CN107312022A - For Fe3+The fluorescein rhodamine ultraviolet molecular probe of B double-Schiff base compounds of detection and its synthesis and application - Google Patents
For Fe3+The fluorescein rhodamine ultraviolet molecular probe of B double-Schiff base compounds of detection and its synthesis and application Download PDFInfo
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- rhodamine
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- 238000001514 detection method Methods 0.000 title claims abstract description 57
- 239000003068 molecular probe Substances 0.000 title claims abstract description 57
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 title claims abstract description 57
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002262 Schiff base Substances 0.000 title claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 title abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title abstract description 9
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 55
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000523 sample Substances 0.000 claims abstract description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000002835 absorbance Methods 0.000 claims abstract description 14
- -1 fluorescein aldehyde Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000012360 testing method Methods 0.000 claims abstract description 10
- 239000003208 petroleum Substances 0.000 claims abstract description 8
- 239000012488 sample solution Substances 0.000 claims abstract description 8
- 238000002211 ultraviolet spectrum Methods 0.000 claims abstract description 8
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000013102 re-test Methods 0.000 claims description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 239000002585 base Substances 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 46
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000007995 HEPES buffer Substances 0.000 abstract 1
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 238000010521 absorption reaction Methods 0.000 description 15
- 229910021645 metal ion Inorganic materials 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 239000003513 alkali Substances 0.000 description 5
- 230000003139 buffering effect Effects 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 230000006820 DNA synthesis Effects 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 208000018565 Hemochromatosis Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WINTXHPCODMMRI-UHFFFAOYSA-N benzene naphthalene Chemical group C1=CC=CC=C1.C1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 WINTXHPCODMMRI-UHFFFAOYSA-N 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 231100000753 hepatic injury Toxicity 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Abstract
For Fe3+The fluorescein rhodamine ultraviolet molecular probe of B double-Schiff base compounds of detection and its synthesis and application, it is related to Fe3+Probe and its synthesis and application.It will solve existing Fe3+Expensive equipment needed for fluorescent molecular probe, the technical problem that ultraviolet probe is easily disturbed.The structural formula of ultraviolet molecular probe of the present invention is：Preparation method：By single imido grpup fluorescein aldehyde and rhodamine B hydrazine condensation reaction, obtained with the mixed solvent of petroleum ether and ethyl acetate by pillar layer separation；Probe is dissolved in DMF and in the mixed liquor of HEPES cushioning liquid, the ultraviolet spectra absorbance that detection is added before and after testing sample, if being the absorbance raising at 323 and 358nm in wavelength, can determine that and contain Fe in sample solution3+, method is simply, quickly.
Description
Technical field
The present invention relates to for Fe3+The synthesis and application of the ultraviolet molecular probe of detection.
Background technology
Ferro element is distributed widely in nature, is one of the most abundant metal ion in organism, oxygen transmission,
Very important effect is played in the biochemical process such as electro transfer, DNA synthesis and reparation, photosynthesis, is that organism can not
One of metallic element lacked.Iron deficioncy and surplus can induce corresponding disease, and the shortage of such as iron can cause to be transported to carefully
The oxygen of born of the same parents is not enough, causes the diseases such as anaemia, hemochromatosis, hepatic injury, diabetes and cancer.It is presently used for Fe3+The chemistry of detection
Sensor is generally fluorescence probe.That is, using fluorescence spectrum when being interacted between fluorescence chemical probe and metal ion
Change realize the detection of metal ion.Chinese patent such as Patent No. 201610201233.7 discloses a kind of couple of Schiff
The symmetric form phenanthro- imidazoles Fe of alkali link3+Fluorescence probe, pH value for 1~9 it is extensive under the conditions of, the fluorescence probe can detect water
Fe in phase system3+.But Fe3+Fluorescence probe can only detect Fe by fluorescence spectrum3+, it is necessary to which expensive, precision is high
XRF complete, the requirement to equipment is higher.
In addition to using fluorescence probe detection metal ion, it would however also be possible to employ ultraviolet spectroscopy detects metal ion.Such as exist
《Sensor and actuator B：Chemistry》(Sensors and Actuators B：Chemical the 17-23 of 227 phases in 2016)
Page discloses the Fe that a kind of structure is benzene-naphthalene diimide derivative3+Ultraviolet probe, passes through ultraviolet probe and Fe3+With 2:1 mode
It is complexed to detect Fe3+, but the ultraviolet probe is to Fe3+Detection when by Cu2+Interference, make its application be restricted.
The content of the invention
The present invention is to solve existing detection Fe3+Fluorescent spectrometry detecting instrument is expensive, ultraviolet spectroscopy is easily by it
There is provided for Fe for his technical problem of metal ion disturbance3+Ultraviolet point of the fluorescein rhodamine B double-Schiff base compounds of detection
Sub- probe and its synthesis and application, Fe is realized using ultraviolet specrophotometer3+Detection.
The present invention's is used for Fe3+The structure of the ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of detection
Formula is：
Above-mentioned is used for Fe3+The synthesis side of the ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of detection
Method is to be obtained using single imido grpup fluorescein aldehyde with rhodamine B hydrazine reaction, and reaction equation is as follows：
Its specific synthesis step is：
First, it is 1 according to the mol ratio of single imido grpup fluorescein aldehyde and rhodamine B hydrazine:(1~3), it is respectively that single imido grpup is glimmering
Light element aldehyde is added in alcohols solvent with rhodamine B hydrazine, is heated to boiling and 3~10h of back flow reaction, after reaction terminates, cooling,
Concentration, obtains mixture；
2nd, mixture is separated by column chromatography chromatogram gradient elution, 200~300 purposes is filled wherein in pillar
Silica gel, eluent is the mixed liquor of petroleum ether and ethyl acetate, obtains being used for Fe3+The double Schiff of fluorescein rhodamine B of detection
The ultraviolet molecular probe of alkali cpd.
Above-mentioned is used for Fe3+The user of the ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of detection
Method is carried out according to the following steps：
First, Fe will be used for3+The ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of detection is dissolved in N, N-
Dimethylformamide (DMF) is visited with the mixed liquor of 4- hydroxyethyl piperazineethanesulfonic acids (HEPES) cushioning liquid, obtaining ultraviolet molecule
Pin solution；DMF buffers molten with HEPES in the wherein pH=7.4 of HEPES cushioning liquid mixed liquor, mixed liquor
The volume ratio of liquid is 9：The concentration of ultraviolet molecular probe is 10~30 μm of ol/L in (1~3), ultraviolet molecular probe solution；
2nd, ultraviolet molecular probe solution is taken, testing sample is added thereto, is well mixed, obtains sample solution；
3rd, it is the absorbance at 323 and 358nm to test ultraviolet molecular probe solution in wavelength with ultraviolet specrophotometer
Difference A1And A2；The ultraviolet spectra of re-test sample solution, wavelength be 323 and 358nm at absorbance be respectively B1With
B2；If B1≥1.5A1、B2≥1.4A2Set up simultaneously, then can determine that and contain Fe in sample solution3+。
The ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of the present invention may be implemented in water environment system
To Fe3+Ultraviolet Selective recognition function, do not disturbed by other metal ions in the aqueous solution, with stronger anti-interference energy
Power.The ultraviolet molecular probe is that Fe is can recognize that in the range of 3~11 in pH value3+, show as the extinction of two UV absorption wavelength
Degree enhancing, detection method is simple, is that can be achieved using only simple ultraviolet specrophotometer, and response is rapid, with detection water body
Fe in based environment3+The ability of detection.
Raw material needed for the synthesis of the ultraviolet molecular probe is simple and easy to get, and cost is low；Step is simple；Reaction condition is gentle, receives
Rate is high, and yield is up to 60~80%.
The ultraviolet molecular probe of the present invention can be applicable to Fe in aqueous systems3+, should with high in the early stage detection of pollution
With value.
Brief description of the drawings
Fig. 1 be in embodiment 1 ultraviolet molecular probe in DMF/HEPES cushioning liquid (v/v=9/1, pH=7.4) system
Ultraviolet spectrogram, abscissa is wavelength, and ordinate is absorbance.
Fig. 2 be in embodiment 1 ultraviolet molecular probe in DMF/HEPES cushioning liquid (v/v=9/1, pH=7.4) system
Add the metal cation (Al of 50 μm of ol/L concentration3+、Zn2+、Ag+、Ca2+、Mg2+、Cu2+、Hg2+、Pb2+、Na+、Ba2+、Ni2+、K+、Cr3+、Co2+、Cd2+And Fe3+) ultraviolet spectra situation of change afterwards, abscissa is wavelength, and ordinate is absorbance.
Fig. 3 be in embodiment 1 ultraviolet molecular probe in DMF/HEPES cushioning liquid (v/v=9/1, pH=7.4) system
Add the Fe of 50 μm of ol/L concentration3+Ultraviolet spectra situation of change after coexistent metallic ions different from 50 μm of ol/L concentration, horizontal seat
Wavelength is designated as, ordinate is absorbance.
Fig. 4 be in embodiment 1 ultraviolet molecular probe in DMF/HEPES cushioning liquid (v/v=9/1, pH=7.4) system
In, ultraviolet spectra is with Fe3+Concentration (0.01~7 equivalent) increased situation of change, abscissa is wavelength, and ordinate is absorbance.
Fig. 5 be in embodiment 1 ultraviolet molecular probe in DMF/HEPES cushioning liquid (v/v=9/1, pH=7.4) system
With Fe3+UV absorption wavelength 323 and 358nm absorbance ratio situation of change when concentration (0~9 equivalent) changes, abscissa is
Wavelength, ordinate is absorbance.
Embodiment
Embodiment one：Present embodiment be used for Fe3+The fluorescein rhodamine B double-Schiff base compounds of detection
The structural formula of ultraviolet molecular probe is：
Embodiment two：It is used for Fe described in embodiment one3+The double Schiff of fluorescein rhodamine B of detection
The synthetic method of the ultraviolet molecular probe of alkali cpd is as follows：
First, it is 1 according to the mol ratio of single imido grpup fluorescein aldehyde and rhodamine B hydrazine:(1~3), it is respectively that single imido grpup is glimmering
Light element aldehyde is added in alcohols solvent with rhodamine B hydrazine, is heated to boiling and 3~10h of back flow reaction, after reaction terminates, cooling,
Concentration, obtains mixture；
2nd, mixture is separated by column chromatography chromatogram gradient elution, 200~300 purposes is filled wherein in pillar
Silica gel, eluent is the mixed liquor of petroleum ether and ethyl acetate, obtains being used for Fe3+The double Schiff of fluorescein rhodamine B of detection
The ultraviolet molecular probe of alkali cpd.
Embodiment three：Present embodiment is from the alcohols solvent in step one unlike embodiment two
Methanol, ethanol, propyl alcohol, isopropanol or butanol；It is other identical with embodiment two.
Embodiment four：Present embodiment and step 2 petrochina ether unlike embodiment two or three with
The mixed liquor petrochina ether of ethyl acetate and the volume ratio of ethyl acetate are 1：(10~2)；It is other with embodiment two or
Three is identical.
Embodiment five：It is used for Fe described in embodiment one3+The double Schiff of fluorescein rhodamine B of detection
The application method of the ultraviolet molecular probe of alkali cpd is carried out according to the following steps：
First, Fe will be used for3+The ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of detection is dissolved in N, N-
Dimethylformamide (DMF) is visited with the mixed liquor of 4- hydroxyethyl piperazineethanesulfonic acids (HEPES) cushioning liquid, obtaining ultraviolet molecule
Pin solution；The volume ratio of DMF and HEPES cushioning liquid is in the wherein pH=7.4 of HEPES cushioning liquid mixed liquor, mixed liquor
9：The concentration of ultraviolet molecular probe is 10~30 μm of ol/L in (1~3), mixed liquor；
2nd, ultraviolet molecular probe solution is taken, testing sample is added thereto, is well mixed, obtains sample solution；
3rd, it is the absorbance at 323 and 358nm to test ultraviolet molecular probe solution in wavelength with ultraviolet specrophotometer
Difference A1And A2；The ultraviolet spectra of re-test sample solution, wavelength be 323 and 358nm at absorbance be respectively B1With
B2；If B1≥1.5A1、B2≥1.4A2Set up simultaneously, contain Fe in the sample that can determine that test3+。
Beneficial effects of the present invention are verified with following examples：
Embodiment 1：The present embodiment be used for Fe3+The ultraviolet molecule of fluorescein rhodamine B double-Schiff base compounds of detection
The synthetic method of probe is as follows：
First, the single imido grpup fluorescein aldehyde of 462mg (1mmol) and 456mg (1mmol) rhodamine B hydrazine are added to 20mL second
In alcohol, it is heated to seething with excitement and maintains the reflux for reacting 6h, after reaction terminates, cool down, concentration obtains mixture；
2nd, mixture is separated by column chromatography chromatogram gradient elution, 200~300 mesh is filled wherein in chromatographic column
Silica gel, eluent is the 1 of the volume ratio of petroleum ether and ethyl acetate:5 mixed liquor, obtains being used for Fe3+The fluorescein of detection
The ultraviolet molecular probe of rhodamine B double-Schiff base compound.It is computed, yield is 80%.
It is manufactured in the present embodiment to be used for Fe3+The ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of detection
Infrared spectrum, elementary analysis and deuterium replace DMSO solvents in1H and13C H NMR spectroscopy data are as follows：
IR(KBr):ν/cm-1：3431,2971,2930,1692,1633,1616,1516.1H NMR(600MHz,DMSO-
d6)δ:9.97 (s, 2H, OH), 8.91 (s, 1H, N=CH), 8.79 (s, 1H, N=CH), 7.88 (t, 1H, ArH), 7.61-7.55
(m, 2H, ArH), 7.35 (s, 2H, ArH), 7.09 (t, J=7.2Hz, 1H, ArH), 6.62 (s, 1H, ArH) 6.46 (s, 1H,
ArH),6.42-6.40(m,2H,ArH),6.37-6.30(m,1H,ArH),6.30-6.28(m,1H,ArH),3.28(q,8H,
CH2), 1.04 (t, J=6.9Hz, 12H, CH3)；13C NMR(150MHz,DMSO-d6)δ:191.3,187.3,165.7,159.7,
152.3,152.7,149.4,149.4,146.9,139.4,136.2,132.5,131.2,129.2,129.2,128.3,
128.5,117.4,114.2,109.9.106.5,105.7,97.7,76.3,47.1,12.9；Elementary analysis (%, C56H48N6O6
Calculated value):W (C)=74.49 (74.65), w (H)=5.32 (5.37), w (N)=9.28 (9.33).
It can obtain manufactured in the present embodiment for Fe from data above3+The fluorescein rhodamine B double-Schiff bases of detection
The structural formula of the ultraviolet molecular probe of compound is as follows：
It is used for Fe by manufactured in the present embodiment3+The ultraviolet molecule of fluorescein rhodamine B double-Schiff base compounds of detection is visited
Pin carries out ultraviolet spectra detection, and method is as follows：Fe will be used for3+The fluorescein rhodamine B double-Schiff base compounds of detection are ultraviolet
Molecular probe is dissolved in DMF/HEPES buffering (v/v=9/1, pH=7.4) solution, and concentration and probe concentration is 10 μm of ol/L, fully mixed
Close, using its ultra-violet absorption spectrum of UV spectrophotometer measuring after 5min, obtained uv absorption spectra is as shown in Figure 1.
As shown in Figure 1, it is manufactured in the present embodiment to be used for Fe3+The ultraviolet molecule of fluorescein rhodamine B double-Schiff base compounds of detection is visited
The ultraviolet absorption peak of pin is respectively 323 and in 358nm.
The ultraviolet emission spectrum after ultraviolet molecular probe manufactured in the present embodiment is acted on different metal ions is tested, specifically
Method is as follows：
Fe will be used for3+The ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of detection is added to DMF/
In HEPES buffering (v/v=9/1, pH=7.4) solution, wherein for Fe3+The fluorescein rhodamine B double-Schiff bases of detection
The concentration of the ultraviolet molecular probe of compound is 10 μm of ol/L, then adds metal ion of the concentration for 50 μm of ol/L, is well mixed,
Its uv-vis spectra is determined after 5min, wherein metal ion is respectively Al3+、Zn2+、Ag+、Ca2+、Mg2+、Cu2+、Hg2+、Pb2+、
Na+、Ba2+、Ni2+、K+、Cr3+、Co2+And Cd2+, obtained ultraviolet-visible spectrogram is as shown in Figure 2.As shown in Figure 2, add not
With metal ion after, the absorption intensity of two UV absorption wavelength at 323nm and 358nm does not change substantially.Work as addition
Fe3+When, the absorption intensity of two UV absorption wavelength at 323 and 358nm has enhancing, and enhancing respectively is original 1.5 times
With 1.4 times.
It is used for Fe by manufactured in the present embodiment3+The ultraviolet molecule of fluorescein rhodamine B double-Schiff base compounds of detection is visited
Pin carries out anti-metal ion interference test, and method is as follows：Fe will be used for3+The fluorescein rhodamine B double-Schiff base chemical combination of detection
The ultraviolet molecular probe of thing is added in DMF/HEPES buffering (v/v=9/1, pH=7.4) solution, wherein for Fe3+That detects is glimmering
The concentration of the ultraviolet molecular probe of light element rhodamine B double-Schiff base compound is 10 μm of ol/L, and it is 50 μm of ol/L to add concentration
Common metal ion (Al3+、Zn2+、Ag+、Ca2+、Mg2+、Cu2+、Hg2+、Pb2+、Na+、Ba2+、Ni2+、K+、Cr3+、Co2+And
Cd2+), after being well mixed, then 50 μm of ol/L Fe is added into above-mentioned solution respectively3+, mix, determined respectively after 5min again
Its uv-vis spectra, as shown in Figure 3.From the figure 3, it may be seen that common metal ion and Fe3+When coexisting, prepared by the present embodiment
For Fe3+The uv-vis spectra that the ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of detection is shown
Two absorption peak strengths and Fe3+Had almost no change during individualism, i.e. two UV absorption peak intensities at 323nm and 358nm
Spend enhancing amplitude and Fe3+It is similar during individualism.This illustrates fluorescein rhodamine B double-Schiff base chemical combination manufactured in the present embodiment
The ultraviolet molecular probe of thing is to Fe3+Detection have selectivity, do not disturbed by other common metal ions.
Detection is manufactured in the present embodiment to be used for Fe3+The ultraviolet molecule of fluorescein rhodamine B double-Schiff base compounds of detection
Probe is to Fe3+The sensitivity of selectivity, specific method is as follows：Fe will be used for3+The fluorescein rhodamine B double-Schiff bases of detection
The ultraviolet molecular probe of compound is added in DMF/HEPES buffering (v/v=9/1, pH=7.4) solution, wherein for Fe3+Detection
The concentration of the ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds be 10 μm of ol/L, add 0.01-7 equivalent
Fe3+, its uv-vis spectra is determined respectively, obtains spectrogram as shown in figure 4, from fig. 4, it can be seen that with Fe3+Concentration
Increase, two absorption peak strengths of the ultraviolet molecular probe at 323nm and 358nm increase simultaneously.Fe3+Ion concentration is less than 70 μ
During mol/L (7 equivalents of body concentration), the UV absorption gathered way at more than 358nm of the UV absorption intensity at 323nm
Intensity gathers way.Work as Fe3+When ion concentration is equal to 70 μm of ol/L (7 equivalents of body concentration), at 323nm and 358nm
UV absorption intensity is quite (as shown in Figure 5).Work as Fe3+When ion concentration is more than 70 μm of ol/L (7 equivalents of body concentration),
The UV absorption intensity gathered way at slightly larger than 358nm of UV absorption intensity at 323nm gathers way.
Embodiment 2：The present embodiment be used for Fe3+The ultraviolet molecule of fluorescein rhodamine B double-Schiff base compounds of detection
The synthetic method of probe is as follows：
First, the single imido grpup fluorescein aldehyde of 462mg (1mmol) and 912mg (2mmol) rhodamine B hydrazine are added to 20mL first
In alcohol, it is heated to seething with excitement and maintains the reflux for reacting 8h, after reaction terminates, cool down, concentration obtains mixture；
2nd, mixture is separated by column chromatography chromatogram gradient elution, 200~300 mesh is filled wherein in chromatographic column
Silica gel, eluent is the 1 of the volume ratio of petroleum ether and ethyl acetate:6 mixed liquor, obtains being used for Fe3+The fluorescein of detection
The ultraviolet molecular probe of rhodamine B double-Schiff base compound.It is computed, yield is 65%.
Embodiment 3：The present embodiment be used for Fe3+The ultraviolet molecule of fluorescein rhodamine B double-Schiff base compounds of detection
The preparation method of probe is as follows：
First, the single imido grpup fluorescein aldehyde of 462mg (1mmol) and 684mg (1.5mmol) rhodamine B hydrazine are added to 20mL
In isopropanol alcohol, it is heated to seething with excitement and maintains the reflux for reacting 7h, after reaction terminates, cool down, concentration obtains mixture；
2nd, mixture is separated by column chromatography chromatogram gradient elution, 200~300 mesh is filled wherein in chromatographic column
Silica gel, eluent is the 1 of the volume ratio of petroleum ether and ethyl acetate:4 mixed liquor, obtains being used for Fe3+The fluorescein of detection
The ultraviolet molecular probe of rhodamine B double-Schiff base compound.It is computed, yield is 82%.
Embodiment 4：The present embodiment be used for Fe3+The ultraviolet molecule of fluorescein rhodamine B double-Schiff base compounds of detection
The synthetic method of probe is as follows：
First, the single imido grpup fluorescein aldehyde of 462mg (1mmol) and 1368mg (3mmol) rhodamine B hydrazine are added to 20mL fourths
In alcohol, it is heated to seething with excitement and maintains the reflux for reacting 6h, after reaction terminates, cool down, concentration obtains mixture；
2nd, mixture is separated by column chromatography chromatogram gradient elution, 200~300 mesh is filled wherein in chromatographic column
Silica gel, eluent is the 1 of the volume ratio of petroleum ether and ethyl acetate:3 mixed liquor, obtains being used for Fe3+The fluorescein of detection
The ultraviolet molecular probe of rhodamine B double-Schiff base compound.It is computed, yield is 70%.
Claims (5)
1. for Fe3+The ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of detection, it is characterised in that this is ultraviolet
The structural formula of molecular probe is：
2. synthesize is used for Fe described in claim 13+The ultraviolet molecule of fluorescein rhodamine B double-Schiff base compounds of detection is visited
The method of pin, it is characterised in that this method is followed the steps below：
First, it is 1 according to the mol ratio of single imido grpup fluorescein aldehyde and rhodamine B hydrazine:(1~3), respectively by single imido grpup fluorescein
Aldehyde is added in alcohols solvent with rhodamine B hydrazine, is heated to boiling and 3~10h of back flow reaction, after reaction terminates, and cooling is dense
Contracting, obtains mixture；
2nd, mixture is separated by column chromatography chromatogram gradient elution, the silica gel of 200~300 mesh is filled wherein in pillar,
Eluent is the mixed liquor of petroleum ether and ethyl acetate, obtains being used for Fe3+The fluorescein rhodamine B double-Schiff base chemical combination of detection
The ultraviolet molecular probe of thing.
3. according to claim 2 be used for Fe3+The ultraviolet molecule of fluorescein rhodamine B double-Schiff base compounds of detection is visited
The synthetic method of pin, it is characterised in that the alcohols solvent described in step one is methanol, ethanol, propyl alcohol, isopropanol or butanol.
4. it is used for Fe according to Claims 2 or 33+Ultraviolet point of the fluorescein rhodamine B double-Schiff base compounds of detection
The synthetic method of sub- probe, it is characterised in that the mixed liquor petrochina ether and ethyl acetate of step 2 petrochina ether and ethyl acetate
Volume ratio be 1：(10~2).
5. it is used for Fe described in claim 13+The ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of detection
Application method, it is characterised in that this method is carried out according to the following steps：
First, Fe will be used for3+The ultraviolet molecular probe of fluorescein rhodamine B double-Schiff base compounds of detection is dissolved in N, N- diformazans
Base formamide (DMF) is with the mixed liquor of 4- hydroxyethyl piperazineethanesulfonic acids (HEPES) cushioning liquid, obtaining ultraviolet molecular probe molten
Liquid；The volume ratio of DMF and HEPES cushioning liquid is 9 in the wherein pH=7.4 of HEPES cushioning liquid mixed liquor, mixed liquor：(1
~3), the concentration of ultraviolet molecular probe is 10~30 μm of ol/L in mixed liquor；
2nd, ultraviolet molecular probe solution is taken, testing sample is added thereto, is well mixed, obtains sample solution；
3rd, it is the absorbance difference at 323 and 358nm to test ultraviolet molecular probe solution in wavelength with ultraviolet specrophotometer
A1And A2；The ultraviolet spectra of re-test sample solution, wavelength be 323 and 358nm at absorbance be respectively B1And B2；Such as
Fruit B1≥1.5A1、B2≥1.4A2Set up simultaneously, contain Fe in the sample that can determine that test3+。
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359444A (en) * | 2018-04-27 | 2018-08-03 | 齐齐哈尔大学 | A kind of detection Fe3+And Fe can be utilized3+Detect Ca2+Fluorescence probe and its preparation and application |
| CN108440548A (en) * | 2018-03-31 | 2018-08-24 | 浙江工业大学 | A kind of rhodamine 6G class fluorescence probe of the group containing hydrazides and its preparation and application |
| CN108440547A (en) * | 2018-03-31 | 2018-08-24 | 浙江工业大学 | A kind of rhodamine 6G Schiff bases fluorescence probe and its preparation and application |
| CN110092792A (en) * | 2018-01-29 | 2019-08-06 | 天津医科大学 | The iron ion probe of rhodamine B lactams schiff bases based on FRET mechanism |
| CN110903467A (en) * | 2019-09-29 | 2020-03-24 | 苏州大学 | Fluorescent conjugated polymer with rhodamine B unit on side group, preparation method and application thereof |
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| CN113045591A (en) * | 2021-04-12 | 2021-06-29 | 延安大学 | Double-molecular rhodamine fluorescent probe R6G-PA and preparation method and application thereof |
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| CN113372282A (en) * | 2021-07-01 | 2021-09-10 | 齐齐哈尔大学 | Fluorescent probe for detecting bisulfite ions in real time and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694866A (en) * | 2016-04-01 | 2016-06-22 | 齐齐哈尔大学 | Bis-Schiff-base-connected symmetrical phenanthroimidazole Fe<3+> fluorescent probe and preparation method thereof |
-
2017
- 2017-08-01 CN CN201710646836.2A patent/CN107312022A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694866A (en) * | 2016-04-01 | 2016-06-22 | 齐齐哈尔大学 | Bis-Schiff-base-connected symmetrical phenanthroimidazole Fe<3+> fluorescent probe and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| ARUNA J.WEERASINGHE ET AL.: "Single- and Multiphoton Turn-On Fluorescent Fe3+ Sensors Based on Bis(rhodamine)", 《J.PHYS.CHEM.B》 * |
| MIN HEE LEE ET AL.: "Two-Color Probe to Monitor a Wide Range of pH Values in Cells", 《ANGEW. CHEM. INT. ED.》 * |
| SHAO LI ET AL.: "A novel solvent-dependently bifunctional NIR absorptive and fluorescent ratiometric probe for detecting Fe3+/Cu2+ and its application in bioimaging", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| VANDANA BHALLA ET AL.: "Rhodamine based fluorescence turn-on chemosensor for nanomolar detection of Fe3+ ions", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| ZHI-QIANG HU ET AL.: "Fe3+-selective fluorescent probe based on rhodamine B and its application in bioimaging", 《SENSORS AND ACTUATORS B:CHEMICAL》 * |
| 赵冰等: "Schiff 碱链接的双菲并咪唑Fe3 + 荧光探针的合成及识别性能研究", 《化学试剂》 * |
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| CN110092792B (en) * | 2018-01-29 | 2022-01-04 | 天津医科大学 | Iron ion probe of rhodamine B lactam Schiff base based on FRET mechanism |
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| CN108440547A (en) * | 2018-03-31 | 2018-08-24 | 浙江工业大学 | A kind of rhodamine 6G Schiff bases fluorescence probe and its preparation and application |
| CN108359444A (en) * | 2018-04-27 | 2018-08-03 | 齐齐哈尔大学 | A kind of detection Fe3+And Fe can be utilized3+Detect Ca2+Fluorescence probe and its preparation and application |
| CN110903467A (en) * | 2019-09-29 | 2020-03-24 | 苏州大学 | Fluorescent conjugated polymer with rhodamine B unit on side group, preparation method and application thereof |
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