CN103389292A - Application of Eu coordination polymer - Google Patents
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- CN103389292A CN103389292A CN2013103137355A CN201310313735A CN103389292A CN 103389292 A CN103389292 A CN 103389292A CN 2013103137355 A CN2013103137355 A CN 2013103137355A CN 201310313735 A CN201310313735 A CN 201310313735A CN 103389292 A CN103389292 A CN 103389292A
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Abstract
The invention discloses an application of a Eu coordination polymer, belonging to the technical field of ion detection and solving the technical problem that an existing coordination polymer fluorescence probe has poor selectivity to molecules and ions and low sensitivity. The Eu coordination polymer disclosed by the invention can be taken as the fluorescence probe to detect Fe<3+> by the following steps of: adding the Eu coordination polymer into an aqueous solution containing Fe<3+>, standing for 20-48 hours, then precipitating, washing and separating to obtain solids; and detecting the intensity of a characteristic emission peak of the solids by 350nm excitation wavelength at a site of 612nm, so as to detect the content of Fe<3+> in the aqueous solution. According to the application of the Eu coordination polymer, Fe<3+> in the aqueous solution can be quickly detected; the Eu coordination polymer has the advantages of high detection sensitivity, low detection limit and the like and is capable of detecting Fe<3+> under physiological conditions.
Description
Technical field
The present invention relates to a kind of application of Eu coordination polymer, belong to the ion detection technical field.
Background technology
Fluorescence probe is as a kind of fabulous molecule, ion transducer, owing to having, detects fast, the remarkable advantages such as method is simple, processing ease, cost is low, selectivity good and sensitivity is high are applied to the ion detection field.
Rare earth ion be due to luminescent lifetime long (can reach Microsecond grade), makes the fluorescence of itself and background that remarkable difference be arranged; The feature luminous spectrum is narrow, there is very high resolution, there is advantage aspect fluorescence detection, but because the f-f transition of rare earth ion is that transition is prohibited, thereby its molar absorptivity is very little, direct light absorbing ability is very weak, and the general organic molecule with chromophore that adopts to close with the rare earth ion huge legendary turtle, by antenna effect, the energy absorbed is passed to rare earth ion, the sensitization rare earth luminescence.Because organic ligand usually has wider absorption band and absorbs more by force near ultraviolet band, the freer rare earth ion of the luminescence efficiency of rare earth compounding and intensity obviously strengthens, and is fabulous fluorescent material.In recent years, rare earth coordination compound fluorescent probe, because of its superior optical characteristics, has been widely used at aspects such as fluoroimmunoassay, ion identification, bioactivator mensuration, fluorescence imagings, more and more demonstrates its superiority.
The rare earth based coordination polymer also claims metal-organic framework materials (Rear earth Metal-Organic Frameworks, RMOFs), its aperture size can be regulated and controled by the size of adjustment organic ligand and the assembling mode of central ion and part, can realize the molecule to different size, the detection of ion; Owing to there being stronger interaction to make this type of framework material there is better thermal stability and chemical stability between metallic ion and organic ligand; And such coordination polymer is convenient to directly prepare and become device.But, the poor selectivity of coordination polymer fluorescence probe to molecule, ion, and sensitivity is not high.
Summary of the invention
The object of the invention is to solve the poor selectivity of coordination polymer fluorescence probe to molecule, ion, and the low technical matters of sensitivity, a kind of application of Eu coordination polymer is provided.
The invention provides a kind of Eu coordination polymer and detect Fe as fluorescence probe
3+application, the constitutional repeating unit of described Eu coordination polymer is EuL
3, L be L=4 '-(4-carboxyl phenyl)-2,2 ': 6 ', 2 " terpyridyls.
Preferably, described Eu coordination polymer detects Fe as fluorescence probe
3+application, comprise the following steps:
(1) the Eu coordination polymer is joined containing Fe
3+aqueous solution in, after 20-48h, through precipitation, washing, separate, and obtains solid;
Described containing Fe
3+aqueous solution in Fe
3+concentration be 0.0001-0.01mol/l, Na
+, K
+, Ca
2+, Mg
2+, Ba
2+, Fe
2+, Ni
2+, Al
3+, Cr
3+, Pb
2+, Cd
2+, Cu
2+, Zn
2+, Ag
+and Co
2+concentration be respectively 0-0.02mol/l, Cl
-, NO
3 -, SO
4 2-and PO
4 3-concentration be respectively 0-0.06mol/l, other ion concentrations are 0;
(2), under room temperature, with the 350nm excitation wavelength, detect the intensity of solid at the characteristic emission peak at 612nm place, and then reach Fe in aqueous solution
3+the detection of content.
Preferably, described containing Fe
3+aqueous solution in also contain the 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) of 0.02mol/l.
Preferably, described Eu coordination polymer adopts the following methods preparation:
(1) by Eu (NO
3)
36H
2o, 4 '-(4-carboxyl phenyl)-2,2 ': 6 ', 2 " terpyridyl and alkaline matter join in reaction vessel, after adding deionized water, at room temperature stir 10-60min, obtain potpourri;
(2) potpourri is warming up to 160 ℃-200 ℃, reaction 12-72h, obtain crude product;
(3) crude product is cooling, the washing, air-dry after, obtain the Eu coordination polymer.
Preferably, described Eu coordination polymer detects Fe as fluorescence probe
3+application, comprise the following steps:
(1) the Eu coordination polymer is distributed in ethanol or aqueous solution, obtains dispersion liquid;
(2) filter paper is dipped in dispersion liquid, takes out after 10-60s, air-dry under room temperature, obtain Eu coordination polymer fluorescent test paper;
(3) Eu coordination polymer fluorescent test paper is dipped into containing Fe
3+aqueous solution in, after 10-120s, take out, air-dry after, be put under uviol lamp, observe the fluorescence intensity of fluorescent test paper, and then reach Fe in aqueous solution
3+the detection of content;
Described containing Fe
3+aqueous solution in Fe
3+concentration be 0.0001-0.01mol/l, Na
+, K
+, Ca
2+, Mg
2+, Ba
2+, Fe
2+, Ni
2+, Al
3+, Cr
3+, Pb
2+, Cd
2+, Cu
2+, Zn
2+, Ag
+and Co
2+concentration be respectively 0-0.02mol/l, Cl
-, NO
3 -, SO
4 2-and PO
4 3-concentration be respectively 0-0.06mol/l, other ion concentrations are 0.
Preferably, step (1) evenly spreads in ethanol or aqueous solution after the Eu coordination polymer is ground.
Preferably, described containing Fe
3+aqueous solution in also contain the 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) of 0.02mol/l.
Preferably, the wavelength of described uviol lamp is 365nm.
Preferably, described Eu coordination polymer adopts the following methods preparation:
(1) by Eu (NO
3)
36H
2o, 4 '-(4-carboxyl phenyl)-2,2 ': 6 ', 2 " terpyridyl and alkaline matter join in reaction vessel, after adding deionized water, at room temperature stir 10-60min, obtain potpourri;
(2) potpourri is warming up to 160 ℃-200 ℃, reaction 12-72h, obtain crude product;
(3) crude product is cooling, the washing, air-dry after, obtain the Eu coordination polymer.
Beneficial effect of the present invention:
(1) Eu coordination polymer of the present invention has the chain structure of one dimension, due to Eu
3+there are much the not yet terpyridyl groups of coordination in carboxyl coordination on preferential and L in the skeleton of the coordination polymer formed, these freely the terpyridyl group can with other metallic ion coordination, meanwhile, Eu
3+as luminescent center because the coordination with L sends strong ruddiness, Fe
3+with terpyridyl coordination freely in skeleton, will hinder L and Eu
3+between energy shift, thereby cause the quick cancellation of fluorescence, so the Eu coordination polymer can detect fast Fe in aqueous solution
3+, there is the advantages such as detection sensitivity height and detectability are low, and realized detecting Fe under physiological condition
3+;
(2) the Eu coordination polymer fluorescent test paper that the present invention makes of the Eu coordination polymer (10s-120s) fast detects Fe in aqueous solution
3+concentration, lowest detection is limited to 0.0001mol/l, in fields such as environment and life sciences, is with a wide range of applications.
The accompanying drawing explanation
The X ray single crystal diffraction collection of illustrative plates that Fig. 1 is the Eu coordination polymer;
The excitation spectrum that Fig. 2 is the Eu coordination polymer and emission spectrum;
When Fig. 3 is the embodiment of the present invention 1 gained solid with the optical excitation of 350nm wavelength, the emission peak relative intensity at 612nm place;
When Fig. 4 is the embodiment of the present invention 2 gained solids with the optical excitation of 350nm wavelength, the emission peak relative intensity at 612nm place;
Fig. 5 is emission peak relative intensity and the Fes of the embodiment of the present invention 2 gained solids at the 612nm place
3+the fluorescent quenching effect Stern-Volmer equation curve of concentration;
When Fig. 6 is the embodiment of the present invention 3 gained solids with the optical excitation of 350nm wavelength, the utilizing emitted light spectrogram of gained;
When Fig. 7 is the embodiment of the present invention 4 gained solids with the optical excitation of 350nm wavelength, the utilizing emitted light spectrogram of gained;
The X-ray powder diffraction figure that Fig. 8 is the embodiment of the present invention 4 gained solids;
Fig. 9 be the embodiment of the present invention 5 gained filter paper under uviol lamp, the fluorescence intensity during by the 365nm wavelength illumination.
Embodiment
The Eu coordination polymer detects Fe as fluorescence probe
3+application:
(1) the Eu coordination polymer is joined containing Fe
3+aqueous solution in, after 20-48h, through precipitation, pure water washing, obtain solid by centrifuging;
The constitutional repeating unit of described Eu coordination polymer is EuL
3, L be L=4 '-(4-carboxyl phenyl)-2,2 ': 6 ', 2 " terpyridyls;
Described containing Fe
3+aqueous solution in Fe
3+concentration be 0.0001-0.01mol/l, Na
+, K
+, Ca
2+, Mg
2+, Ba
2+, Fe
2+, Ni
2+, Al
3+, Cr
3+, Pb
2+, Cd
2+, Cu
2+, Zn
2+, Ag
+and Co
2+concentration be respectively 0-0.02mol/l, Cl
-, NO
3 -, SO
4 2-and PO
4 3-concentration be respectively 0-0.06mol/l, other ion concentrations are 0;
(2), under fixed temperature, with the 350nm excitation wavelength, detect the intensity of solid at the characteristic emission peak at 612nm place, and then reach Fe in aqueous solution
3+the detection of content.
In the present invention, work as Fe
3+aqueous solution in only contain Fe
3+, Cl
-, NO
3 -, SO
4 2-and PO
4 3-the most accurate.
In the present invention, containing Fe
3+aqueous solution in also contain the 4-hydroxyethyl piperazine ethanesulfonic acid of 0.02mol/l, be used under physiological condition and detect Fe
3+ion.
In the present invention, the Eu coordination polymer joins containing Fe
3+aqueous solution in not restriction of amount, as long as arranged adding of Eu coordination polymer, the terpyridyl structure of Eu coordination polymer will with Fe
3+coordination, hinder energy and shift, and causes the quick cancellation of fluorescence, and addition is more, and effect is more obvious, and the embodiment of the present invention provides the Eu coordination polymer and contains Fe
3+the mass ratio of the aqueous solution test experience that is 5:1, but the invention is not restricted to this.
In the present invention, Fe in aqueous solution
3+the detection of content, can realize by fluorescent quenching effect Stern-Volmer equation curve.
The Eu coordination polymer detects Fe as fluorescence probe
3+application:
The present invention also provides a kind of Eu coordination polymer to detect Fe as fluorescence probe
3+application:
(1) the Eu coordination polymer is distributed in ethanol or aqueous solution, obtains dispersion liquid;
The constitutional repeating unit of described Eu coordination polymer is EuL
3, L be L=4 '-(4-carboxyl phenyl)-2,2 ': 6 ', 2 " terpyridyls;
(2) filter paper is dipped in dispersion liquid, takes out after 10-60s, air-dry under room temperature, obtain Eu coordination polymer fluorescent test paper;
(3) Eu coordination polymer fluorescent test paper is dipped into containing Fe
3+aqueous solution in, 60s takes out later, air-dry after, be put under uviol lamp, use the 365nm wavelength illumination, observe the fluorescence intensity of fluorescent test paper, and then reach Fe in aqueous solution
3+the detection of content;
Described containing Fe
3+aqueous solution in Fe
3+concentration be 0.0001-0.01mol/l, Na
+, K
+, Ca
2+, Mg
2+, Ba
2+, Fe
2+, Ni
2+, Al
3+, Cr
3+, Pb
2+, Cd
2+, Cu
2+, Zn
2+, Ag
+and Co
2+concentration be respectively 0-0.02mol/l, Cl
-, NO
3 -, SO
4 2-and PO
4 3-concentration be respectively 0-0.06mol/l, other ion concentrations are 0.
In the present invention, work as Fe
3+aqueous solution in only contain Fe
3+, Cl
-, NO
3 -, SO
4 2-and PO
4 3-the most accurate.
In the present invention, better for the degree of scatter that makes dispersion liquid, step (1) can evenly spread in ethanol or aqueous solution after grinding again.
In the present invention, the Eu coordination polymer is distributed to the not restriction of amount in ethanol or aqueous solution, as long as arranged adding of Eu coordination polymer, the quick cancellation of fluorescence will occur in Eu coordination polymer fluorescent test paper, addition is more, effect is more obvious, and the embodiment of the present invention provides the Eu coordination polymer to be distributed to the test experience in ethanol or aqueous solution with mass ratio 5:1, but the invention is not restricted to this.
In the present invention, filter paper is the common filter paper of two circle board.
Eu coordination polymer of the present invention is prior art (A series of lanthanide coordination polymers with 4 ' (4-carboxyphenyl)-2,2 ': 6 ', 2 " terpyridine:Syntheses; crystal structures and luminescence properties; Inorganic Chemistry Communications; 14 (2011), 484-488), its constitutional repeating unit is EuL
3, in formula L be 4 '-(4-carboxyl phenyl)-2,2 ': 6 ', 2 " terpyridyls; With Eu (NO
3)
36H
2o, L and alkaline matter are raw material, by hydro-thermal method, prepare, and the invention provides a kind of its preparation method, specifically comprise the following steps:
(1) by Eu (NO3) 36H2O, 4 '-(4-carboxyl phenyl)-2,2 ': 6 ', 2 " terpyridyl and alkaline matter join in reaction vessel, after adding deionized water, at room temperature stir 10-60min;
(2) the gained potpourri is transferred in reactor, be warming up to 160 ℃-200 ℃, and maintain 12-72h in this temperature;
(3) cooling, the washing, air-dry after, obtain the Eu coordination polymer.
In the preparation of Eu coordination polymer, alkaline matter generally adopts NaOH, KOH or ammoniacal liquor.
In the preparation of Eu coordination polymer, Eu (NO
3)
36H
2o, 4 '-(4-carboxyl phenyl)-2,2 ': 6 ', 2 " amount of substance of terpyridyl and alkaline matter can be selected than for 1:1:1.
As shown in Figure 1, the crystal of this collection of illustrative plates of X ray single crystal diffraction collection of illustrative plates of Eu coordination polymer is the chain structure of one dimension, each Eu
3+ion, with six oxygen atoms on the mode of nine coordinations and three ligand L and three nitrogen-atoms coordinations on another ligand L, in the Eu coordination polymer, has the terpyridyl groups that much do not participate in coordination, these freely the terpyridyl group can and Fe
3+coordination, meanwhile, Eu
3+as luminescent center because the coordination with L sends strong ruddiness, Fe
3+with terpyridyl coordination freely in skeleton, will hinder L and Eu
3+between energy shift, thereby cause the quick cancellation of fluorescence, to realize Fe
3+detection.
As shown in Figure 2, the excitation spectrum that curve 1 is the Eu coordination polymer, the emission spectrum that curve 2 is the Eu coordination polymer, as can be seen from Figure 2, when the optical excitation with the 350nm wavelength, the Eu coordination polymer is at 592nm, 612nm, 649nm and 696nm expression characteristics emission peak, especially the peak at the 612nm place is the strongest, so adopt the emission peak intensity that detects the gained solid at place, 612nm characteristic emission peak.
Further illustrate technical scheme of the present invention below in conjunction with accompanying drawing and embodiment.
In conjunction with Fig. 3, embodiment 1 is described
With pure water and KNO
3, NaCl, MgCl
2, Mg
3(PO
4)
2, MgCl
2, Mg (NO
3)
2, MgSO
4, CaCl
2, BaCl
2, FeSO
4, NiCl
2, Al (NO
3)
3, CrCl
3, Pb (NO
3)
2, CdCl
2, Cu (NO
3)
2,
Zn (NO
3)
2, AgNO
3, CoCl
2, Fe (NO
3)
3, preparation is containing 0.02mol/lK respectively
+, containing 0.02mol/lNa
+, containing 0.02mol/lMg
2+, containing 0.06mol/PO
4 3-, containing 0.06mol/lCl
-, containing 0.06mol/lSO
4 2-, containing 0.06mol/lNO
3 3-containing 0.02mol/lCa
2+, containing 0.02mol/lBa
2+, containing 0.02mol/lFe
2+, containing 0.02mol/lNi
2+, containing 0.02mol/lAl
3+, containing 0.02mol/lCr
3+, containing 0.02mol/lPb
2+, containing 0.02mol/lCd
2+, containing 0.02mol/lCu
2+, containing 0.02mol/lZn
2+, containing 0.02mol/lAg
+, containing 0.02mol/lCo
2+, containing 0.02mol/lFe
3+aqueous solution, the 5mgEu coordination polymer is dissolved into respectively to the pure water of 2ml and containing in the aqueous solution of above-mentioned metallic ion of 2ml, place 20h, precipitation, pure water washing, obtain solid by centrifuging, after air-dry, at 25 ℃, with the fixing excitation wavelength of 350nm, the solid respectively reactant aqueous solution containing the different metal ion obtained carries out the fluorescence spectrum detection, obtains the emission peak relative intensity of solid at the 612nm place.
Fig. 3 be the embodiment of the present invention 1 gained solid under the optical excitation of 350nm wavelength, the emission peak relative intensity at 612nm place, wherein, Cl
-, NO
3 -, SO
4 2-and PO
4 3emission peak relative intensity and Mg
2-identical, so only mark in the drawings Mg
2-relative intensity; As can be seen from Figure 3, concentration is the Cl of 0-0.06mol/l
-, NO
3 -, SO
4 2-and PO
4 3-can not cause fluorescent quenching to Eu, metallic ion has caused fluorescent quenching in various degree, Fe to Eu
3+the fluorescent quenching of ion is the most obvious, so can detect fast and accurately the Fe in solution with the Eu coordination polymer
3+ion.
In conjunction with Fig. 4 and Fig. 5, embodiment 2 is described
With pure water and Fe (NO
3)
3preparation Fe
3+concentration is respectively 0.0001mol/l, 0.0002mol/l, 0.0005mol/l, 0.001mol/l, 0.002mol/l, 0.005mol/l, the Fe (NO of 0.01mol/l
3)
3aqueous solution, be distributed to the above-mentioned different Fe of 2ml by the 5mgEu coordination polymer
3+fe (the NO of concentration
3)
3in aqueous solution, after soaking 24h, precipitation, the pure water washing, obtain solid by centrifuging, air-dry after, at 25 ℃, with the fixing excitation wavelength of 350nm, respectively the solid obtained is carried out to the fluorescence spectrum detection, obtain the emission peak relative intensity of solid at the 612nm place.
Fig. 4 is the different Fe of embodiment 2
3+fe (the NO of concentration
3)
3the solid that aqueous solution obtains is in the emission peak relative intensity at 612nm place, as can be seen from Figure 4, and along with Fe
3+the increase of concentration, solid emission peak relative intensity is lower, and fluorescent quenching is more obvious.
Fig. 5 is the different Fe of embodiment 2
3+fe (the NO of concentration
3) solid that obtains of aqueous solution is at emission peak relative intensity and the Fe at 612nm place
3+the fluorescent quenching effect Stern-Volmer equation curve of concentration, obtaining equation is I
0/ I=0.17+4.1 * 10
3[Fe
3+], in formula, I
0for original transmitted peak relative intensity, I is for recording emission peak relative intensity, [Fe
3+] be Fe
3+concentration, constant is 4.1X10
3l/mol, illustrate that detection sensitivity of the present invention is high, and detectability is low, reaches 0.0001mol/l.
In conjunction with Fig. 6, embodiment 3 is described
With pure water and Fe (NO
3)
3prepare 9 groups of Fe
3+fe (the NO that concentration is 0.01mol/l
3) aqueous solution, the 5mgEu coordination polymer is distributed to the above-mentioned Fe (NO of 2ml
3)
3in aqueous solution, soak respectively 10min, 20min, 30min, 1h, 1.5h, 2h, 2.5h, 19h, after 24h, precipitation, pure water washing, obtain solid by centrifuging, air-dry after, at 25 ℃, with the fixing excitation wavelength of 350nm, respectively the solid obtained is carried out to the fluorescence spectrum detection, obtain the emission peak relative intensity of solid at the 612nm place.
The utilizing emitted light spectrogram that Fig. 6 is the different soak time gained of embodiment 3 solid, curve 1 is for soaking the utilizing emitted light spectrogram of 10min gained solid, curve 2 is for soaking the utilizing emitted light spectrogram of 20min gained solid, curve 3 is for soaking the utilizing emitted light spectrogram of 30min gained solid, curve 4 is for soaking the utilizing emitted light spectrogram of 1h gained solid, curve 5 is for soaking the utilizing emitted light spectrogram of 1.5h gained solid, curve 6 is for soaking the utilizing emitted light spectrogram of 2h gained solid, curve 7 is for soaking the utilizing emitted light spectrogram of 2.5h gained solid, curve 8 is for soaking the utilizing emitted light spectrogram of 19h gained solid, curve 9 is for soaking the utilizing emitted light spectrogram of 24h gained solid, as can be seen from Figure 6, after 10min, the fluorescence intensity of gained solid has weakened more than half part, this is due to Fe
3+can be diffused into fast EuL
3duct in, and with terpyridyl coordination, Fe
3+weakened Eu with the bonding action of L
3+and the energy between L shifts, thereby cause the quick cancellation of fluorescence.
In conjunction with Fig. 7 and Fig. 8, embodiment 4 is described
With pure water and Fe (NO
3)
3preparation Fe
3+concentration is respectively 0.0001mol/l, 0.001mol/l, the Fe (NO of 0.01mol/l
3)
3aqueous solution, Fe (NO
3)
3aqueous solution also contains respectively the HEPES (simulation physiological environment) of 0.02mol/l, and the 5mgEu coordination polymer is distributed to 2ml pure water (HEPES that contains 0.02mol/l) and the above-mentioned Fe (NO of 2ml
3)
3in aqueous solution, after soaking 24h, precipitation, the pure water washing, obtain solid by centrifuging, air-dry after, at 25 ℃, with the fixing excitation wavelength of 350nm, respectively the solid obtained is carried out to the fluorescence spectrum detection, obtain the emission peak relative intensity of solid at the 612nm place.
When Fig. 7 is the embodiment of the present invention 4 gained solids with the optical excitation of 350nm wavelength, the utilizing emitted light spectrogram of gained, the utilizing emitted light spectrogram that curve 1 is pure water gained solid, curve 2 is Fe
3+fe (the NO that concentration is 0.0001mol/l
3)
3the utilizing emitted light spectrogram of aqueous solution gained solid, curve 3 is Fe
3+fe (the NO that concentration is 0.001mol/l
3)
3the utilizing emitted light spectrogram of aqueous solution gained solid, curve 4 is Fe
3+fe (the NO that concentration is 0.01mol/l
3)
3the utilizing emitted light spectrogram of aqueous solution gained solid; The X-ray powder diffraction figure that Fig. 8 is the embodiment of the present invention 5 gained solids, the X-ray powder diffraction figure that curve 1 is pure water gained solid, curve 2 is Fe
3+fe (the NO that concentration is 0.0001mol/l
3)
3the X-ray powder diffraction figure of aqueous solution gained solid, curve 3 is Fe
3+fe (the NO that concentration is 0.001mol/l
3)
3the X-ray powder diffraction figure of aqueous solution gained solid, curve 4 is Fe
3+fe (the NO that concentration is 0.01mol/l
3)
3the X-ray powder diffraction figure of aqueous solution gained solid; In conjunction with Fig. 7 and Fig. 8 explanation, in simulation physiological environment situation, obvious fluorescent quenching has also occurred in the solid obtained, and works as Fe
3+concentration is 0.01mol/l, after soaking 24h, and the complete cancellation of fluorescence, this is similar to the situation in aqueous solution, and therefore, the Eu coordination polymer detects Fe as fluorescence probe
3+can be applied to living things system.
In conjunction with Fig. 9, embodiment 5 is described
With pure water and Fe (NO
3)
3preparation Fe
3+concentration is respectively 0.0001mol/l, 0.0005mol/l, 0.001mol/l, 0.005mol/l, the Fe (NO of 0.01mol/l
3)
3aqueous solution, standby.
(1) the 5mgEu coordination polymer is ground, be distributed to uniformly in the 2ml ethanolic solution, obtain dispersion liquid;
(2) filter paper is cut into to strip, be dipped in dispersion liquid, take out after 1min, air-dry under room temperature, obtain Eu coordination polymer fluorescent test paper;
(3) the Eu coordination polymer fluorescent test paper made is dipped into to the Fe of pure water and above-mentioned variable concentrations
3+aqueous solution in take out after 1min, air-dry after, be put under uviol lamp, use the 365nm wavelength illumination, observe the fluorescence intensity of fluorescent test paper.
The filter paper that Fig. 9 is embodiment 5 under uviol lamp, during by the 365nm wavelength illumination, the fluorescence intensity observed; Fig. 9 is a) fluorescence intensity of pure water gained fluorescent test paper; Fig. 9 b) be Fe
3+fe (the NO of concentration 0.0001mol/l
3)
3the fluorescence intensity of aqueous solution gained fluorescent test paper; Fig. 9 c) be Fe
3+fe (the NO of concentration 0.0005mol/l
3)
3the fluorescence intensity of aqueous solution gained fluorescent test paper; Fig. 9 d) be Fe
3+fe (the NO of concentration 0.001mol/l
3)
3the fluorescence intensity of aqueous solution gained fluorescent test paper; Fig. 9 e) be Fe
3+fe (the NO of concentration 0.005mol/l
3)
3the fluorescence intensity of aqueous solution gained fluorescent test paper; Fig. 9 f) be Fe
3+fe (the NO of concentration 0.01mol/l
3)
3the fluorescence intensity of aqueous solution gained fluorescent test paper; As can be seen from Figure 9, along with Fe
3+the increase of concentration, fluorescent quenching is more obvious.
Obviously, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (9)
1.Eu coordination polymer detects Fe as fluorescence probe
3+application, the constitutional repeating unit of described Eu coordination polymer is EuL
3, L be L=4 '-(4-carboxyl phenyl)-2,2 ': 6 ', 2 " terpyridyls.
2. Eu coordination polymer according to claim 1 detects Fe as fluorescence probe
3+application, it is characterized in that, comprise the following steps:
(1) the Eu coordination polymer is joined containing Fe
3+aqueous solution in, after 20-48h, through precipitation, washing, separate, and obtains solid;
Described containing Fe
3+aqueous solution in Fe
3+concentration be 0.0001-0.01mol/l, Na
+, K
+, Ca
2+, Mg
2+, Ba
2+, Fe
2+, Ni
2+, Al
3+, Cr
3+, Pb
2+, Cd
2+, Cu
2+, Zn
2+, Ag
+and Co
2+concentration be respectively 0-0.02mol/l, Cl
-, NO
3 -, SO
4 2-and PO
4 3-concentration be respectively 0-0.06mol/l, other ion concentrations are 0;
(2), under room temperature, with the 350nm excitation wavelength, detect the intensity of solid at the characteristic emission peak at 612nm place, and then reach Fe in aqueous solution
3+the detection of content.
3. Eu coordination polymer according to claim 2 detects Fe as fluorescence probe
3+application, it is characterized in that, described containing Fe
3+aqueous solution in also contain the 4-hydroxyethyl piperazine ethanesulfonic acid of 0.02mol/l.
4. Eu coordination polymer according to claim 2 detects Fe as fluorescence probe
3+application, it is characterized in that, described Eu coordination polymer adopts the following methods preparation:
(1) by Eu (NO
3)
36H
2o, 4 '-(4-carboxyl phenyl)-2,2 ': 6 ', 2 " terpyridyl and alkaline matter join in reaction vessel, after adding deionized water, at room temperature stir 10-60min, obtain potpourri;
(2) potpourri is warming up to 160 ℃-200 ℃, reaction 12-72h, obtain crude product;
(3) crude product is cooling, the washing, air-dry after, obtain the Eu coordination polymer.
5. Eu coordination polymer according to claim 1 detects Fe as fluorescence probe
3+application, it is characterized in that, comprise the following steps:
(1) the Eu coordination polymer is distributed in ethanol or aqueous solution, obtains dispersion liquid;
(2) filter paper is dipped in dispersion liquid, takes out after 10-60s, air-dry under room temperature, obtain Eu coordination polymer fluorescent test paper;
(3) Eu coordination polymer fluorescent test paper is dipped into containing Fe
3+aqueous solution in, after 10-120s, take out, air-dry after, be put under uviol lamp, observe the fluorescence intensity of fluorescent test paper, and then reach Fe in aqueous solution
3+the detection of content;
Described containing Fe
3+aqueous solution in Fe
3+concentration be 0.0001-0.01mol/l, Na
+, K
+, Ca
2+, Mg
2+, Ba
2+, Fe
2+, Ni
2+, Al
3+, Cr
3+, Pb
2+, Cd
2+, Cu
2+, Zn
2+, Ag
+and Co
2+concentration be respectively 0-0.02mol/l, Cl
-, NO
3 -, SO
4 2-and PO
4 3-concentration be respectively 0-0.06mol/l, other ion concentrations are 0.
6. Eu coordination polymer according to claim 5 detects Fe as fluorescence probe
3+application, it is characterized in that, described containing Fe
3+aqueous solution in also contain the 4-hydroxyethyl piperazine ethanesulfonic acid of 0.02mol/l.
7. Eu coordination polymer according to claim 5 detects Fe as fluorescence probe
3+application, it is characterized in that, step (1) evenly spreads in ethanol or aqueous solution after will the Eu coordination polymer grinding.
8. Eu coordination polymer according to claim 5 detects Fe as fluorescence probe
3+application, it is characterized in that, the wavelength of described uviol lamp is 365nm.
9. Eu coordination polymer according to claim 5 detects Fe as fluorescence probe
3+application, it is characterized in that, described Eu coordination polymer adopts the following methods preparation:
(1) by Eu (NO
3)
36H
2o, 4 '-(4-carboxyl phenyl)-2,2 ': 6 ', 2 " terpyridyl and alkaline matter join in reaction vessel, after adding deionized water, at room temperature stir 10-60min, obtain potpourri;
(2) potpourri is warming up to 160 ℃-200 ℃, reaction 12-72h, obtain crude product;
(3) crude product is cooling, the washing, air-dry after, obtain the Eu coordination polymer.
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