CN105987892B - Measure the method and its kit of fluorine ion - Google Patents
Measure the method and its kit of fluorine ion Download PDFInfo
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- CN105987892B CN105987892B CN201510760191.6A CN201510760191A CN105987892B CN 105987892 B CN105987892 B CN 105987892B CN 201510760191 A CN201510760191 A CN 201510760191A CN 105987892 B CN105987892 B CN 105987892B
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000000523 sample Substances 0.000 claims abstract description 71
- 238000002360 preparation method Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 3
- 239000012723 sample buffer Substances 0.000 claims 2
- 238000001514 detection method Methods 0.000 abstract description 12
- -1 naphthalimide class compound Chemical class 0.000 abstract description 12
- 238000004458 analytical method Methods 0.000 abstract description 7
- 230000007774 longterm Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005259 measurement Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 18
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000012043 crude product Substances 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000012491 analyte Substances 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229940006460 bromide ion Drugs 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 4
- 229940006461 iodide ion Drugs 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 208000004042 dental fluorosis Diseases 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 229940005654 nitrite ion Drugs 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001228 spectrum Methods 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
- 206010016818 Fluorosis Diseases 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003262 anti-osteoporosis Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000037180 bone health Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
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- 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
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- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention relates to the methods and its kit of measurement fluorine ion.Specifically, probe of the invention is a kind of naphthalimide class compound, can be used as detection of the fluorine ion colorimetric fluorescence probe for fluorine ion.This kind of probe can realize following at least one of technical effect: identify fluorine ion with high selectivity；Quickly fluorine ion can be realized and be responded；The High Sensitive Analysis to fluorine ion may be implemented；Property is stablized, and can be used with long-term preservation；And it has strong anti-interference ability.
Description
Technical field
The present invention relates to naphthoyl imide compounds as fluorine ion fluorescence probe, can be highly selective to fluorine ion rapidly
Sensitive identification or its concentration that can measure fluorine ion in sample.
Background technique
Fluorine is that one of microelement important in human body, fluoride and human life activity and tooth, skeletal tissue are metabolized
It is closely related.A small amount of fluorine facilitates the normal development of tooth, the resistance that tooth enamel confrontation bacterial acid can be promoted to corrode,
Saprodontia is prevented, therefore water treatment plant generally can all add a small amount of fluorine in tap water, drinking water.Meanwhile fluorine is good for bone
Health, especially pre- anti-osteoporosis are quite helpful.The imbalance of fluorine ion will cause serious injury to body in human body, tooth
Scarce fluorine will lead to saprodontia.Increase odontopathy and other patients although lacking fluorine, illness caused by fluorine excess is not allowed to neglect yet
Depending on.Fluorine poisoning is a kind of chronic endemic disease for seriously endangering human health.Its main feature is that in the environment of fluorosis, people or dynamic
The fluoride of the long-term excess intake of object, accumulation in vivo and fall ill, be with tooth and bone damage based on and feed through to angiocarpy and
The systemic disease of nervous system.Children's fluorine poisoning is mainly shown as den tal fluorosis；Adult is mainly shown as fluorosis of bone.Human body is to fluorine
Content it is most sensitive, fluorine is more much narrower than other microelements to the safe range of human body.
In consideration of it, development can effectively detect the analysis method that can especially detect fluorine ion under the conditions of physiological level
It is of crucial importance and significant.Nowadays the analysis method for the detection fluorine ion reported includes volumetric analysis, optics point
Analysis method, the chromatography of ions (IC), Fluoride ion selective electrode method, the methods of on-line analysis method.In these numerous detection methods
Colorimetric fluorescence probe is researcher's focus of attention since its peculiar advantage forms.However, the colorimetric reported at present and glimmering
There are still some problems for light probe, including selectivity is not good enough, response speed is not fast enough, synthesis is complicated.Since life is intracorporal
Other ions such as sulfurous acid hydrogen radical ion, iodide ion, sulfate ion, bromide ion, sulfite ion, chloride ion, nitrate anion
Other metal ions such as ion, nitrite ion, phosphate anion and sulphion, it can constitute the detection of fluorine ion potential
Interference, therefore, developing quick high-selectivity probe becomes project urgently to be solved.The suitable concentration of fluoride ion is in drinking-water
This to the detection of fluorine ion brings very big difficulty to 0.5~1.0mg/L, thus develop can in high sensitivity detection life entity fluorine from
The analysis method of son is necessary.In short, development is quickly, highly selective, highly sensitive, the simple fluorine ion colorimetric fluorescence of synthesis
Binary channels probe is that those skilled in the art are urgently to be solved.
Summary of the invention
This field be badly in need of it is a kind of prepare simple quick high-selectivity fluorine ion colorimetric fluorescence probe, so as to effectively examine
Survey detection fluorine ion.For this purpose, the present invention has synthesized the colorimetric fluorescence probe of a kind of novel fluorine ion, synthesis is simple, selects
Property height, can identify fluorine ion at high sensitivity at once.Specifically, being the present invention provides a kind of fluorine ion fluorescence probe
Naphthoyl imide compounds, structure are as follows:
Preferably, fluorescence probe of the invention is:
It is by the way that probe of the invention will be corresponded to the present invention also provides the preparation method of fluorine ion fluorescence probe
Corresponding naphthoyl imide compounds and parahydroxyben-zaldehyde flow back 6 hours in ethanol solution and synthesize and be made.It is preferred that
, the corresponding naphthoyl imide compounds corresponding to probe of the invention of the invention are nitrogen butyl -4- hydrazine -1,8- naphthalene diformazans
Amide.
The present invention also provides the detection preparations or kit for detecting fluorinion concentration in sample, and it includes the present invention
Probe.Preferably, detection preparation of the invention or kit also include the operation instructions of product.It is further preferred that of the invention
Kit also include buffer for measuring the fluorinion concentration in sample.
The present invention also provides the methods of fluorinion concentration in detection sample comprising by probe of the invention and to test sample
The step of this contact.
The present invention also provides probe of the invention in preparation for detecting the use in sample in the preparation of fluorinion concentration
On the way.
It is dense for detecting fluorine ion in sample (such as water sample sample) in preparation that the present invention also provides probes of the invention
Purposes in the kit of degree.
Fluorine ion colorimetric fluorescence probe of the invention can be acted on fluorine ion, generate fluorescence spectrum and UV absorption light
The variation of spectrum, to realize the quantitative detection to fluorine ion.
Specifically, fluorine ion colorimetric fluorescence probe of the invention respectively with sulfurous acid hydrogen radical ion, iodide ion, sulfate radical
Ion, bromide ion, sulfate ion, chloride ion, nitrate ion, nitrite ion, phosphate anion and sulphion etc. its
His ion, which is acted on, cannot lead to substantially changeing for fluorescence spectrum and ultra-violet absorption spectrum, to realize the choosing to fluorine ion
The identification of selecting property, and then can be optionally used for excluding these sulfurous acid hydrogen radical ions, iodide ion, sulfate ion, bromide ion, sulfurous
Other ions in acid ion, chloride ion, nitrate ion, nitrite ion, phosphate anion and sulphion and human body
Interference of the presence to the quantitative determination of fluorine ion.
Fluorine ion colorimetric fluorescence probe of the invention reacts very sensitive with fluorine ion, to be conducive to the fast of fluorine ion
Speed detection.
Selectively, the stability of fluorine ion fluorescence probe of the invention is good, and then being capable of long-term preservation use.
Further, fluorine ion colorimetric fluorescence probe of the invention is the glimmering color probe of quick high-selectivity fluorine ion colorimetric,
And synthesis is simple, is conducive to commercialized popularization and application.
Detailed description of the invention
Fig. 1 a is (10 μM) addition F of probe-Fluorescence spectrum before and after (400 μM), Fig. 1 b are (10 μM) addition F of probe-(400
μM) before and after absorption spectrum.
Fig. 2 a various concentration F-The influence of (0-500 μM) to probe (10 μM) fluorescence spectrum；Fig. 2 b various concentration F-(0-
500 μM) influence to probe (10 μM) abosrption spectrogram.Fig. 2 c various concentration F-(0-60 μM) is to probe (10 μM) A596/A476
Meet good linear relationship.
Fig. 3 a and 3b are influence of the different ions analyte (400 μM) to the fluorescence intensity and absorbance of probe (10 μM).
Specific embodiment:
The present invention provides synthetic route, method and its spectrum of above-mentioned quick high-selectivity fluorine ion fluorescence probe
Energy.
Fluorine ion colorimetric fluorescence probe of the invention is a kind of naphthoyl imide compounds, has following structure general formula
In above formula: R1, R2, R3, R4, R5,R6, R7, R8, R9, it is hydrogen atom, linear or branched alkyl group, linear chain or branched chain alcoxyl
Base, sulfonic group, ester group, carboxyl；R1, R2, R3, R4, R5, R6, R7, R8And R9, can be identical or different.
The synthetic route and method of the F-like ion colorimetric Fluorescence Fluorescence probe are as follows:
Specifically, colorimetric fluorescence probe of the invention can be prepared via a method which, by certain mol proportion (example 1:1-1:
1.5) naphthoyl imide compounds (such as nitrogen butyl -4- hydrazine -1,8- aphthalimide) are dissolved in anhydrous with parahydroxyben-zaldehyde
Cooling in ethyl alcohol, the molar ratio of the two is that (1:1.3) is then refluxed for a period of time (such as 6h), is then taken out using high-pressure pump
Filter, obtains filter cake, and filter cake becomes our crude product.If obtaining purer product, can by filter cake methylene chloride and
The mixed system (such as v/v, 1:5) of petroleum ether carries out being recrystallized to give sterling.
Therefore, the present invention also provides parahydroxyben-zaldehydes in preparing the colorimetric fluorescence probe for detecting fluorine ion
Purposes.
The present invention also provides naphthoyl imide compounds (such as nitrogen butyl -4- hydrazine -1,8- aphthalimide) to prepare
The purposes in colorimetric fluorescence probe for detecting fluorine ion.
The highly sensitive identification fluorine ion colorimetric fluorescence probe of quick high-selectivity of the invention is noteworthy characterized by can be quick
Highly selective sensitive identification fluorine ion and accurately fluorine ion can be quantified in the presence of other intracorporal ions of people
Analysis.
It below will be by the way that the present invention be described in more detail by following embodiment.Following embodiment is merely illustrative,
It should be understood that the present invention is not limited by following embodiments.
Embodiment 1
283mg (1mmol) nitrogen butyl -4- hydrazine -1,8- aphthalimide is dissolved in 15mL dehydrated alcohol by (scheme 1), then
173mg (1mmol) parahydroxyben-zaldehyde reflux 6h is added, is then filtered using high-pressure pump, filter cake is obtained, filter cake becomes me
Crude product.It, can be by the mixed system of filter cake methylene chloride and petroleum ether (such as v/ if obtaining purer product
V, 1:5) it carries out being recrystallized to give sterling.Obtain orange pure product 321.2mg, yield 82%.
283mg (1mmol) nitrogen butyl -4- hydrazine -1,8- aphthalimide is dissolved in 15mL dehydrated alcohol by (scheme 2), then
224.9mg (1.3mmol) parahydroxyben-zaldehyde is added to flow back 6h, is then filtered using high-pressure pump, obtains filter cake, filter cake at
For our crude product.It, can be by the mixed system (example of filter cake methylene chloride and petroleum ether if obtaining purer product
Such as v/v, 1:5) it carries out being recrystallized to give sterling.Obtain orange pure product 359.9mg, yield 93%.
283mg (1mmol) nitrogen butyl -4- hydrazine -1,8- aphthalimide is dissolved in 15mL dehydrated alcohol by (scheme 3), then
259.5mg (1.5mmol) parahydroxyben-zaldehyde is added to flow back 6h, is then filtered using high-pressure pump, obtains filter cake, filter cake at
For our crude product.It, can be by the mixed system (example of filter cake methylene chloride and petroleum ether if obtaining purer product
Such as v/v, 1:5) it carries out being recrystallized to give sterling.Obtain orange pure product 328.9mg, yield 85%.
283mg (1mmol) nitrogen butyl -4- hydrazine -1,8- aphthalimide is dissolved in 20mL dehydrated alcohol by (scheme 4), then
346mg (2mmol) parahydroxyben-zaldehyde reflux 6h is added, is then filtered using high-pressure pump, filter cake is obtained, filter cake becomes me
Crude product.It, can be by the mixed system of filter cake methylene chloride and petroleum ether (such as v/ if obtaining purer product
V, 1:5) it carries out being recrystallized to give sterling.Obtain orange pure product 340.5mg, yield 88%.
283mg (1mmol) nitrogen butyl -4- hydrazine -1,8- aphthalimide and 173mg (1mmol) are dissolved in 15mL by (scheme 5)
In dehydrated alcohol, 224.9mg (1.3mmol) parahydroxyben-zaldehyde reflux 10h is added, is then filtered using high-pressure pump,
Filter cake is obtained, filter cake becomes our crude product.It, can be by filter cake methylene chloride and petroleum if obtaining purer product
The mixed system (such as v/v, 1:5) of ether carries out being recrystallized to give sterling.Orange pure product 367.7mg is obtained, yield is
95%.
1H-NMR(400MHz,DMSO-d6)δ(*10-6): 0.93 (t, J=8Hz, 3H), 1.30-1.39 (m, 2H), 1.56-
1.64 (m, 2H), 4.03 (t, J=8Hz, 2H), 6.87 (d, J=8Hz, 2H), 7.65-7.70 (m, 3H), 7.78 (t, J=8Hz,
1H), 8.37 (t, J=8Hz, 2H), 8.48 (d, J=8Hz, 1H), 8.79 (d, J=8Hz, 1H), 9.94 (s, 1H), 11.34 (s,
1H).ESI-MS calcd for C23H20N3O3[M-H]-386,found 386.
Embodiment 2
Fig. 1 (a) is (10 μM) addition F of probe-Fluorescence spectrum before and after (400 μM), it is by illustration it may be seen that glimmering
Light changes clearly.
Fig. 1 (b) is (10 μM) addition F of probe-Absorption spectrum before and after (400 μM), by illustration, we can be clearly
The variation of absorption spectrum, and by the variation of color, naked eye may be implemented.
Embodiment 3
Fig. 2 a various concentration F-The influence of (0-500 μM) to probe (10 μM) fluorescence spectrum；Fig. 2 b various concentration F-(0-
500 μM) to probe (10 μM) uv absorption spectra；Fig. 2 c various concentration F-(0-60 μM) is to probe (10 μM) A596/A476It is full
The good linear relationship of foot.
As can be seen that along with F in probe solution-The increase of concentration, fluorescence intensity gradually weaken, and in (0-60 μM) F-
In concentration range, F-Concentration and A596/A476It is linear.The suitable concentration of fluoride ion is 0.5~1.0mg/ in drinking-water
Therefore, L. probe of the invention can relatively accurately determine the content of fluorine ion in sample to be tested.
Embodiment 4
Fluorescence intensity of Fig. 3 different ions analyte (400 μM) to probe (10 μM).All measurements are all to measure at once,
Response time is especially fast.
Analyte includes: sulfurous acid hydrogen radical ion (HSO3 -), iodide ion (I-), sulfate ion (SO42-), bromide ion
(Br-), sulfite ion (SO3 2-), chloride ion (Cl-), nitrate ion (NO3 -), nitrite ion (NO2 -), phosphate radical
Ion (HPO4 -) and sulphion (S2-).Their concentration is 400 μM.All test conditions are completed in DMSO, used
Probe is probe prepared in embodiment 1, and all spectrum are all that analyte measures at once after being added at 25 DEG C.Specifically
Ground, the probe stock solution (1mM) for pipetting 50 μ L are put into 10mL colorimetric cylinder, 5mL DMSO are then added, then to pipette 20 μ L above-mentioned
Analyte stock solution (10mM) is added in colorimetric cylinder, is finally settled to 10mL with DMSO.It shakes up, measures immediately.As a result such as Fig. 3 institute
Show.
Can be seen that existing common ion in organism from Fig. 3 a, will not to significantly interfere with probe strong to the fluorescence of fluorine ion
Degree；Can be seen that existing common ion in organism from Fig. 3 b can not or can not significantly interfere with probe to the absorbance of fluorine ion,
Therefore probe has good selectivity.
Although with above embodiments describe the present invention, it should be appreciated that before without departing substantially from spirit of the invention
It puts, the present invention further can be modified and be changed, and these modifications and variation all belong to the scope of protection of the present invention it
It is interior.
Claims (9)
1. the kit for detecting content of fluoride ion in sample, it includes the compounds having following structure:
2. kit according to claim 1, wherein the sample is water sample sample.
3. kit described in any one of -2 according to claim 1 further includes operation instructions.
4. kit described in any one of -2 according to claim 1 further includes for detecting content of fluoride ion in sample
Buffer.
5. the method for detecting content of fluoride ion in sample comprising contact sample with the compound defined in claim 1.
6. according to the method described in claim 5, wherein the sample is water sample sample.
7. use of the compound in kit of the preparation for content of fluoride ion in test sample defined in claim 1
On the way.
8. purposes according to claim 7, wherein the sample is water sample sample.
9. purposes according to claim 7, wherein the kit further includes for detecting content of fluoride ion in sample
Buffer.
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| CN201510760191.6A CN105987892B (en) | 2015-11-10 | 2015-11-10 | Measure the method and its kit of fluorine ion |
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| CN201510760191.6A CN105987892B (en) | 2015-11-10 | 2015-11-10 | Measure the method and its kit of fluorine ion |
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| CN105987892A CN105987892A (en) | 2016-10-05 |
| CN105987892B true CN105987892B (en) | 2019-08-20 |
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| CN111943887B (en) * | 2020-09-11 | 2022-06-24 | 济南大学 | Fluorescent probe for high-selectivity recognition of phosphate, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1705881A (en) * | 2003-05-20 | 2005-12-07 | 原子能委员会 | Method for the detection of fluoride or hydrogen fluoride and detection kit |
| CN101153848A (en) * | 2007-10-10 | 2008-04-02 | 吉林大学 | Fluorescent ion probe and its application in ion detecting |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8828735B2 (en) * | 2012-06-21 | 2014-09-09 | Indian Institute Of Technology Madras | Visual detection of fluoride ions |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1705881A (en) * | 2003-05-20 | 2005-12-07 | 原子能委员会 | Method for the detection of fluoride or hydrogen fluoride and detection kit |
| CN101153848A (en) * | 2007-10-10 | 2008-04-02 | 吉林大学 | Fluorescent ion probe and its application in ion detecting |
Non-Patent Citations (2)
| Title |
|---|
| F-/OH- Triggered Optical Switching Functions of Naphthalimide Chromophoric Materials;Li，Xiaochuan 等;《Molecular Crystals and Liquid Crystals》;20141215;第604卷;第185页Experimental部分-第191页Results and Discussion部分 |
| 水中氟化物现场快速测试盒的研制;秦惠 等;《现代化工》;20110930;第31卷(第9期);前序部分-第2部分 |
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