CN103865520A - Zinc ion fluorescent probe based on chelating-induced fluorescence enhancement and its application - Google Patents
Zinc ion fluorescent probe based on chelating-induced fluorescence enhancement and its application Download PDFInfo
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Abstract
The invention discloses based a zinc ion fluorescent probe based on chelating-induced fluorescence enhancement and its application, the probe is obtained by Schiff base reaction condensation of salicylaldehyde and its derivative and 1,3-diamino-isopropanol, a complexe single crystal [Zn3(L1)2(OAc)2] is also obtained, and the complexe single crystal [Zn3(L1)2(OAc)2] is obtained by coordinate bond of 1,3-di(5-chloro salicylaldehyde-amido)-isopropanol and zinc acetate. The fluorescent probe itself has good chemical and optical stability, has specific response to zinc ions based o fluorescence enhancement, has a detection limit reaching nanomolar level, may not be interfered by other ions, and is rapid in response.
Description
Technical field
The invention belongs to coordination chemistry field, more particularly, relate to the title complex of zinc ion fluorescent that a class strengthens based on chelation evoked fluorescence and such probe representative compound and zine ion synthetic and apply.
Background technology
Zine ion is second largest transition metal ion in organism, and in mankind's physiological and pathological, plays different effects, and it focuses mostly in cerebral tissue, and concentration can reach 0.1-0.5mM.The total content of zinc is very high in body, can reach 2-3g, but lower and by the tight control of body with the Free Zinc concentration ratio of the lax combination of protein.The verified free zinc stable state of current experiment can produce alzheimer's disease, amyotrophic lateral sclerosis (ALS), parkinsonism, local asphyxia and epilepsy after being upset.In addition, Free Zinc is also relevant with necrocytosis, for example apoptosis.Therefore, a kind of sensitive being but very important without technology tracking and the video picture Free Zinc of injury.So zine ion has very strong selectivity because having 3d electronic configuration, therefore becomes an important research direction of fluorescent probe future development simultaneously.
Material molecule, atomic absorption optical radiation are excited, then launch the light identical or longer with absorbing wavelength, become photoluminescence, and modal is fluorescence and phosphorescence.Fluorescent molecular probe technology is applied to the detection of transition metal and heavy metal ion, can realize the in situ detection in microenvironment.Become at present in detection bodies and the strong instrument of external biological related substances and its function, and as can not need the indispensable instrument of the alone visual inspection ion of other specific apparatus on molecular level.The actual fluorescent molecular probe of selecting must make desirable analyte optionally in conjunction with producing an optical signal with penetration power, (1/4) signal and excitation wavelength that the interior fluorescent molecular probe of desirable cell should have a high quantum production rate exceed 340nm, and another feature is to allow to use glass micro objective and the cell injury that stops UV to induce.The emission wavelength of good fluorescent molecular probe should approach 500nm, can effectively stop and derive from autofluorescence that in cell, material produces and fluorescent microscope spectral filter operation that can we selected typical.In addition, probe must have the passive irreversible ability that is written into cell.Fluorescent molecular probe through particular design has highly sensitive, and high specific, can carry out real-time Single Molecule Detection, and therefore the advantages such as safe ready have important scientific meaning and wide application prospect to the research of fluorescent molecular probe.
The biologic applications zinc ion fluorescent of report can be divided into six large classes by the mechanism of action at present, and wherein a class is to close based on huge legendary turtle the fluorescent probe that induced fluorescence strengthens.Research is found, the hard and soft property of probe molecule skeleton, fluorescence intensity to molecule has material impact, when the molecular structure complanation that becomes, space torsion capacity reduces can make fluorescence strengthen, so after probe molecule coordinates with metal ion, the skeleton rigidity of molecule increases, above-mentioned various electronics or energy are shifted and be affected, thereby cause that fluorescence strengthens, reported many Zn that close induced fluorescence enhancing based on this huge legendary turtle at present
2+fluorescent probe.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the compound that can be used as highly sensitive fluorescent probes for quantitation of zinc and be used is provided, compare with zine ion probe (compound) in existing document, probe of the present invention has highly sensitive, detection lower limit is low, fast response time, and selectivity is high, the advantages such as stability is strong, and simple, the synthetic cost of preparation is low.
Object of the present invention is achieved by following technical proposals:
The zinc ion fluorescent structure strengthening based on chelation evoked fluorescence, i.e. molecular structure of compounds, as follows:
R in formula
1for H or OCH
3.
R
2for H, Cl, Br, SO
3na or OCH
3.
R
3for H or OCH
3.
R
4for H or OCH
3.
R
5for H or OCH
3.
R
6for H or OCH
3.
R
7for H, Cl, Br, SO
3na or OCH
3.
R
8for H or OCH
3.
R
9for H or OH.
In described compound structure, preferably symmetrical structure, the i.e. substituent R in molecule of replacing
1with R
8identical, R
2with R
7identical, R
3with R
6identical, R
4with R
5identical so that described compound molecule with
for symmetry axis, such as:
1H?NMR(CDCl
3):δ13.06(s,2H),8.34(s,2H),6.80-7.26(m,6H,Ar),4.27(m,1H),3.87(d,2H),3.74(d,2H),1.58(s,1H)(Inorg.Chem.1997,36,1829-1837)
L2.
1H?NMR(CDCl
3):δ13.02(s,2H),8.35(s,2H),6.8-6.92(m,8H,Ar),4.28(m,1H),3.84(d,4H)(Inorg.Chem.1997,36,1829-1837)
L3.
1H?NMR(CDCl3):δ13.06(s,2H),8.56(s,2H),7.02–7.66(m,8H,Ar),3.71(t,4H),2.01(m,2H)(Acta?Crystallogr,Sect,E.2004,60,m582)
L4.
1H?NMR(CDCl
3):δ13.06(s,2H),8.54(s,2H),6.81–7.80(m,6H,Ar),4.27(m,1H),3.87(d,2H),3.74(d,2H),1.58(s,1H)(Inorganic?Chemistry?Communications.2005,8,235–238)
L5.
1H?NMR(D
2O):δ13.06(s,2H),8.35(s,2H),6.507.80(m,6H,Ar),4.4-4.8(m,5H);
13C?NMR(D
2O)δ175.52(Ar),168.62(CH=N),133.62,132.48,128.96,122.41,114.18(Ar),67.9(R
2CH-OH),54,90(N-CH
2-CHOH-);Significant?IR?bands(KBr,νcm
-1):νOH?3420(broad),νC=N?1613,νSO
3?1108/1034;UV-visible(UV-vis)λmax(nm)inH
2O:222,234,255(sh),330(sh),375(Journal?of?Inorganic?Biochemistry?104(2010)496-502)
L6.
1H?NMR(D2O):δ13.06(s,2H),8.40(s,2H),6.6–7.9(m,6H,Ar),3.77(t,4H),2.11m,2H);
13C?NMR(D2O,δ)176.45(Ar),167.92(CH=N),133.53,132.56,128.46,122.70,113.86(Ar),49.00(N—CH2—R),29.00(N—CH2—CH2—CH2—N);Significant?IR?bands(KBr,νcm-1):νOH?3405(broad),νC=N1612,νSO3?1108/1035.;UV-visλmax(nm)in?H2O:222,236,254(sh),331(sh),373(Journal?of?InorganicBiochemistry?104(2010)496–502)
L7
1H?NMR(CDCl
3):δ13.26(s,2H),8.56(s,2H),7.33(s,2H),6.91(d,2H),6.89(d,2H),4.27(s,1H),3.87(d,2H),3.83(s,6H),3.74(d,2H),1.58(s,1H)(ActaCrystallogr,Sect,E,(2004)60,m582)
L8.
1H?NMR(CDCl
3):δ13.59(bs,2H),8.35(s,2H),6.80to?6.92(d’s?and?t,6H,J=8.0Hz),3.98(s,4H),3.90(s,6H)(Journal?of?Molecular?Structure?693(2004)225–234).
L9.
1H?NMR(CDCl
3):δ13.25(s,2H),8.56(s,2H),7.71(d,2H),6.62(d,2H),6.48(s,2H),4.27(s,1H),3.87(d,2H),3.83(s,6H),3.74(d,2H),1.58(s,1H)(Z.Naturforsch,TeilB(2001)56,1315)
L10.
1H?NMR(CDCl
3):δ13.24(s,2H),8.67(s,2H),7.24(m,2H),6.82(d,2H),6.58(d,2H),4.27(s,1H),3.87(d,2H),3.83(s,6H),3.74(d,2H),1.58(s,1H)(ActaCrystallogr,Sect,E,(2004)60,m582)
The compound of said structure is as the application of zinc ion fluorescent molecule, can strengthen based on chelation evoked fluorescence, and wherein, taking the compound of following structure as representative compound L1, molecular formula is C
17h
16cl
2n
2o
3
Shown in the following reaction formula of its synthetic technology route:
In technical scheme of the present invention, utilize above-claimed cpd and zine ion to form title complex, taking representative compound L1 as example, be combined with zinc acetate coordination and form title complex, and adopt solvent evaporation method to prepare complex monocrystal, wherein the mol ratio of zinc acetate and representative compound L1 is (1.5-2): 1, the mixed solvent that adopts acetonitrile and methyl alcohol to coordinate, zinc acetate and representative compound L1 are dissolved in the mixed solvent (the preferred 1:1 of described both volumes) of acetonitrile and methyl alcohol, under room temperature, under 20-25 degrees Celsius, stir (stirring velocity is selected 60-100 turn/min) reaction at least 2 hours, preferably 2-6 hours, filter afterwards, filtrate is adopted to solvent evaporation method, under room temperature, (be generally 20-25 degrees Celsius) and treat that solvent slowly volatilizees, leave standstill to place after about one week and (generally can select at least 160h storage period, preferably 160-180h), attached wall grows yellow block crystallization, analyzes (using SHELXTL-97 software to analyze X ray single crystal diffraction data cif) determine that this crystal molecule formula is C through X-ray single crystal diffraction
38h
34cl
4n
4o
10zn
3, belonging to oblique system, spacer is P2 (1)/c, unit cell parameters is a=11.018 (5)
b=19.468 (8)
c=9.225 (4)
α=90.00 °, β=103.130 (8) °, γ=90.00 °, unit-cell volume V=1926.9 (15)
its agent structure is [Zn
3(L1)
2(OAc)
2].X-Ray crystal analysis result shows [Zn
3(L1)
2(OAc)
2] be two parts (compound L 1) and three three core Zn complex structures that zinc atom forms.The phenolic hydroxyl group of two acetates and two parts (compound L 1) is bridging center zinc atom Zn (2) and two the zinc atom Zn in outer end (1), Zn (1A) respectively.That is: the zinc atom Zn (1) of outer end, Zn (1A) are connected to form pentacoordinate configuration with two phenolic hydroxyl group oxygen of contiguous part (compound L 1) separately and two imino-nitrogen and acetate oxygen respectively; Center zinc atom Zn (2) connects four phenolic hydroxyl group oxygen and two acetate oxygen of two parts (compound L 1), forms hexa-coordinate configuration.
Representative compound L1 be combined with zinc acetate coordination form title complex, in emission maximum light wavelength lambda
em=455nm place has very strong fluorescence peak, and maximum excitation wavelength is 244nm, and within the scope of 0.3-1.5 μ M zinc ion concentration, this fluorescence probe intensity presents good linear relationship, can be used for the concentration of detection by quantitative zine ion.
The principle that the design of fluorescent probe molecule of the present invention strengthens based on chelation evoked fluorescence, probe molecule is having significantly and is increasing in conjunction with fluorescence quantum yield before and after zine ion.Fluorescent probe molecule has good selectivity to zine ion, and is not subject to such as K of other ions
+, Mg
2+, Ca
2+, Cu
2+, Mn
2+, Fe
2+, Fe
3+deng interference, response is rapidly.Fluorescent probe of the present invention has selectivity for the negatively charged ion of zinc salt, and zinc acetate is the strongest, be secondly respectively zinc chloride, zinc nitrate, zinc bromide, zinc perchlorate, and zinc sulfate and probe produces fluorescence hardly.Fluorescent probe molecule of the present invention is extremely low to the fluoroscopic examination lower limit of zine ion, and fluorescence produces rapidly, and the time of response is extremely short, and continual and steady.
Brief description of the drawings
Fig. 1 be compound L 1 be combined with zinc acetate coordination form title complex [Zn
3(L1)
2(OAc)
2] the ball-and-stick model figure (SHELXTL-97 software) of crystal, the ratio of part and zinc is 2:3, two acetates bridging center zinc atom and two zinc atoms of far-end respectively.
Fig. 2 is Zn
2+the graph of a relation of concentration and fluorescence intensity, wherein ordinate zou is fluorescence intensity, X-coordinate is wavelength of transmitted light (λ
em/ nm, excitation wavelength is 244nm).
Fig. 3 is Zn
2+the linear relationship chart of concentration and fluorescence intensity, wherein with maximum emission wavelength (λ
em=455nm, excitation wavelength is 244nm) to locate fluorescence intensity be ordinate zou, zinc acetate Zn
2+concentration is X-coordinate mapping.
Fig. 4 is that the ethanolic soln of probe compound L1 (1.0 μ M) and zinc acetate (1.5 μ M) is in the fluorescence intensity of each time point of emission wavelength 455nm.
Fig. 5 is the selectivity that fluorescent probe is identified various common metal ion, and wherein ordinate zou is fluorescence intensity, and X-coordinate is wavelength of transmitted light (λ
em/ nm, excitation wavelength is 244nm).
Fig. 6 is the relation of zinc salt negatively charged ion and fluorescence intensity, and wherein ordinate zou is fluorescence intensity, and X-coordinate is wavelength of transmitted light (λ
em/ nm, excitation wavelength is 244nm).
Fig. 7 is the relation that adds EDTA and fluorescence intensity, and wherein ordinate zou is fluorescence intensity, and X-coordinate is wavelength of transmitted light (λ
em/ nm, excitation wavelength is 244nm).
Fig. 8 be probe representative compound L1 be combined with zinc acetate coordination form title complex monocrystalline respectively different light rays irradiate under clap picture, wherein (1) UV-light (190-400nm), (2) blue light (390-455nm), (3) green glow (455-492nm).
Fig. 9 is the fluorescence color that the ethanolic soln (d) of ethanolic soln (c), 1 μ M probe representative compound and the 1.5 μ M zinc acetates of ethanolic soln (b), 10 μ M probe representative compound and the 15 μ M zinc acetates of ethanolic soln (a), 100 μ M probe representative compound L1 and the 150 μ M zinc acetates of 100 μ M probe representative compound L1 is placed in 365nm ultraviolet lamp camera bellows, is wherein respectively from left to right (a) and (b), (c), (d).
Embodiment
Further illustrate technical scheme of the present invention below in conjunction with specific embodiment, use instrument as shown in the table
Title | Model | Producer |
Melting point apparatus | X-4 digital display micro melting point is measured 0010-548 | Tyke, Beijing |
Infrared spectra | Nicolet?380 | Thermo?Electron |
H nuclear magnetic resonance measuring instrument | UNITY-plus400 | U.S. VARIAN |
Fluorescence spectrophotometer | RF-5301 | Japan's Shimadzu |
Advances in crystal X-ray diffraction instrument | Rigaku Saturn 724 types | Rigaku |
Full-automatic inverted microscope | Nikon?ECLIPSE?Ti | Japanese Nikon |
Add 5-chloro-salicylic aldehyde 3.13 grams (20mmol) and 1,3-diamino-2-hydroxy propane 0.9(10mmol) gram, being dissolved in methanol solution, 70 DEG C of backflows of heating 3 hours dewater, TLC detects, reaction finishes rear filtration, and filtrate is revolved to steam and removed a part of methanol solvate, the cooling yellow solid of separating out, suction filtration, filter cake again with recrystallizing methanol once, obtain 2.76 grams of products, productive rate is 88.2%.It is 127.3 ~ 127.6 DEG C that X-4 digital display micro melting point apparatus records its fusing point, 1H-NMR(400MHZ, CDCl3, ppm): δ 13.06(d, 2H), δ 8.34(d, 2H), δ 7.26(m, 4H), δ 7.24(d, 2H), δ 4.27(m, 1H), δ 3.8(m, 2H), δ 3.74(m, 2H), δ 1.58(s, 1H), there is following reaction:
The L1 part of 0.4mol zinc acetate and 0.2mol is dissolved in the acetonitrile of 20ml: in methyl alcohol (v/v=1:1), stirring reaction 2 hours, filters.Filtrate adopts solvent evaporation method, under room temperature, (be generally 2025 degrees Celsius) and treat that solvent slowly volatilizees, placement after one week (calculating according to 24 × 7=168 hour) for one week, attached wall grows yellow block crystallization, obtain crystalline diffraction data through the analysis of X-ray single crystal diffraction, then diffraction data is obtained to crystal molecule information by SHELXS-97 and SHELXL-97 software analysis function: this crystal molecule formula is C
38h
34cl
4n
4o
10zn
3, oblique system, spacer is P2 (1)/c, unit cell parameters is a=11.018 (5)
b=19.468 (8)
c=9.225 (4)
α=90.00 °, β=103.130 (8) °, γ=90.00 °, unit-cell volume V=1926.9 (15)
crystalline structure ball-and-stick model figure is shown in Fig. 1.
The susceptibility of embodiment 3 probe representative compound L1 to zinc
Use synthetic probe representative compound L1 to evaluate its susceptibility to zine ion.1 μ M probe representative compound L1 is joined in the sample pool containing 2ml ethanol, then add respectively successively the zinc acetate of 0.0,0.3,0.6,0.9,1.2,1.5 μ M, excitation wavelength is 244nm, and maximum emission wavelength is at 455nm, and test result is shown in Fig. 2.As can be seen from Figure 2 L1 has very high susceptibility to zine ion, the fluorescence that generation is very large that adds of zine ion strengthens, along with the concentration of zine ion increases and strengthens, and as shown in Figure 3, within the scope of 0.3-1.5 μ M zinc ion concentration, keep good linear relationship.
Response speed and the fluorescence intensity stability of embodiment 4 probe representative compound L1 Dichlorodiphenyl Acetate zinc
1 μ M probe representative compound L1 is joined in the sample pool containing 2ml ethanol, then add the zinc acetate of 1.5 μ M.Excitation wavelength is made as 244nm, record the intensity of 455nm emitting fluorescence after 0,0.5,1,1.5,2,2.5,3,4,5,6 hour, as shown in Figure 4, within 0 hour, locate to record immediately after mixing with zinc acetate for probe compound, illustrate that probe compound is exceedingly fast to the response speed of zinc, and in follow-up 6 hours, fluorescence intensity does not have considerable change, shows splendid stability.
The selectivity to zinc of embodiment 5 probe representative compound L1
Use synthetic probe representative compound L1 to evaluate its selectivity to zine ion.1 μ M probe representative compound L1 is joined in the sample pool containing 2ml ethanol, then add respectively successively the zinc acetate of 1.5 μ M, 400eq(400 times of concentration, i.e. 600 μ M) Potassium ethanoate, sodium-acetate, calcium acetate, 40eq(40 times of concentration, i.e. 60 μ M) Iron diacetate, neutralized verdigris, magnesium acetate, cadmium acetate, nickel acetate, manganese acetate, Cobaltous diacetate, excitation wavelength is 244nm, test result is shown in Fig. 5.The fluorescence that can find out zine ion and probe representative compound L1 generation in figure is the strongest, and sodium, potassium, calcium, magnesium, copper plasma disturb not detecting.
The selectivity to zinc salt negatively charged ion of embodiment 6 probe representative compound L1
Use its selectivity to zinc salt negatively charged ion of evaluation of synthetic probe representative compound L1.1 μ M probe representative compound L1 is joined in the sample pool containing 2ml ethanol, then add respectively successively zinc acetate, zinc chloride, zinc perchlorate, zinc nitrate, zinc sulfate, the zinc bromide of 1.5 μ M, excitation wavelength is 244nm, and test result is shown in Fig. 6.This probe has selectivity to the negatively charged ion of zinc salt as seen from the figure, and the fluorescence intensity of zinc acetate is the strongest, be secondly respectively zinc chloride, zinc nitrate, zinc bromide, zinc perchlorate, and zinc sulfate and probe produces fluorescence hardly.
The fluorescence that embodiment 7 metal chelator EDTA quenching probes representative compound L1 and zinc acetate produce
The zinc acetate of 1 μ M probe representative compound L1 and 1.5 μ M is joined in the sample pool containing 2ml ethanol, then add respectively successively 0,0.2,0.4,0.6,0.8,1.0, the EDTA(of 2.0eq corresponds to respectively A in figure, B, C, D, E, F, G curve; H is probe representative compound L1), excitation wavelength is 244nm, test result is shown in Fig. 7.As seen from the figure, along with adding of EDTA, the fluorescence that probe and zinc acetate produce is weak gradually, until add fluorescence completely dissolve after the EDTA of qdx, illustrate that the fluorescence of probe and the chelation evoked generation of zinc can be competed combination and cancellation by EDTA.
Light brown [the Zn that Liquid Phase Diffusion is grown
3(L1)
2(OAc)
2] crystal be placed in respectively under the illumination of UV-light (190-400nm), blue light (390-455nm), three kinds of different-wavebands of green glow (455-492nm), take photo as shown in Figure 8.Under three kinds of different-wavebands irradiate, crystallofluorescence color is variant, as: UV-light (190-400nm) irradiate lower show blue, blue light (390-455nm) irradiate lower show green, under green glow (455-492nm) irradiates demonstration redness, illustrate that this title complex has the characteristic of fluorescence variable color, this specific character can be applicable to the fields such as fluorescence falsification preventing, fluorescent decoration material, fluorescent ink, fluorescence storage fiber, anti-false fiber, photosensitive colour-changing material, optical recording material.
The ethanolic soln of ethanolic soln, 1 μ M probe representative compound L1 and the 1.5 μ M zinc acetates of ethanolic soln, 10 μ M probe representative compound L1 and the 15 μ M zinc acetates of ethanolic soln, 100 μ M probe representative compound L1 and the 150 μ M zinc acetates of the 100 μ M probe representative compound L1 that prepare is contained in respectively and in phial, is placed in 365nm ultraviolet lamp camera bellows, take photo as shown in Figure 9, probe compound ethanolic soln does not have fluorescence, the ethanolic soln of probe compound and zinc acetate all can emitting fluorescence, and the solution fluorescent brightness that concentration is large is stronger.
Ethanolic soln (concentration of probe compound L1L10 is 1 μ M), the probe compound (L1-L10) of embodiment 9 probe compounds (L1-L10) carry out respectively fluorescence intensity test with the ethanolic soln (wherein the concentration of probe compound (L1-L10) is 1 μ M, and acetic acid zinc concentration is 1.5 μ M) of zinc acetate.
Wherein E
x(nm) be maximum excitation wavelength, E
m(nm) for maximum emission wavelength, L (x) fluorescence intensity are fluorescence intensity, L (the x)+Zn of probe compound (L1-L10) at maximum emission wavelength place
2+fluorescence intensity is probe compound (L1-L10) and Zn
2+title complex is in the fluorescence intensity at maximum emission wavelength place.
Above the present invention is done to exemplary description; should be noted that; in the situation that not departing from core of the present invention, the replacement that is equal to that any simple distortion, amendment or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (9)
1. the fluorescent probe compounds molecule based on chelation evoked fluorescence enhancing, as the application of zinc ion fluorescent molecule, is characterized in that, described fluorescent probe compounds molecular structure is as follows:
R in formula
1for H or OCH
3
R
2for H, Cl, Br, SO
3na or OCH
3
R
3for H or OCH
3
R
4for H or OCH
3
R
5for H or OCH
3
R
6for H or OCH
3
R
7for H, Cl, Br, SO
3na or OCH
3
R
8for H or OCH
3
R
9for H or OH.
2. the fluorescent probe compounds molecule strengthening based on chelation evoked fluorescence according to claim 1, as the application of zinc ion fluorescent molecule, is characterized in that, in described compound structure, and preferably symmetrical structure, the i.e. substituent R in molecule of replacing
1with R
8identical, R
2with R
7identical, R
3with R
6identical, R
4with R
5identical so that described compound molecule with
for symmetry axis.
3. the fluorescent probe compounds molecule based on chelation evoked fluorescence enhancing, as the application of zinc ion fluorescent molecule, is characterized in that, described fluorescent probe compounds molecular formula is C
17h
16cl
2n
2o
3, molecular structure is as follows:
Described compound molecule is in conjunction with before and after zine ion, and fluorescence quantum yield has significantly and increases, and zine ion is had to good selectivity, and is not subject to other cationic interference; Negatively charged ion to zinc salt has selectivity, and zinc acetate is the strongest, be secondly respectively zinc chloride, zinc nitrate, zinc bromide, zinc perchlorate, and zinc sulfate and probe produces fluorescence hardly; Described fluorescent probe molecule is low to the fluoroscopic examination lower limit of zine ion.
4. the fluorescent probe compounds molecule strengthening based on chelation evoked fluorescence according to claim 3, as the application of zinc ion fluorescent molecule, is characterized in that, described other positively charged ions are K
+, Mg
2+, Ca
2+, Cu
2+, Mn
2+, Fe
2+or Fe
3+, under described fluoroscopic examination, be limited to 0.3-1.5 μ M, within the scope of 0.3-1.5 μ M zinc ion concentration, described fluorescence probe intensity presents good linear relationship, can be used for the concentration of detection by quantitative zine ion.
5. the title complex that the fluorescent probe compounds strengthening based on chelation evoked fluorescence and zine ion form, is characterized in that, described fluorescent probe compounds molecular formula is C
17h
16cl
2n
2o
3, molecular structure is as follows:
Described compound molecule is combined with zinc acetate coordination and is formed title complex, and adopts solvent evaporation method to prepare complex monocrystal, and this crystal molecule formula is C
38h
34cl
4n
4o
10zn
3, belonging to oblique system, spacer is P2 (1)/c, unit cell parameters is a=11.018 (5)
b=19.468 (8)
c=9.225 (4)
α=90.00 °, β=103.130 (8) °, γ=90.00 °, unit-cell volume V=1926.9 (15)
its agent structure is [Zn
3(L1)
2(OAc)
2].
6. title complex according to claim 5, is characterized in that, described complex monocrystal is in emission maximum light wavelength lambda
em=455nm place has very strong fluorescence peak, and maximum excitation wavelength is 244nm.
7. prepare the method for title complex as claimed in claim 5 for one kind, it is characterized in that, the mol ratio of zinc acetate and compound is (1.5-2): 1, the mixed solvent that adopts acetonitrile and methyl alcohol to coordinate, zinc acetate and compound molecule are dissolved in the mixed solvent of acetonitrile and methyl alcohol to stirring reaction at least 2 hours under room temperature; Filter afterwards, filtrate is adopted to solvent evaporation method, leave standstill to place under room temperature and treat that solvent slowly volatilizees, attached wall grows yellow block crystallization, obtains complex monocrystal.
8. preparation method according to claim 7, is characterized in that, described acetonitrile and the preferred 1:1 of methyl alcohol volume; Described room temperature is 20-25 degrees Celsius; Described stirring velocity is selected 60-100 turn/min; Preferably 2-6 hours stirring reaction time under described room temperature; At least 160h of the selection of time of described standing placement, preferably 160-180h.
9. title complex as claimed in claim 5 stores the application in fiber, anti-false fiber, photosensitive colour-changing material, optical recording material field at fluorescence falsification preventing, fluorescent decoration material, fluorescent ink, fluorescence, it is characterized in that, utilize the fluorescence color shifting properties of described title complex, under different-waveband excitation light irradiation, crystallofluorescence color is different.
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