=1～27.
The preparation method of the poly-naphthalene of above-mentioned fluorescence comprises step: the polymerization reaction take place in organic solvent by naphthalene monomer and lewis acid, after reaction finishes, the gained sediment after filtration, washing, obtain after drying and gather the naphthalene powder.
Preferably, the concentration of naphthalene monomer in organic solvent is 20mM～80mM.
Preferably, the mol ratio of lewis acid and naphthalene monomer is 3: 1～15: 1; Be preferably 3～5: 1, more preferably 5: 1.
Preferably, polymerization reaction time is 1～50 hour; Polymeric reaction temperature is 10～80 ℃, is preferably 30～70 ℃.
Described lewis acid is selected from ferric trichloride, aluminium choride and molybdenum pentachloride, is preferably ferric trichloride.
Described organic solvent is selected from nitromethane, nitroethane and second cyanogen, is preferably nitromethane.
Described by naphthalene monomer and lewis acid polymerization reaction take place in nitroparaffins, concrete steps are: lewis acid and naphthalene monomer are dissolved in respectively to wiring solution-forming in organic solvent, and respectively at after 10～80 ℃ (being preferably 30 ℃) lower constant temperature, then by gained solution blending polymerization reaction take place.
The poly-naphthalene of above-mentioned fluorescence provided by the present invention is synthetic the obtaining of method that adopts chemical oxidising polymerisation in organic solvent.After reaction finishes, the gained sediment after filtration, washing (to remove byproduct of reaction, unreacted monomer), pay special attention to the oxidizer product of wash residual.The gained powder obtains the poly-naphthalene of product after drying.
Concrete, the process of described precipitation, washing comprises step: the gained sediment is washed to cleansing solution with ethanol colourless, then with the deionized water washing to neutral; Then use salt acid treatment sediment 2～3 times, extremely neutral with the deionized water washing; And then sediment is added to stir process in ammonia spirit, and centrifuging, the gained solid is extremely neutral with the deionized water washing.
The poly-naphthalene of above-mentioned fluorescence provided by the present invention can be used as the fluorescence chemical sensor that iron concentration is surveyed, and the poly-naphthalene of above-mentioned fluorescence can be used for surveying iron concentration.Described iron concentration is 5.0 * 10
-6mol/L～1.0 * 10
-3mol/L.
The present invention also further discloses a kind of poly-naphthalene solution fluorescence chemical sensor, for the poly-naphthalene of above-mentioned fluorescence is dissolved in organic solvent and makes.
Preferably, the organic solvent of preparing above-mentioned fluorescent optical sensor is selected from tetrahydrofuran, dimethyl sulfoxide (DMSO) and 1-METHYLPYRROLIDONE, is preferably tetrahydrofuran.
Preferably, in described poly-naphthalene solution fluorescent optical sensor, the concentration of described poly-naphthalene in organic solvent is 5-200mg/L, is preferably 10-50mg/L, more preferably 25mg/L.
The detectable analysis matter of above-mentioned poly-naphthalene solution fluorescence chemical sensor is that concentration is 5.0 * 10
-6mol/L～1.0 * 10
-3the Fe of mol/L
3+.
The structure of above-mentioned poly-fluorescent naphthalimide chemical sensor provided by the present invention, concrete steps are as follows:
The preparing metal deionized water solution.Can use nitrate, sulfate or chloride, use deionized water to be made into 1.0 * 10
-3the aqueous solution of mol/L.These metallic ions are Na
+, K
+, Mg
2+, Ca
2+, Mn
2+, Fe
3+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Hg
2+.The Fe of concentration at different levels
3+standard solution is by 1.0 * 10
-3the Fe of mol/L
3+storing solution stepwise dilution and obtaining.
Preparation coexistent metallic ion aqueous solution: select Na
+, K
+, Mg
2+, Fe
3+be mixed with 2.8 * 10 with deionized water respectively
-2the above-mentioned four metal ion species aqueous solution of mol/L, then according to volume ratio 1: 1: 1: 1 mixes, and obtains 7.0 * 10
-3mol/L containing Na
+, K
+, Mg
2+, Fe
3+the coexistent metallic ion aqueous solution.And the coexistent metallic ion aqueous solution is adopted to stepwise dilution method preparation 7.0 * 10
-4the coexistent metallic ion aqueous solution of mol/L.
Secondly, the poly-fluorescent naphthalimide solution of preparation.For example: take the poly-naphthalene of 2.50mg and be dissolved in the 100mL organic solvent, ultrasonic it is fully dissolved, the concentration of such prepared fluorescence solution is 25.0mg/L.
Again, the mixed solution of preparing metal ion and poly-naphthalene.The various metallic ion aqueous solution of getting 0.50mL add the poly-naphthalene solution of 4.5mL, mix stand-by.
Finally, measure the fluorescence spectrum of mixed solution by fluorescence spectrophotometer, record the intensity of fluorescent emission peak-to-peak value.According to fluorescence peak intensity, the linear relationship of matching fluorescence intensity and concentration of metal ions, obtain calibration curve.
Beneficial effect of the present invention: the present invention be take lewis acid as oxygenant, the poly-naphthalene of single step reaction preparation.Have simple to operately, preparation cost is low, is easy to the advantages such as industrialized mass production.Poly-naphthalene prepared by the present invention has clear and definite linear structure feature, and the degree of polymerization is in 3～29 scopes.Should poly-naphthalene be the blue-fluorescence emitter, luminous power be better than the naphthalene monomer far away, by the Fe of its structure
3+quencher type fluorescence chemical sensor, can realize 10
-6mol/L～10
-3fe in the mol/L concentration range
3+the sensor measuring of ion, the recovery is between 95.3%～103.1%, and relative error is less than 1.54%, and relative standard deviation is less than 1.83%.And antijamming capability is strong, alkali metal ion, alkaline-earth metal ions and transition metal ion are as Hg
2+, Co
2+and Pb
2+deng it is surveyed all without substantial effect.This polymkeric substance is with a wide range of applications in fields such as chemical, sensor measuring and analytical tests.Comparatively speaking, poly-naphthalene prepared by the electrochemical synthesis of bibliographical information also has fluorescence, but has only provided its fluorescence Spectra, and its application is not studied.The output that adds the poly-naphthalene that galvanochemistry is synthetic is limited, the extensive synthetic advantage that does not have chemical oxidative polymerization to have.And survey ferric ion for the fluorescence chemical sensor based on organic compound, some reports are arranged, but these compounds are the aromaticity organic compound, all physical environment are had to harm in various degree, the detecting concentration scope of some sensor is also narrower.As the Fe based on Cefradine or cup [4] arene Nanoparticle
3+survey fluorescence chemical sensor, investigative range is less than the present invention.
The accompanying drawing explanation
The Matrix-assisted time-of-flight mass spectrometry of synthetic poly-naphthalene under Figure 130 ℃ and 70 ℃.
The WAXD collection of illustrative plates of the poly-naphthalene of Fig. 2 naphthalene monomer and 10 ℃ and 70 ℃ lower synthesizeds.
The poly-naphthalene of Fig. 3 naphthalene monomer and 30 ℃, 50 ℃, 70 ℃ and 80 ℃ lower synthesizeds
1the H-NMR collection of illustrative plates.
The fluorescence emission spectrum of the poly-naphthalene solution of Fig. 4 variable concentrations.
The fluorescence emission spectrum of synthetic poly-naphthalene under Fig. 5 different temperatures.
The regular progressively quencher of Fig. 6 ferric ion to poly-naphthalene solution fluorescence.
The calibration curve that the poly-naphthalene chemical sensor of Fig. 7 is surveyed ferric ion.
The quencher of the poly-naphthalene of other ion pair of Fig. 8 and the comparison of ferric ion.
Embodiment
Further set forth the present invention below in conjunction with embodiment.Should be understood that these embodiment are only for the present invention is described, but not limit the scope of the invention.
Embodiment 1～9: gather the synthetic of naphthalene
Embodiment 1: the ferric trichloride of 1622.0mg (10.00mmol) is dissolved in the 20mL nitromethane, short its dissolving in ultrasonic 10 minutes, then adopt the individual layer Filter paper filtering, removes impurity, obtain the nitromethane solution of ferric trichloride, and survey the pH value of liquor ferri trichloridi with accurate pH test paper; The naphthalene monomer of 256.4mg (2.00mmol) is dissolved in the 5mL nitromethane to short its dissolving in ultrasonic 5 minutes.The nitromethane solution of ferric trichloride and the nitromethane solution of naphthalene are placed on respectively in the thermostat water bath that temperature is 50 ℃ constant temperature 30 minutes.By in the disposable nitromethane solution that adds the naphthalene monomer of the nitromethane solution of ferric trichloride, open stirring apparatus, the close observation reacting phenomenon afterwards.Dip mixed liquor with glass bar and survey its pH value, and be placed on the taper bottleneck with moistening accurate pH test paper, detect and whether have sour gas to emit.React after 24 hours, take out reactant liquor, centrifuging.The lower sediment thing washs to cleansing solution colourless with ethanol, more extremely neutral with the deionized water washing.Then use 1mol/L salt acid treatment sediment 2～3 times, extremely neutral with the deionized water washing.And then sediment is added in the ammonia spirit of 0.2mol/L of 20mL to stir process 1 day, and centrifuging, to neutral, put into surface plate dry 1 day with the deionized water washing, and weighing and calculating productive rate is 65.3%.
Embodiment 2: repeat embodiment 1, but change oxygenant and monomer mole ratio are 3/1, take iron chloride 984.42mg (6.00mmol), all the other operate with embodiment 1, and must gather the naphthalene productive rate is 50.1%.
Embodiment 3: repeat embodiment 1, but use acetonitrile solvent to replace nitromethane, all the other operate with embodiment 1, and must gather the naphthalene productive rate is 21.7%.
Embodiment 4-9: repeating embodiment 1, is 10 ℃, 30 ℃, 60 ℃, 65 ℃, 70 ℃, 80 ℃ but change polymerization temperature, and all the other operate with embodiment 1, must gather the naphthalene productive rate and be respectively 58.1%, 69.6%, 58.2%, 58.0%, 56.6%, 53.2%.Wherein the poly-naphthalene of 30 ℃ of lower synthesizeds is after the Matrix-assisted time-of-flight mass spectrometry is analyzed, and its degree of polymerization reaches as high as 19, and corresponding molecular weight is in 2400 left and right.And the poly-naphthalene of 70 ℃ of lower synthesizeds is after the Matrix-assisted time-of-flight mass spectrometry is analyzed, its degree of polymerization reaches as high as 29, and corresponding molecular weight is in the 3600g/mol left and right.See Fig. 1.
Utilize the poly-naphthalene of 10 ℃ and 70 ℃ lower synthesizeds of D/max 2550 wide-angle X ray diffractor tests and the X ray diffracting spectrum of naphthalene monomer, see Fig. 2.The naphthalene monomer is white crystalline solid, and it is 12.0 ° at Bragg angle, and 19.5 °, 21.4 °, 24.3 °, 25.5 °, a series of diffraction peaks appear in 30.0 ° of places of grade, present the highly crystalline feature; With respect to the naphthalene monomer, the wide-angle x-ray diffracting spectrum of poly-naphthalene is fully different, only at 2 θ, is 24.5 ° and locates a more wide in range diffraction peak, and this is to cause because the molecular weight that gathers naphthalene is higher and chain structure is more unordered.The poly-naphthalene that accordingly prepared by known chemical oxidization method is unformed shape.And, after this also illustrates the naphthalene polymerization, state of matter changes, and from crystalline state, is transformed into amorphous state.
Utilize Bruker DQX-400 nuclear magnetic resonance analyser, record the one dimension of naphthalene monomer and 30 ℃, 50 ℃, 70 ℃ and 80 ℃ and synthetic poly-naphthalene in the DMSO-d6 solvent
1h-NMR, be shown in Fig. 3.For the naphthalene monomer, chemical shift is 7.9 and 7.5 to belong to respectively naphthalene monomer H
isosorbide-5-Nitrae, 5,8and H
2,3,6,7cloud density on every side, two kinds of hydrogen abundances are the same.After polymerization, due to the generation of molecular weight distribution and the increase of conjugated degree, obvious broadening mobile to low appears in resonance peak.The 1D of the poly-naphthalene but prepared under the polymerization temperature different condition
1h-NMR is divided into obvious two kinds of features.The poly-naphthalene one dimension prepared under 30 ℃ and 50 ℃ of conditions
1h-NMR is similar, and the poly-naphthalene one dimension prepared under 70 ℃ and 80 ℃ of conditions
1h-NMR is the collection of illustrative plates of another form.The latter is relatively simple, only contains two strong vibration peaks (7.52ppm) and (7.92ppm) weak vibration peak (7.73ppm).And 30 ℃ and 50 ℃ of synthetic poly-naphthalene nuclear magnetic resoance spectrum slightly complicated, each peak is attributed to: strong vibration peak (7.52ppm), and (7.92ppm) and (8.13ppm); In strong peak (7.62ppm) and weak strong peak (7.73ppm).Simulate by ChemOffice, can find that the poly-naphthalene connection that only contains a kind of aniso-adjacent hydrogen coupling peak has Isosorbide-5-Nitrae-connection, 2,6-connects and 2,7-connects; And the poly-naphthalene connection that contains two aniso-adjacent hydrogen coupling peaks only has 1,5-connects.In conjunction with Infrared spectroscopy, 70 ℃ are more prone to be connected polymerization at Isosorbide-5-Nitrae with the poly-naphthalene DMSO soluble fraction of 80 ℃ of preparations.The poly-naphthalene prepared under 30 ℃ and 50 ℃ of conditions may be more a kind of structure of transition state, has Isosorbide-5-Nitrae and 1,5 syndeton concurrently.Therefore, can reach a conclusion, the synthetic poly-naphthalene of this method is a kind of by the 1-of naphthalene unit, 4-and 1-, the poly-naphthalene that the 5-position is connected by covalent bond.
Embodiment 10: the high carbon residue of poly-naphthalene
The poly-naphthalene high temperature (1000 ℃) of embodiment 1～9 synthesized is processed rear carbon yield all up to more than 70%, the poly-naphthalene wherein synthesized under 70 ℃, the carbon yield of the insoluble part of its THF is especially up to 78.2%, and coke has very high conductivity, 56.3S cm
-1.The carbon yield of poly-naphthalene is slightly larger than poly-pyrene (being 70.6% under 1300 ℃), much larger than poly-fluoranthene (being 24% under 855 ℃), polyacrylonitrile (being 50% at 900 ℃) and poly-luxuriant and rich with fragrance (being 65% at 907 ℃).And the low price of the raw naphthalene material monomer of poly-naphthalene makes it have more the commercial applications potentiality.
Embodiment 11～16: the fluorescence of the poly-naphthalene solution of variable concentrations
Accurately take the synthetic poly-naphthalene of 0.625mg embodiment 4, be dissolved in the tetrahydrofuran of 100mL, place and ultrasonic again after 2 hours it is fully dissolved, obtaining concentration is the poly-naphthalene solution of 6.25mg/L.This solution is placed in to the sample cell of fluorescence spectrophotometer, the wavelength that records its fluorescence emission largest light intensity under the optical excitation of 334nm wavelength is 420nm (Fig. 4).
Repeat aforesaid operations, but change the amount of taking of the synthetic poly-naphthalene of embodiment 4, be respectively 1.25mg, 2.5mg, 5.0mg, 10.0mg, 20.0mg, record its fluorescence emission spectrum and see Fig. 4.
Accurately take the synthetic poly-naphthalene of 2.50mg embodiment 5, be dissolved in the tetrahydrofuran of 100mL, place and ultrasonic again after 2 hours it is fully dissolved, obtaining concentration is the poly-naphthalene solution of 25.0mg/L.This solution is placed in to the sample cell of fluorescence spectrophotometer, the wavelength that records its fluorescence emission largest light intensity under the optical excitation of 334nm wavelength is 420nm (Fig. 5).
Repeat aforesaid operations, but use respectively the synthetic poly-naphthalene of embodiment 6～9, record its fluorescence emission spectrum and see Fig. 5.
Embodiment 22～31: the structure of ferric ion fluorescence chemical sensor
The poly-naphthalene tetrahydrofuran solution of embodiment 4 synthesizeds that to measure 4.5mL concentration be 25.0mg/L, put into beaker, then pipette the deionized water of 0.50mL.The two mixing is shaken up in the sample cell that is placed on fluorescence spectrophotometer, test its fluorescent intensity under the optical excitation of 334nm wavelength, record the fluorescence peak intensity level F of its peak value 420nm wavelength
0.
The poly-naphthalene tetrahydrofuran solution of embodiment 4 synthesizeds that to measure 4.5mL concentration be 25.0mg/L, put into beaker, then the concentration that pipettes 0.5mL is 5.0 * 10
-6the ferric chloride in aqueous solution of mol/L.The two mixing is shaken up in the sample cell that is placed on fluorescence spectrophotometer, test its fluorescent intensity under the optical excitation of 334nm wavelength, record the fluorescence peak intensity level F of its peak value 420nm wavelength.
Repeat aforesaid operations, but change respectively the concentration of ferric chloride in aqueous solution into 1.0 * 10
-5mol/L, 5.0 * 10
-5mol/L, 7.0 * 10
-5mol/L, 1.0 * 10
-4mol/L, 2.5 * 10
-4mol/L, 5.0 * 10
-4mol/L, 7.0 * 10
-4mol/L, 9.0 * 10
-4mol/L, 1.0 * 10
-3mol/L, then test the fluorescence of corresponding mixing, and record the fluorescence peak intensity level F of its peak value 420nm wavelength.
The fluorescence spectrum of testing in above-described embodiment is shown in Fig. 6.Relatively all fluorescence spectrums of gained are found, along with the raising of iron concentration, fluorescence intensity weakens gradually.F/F with the ratio of fluorescence intensity
0for ordinate, iron concentration are the horizontal ordinate mapping, experimental data is carried out to linear fit, obtain working curve, calibration curve, obtain Fig. 7, and the corresponding linear relationship simulated is:
F/F
0＝1.00731-0.90099c...................(1)
F in formula
0represent respectively the non-iron-ion quencher and the fluorescence intensity of the mixed solution of ferric ion quencher at 420nm arranged with F.Can find out that by formula (1) fluorescence chemical sensor of poly-naphthalene is to Fe
3+the concentration range 5 * 10 of surveying
-6-1 * 10
-3mol/L.The linearly dependent coefficient R of matching linearity is all higher, is 0.9994.
Embodiment 32-42: the selectivity of ferric ion fluorescence chemical sensor
The poly-naphthalene tetrahydrofuran solution of embodiment 4 synthesizeds that to measure 4.5mL concentration be 25.0mg/L, put into beaker, then to pipette 0.5mL concentration be 1.0 * 10
-3the sodium-chloride water solution of mol/L.The two mixing is shaken up in the sample cell that is placed on fluorescence spectrophotometer, test its fluorescent intensity under the optical excitation of 334nm wavelength, record the fluorescence peak intensity level F of its peak value 420nm wavelength.
Repeating aforesaid operations, is 1.0 * 10 but add respectively 0.5mL concentration
-3the aqueous solution of the potassium nitrate of mol/L, magnesium nitrate, calcium nitrate, cupric chloride, zinc nitrate, cadmium sulfate, plumbi nitras, cobalt nitrate, mercuric nitrate, ferric trichloride, the two mixing is shaken up in the sample cell that is placed on fluorescence spectrophotometer, test its fluorescent intensity under the optical excitation of 334nm wavelength, record the fluorescence peak intensity level F of its peak value 420nm wavelength.
Fig. 8 is shown in above-mentioned test.Can find out, other ion except ferric ion, to the fluorescence of poly-naphthalene substantially without quenching effect.In other words, poly-naphthalene has good detection selectivity as the ferric ion fluorescence chemical sensor.Other ion substantially can not produce and disturb the detection of ferric ion.
Embodiment 43: the ferric ion fluorescence chemical sensor is to strengthening the mensuration of ferric ion in the mineral spring water sample
Commercially available NongFuShanQuan brand mineral water (characteristics index, the μ g/L:Ca of unit >=4000 by 0.50mL; Mg >=500; K >=350; Na >=800) add the synthetic poly-naphthalene solution of implementation column 4 of 4.5mL, fluorescence detection intensity does not almost change, and wherein non-iron-ion is described.By two kinds of concentration (1.0 * 10 of above-mentioned mineral water preparation
-3mol/L and 6.0 * 10
-3mol/L) containing Fe
3+the enhancing water sample: adding concentration in the 25.00mL volumetric flask is 3.0 * 10
-2mol/L (or 5.0 * 10
-3mol/L) Fe
3+solution 5.0mL, be 25mL with the mineral water constant volume, obtains like this Fe
3+concentration is 6.0 * 10
-3mol/L (or 1.0 * 10
-3mol/L) enhancing water sample.This enhancing water sample of getting 0.5mL adds the poly-naphthalene solution of 4.5mL, after mixing, by fluorescence spectrophotometer, measures the fluorescence spectrum of mixed solution under the optical excitation of 334nm wavelength, records the intensity of fluorescent emission peak-to-peak value.According to fluorescence peak intensity, according to standard working curve, try to achieve iron concentration.Every kind strengthens the parallel repeated experiments of water sample 5 times, and the results are shown in Table 1, the recovery wherein, relative error, standard variance according under the calculating that establishes an equation:
The poly-fluorescent naphthalimide chemical sensor of table 1 is to strengthening the measurement result of ferric ion in the mineral spring water sample
Claims (8)
1. one kind for surveying the poly-naphthalene solution fluorescence chemical sensor of iron concentration, for the poly-naphthalene of the fluorescence that will have following structural formula is dissolved in organic solvent, makes;
Wherein, m and n are integer, and m+n=1～27; The poly-concentration of naphthalene in organic solvent of described fluorescence is 5-200mg/L.
2. poly-naphthalene solution fluorescence chemical sensor as claimed in claim 1, is characterized in that, described organic solvent is selected from tetrahydrofuran, dimethyl sulfoxide (DMSO) and 1-METHYLPYRROLIDONE.
3. as arbitrary described poly-naphthalene solution fluorescence chemical sensor in claim 1-2, it is characterized in that, the poly-naphthalene of described fluorescence is obtained by following methods: the polymerization reaction take place in organic solvent by naphthalene monomer and lewis acid, after reaction finishes, the gained sediment after filtration, washing, obtain poly-naphthalene powder after drying.
4. poly-naphthalene solution fluorescence chemical sensor as claimed in claim 3, is characterized in that, the concentration of described naphthalene monomer in organic solvent is 20mM～80mM; The mol ratio of lewis acid and naphthalene monomer is 3:1～15:1.
5. poly-naphthalene solution fluorescence chemical sensor as claimed in claim 3, is characterized in that, polymerization reaction time is 1～50 hour, and polymeric reaction temperature is 10～80 ℃.
6. poly-naphthalene solution fluorescence chemical sensor as claimed in claim 3, is characterized in that, described lewis acid is selected from ferric trichloride, aluminium choride and molybdenum pentachloride; Described organic solvent is selected from nitromethane, nitroethane and second cyanogen.
7. as the purposes of arbitrary described poly-naphthalene solution fluorescence chemical sensor in claim 1-6, it is characterized in that, described poly-naphthalene solution fluorescence chemical sensor is for surveying iron concentration.
8. the purposes of poly-naphthalene solution fluorescence chemical sensor as claimed in claim 7, is characterized in that, described iron concentration is 5.0 * 10
-6mol/L～1.0 * 10
-3mol/L.
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|---|---|---|---|---|
| CN1769251A (en) * | 2004-10-29 | 2006-05-10 | 株式会社半导体能源研究所 | Oligonaphthalene derivatives, and light-emitting element and light-emitting device using oligonaphthalene derivatives |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769251A (en) * | 2004-10-29 | 2006-05-10 | 株式会社半导体能源研究所 | Oligonaphthalene derivatives, and light-emitting element and light-emitting device using oligonaphthalene derivatives |
Non-Patent Citations (5)
| Title |
|---|
| 《碳氢稠环芳烃的电化学聚合及其聚合物的多功能性》;黄美荣等;《石油化工》;20091231;第38卷(第7期);697-698页 * |
| 《聚萘的合成及其光电器件》;黄美荣等;《化学进展》;20100131;第22卷(第1期);摘要，第114页 * |
| 胡育林.《对Fe(Ⅲ)具有敏感性的荧光高分子材料的制备及其荧光性质的研究》.《中国博士学位论文全文数据库(电子期刊)-工程科技1辑》.2009, * |
| 黄美荣等.《碳氢稠环芳烃的电化学聚合及其聚合物的多功能性》.《石油化工》.2009,第38卷(第7期), |
| 黄美荣等.《聚萘的合成及其光电器件》.《化学进展》.2010,第22卷(第1期), |
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| CN102636468A (en) | 2012-08-15 |
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