CN103865520B - Based on zinc ion fluorescent and the application thereof of chelation evoked Fluorescence Increasing - Google Patents
Based on zinc ion fluorescent and the application thereof of chelation evoked Fluorescence Increasing Download PDFInfo
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Abstract
The open zinc ion fluorescent based on chelation evoked Fluorescence Increasing of the present invention and application thereof, this probe is by salicylic aldehyde and derivative and 1 thereof, the condensation of 3-diamino isopropanol schiff base reaction forms, and obtain wherein 1,3-bis-(5-chloro-salicylic aldehyde contracting amido) Virahol and be combined the complex monocrystal [Zn formed with zinc acetate coordination
3(L1)
2(OAc)
2].This fluorescent probe itself has good chemistry, optical stability; Zine ion is had to the specificly-response of Fluorescence Increasing, detectability can reach nmole level, and not by the interference of other ions, and response rapidly.
Description
Technical field
The invention belongs to coordination chemistry field, more particularly, relate to a class and synthesize based on the title complex of the zinc ion fluorescent of chelation evoked Fluorescence Increasing and such probe representative compound and zine ion and apply.
Background technology
Zine ion is second largest transition metal ion in organism, and plays different effects in human physiological's pathology, and it focuses mostly in cerebral tissue, and concentration can reach 0.1-0.5mM.In body, the total content of zinc is very high, can reach 2-3g, but lower and by the tight control of body with the relax Free Zinc concentration that combines 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, such as apoptosis.Therefore, a kind of sensitive but fanout free region technology follow the trail of and video picture Free Zinc be very important.Simultaneously zine ion is because having 3d electronic configuration so there is very strong selectivity, therefore becomes the research direction that of fluorescent probe future development is important.
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 in detection bodies at present and the strong instrument of external biological related substances and its function, and as can not needing the indispensable instrument of other specific apparatus alone visual inspection ion on a molecular scale.The actual fluorescent molecular probe selected must make ideal analyte optionally have the optical signal of penetration power in conjunction with generation one, desirable intracellular Fluorescence molecular probe should have (1/4) signal of a high quantum production rate and excitation wavelength more than 340nm, another feature is then the cell injury allowing to use Glass microscope object lens and stop UV induction.The emission wavelength of good fluorescent molecular probe should close to 500nm, can effectively stop to derive from autofluorescence that material in cell produces and can the fluorescent microscope spectral filter operation of we selected typical.In addition, probe must have the ability of passive irreversible loading cell.Fluorescent molecular probe through particular design has highly sensitive, high specific, can carry out real-time Single Molecule Detection, the advantages such as safe ready, therefore has important scientific meaning and wide application prospect to the research of fluorescent molecular probe.
The biologic applications zinc ion fluorescent of current report can be divided into six large classes by the mechanism of action, and wherein a class is close the fluorescent probe of induced fluorescence enhancing based on huge legendary turtle.Research finds, the hard and soft of probe molecule skeleton, material impact is had to the fluorescence intensity of molecule, when molecular structure becomes complanation, space torsion capacity reduces can make Fluorescence Increasing, so when after probe molecule and metal ion complexation, the skeleton rigidity of molecule increases, above-mentioned various electronics or energy trasfer are affected, thus cause Fluorescence Increasing, reported many Zn closing 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 is provided, compare with zine ion probe (compound) in existing document, probe of the present invention has highly sensitive, Monitoring lower-cut is low, fast response time, and selectivity is high, the advantages such as stability is strong, and preparation is simple, synthesis cost is low.
Object of the present invention is achieved by following technical proposals:
Based on the zinc ion fluorescent structure of chelation evoked Fluorescence Increasing, 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 replacement structure, i.e. substituent R in molecule
1with R
8identical, R
2with R
7identical, R
3with R
6identical, R
4with R
5identical, with make described compound molecule with
for symmetry axis, such as:
1HNMR(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.
1HNMR(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.
1HNMR(CDCl3):δ13.06(s,2H),8.56(s,2H),7.02–7.66(m,8H,Ar),3.71(t,4H),2.01(m,2H)（ActaCrystallogr,Sect,E.2004,60,m582）
L4.
1HNMR(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)（InorganicChemistryCommunications.2005,8,235–238）
L5.
1HNMR(D
2O):δ13.06(s,2H),8.35(s,2H),6.507.80(m,6H,Ar),4.4-4.8(m,5H)；
13CNMR(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-)；SignificantIRbands(KBr,νcm
-1):νOH3420(broad),νC=N1613,νSO
31108/1034；UV-visible(UV-vis)λmax(nm)inH
2O:222,234,255(sh),330(sh),375（JournalofInorganicBiochemistry104(2010)496-502）
L6.
1HNMR(D2O):δ13.06(s,2H),8.40(s,2H),6.6–7.9(m,6H,Ar),3.77(t,4H),2.11m,2H)；
13CNMR(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)；SignificantIRbands(KBr,νcm-1):νOH3405(broad),νC＝N1612,νSO31108/1035.；UV-visλmax(nm)inH2O:222,236,254(sh),331(sh),373（JournalofInorganicBiochemistry104(2010)496–502）
L7
1HNMR(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.
1HNMR(CDCl
3):δ13.59(bs,2H),8.35(s,2H),6.80to6.92(d’sandt,6H,J=8.0Hz),3.98(s,4H),3.90(s,6H)（JournalofMolecularStructure693(2004)225–234）.
L9.
1HNMR(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.
1HNMR(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, can based on chelation evoked Fluorescence Increasing as the application of zinc ion fluorescent molecule, wherein with the compound of following structure for representative compound L1, molecular formula is C
17h
16cl
2n
2o
3
Shown in the following reaction formula of its synthetic technology route:
In the inventive solutions, above-claimed cpd and zine ion is utilized to form title complex, for representative compound L1, 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, adopt the mixed solvent that acetonitrile and methyl alcohol coordinate, zinc acetate and representative compound L1 are dissolved in the mixed solvent (both preferred 1:1 of volume described) of acetonitrile and methyl alcohol, (stirring velocity selects 60-100 turns/min) reaction at least 2 hours is stirred under 20-25 degrees Celsius under room temperature, preferably 2-6 hours, filter afterwards, filtrate is adopted solvent evaporation method, (be namely generally 20-25 degrees Celsius) under room temperature and treat that solvent slowly volatilizees, after standing placement about a week, (storage period generally can select at least 160h, preferably 160-180h), attached wall grows yellow lump shaped crystalline, 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, belong to oblique system, spacer is P2 (1)/c, and 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 display [Zn
3(L1)
2(OAc)
2] be the three core Zn complex structures that two parts (compound L 1) and three zinc atoms are formed.Phenolic hydroxyl group bridging center zinc atom Zn (2) and two, outer end zinc atom Zn (1), the Zn (1A) respectively of two acetates and two parts (compound L 1).That is: zinc atom Zn (1), the Zn (1A) of outer end are connected to form pentacoordinate configuration with two phenolic hydroxyl group oxygen of respective contiguous part (compound L 1) 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 is combined with zinc acetate coordination the title complex formed, 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 μM of zinc ion concentration, this fluorescence probe intensity presents good linear relationship, can be used for the concentration of detection by quantitative zine ion.
The design of fluorescent probe molecule of the present invention is based on the principle of chelation evoked Fluorescence Increasing, and probe molecule significantly increases having in conjunction with fluorescence quantum yield before and after zine ion.Fluorescent probe molecule has good selectivity to zine ion, and not by other ions such as K
+, 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 zinc chloride, zinc nitrate, zinc bromide, zinc perchlorate respectively, and zinc sulfate and probe produces fluorescence hardly.The fluoroscopic examination lower limit of fluorescent probe molecule of the present invention to zine ion is extremely low, and fluorescence produces rapidly, and the time of response is extremely short, and continually and steadily.
Accompanying drawing explanation
Fig. 1 is that compound L 1 is combined the title complex [Zn formed with zinc acetate coordination
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 atoms and far-end two zinc atoms respectively.
Fig. 2 is Zn
2+the graph of a relation of concentration and fluorescence intensity, wherein ordinate zou is fluorescence intensity, and 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) place's fluorescence intensity is ordinate zou, zinc acetate Zn
2+concentration is X-coordinate mapping.
Fig. 4 is the fluorescence intensity of ethanolic soln at each time point of emission wavelength 455nm of probe compound L1 (1.0 μMs) and zinc acetate (1.5 μMs).
Fig. 5 is the selectivity of the various common metal ion of fluorescent probe identification, 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 adding 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 is the picture that monocrystalline that probe representative compound L1 is combined with zinc acetate coordination the title complex formed is clapped respectively under different light rays is irradiated, wherein (1) UV-light (190-400nm), (2) blue light (390-455nm), (3) green glow (455-492nm).
Fig. 9 is the ethanolic soln (a) of 100 μMs of probe representative compound L1, the ethanolic soln (d) of the ethanolic soln (b) of 100 μMs of probe representative compound L1 and 150 μM zinc acetates, 10 μMs of probe representative compound and the ethanolic soln (c) of 15 μMs of zinc acetates, 1 μM of probe representative compound and 1.5 μMs of zinc acetates is placed in the fluorescence color of 365nm ultraviolet lamp camera bellows, is wherein respectively (a) and (b), (c), (d) from left to right.
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 measures 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 type | Rigaku |
| Full-automatic inverted microscope | Nikon ECLIPSE Ti | Japanese Nikon |
The synthesis of embodiment 1 probe representative compound L1
Add 5-chloro-salicylic aldehyde 3.13 grams (20mmol) and 1,3-diamino-2-hydroxy propane 0.9(10mmol) gram, be dissolved in methanol solution, the heating 70 DEG C that dewaters backflow 3 hours, TLC detects, reaction terminates rear filtration, and filtrate is revolved and steamed a part of methanol solvate of removing, and yellow solid is separated out in cooling, 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), namely there is following reaction:
Embodiment 2 utilizes representative compound L1 synthetic compound [Zn
3(L1)
2(OAc)
2]
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, (be namely generally 2025 degrees Celsius) under room temperature and treat that solvent slowly volatilizees, placement after one week (calculating according to 24 × 7=168 hour) for one week, attached wall grows yellow lump shaped crystalline, obtain crystalline diffraction data through the analysis of X-ray single crystal diffraction, then diffraction data is obtained 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, and 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.
Embodiment 3 probe representative compound L1 is to the susceptibility of zinc
The probe representative compound L1 of synthesis is used to evaluate its susceptibility to zine ion.1 μM of probe representative compound L1 is joined in the sample pool containing 2ml ethanol, then the zinc acetate of 0.0,0.3,0.6,0.9,1.2,1.5 μM is added successively respectively, 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, zine ion add the very large Fluorescence Increasing of generation, concentration along with zine ion increases and strengthens, and as shown in Figure 3, within the scope of 0.3-1.5 μM of zinc ion concentration, maintains good linear relationship.
The response speed of embodiment 4 probe representative compound L1 Dichlorodiphenyl Acetate zinc and fluorescence intensity stability
1 μM of probe representative compound L1 is joined in the sample pool containing 2ml ethanol, then adds the zinc acetate of 1.5 μMs.Excitation wavelength is set to 244nm, the intensity of record 455nm emitting fluorescence after 0,0.5,1,1.5,2,2.5,3,4,5,6 hour, as shown in Figure 4,0 hour place records after probe compound mixes with zinc acetate immediately, illustrate that the response speed of probe compound to zinc is exceedingly fast, 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
The probe representative compound L1 of synthesis is used to evaluate its selectivity to zine ion.1 μM of probe representative compound L1 is joined in the sample pool containing 2ml ethanol, then the zinc acetate of 1.5 μMs is added successively respectively, 400eq(400 times of concentration, namely 600 μMs) Potassium ethanoate, sodium-acetate, calcium acetate, 40eq(40 times of concentration, namely 60 μMs) Iron diacetate, neutralized verdigris, magnesium acetate, cadmium acetate, nickel acetate, manganese acetate, Cobaltous diacetate, excitation wavelength is 244nm, and test result is shown in Fig. 5.Can find out in figure that the fluorescence that zine ion and probe representative compound L1 produce is the strongest, sodium, potassium, calcium, magnesium, copper plasma are to detection not interference.
The selectivity to zinc salt negatively charged ion of embodiment 6 probe representative compound L1
Use synthesis probe representative compound L1 evaluation its to the selectivity of zinc salt negatively charged ion.1 μM of probe representative compound L1 is joined in the sample pool containing 2ml ethanol, then zinc acetate, zinc chloride, zinc perchlorate, zinc nitrate, zinc sulfate, the zinc bromide of 1.5 μMs is added successively respectively, excitation wavelength is 244nm, and test result is shown in Fig. 6.The negatively charged ion of this probe to zinc salt has selectivity as seen from the figure, and the fluorescence intensity of zinc acetate is the strongest, be secondly zinc chloride, zinc nitrate, zinc bromide, zinc perchlorate respectively, 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 μM of probe representative compound L1 and 1.5 μM is joined in the sample pool containing 2ml ethanol, then adds 0 successively respectively, 0.2,0.4,0.6,0.8,1.0, the EDTA(of 2.0eq corresponds to A, B, C, D, E, F, G curve in figure respectively; H is probe representative compound L1), excitation wavelength is 244nm, and 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 fluorescence completely dissolve after adding the EDTA of qdx, illustrates that the fluorescence of probe and the chelation evoked generation of zinc can the cancellation by EDTA competition binding.
Embodiment 8 crystal at different wavelengths and part and zinc acetate ethanolic soln, the color performance of powder under ultraviolet lamp
Light brown [the Zn that Liquid Phase Diffusion is grown
3(L1)
2(OAc)
2] crystal take under being placed in the illumination of UV-light (190-400nm), blue light (390-455nm), green glow (455-492nm) three kinds of different-wavebands respectively photo as shown in Figure 8.Under three kinds of different-wavebands irradiate, crystallofluorescence color is variant, as: under UV-light (190-400nm) is irradiated, show blueness, under blue light (390-455nm) irradiates, show green, under green glow (455-492nm) irradiates, show redness, illustrate that this title complex has the characteristic of fluorescence variable color, this characteristic can be applicable to the field 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 the ethanolic soln of the ethanolic soln of prepare 100 μMs of probe representative compound L1,100 μMs of probe representative compound L1 and 150 μM zinc acetates, 10 μMs of probe representative compound L1 and 15 μM zinc acetates, the ethanolic soln of 1 μM of probe representative compound L1 and 1.5 μM zinc acetate are contained in respectively in phial and are 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 fluorescence brightness that concentration is large is stronger.
Ethanolic soln (concentration of probe compound L1L10 is 1 μM), the probe compound (L1-L10) of embodiment 9 probe compound (L1-L10) carry out fluorescence intensity test respectively with the ethanolic soln (wherein the concentration of probe compound (L1-L10) is 1 μM, and acetic acid zinc concentration is 1.5 μMs) of zinc acetate.
Wherein E
x(nm) be maximum excitation wavelength, E
m(nm) for maximum emission wavelength, L (x) fluorescence intensity are probe compound (L1-L10) fluorescence intensity at maximum emission wavelength place, L (x)+Zn
2+fluorescence intensity is probe compound (L1-L10) and Zn
2+title complex is in the fluorescence intensity at maximum emission wavelength place.
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.
Claims (10)
1. based on the fluorescent probe compounds molecule of chelation evoked Fluorescence Increasing as the application of zinc ion fluorescent molecule, it 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 based on chelation evoked Fluorescence Increasing according to claim 1 is as the application of zinc ion fluorescent molecule, it is characterized in that, in described compound structure, and preferably symmetrical replacement structure, i.e. substituent R in molecule
1with R
8identical, R
2with R
7identical, R
3with R
6identical, R
4with R
5identical, with make described compound molecule with
for symmetry axis.
3. based on the fluorescent probe compounds molecule of chelation evoked Fluorescence Increasing as the application of zinc ion fluorescent molecule, it 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 and significantly increases, and has good selectivity to zine ion, and not by other cationic interference; Have selectivity to the negatively charged ion of zinc salt, zinc acetate is the strongest, be secondly zinc chloride, zinc nitrate, zinc bromide, zinc perchlorate respectively, and zinc sulfate and probe produces fluorescence hardly; The fluoroscopic examination lower limit of described fluorescent probe molecule to zine ion is low.
4. the fluorescent probe compounds molecule based on chelation evoked Fluorescence Increasing according to claim 3 is as the application of zinc ion fluorescent molecule, it is characterized in that, other positively charged ions described are K
+, Mg
2+, Ca
2+, Cu
2+, Mn
2+, Fe
2+or Fe
3+, the lower limit of described fluoroscopic examination is 0.3-1.5 μM, and within the scope of 0.3-1.5 μM of zinc ion concentration, described fluorescence probe intensity presents good linear relationship, can be used for the concentration of detection by quantitative zine ion.
5. based on the title complex that fluorescent probe compounds and the zine ion of chelation evoked Fluorescence Increasing are formed, it is characterized in that, described fluorescent probe compounds molecular formula is C
17h
16cl
2n
2o
3, molecular structure is as follows, i.e. compound L 1:
Described compound molecule is combined with zinc acetate coordination and forms title complex, and adopts solvent evaporation method to prepare complex monocrystal, and this crystal molecule formula is C
38h
34cl
4n
4o
10zn
3, belong to oblique system, spacer is P2 (1)/c, and unit cell parameters is
α=90.00 °, β=103.130 (8) °, γ=90.00 °, unit-cell volume
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, adopt the mixed solvent that acetonitrile and methyl alcohol coordinate, zinc acetate and compound molecule are dissolved in the mixed solvent of acetonitrile and methyl alcohol, stirred at ambient temperature reaction at least 2 hours; Filter afterwards, filtrate is adopted solvent evaporation method, leave standstill under placing room temperature and treat that solvent slowly volatilizees, attached wall grows yellow lump shaped crystalline, namely obtains complex monocrystal.
8. preparation method according to claim 7, is characterized in that, described acetonitrile and methyl alcohol volume are 1:1; Described room temperature is 20-25 degrees Celsius; Described stirring velocity selects 60-100 turns/min; The described stirred at ambient temperature reaction times is 2-6 hours; The selection of time at least 160h of described standing placement.
9. preparation method according to claim 7, is characterized in that, the time of described standing placement is 160-180h.
10. title complex as claimed in claim 5 is in the application in fluorescence falsification preventing, fluorescent decoration material, fluorescent ink, fluorescence storage fiber, anti-false fiber, photosensitive colour-changing material, optical recording material field, it is characterized in that, utilize the fluorescence color shifting properties of described title complex, namely under different-waveband excitation light irradiation, crystallofluorescence color is different.
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| CN104650121A (en) * | 2015-02-11 | 2015-05-27 | 桂林理工大学 | Synthesis method and application of complex [Zn(H2L2)2](H2O)5 with anticancer activity |
| CN105713024B (en) * | 2016-01-22 | 2018-02-09 | 辽宁大学 | One kind is based on ZnⅡMetal organic framework and its preparation method and application |
| CN105694866B (en) * | 2016-04-01 | 2017-09-29 | 齐齐哈尔大学 | Symmetric form phenanthro- imidazoles Fe3+ fluorescence probes of double-Schiff base link and preparation method thereof |
| CN107698627B (en) * | 2017-04-19 | 2018-07-13 | 南京晓庄学院 | A kind of preparation method of multi signal probe |
| CN108384018B (en) * | 2018-01-22 | 2021-08-13 | 西北师范大学 | MOF (metal organic framework) complex, synthesis thereof and application thereof in fluorescent recognition of iron ions |
| CN109265697B (en) * | 2018-09-20 | 2021-05-18 | 平顶山学院 | Zinc coordination polymer single crystal with green fluorescent property and preparation method thereof |
| CN111019642B (en) * | 2018-10-09 | 2021-09-14 | 北京大学 | Preparation method of dual-wavelength detection and full-spectrum adjustment composite fluorescent micelle and application of composite fluorescent micelle in aqueous anti-counterfeiting ink |
| CN109970600B (en) * | 2019-03-26 | 2021-11-02 | 菏泽学院 | Triphenylamine derivative Schiff base organic fluorescent probe and preparation method thereof |
| CN110372876A (en) * | 2019-07-29 | 2019-10-25 | 南京工业大学 | A kind of method that solvent evaporation induction prepares metal-organic framework materials |
| CN110835531B (en) * | 2019-11-18 | 2022-10-18 | 南京林业大学 | POSS-salicylaldehyde fluorescent probe for detecting zinc ions and histidine and preparation method thereof |
| CN110964514B (en) * | 2019-12-13 | 2021-05-04 | 菏泽学院 | Novel pyrazine Schiff base fluorescent probe, and synthetic method and application thereof |
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| Magnetic Super-Exchange Mechanism and Crystal Structure of a Binuclear ÿ-Acetato-Bridged Copper(II) Complex of Pentadentate Binucleating Ligand.An Influence of Overlap Interactions to Magnetic Properties;Ebru Kavlakoglu等;《Verlag der Zeitschrift fur Naturforschung》;20021231;第323-330页 * |
| Self-Assembly of Luminescent Hexanuclear Lanthanide Salen;Sen Liao等;《crystal growth design》;20111215;第970-974页 * |
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