CN102495038B - Optical ion sensing film for detecting metal ions, and preparation method and application thereof - Google Patents
Optical ion sensing film for detecting metal ions, and preparation method and application thereof Download PDFInfo
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- CN102495038B CN102495038B CN201110407433.5A CN201110407433A CN102495038B CN 102495038 B CN102495038 B CN 102495038B CN 201110407433 A CN201110407433 A CN 201110407433A CN 102495038 B CN102495038 B CN 102495038B
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- 150000002500 ions Chemical class 0.000 title claims abstract description 67
- 230000003287 optical effect Effects 0.000 title claims abstract description 37
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001514 detection method Methods 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000002073 nanorod Substances 0.000 claims abstract description 16
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- 229910021538 borax Inorganic materials 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims description 38
- 150000001455 metallic ions Chemical class 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910001424 calcium ion Inorganic materials 0.000 claims description 13
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses an optical ion sensing film for detecting metal ions. The optical ion sensing film comprises the following components in percentage by weight: 0.34 to 0.38 percent of ETH5418, 0.46 to 0.91 percent of quadri[3,5-bi-( trifluoromethyl)benzene]-sodium-tetraborate, 0.43 to 2.17 percent of metal ion carrier, 2.01 to 2.17 percent of up-conversion nanorod, 31.41 to 32.71 percent of polrvinyl chloride and the balance of bis(2-ethylhexyl)decandeionate or o-npoe 2-nitrophenyl octyl ether or dioctyl phthalate. The invention also discloses a preparation method for the sensing film and application of the sensing film to detection of the metal ions. The sensing film is excited by light with wavelength of 980 nanometers and the light of the sensing film is transmitted in a near infrared region, so that the sensor is not interfered with background absorption and background fluorescence; furthermore, compared with the conventional organic system, the system has higher quantum yield, and can produce high-intensity fluorescence.
Description
Technical field
The invention belongs to the chemical detection technique field, be specifically related to a kind of optical ion sensing membrane for detection of metallic ion and preparation method thereof and application.
Background technology
The ion transducer that is used for biological and environment measuring that development has high selectivity and sensitivity causes people's broad interest in recent years.Ion in the detection of biological system has key effect for the problems such as signal transmission in postgraduate's object, and in environment, the detection of high toxicity heavy metal has promoted the development of ion transducer too.Be applied to the detection of various ions in living things system and environment based on the optical sensor of macromolecular material, for ion sensor provides a reliable platform
1-7Auroral poles commonly used all carries out sensing by the variation of uv absorption or fluorescence intensity, and wherein fluoroscopic examination often is used to the clinical detection of biological sample due to its high sensitivity.At present, using maximum chromogenic ion carriers is the compound of ETH series, comprises ETH 5294, and ETH 2439, and ETH 5418, and ETH 5315, and ETH 2412, ETH 7075 and ETH7061, but their fluorescence is all very weak, and what have does not almost have fluorescence.Can not be used for the detection of blood sample based on the auroral poles of chromogenic ion carrier, because blood sample itself has very strong background absorption and fluorescence, and have strong scattering to exist in the Uv and visible light district.
The fluoroscopic examination of near-infrared region (650nm-1000nm) is also paid close attention to by increasing researcher.Near infrared light can transdermal be deeply organized and is reached several millimeters, and most living things system can not produce background interference in this wavelength coverage
8Especially for the detection system of blood, in the near-infrared region, background absorption and fluorescence disturb minimum, and therefore the optical sensor based on long wavelength's scope becomes Hot spots for development
9In numerous near-infrared light-emitting materials, up-conversion nano material has unique optical characteristics, for example can launch visible range fluorescence under near infrared light excites, larger anti-Stokes displacement has also guaranteed clearly to be distinguished each other between two emission peaks and exciting light
10, and up-conversion fluorescence is stable, excites for a long time lower light intensity can not change
11, cytotoxicity is low
12, therefore be successfully applied to animal tissue and cell imaging
12,13In up-conversion, NaYF
4It is the highest that the doping system of crystal is proved to be conversion efficiency
14,15
Currently reportedly show that up-conversion nano material is used for biological detection as fluorescence labeling or as the donor that resonance energy shifts (FRET)
16Modify by effects on surface, this material can have water-soluble preferably, can detect DNA in aqueous solution
17-19, protein molecular
20Activity with enzyme
21Yet, often can not realize the detection of continuous repetition in homogeneous phase, but as long as up-conversion nano material and suitable probe are joined together, just can satisfy these requirements based on the chemical sensor of this material.A series of such sensors have been developed in the Wolfbeis group, for detection of pH
22, carbon dioxide
23And ammonia
24Both but have the polystyrene macromolecular material of gas-premeable to realize with the nonionic penetrability afterwards, and when gas enters system, pH wherein can change, thereby can be detected.Recently, they have developed again a kind of sensor that detects oxygen content
25
Summary of the invention
Technical matters to be solved by this invention is to overcome defects, and a kind of optical ion sensing membrane based on up-conversion nano material for detection of metallic ion is provided.
The technical matters that the present invention also will solve is to provide the preparation method of above-mentioned optical ion sensing membrane.
The technical matters that the present invention will solve at last is to provide the application of above-mentioned optical ion sensing membrane in metal ion detection.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of optical ion sensing membrane for detection of metallic ion, it comprises the component of following percentage by weight:
Chromogenic ion carrier ETH5418 0.34%-0.38%;
Ion exchanger four [3,5-two-(trifluoromethyl) benzene] sodium borate (NaTFPB) 0.46%-0.91%;
Carriers of metal ions 0.43%-2.17%;
Upper conversion nano rod 2.01%-2.17%;
Polyvinylchloride (PVC) 31.41%-32.71%;
Plastifier decanedioic acid two (2-ethylhexyl) ester (DOS) or ortho-nitrophenyl octyl ether (NPOE) or dioctyl phthalate (DOP) complement to 100%.
Wherein, described metallic ion is calcium ion, potassium ion, sodion or copper ion.
Wherein, described optical ion sensing membrane for detection of metallic ion, the thickness of its film is 5-7 μ m.
Wherein, described upper conversion nano rod is NaYF
4: Er, Yb nanometer rods, preparation method's list of references 18.Described carriers of metal ions is: sodion carrier Na (X), potassium ion carrier valinomycin, Calcium ionophore AU-1 or copper ion carrier N, N, N ', N '-Fourth Ring hexyl-3-sulfo-glutaramide.
The preparation method of above-mentioned optical ion sensing membrane for detection of metallic ion, ETH5418, four (3 with formula ratio, 5-two (trifluoromethyl) phenyl) sodium borate, carriers of metal ions, upper conversion nano rod, Polyvinylchloride and di-n-octyl sebacate or ortho-nitrophenyl octyl ether mix or dioctyl phthalate, use organic solvent dissolution, fully after mixing on matrix uniform coating, room temperature lucifuge drying and moulding and get final product.
Wherein, described organic solvent is tetrahydrofuran or cyclohexanone.
Wherein, the ratio that adds volume and ETH5418, four (3,5-two (trifluoromethyl) phenyl) sodium borate, carriers of metal ions, upper conversion nano rod, Polyvinylchloride and di-n-octyl sebacate or ortho-nitrophenyl octyl ether general assembly (TW) of organic solvent is 10mL: 1g.
Wherein, described matrix is optical fiber or piezoid or not by the light transmission plastic-substrates of organic solvent used (tetrahydrofuran or cyclohexanone) dissolving.
The above-mentioned application of optical ion sensing membrane in metal ion detection for detection of metallic ion.
The above-mentioned concrete using method of optical ion sensing membrane for detection of metallic ion is sensing membrane to be placed in solution to be measured, according to the concentration of the metallic ion in the variation detection solution of fluorescence intensity.Using method is more specifically, sensing membrane is placed in the solution of different known metal ions, the variation of the fluorescence intensity of test sensing membrane, and do typical curve; Then sensing membrane is placed in solution to be detected, the fluorescence intensity of test sensing membrane is according to the concentration of metal ions in typical curve calculating solution to be measured.In above-mentioned testing process, sensing membrane is used washed with de-ionized water after detecting EO at every turn, reuses.
One large advantage of optical ion sensing membrane is and can realizes the mensuration of high selectivity by adding the ion selectivity carrier.Usually contain the chromogenic ion carrier that hydrogen ion is had response in sensing membrane, by the adjusting to buffer solution pH, metallic ion and hydrogen ion form to be competed and reaches balance
37Based on this principle, the present invention has prepared the ion selectivity auroral poles, wherein contains nanometer rods, and ETH5418 and different ions are selected carrier.Ionic equilibrium in the auroral poles film can be shown below:
Wherein, I
z+Expression kation, L represent ion selection carrier, and C represents chromogenic ion carrier ETH5418.As metallic ion I
z+Enter the light film, in order to keep the electric neutrality of film, the hydrogen ion in film can be released, thereby makes ETH5418 gradually become the deprotonation form from its protonated form.Based on previously described inner filtering effect, the 542nm peak shows reducing tendency, and the 656nm peak strengthens gradually.
Beneficial effect: the present invention compared with prior art has following advantage:
A. use the optical excitation of 980nm wavelength, and launch in the near-infrared region yet, sensor can not be subject to the interference of background absorption and background fluorescence;
B. with respect to traditional organic system body series, higher quantum yield is arranged, can produce high strength fluorescence.
Description of drawings
The ultra-violet absorption spectrum of Fig. 1 master map: ETH5418 in the PVC-DOS system.(a) in 0.01M NaOH (b) in 0.01M HCl; And the 980nm wavelength excites the fluorescence of lower upper conversion nano rod in the PVC-DOS system.Little figure is scanning electron microscope (SEM) photo of upper conversion nano rod.
Fig. 2 master map: (a) based on up-conversion contains the sodium ion selective auroral poles of Sodium X to Na
+Response, (b) contain the calcium ion selective auroral poles of AU-1 to Ca
2+Response.(c) contain the right K of potassium ion selective auroral poles of valinomycin
+Response (d) contains N, N, and N ', the copper ion of N '-Fourth Ring hexyl-3-sulfo-glutaramide select auroral poles to the response of Cu2+.Wherein, i, iii are the response curve at the 656nm place, and ii, iv are the response curve of 656nm and 542nm ratio, I
0Blank response for film in the gly-HCl of pH4.8 damping fluid.Little figure: the Ca of calcium ion selective auroral poles to low concentration
2+The response curve of ion, iii are the response curve at the 656nm place, and iv is the response curve of 656nm and 542nm ratio.
Fig. 3 is based on (a) sodium ion selective auroral poles of up-conversion and (b) the selectivity schematic diagram of calcium ion selective auroral poles.What adopt is the intensity at peak, 656nm place, with (I-I
0)/I
0Calculate, wherein I
0Blank response for film in the gly-HCl of pH4.8 damping fluid, I is the peak intensity of film in the different metal solion.Solution concentration used is (a) 10
-2M and (b) 10
-3M。
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described content of embodiment only is used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
Following examples material therefor and instrument are as follows:
Oleic acid, YbCl
3, ErCl
3And YCl
36H
2O buys from Alfa Aesar, and NaF buys from Acros Organics, and tetrahydrofuran (THF), PVC and decanedioic acid two (2-ethylhexyl) ester (DOS) is purchased from Sigma-Aldrich.Other ionophore and chromogenic ion carrier and all inorganic salts are all buied from Fluka.Cationite four [3,5-two-(trifluoromethyl) benzene] sodium borate (NaTFPB) is purchased from Dojindo Laboratores.Whole blood sample extracts from mouse, collects with the anticoagulant heparin pipe.
Buffer solution: phosphate buffered solution (PBS) is that the potassium hydroxide solution with 10mM after the potassium dihydrogen phosphate dissolving of 10mM is adjusted to required pH.Glycocoll-hydrochloric acid (Gly-HCl) buffer solution is that the rear hydrochloric acid solution with 0.1M of the glycocoll dissolving of 10mM is regulated pH to 4.8.The whole blood sample of dilution is to obtain after with corresponding buffer solution, whole blood being diluted 20 times, and uses after dilution at once.Pure water used is the deionized water that uses Milli-Q pure water instrument purifying (18.2M Ω/cm).
Instrument: X-ray powder diffraction is completed on Shimadzu XRD-6000, use be the K of copper target
αRay (λ=0.15418nm).Ultraviolet spectrum data obtains on the Nonodrop-2000C spectrometer.Scanning electron microscope image (SEM) is obtained by Hitachi's S-4800 scanning electron microscope.Up-conversion fluorescence spectrum records on the ZLX-UPL up-conversion fluorescence spectrometer of standing upright, and light source used is external 1w 980nm laser instrument.
Embodiment 1:NaYF
4: Er, Yb nanometer rods synthetic.
NaYF
4: Er, the synthetic of Yb nanometer rods carries out according to document
18
Concrete steps are: with NaOH (1.2g, 30mmol), and water (7mL), ethanol (12mL) and oleic acid (22mL) mix, and stir to make it form a kind of transparent solution.Adding total amount under magnetic agitation ceaselessly is the rare earth-iron-boron (2mL altogether of 1mmol, 0.5M, the doping ratio of rare earth ion is according to mol ratio: 78mol%Y+20mol%Yb+2mol%Er) aqueous solution dropwise adds the Fluorinse 5mL of 1M after stirring.Mix the about 10min of solution, they are transferred in the hydrothermal reaction kettle of a 50mL, encapsulation is at 195 ℃ of hydrothermal treatment consists 16h.After naturally cooling, with cyclohexane dissolving and collection sample, add ethanol that sample is separated out, centrifuging, final vacuum is dry several times with second alcohol and water cyclic washing.
Can see that from the SEM characterization result nanometer rods has good homogeneity, diameter is approximately 200nm, and length is approximately 1 μ m (seeing Fig. 1).Can learn from the XRD analysis result, nanometer rods is the NaYF of six side's phases
4: Er, Yb is with standard card JCPDS No.28-1192
28Match.Fourier's infrared spectrum confirms that plane of crystal is enclosed with oleic acid molecular, and it well is dispersed in organic phase.Under the 980nm laser instrument excited, crystal had two sharp-pointed emission peaks, respectively at the 542nm of green Region and the 656nm of red light district (Fig. 1).Upper conversion crystal has chemical stability preferably, and fluorescence has higher quantum yield
29,30, and compared the nano particle of Emission in Cubic, the nanometer rods of six side's phases has higher fluorescence intensity, and all remains unchanged in the scope of pH 2 to 11
22These characteristics make them become the good selection of fluorescent tag molecule, but limited again simultaneously they as the environment sensitive probe in the application aspect sensor.
Embodiment 2: for detection of the preparation of the optical ion sensing membrane of calcium ion.
As following weight percent each component is mixed with the 100mg potpourri:
Chromogenic ion carrier ETH5418 0.34%;
Ion exchanger NaTFPB 0.88%;
Calcium ionophore AU-1 is (according to document
26Synthetic) 1.68%;
Upper conversion nano rod (embodiment 1 makes) 2.17%;
PVC 31.74%;
Plastifier DOS 63.19%.
Said mixture dissolves with the THF of 1mL.Gained solution acutely rocks ultrasonic 0.5h at least after 0.5h, obtains homogeneous solution.The mixed solution of getting 50 μ L with pipettor is coated on a clean rectangle piezoid uniformly, allows the solvent lucifuge volatilize before use 0.5 hour, obtains the optical ion sensing membrane for detection of calcium ion, and the thickness of film is 5-7 μ m.
To vertically insert with the piezoid of auroral poles film during detection in the quartz colorimetric utensil with slot, put into the sample chamber of detecting instrument, excite vertical with the light path of collecting.Prepare in advance the solution of a series of different calcium ion concentrations with buffer solution.Add corresponding solution during detection in cuvette, gather spectrum, after pour out, after changing a kind of solution rinse light film, add in cuvette and measure, method of operating is the same.
Embodiment 3: for detection of the preparation of the optical ion sensing membrane of sodion.
As following weight percent each component is mixed with the 100mg potpourri:
Chromogenic ion carrier ETH5418 0.36%;
Ion exchanger NaTFPB 0.46%;
Sodion carrier Na (X) (being purchased from Fluka) 0.98%;
Upper conversion nano rod (embodiment 1 makes) 2.05%;
PVC 31.96%;
Plastifier NPOE 64.19%.
Said mixture dissolves with the cyclohexanone of 1mL.Gained solution acutely rocks ultrasonic 0.5h at least after 0.5h, obtains homogeneous solution.The mixed solution of getting 50 μ L with pipettor is coated in fiber tip uniformly, allows the solvent lucifuge volatilize before use 0.5 hour, obtains the optical ion sensing membrane for detection of sodion, and the thickness of film is 5-7 μ m.
Embodiment 4: for detection of the preparation of the optical ion sensing membrane of potassium ion.
As following weight percent each component is mixed with the 100mg potpourri:
Chromogenic ion carrier ETH541 80.38%;
Ion exchanger NaTFPB 0.91%;
Potassium ion carrier valinomycin (being purchased from Fluka) 2.17%;
Upper conversion nano rod (embodiment 1 makes) 2.09%;
PVC 31.41%;
Plasticizer DOP 63.04%.
Said mixture dissolves with the cyclohexanone of 1mL.Gained solution acutely rocks ultrasonic 0.5h at least after 0.5h, obtains homogeneous solution.The mixed solution of getting 50 μ L with pipettor is coated in not on the light transmission plastic-substrates of being dissolved by cyclohexanone uniformly, allows solvent lucifuge volatilization 0.5 hour before use, obtains the optical ion sensing membrane for detection of potassium ion, and the thickness of film is 5-7 μ m.
Embodiment 5: for detection of the preparation of the optical ion sensing membrane of copper ion.
As following weight percent each component is mixed with the 100mg potpourri:
Chromogenic ion carrier ETH5418 0.38%;
Ion exchanger NaTFPB 0.48%;
Copper ion carrier N, N, N ', N '-Fourth Ring hexyl-3-sulfo-glutaramide is (according to document
27Synthetic) 0.43%;
Upper conversion nano rod (embodiment 1 makes) 2.01%;
PVC 32.71%;
Plastifier DOS 63.99%.
Said mixture dissolves with the THF of 1mL.Gained solution acutely rocks ultrasonic 0.5h at least after 0.5h, obtains homogeneous solution.The mixed solution of getting 50 μ L with pipettor is coated on a clean rectangle piezoid uniformly, allows the solvent lucifuge volatilize before use 0.5 hour, obtains the optical ion sensing membrane for detection of copper ion, and the thickness of film is 5-7 μ m.
Embodiment 6: based on the sign of the ion selectivity optical ion sensing membrane of upper conversion nano rod.
By adding sodion carrier Na (X) and Calcium ionophore AU-1, the present invention has prepared respectively the sodion selection and calcium ion is selected auroral poles.In order to make auroral poles can be applied to the detection of living things system, at first experiment is carried out in the tris-HCl of pH7.4 buffer system.Yet, due to the pK of ETH5418
aLower, the light film for the response of ion all in very low concentration range.Therefore the experiment after is all carried out in buffer system glycocoll-hydrochloric acid (pH4.8) of lower pH, so that the light film responds under higher concentration for ion.
As shown in Figure 2, all along with effects of ion concentration increases and increases, two kinds of data recording modes have all shown identical response modes for the unimodal and 656nm at 656nm place and the ratio of 542nm peak intensity.To the response of sodion 10
-5-10
-2M, higher ion concentration can make the intensity of two emission peaks of up-conversion fluorescence all significantly reduce, but the ratio at two peaks is unaffected, still rises by trend.The calcium ion selective auroral poles has also been observed same phenomenon, and its upper limit of detection is 10
-4M。Theoretical according to ion-exchange, in the solution of high concentration, after the carrier in film is saturated, also has metallic ion and enter the film phase in the coextraction mode.This part free ion that enters the film phase may exert an influence by electrostatic interaction to the oleic acid of parcel crystal, thereby fluorescence intensity is reduced.
Can notice from Fig. 2, the detection lower limit of calcium ion selective auroral poles is low more than the result that obtains with ETH5294 in traditional system
26The present invention has specially studied this phenomenon, as shown in result figure as medium and small in Fig. 2.Auroral poles also has response to the calcium ion of trace, and this result can not be compared with ETH5418 lower pK with ETH5294
aValue is explained.The existence of up-conversion may impact the character of film, and the long carbochain of its coated outside may make the polarity of film change, thereby makes the pK of ETH5418
aChange.In order to verify this guess, the present invention has prepared two kinds of PVC polymeric membrane systems with different elasticizer plasticizings, a kind of with DOS (ε=3), another kind of with NPOE (ε=24), the responding range that two individual system finally obtain and ionophoric complexation constant are identical, illustrate that the nonpolar long carbochain of parcel nanometer rods has reduced the polarity of PVC-NPOE film.This result has also illustrated that upper conversion nano rod and some metallic ion of oleic acid parcel may have some interactions simultaneously.By the light film being immersed the solution of different metal ion, the present invention has also obtained the selectivity of film, as shown in Figure 3.The sodium ion selective auroral poles has good selectivity to sodion, and to other ions such as K
+, Ca
2+And Mg
2+Almost not response.But calcium ion selective auroral poles selectivity is relatively relatively poor, and this is because the own selectivity of ionophore AU-1 used is just not high, and the selectivity of divalent ion in nonpolar film also can be greatly affected.The copper ion selectivity auroral poles of the potassium ion selective auroral poles of preparation and the preparation take Fourth Ring hexyl sulfo-glutaramide as carrier all has sensitive response and good selectivity for object ion at pH in 4.8 buffer solution take valinomycin as carrier, and responding range is respectively 10
-7-10
-4M and 10
-6-10
-3M。
In accuracy was measured, accurately the detected solution of concentration was determined in preparation, as 1.03 * 10
-5Then M KCl will be placed in the cuvette that contains this sample based on the potassium ion sense light film of up-conversion, record fluorescence intensity, and to try to achieve corresponding potassium concentration value from the working curve of Fig. 2 be 1.07 * 10
-5M, error is less than 5%.
To be placed in the not buffer solution of metal ion through the ormosils of measuring after using, its fluorescence intensity returns to the identical numerical value before using, and sensor response process completely reversibility is described, sensor has good repeatability, repeatedly Reusability.
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Claims (10)
2. the optical ion sensing membrane for detection of metallic ion according to claim 1, is characterized in that, the thickness of film is 5-7 μ m.
3. the optical ion sensing membrane for detection of metallic ion according to claim 1, is characterized in that, described upper conversion nano rod is NaYF
4: Er, Yb nanometer rods; Described carriers of metal ions is: sodion carrier Na(X), potassium ion carrier valinomycin, Calcium ionophore AU-1 or copper ion carrier N, and N, N ', N '-Fourth Ring hexyl-3-sulfo-glutaramide.
4. the preparation method of the optical ion sensing membrane for detection of metallic ion claimed in claim 1, it is characterized in that, ETH5418, four [3 with formula ratio, 5-two-(trifluoromethyl) benzene] sodium borate, carriers of metal ions, upper conversion nano rod, Polyvinylchloride and decanedioic acid two (2-ethylhexyl) ester or ortho-nitrophenyl octyl ether or dioctyl phthalate mix, use organic solvent dissolution, fully after mixing on matrix uniform coating, room temperature lucifuge drying and moulding and get final product.
5. the preparation method of the optical ion sensing membrane for detection of metallic ion according to claim 4, is characterized in that, described organic solvent is tetrahydrofuran or cyclohexanone.
6. the preparation method of according to claim 4 or 5 described optical ion sensing membrane for detection of metallic ion, it is characterized in that, the ratio that adds volume and ETH5418, four [3,5-two-(trifluoromethyl) benzene] sodium borate, carriers of metal ions, upper conversion nano rod, Polyvinylchloride and decanedioic acid two (2-ethylhexyl) ester or ortho-nitrophenyl octyl ether or dioctyl phthalate ether general assembly (TW) of organic solvent is 10mL:1g.
7. the preparation method of the optical ion sensing membrane for detection of metallic ion according to claim 4, is characterized in that, described matrix is optical fiber or piezoid or not by the light transmission plastic-substrates of organic solvent dissolution used.
8. the application of optical ion sensing membrane in metal ion detection for detection of metallic ion claimed in claim 1.
9. application according to claim 8, is characterized in that, the optical ion sensing membrane that detects metallic ion is placed in solution to be measured, according to the concentration of metal ions in the variation detection solution of fluorescence intensity.
10. application according to claim 9, is characterized in that, after the optical ion sensing membrane of detection metallic ion detects end at every turn, uses washed with de-ionized water, reuses.
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