CN1730485A - Fluorion sensing test paper for visual colorimetry and its uses - Google Patents
Fluorion sensing test paper for visual colorimetry and its uses Download PDFInfo
- Publication number
- CN1730485A CN1730485A CN200510041353.7A CN200510041353A CN1730485A CN 1730485 A CN1730485 A CN 1730485A CN 200510041353 A CN200510041353 A CN 200510041353A CN 1730485 A CN1730485 A CN 1730485A
- Authority
- CN
- China
- Prior art keywords
- fluorion
- solution
- title complex
- formula
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000000007 visual effect Effects 0.000 title claims abstract description 5
- 238000012360 testing method Methods 0.000 title claims description 37
- 238000004737 colorimetric analysis Methods 0.000 title abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 27
- 239000003446 ligand Substances 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 26
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000003419 tautomerization reaction Methods 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 35
- -1 2,4-dinitro phenyl hydrazone Chemical class 0.000 abstract description 12
- 238000001514 detection method Methods 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 22
- 150000002500 ions Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 208000004042 dental fluorosis Diseases 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 206010016818 Fluorosis Diseases 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 208000025636 skeletal fluorosis Diseases 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QPFYXYFORQJZEC-FOCLMDBBSA-N Phenazopyridine Chemical group NC1=NC(N)=CC=C1\N=N\C1=CC=CC=C1 QPFYXYFORQJZEC-FOCLMDBBSA-N 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 244000197975 Solidago virgaurea Species 0.000 description 1
- 235000000914 Solidago virgaurea Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Abstract
The invention discloses a high performance selection coloration compound, the fluorinion detection method and fluorinion reagent paper based on the compound, the compound being coordinated complex characterized by single (2,4-dinitro phenyl hydrazone,10-orthophenanthrolene-5,6-diketone ligand coordination, the compound can be used for the detection of fluorinion within the concentration range of 10-5M, wherein absorption spectrophotometry or naked eye visual colorimetry detections can be employed. The color change reagent paper made through impregnating the compound can appreciably detect fluorine ions whose concentration is below 10mg/L.
Description
Technical field
The invention belongs to the ion detection technical field of the compound formation of discerning combination and being used for optical detection negatively charged ion, positively charged ion and neutral ion, be specifically related to utilize compound for discerning the fluorion test paper of colour developing with metal-complexing functional group.
Background technology
Healthy most important to the people of the trace element in the water particularly in the environment.For example: the fluorine in the drinking-water, low fluorine water area children caries rate uprises, and water of high fluorine content area crowd's dental fluorosis, skeletal fluorosis morbidity increase.The severe fluorosis can cause allowing the very painful osteofluorosis of people.China's fluorosis has drinking water type, coal-burning and three types on the type of drinking tea.According to the investigation of 2005-07-22 lookout Newsweek, the patient of national dental fluorosis has people more than 100,000,000, and skeletal fluorosis patient has three or four thousand ten thousand, may cause that the regional population of poisoning has more than 400,000,000.
Fluorinion concentration can for the normal low developed area that takes place of fluorosis, be not suitable for the daily use of ordinary people more conveniently with the ion specific electrode test of opportunity lanthanum fluoride wafer.Set up a cover and be suitable for for example colouring reagents or the test paper that can differentiate of bore hole of testing method that the ordinary people can detect fluorine content of drinking water, for preventing that the fluorine chronic poisoning is extremely useful.
At the identification fluorion is the report that many fundamental researchs are arranged aspect the typical negatively charged ion, its mechanism is to have in the molecule to form hydrogen bond with negatively charged ion such as fluorion, and by cause with forming of hydrogen bond the system of gripping altogether variation produce the variation of spectral signal and reach anionic purposes such as detecting fluorine.Typical system has sapphyrins, cup pyrroles, polyamines, guanidine.U.S. Pat 6,482,949B1 has reported a kind of colorimetric sensor based on polypyrrole that detects fluorion, the sensing electrochromic compound is fixed on polyoxyethylene glycol, fluorion to the 4-butyl amine fluorine in the DMSO organic solvent has the colour-change response, the logarithm of the highest binding constant K to fluorine of report is log K=4.36, calculates that successively the fluorine concentration that can measure is 10
-3The M scope.Physical chemistry institute of the Chinese Academy of Sciences has delivered in nanometer organic photoelectric laboratory the colorimetric sensor principle of utilizing based on the C=N-NH group of hydrazone to the variable color response of fluorine in 2004, sensing electrochromic compound concentration is 10 in MeCN solution
-5During M, the fluorine of 100 times 4-butyl amine fluorine from selective colour developing, is inferred fluorine concentration successively 10
-3The M scope.(TetrahedronLetters 2001,42,5447-5449) delivered the colorimetric sensing fluorion device of azo-based phenolic group group, and the colour developing to the fluorion of 4-butyl amine fluorine in MeCN solution changes 10 for the Kwan Hee Lee of Korea S
-5The M scope.
Above method, be actually used in environment measuring especially for tap water in fluorion when detecting, can run into the concentration limit that detects fluorine and not reach the safe drinking water scope, and the deficiency that can not test with water sample.
The inventor finds to utilize a kind of metal complexes that has the phenazo group through research with keen determination, can and can make test paper in lower detectable level work, and the selectivity that is used for fluorion detects.
Summary of the invention
Purpose of the present invention provides a kind of selectivity to detect the color-developing compounds of fluorion, further provides a kind of and utilizes the method for this kind compound test fluorion and easy fluorion test paper, and can be directly used in the detection of water sample.
The objective of the invention is to be achieved through the following technical solutions.
At first found a kind of by formula 1 expression fluorion is had the coordination compound of high efficiency selected colour developing,
[L
1]
a(L
2)
bM] A
cFormula 1, in the formula 1, a=0-2, b=1-3, a+b=3, M are the thulium of divalence, and A is that A is a negatively charged ion, and c gets 1,2, makes charge balance, L
1For nitrogen-atoms and/or Sauerstoffatom are the bitooth ligand of ligating atom, L
2Part for formula 2 exists with tautomerism,
When forming metal complexes, as long as L
1The part that metallic ion coordination is formed more stable coordination compound get final product, can be the part of bidentate, three teeth or four teeth, and bitooth ligand is better usually, and ligating atom can nitrogen-atoms, sulphur atom, Sauerstoffatom, and what common market can get gets final product.Consider the stability and the fluorescence intensity of title complex, part can select to have the part of aromatic ring, and for example 2,2-dipyridyl, parts such as phenanthrolene.Central metallic ions M be usually as long as can form stable title complex, because the formation title complex promotes sensitivity that fluorion is developed the color, can select from testing.Usually select rare earth metal better, can also utilize its change in fluorescence to detect, concrete example has ruthenium, europium, and rhodium, the divalent-metal ion of palladium etc., wherein the OPTICAL PROPERTIES of the title complex of ruthenium is detailed, selects ruthenium better.As long as negatively charged ion A wherein satisfies charge balance and the colour developing of later fluorion is not produced detrimentally affect, consider the synthetic and purifying that in organic solvent, carries out compound, it is better to be chosen in the organic solvent dissolved salt anionoid, for example hexafluoro-phosphate radical (PF
6 -).
This compounds is characterised in that wherein have a part at least, i.e. L in the formula 1
2Be the part of formula 2, in solution, exist with pure keto tautomer.
This compounds is when interacting colour developing with fluorion, mainly in ligand L
2The interaction of last generation and fluorion, the variation of this part can be expressed as:
Because fluorion (F
-) form hydrogen bond with proton, cause the variation of electron distributions in the molecule and colour-change takes place, reach the purpose that detects fluorion.Chlorion, bromide anion, iodide ion, hydrogen sulfate ion, nitrate ion, dihydrogen phosphate ions etc. can not cause colour-change with its effect.
Title complex can at first contain 1 according to document is synthetic, 10-phenanthrolene-5, the title complex of 6-diketone and other parts, for example two (2,2 '-dipyridyl) (1,10-phenanthrolene-5, the 6-diketone) closes ruthenium, react direct acquisition coordination compound of the present invention with it with 2,4 dinitrophenyl hydrazine, for example, 2 L
1Be 2,2 '-dipyridyl and a L
2Ruthenium complexe for formula 2.This moment 1,10-phenanthrolene-5,6-diketone and 2,4 dinitrophenyl hydrazine reaction have generated feature ligand L used in the present invention
2Ligand L
2Synthetic also can synthesize or from for example Aldrich acquisition of supplier according to document reminding method (Aust.J.Chem.1970,23,1023).
The structure of synthetic coordination compound usually can be by ultimate analysis, mass spectrum, nucleus magnetic resonance, and ultraviolet-visible absorption spectroscopy characterizes.
The second, compound of the present invention can be made into organic solution, and the selectivity colorimetric that is used for fluorion detects.Generally with coordination compound of the present invention, 2 L in the formula 1 for example
1Be two (2,2 '-dipyridyl) and a L
2Ruthenium complexe for formula 2 is dissolved in organic solvent, is made into finite concentration.As long as this organic solvent can dissolve such coordination compound and be beneficial to dissolving sample to be tested, can use methyl-sulphoxide (DMSO) easily, acetonitriles (MeCN) etc. are as solvent.Concentration can determine that for compound of the present invention, can be made into volumetric molar concentration is 10 according to test condition and colour-change degree
-3-10
-6M, the concentration of conventional testing method can be made into 10
-4-10
-5M.Test concentrations after the sample of the fluoride ion to be measured of test adds is 10
-6-10
-3M is better, and 10
-5-10
-4The M scope is better.Concrete test can utilize the standard working curve method, or directly uses the bore hole visual colorimetry to extrapolate fluorine concentration.In order to obtain sensitiveer correct result, can adopt absorption spectrophotometry, fluorophotometric method to test.
The 3rd, coordination compound of the present invention can be made the test paper of testing fluorion easily.Coordination compound of the present invention can be mixed with certain density solution, for example filter paper of usefulness is usually soaked in this solution.Can use methyl-sulphoxide (DMSO) easily, acetonitrile (MeCN) etc. are as solvent, and strength of solution can be prepared according to the variable color degree of the test paper of making, and is generally 5 * 10
-4-10
-2M is preferably 1 * 10
-3-9 * 10
-3M, infiltrating time needn't limit especially, and the general several seconds gets final product, then airing in air.Also can repeatedly soak into airing so that the variable color of test paper is obvious.Make test paper color color change difference can make Standard colour board according to different fluorine content,, treat water sample behind airing on the test paper, judge that according to the color of colour-change the content of fluorine is better as pH test paper test water solution.
In sum, technique effect of the present invention is tangible.Coordination compound of the present invention has good selectivity identification to fluorion, and can be to the special colour developing of low dose fluoride sample, use method of the present invention, bore hole can be differentiated, and also can adopt absorption spectrophotometry and fluorophotometric method to carry out more sensitive test, fluorine test paper of the present invention, easy to use, differentiate succinctly, cheap, be fit to the daily use of economically underdeveloped area.
Description of drawings
The acetonitrile solution (2.5 * 10 of the result of Fig. 1 embodiment 3: embodiment 2 compounds
-5M) variation that adds the absorption spectrum of various anionic equivalent mole 4-butyl amine salts solutions in.
The acetonitrile solution (2.5 * 10 of the result of Fig. 2 embodiment 3: embodiment 2 compounds
-5M) variation that adds the fluorescence spectrum of various anionic equivalent mole 4-butyl amine salts solutions in.
The acetonitrile solution (2.5 * 10 of the result of Fig. 3 embodiment 4: embodiment 2 compounds
-5Absorption spectrum when dripping 4-butyl amine fluorine solution M) changes, and arrow is represented to absorb the direction that changes along with dripping among the figure.
The fluorion equivalent of the adding of Fig. 4 Fig. 3 correspondence and the variation of absorption value.
Fig. 5 embodiment 7 test paper are tested the colour-change result (color has become the figure of different gray tones in the drawings) of different fluorine concentration of aqueous solution.
Embodiment
In order to be illustrated more clearly in content of the present invention, be described as follows with specific embodiment, specific embodiment does not limit context of the present invention.
Embodiment 1 (synthesizing of coordination compound)
With 0.538 gram Ru (bpy)
2Cl
23H
2O (1 mmole), 0.243 gram 1,10-phenanthrolene-5,6-diketone (1 mmole) adds and contains 30 milliliters of ethanol and 30 milliliters of H
2In the mixed solvent of O, under nitrogen atmosphere, refluxed 3 hours, be concentrated into 20 milliliters, add KPF
6Saturated aqueous solution, separate out brown precipitate, leach washing with alcohol final vacuum drying.Productive rate 80%.(bpy=2,2-dipyridyl).
Embodiment 2 (synthesizing of coordination compound)
With 2 of 0.198 gram (1 mmole), title complex 0.9 gram (1 mmole) of 4-dinitrophenylhydrazine, embodiment 1 joins in the alcoholic acid mixing solutions of 25 milliliters acetonitrile containing 5 milliliters of phosphoric acid and 25 milliliters, in nitrogen atmosphere, refluxed 8 hours, be concentrated into 5 milliliters, add 100 milliliters of ethanolic solns, separate out red-purple precipitation, filter and with washing with alcohol three times.Precipitation is dissolved in 5 ml waters, adds KPF
6The aqueous solution, separate out red-purple precipitation, leach washing with alcohol final vacuum drying, productive rate 60%.Ultimate analysis (C
10H
8N
2)
2Ru (C
18H
10N
6O
5) (PF
6)
2Value is C, 41.6; H, 2.5; N, 12.7%, theoretical value is C, 41.7; H, 2.4; N, 12.8%.Nuclear magnetic resonance spectroscopy
1H NMR (500MHz, CD
3CN), δ (ppm): 9.11 (br, 1H ,-NH), 8.97 (br, 1H, H
a), 8.74 (d, 1H, H
6), 8.52 (m, 6H, H
b, H
6' and bipy), 8.05 (m, 7H, H
c, H
4, H
4' and bipy), 7.68 (m, 4H, bipy), 7.58 (t, 1H, H
5), 7.53 (t, 1H, H
5'), 7.37 (m, 2H, bipy), 7.32 (m, 2H, bipy).Electrospray ionization mass spectrum m/z=803.1 and 948.9, ownership is [Ru (bpy) respectively
2L]
+[Ru (bpy)
2(HL) (PF
6)]
+
Embodiment 3 (selectivity experiment)
The acetonitrile solution (2.5 * 10 of the compound of preparation embodiment 2
-5M), add F respectively
-, Cl
-, Br
-, I
-, HSO
4 -, NO
3 -, H
2PO
4 -The 4-butyl amine salts solution, measure absorption spectrum such as Fig. 1 and fluorescence spectrum such as Fig. 2.The compound of expression embodiment 2 is to F
-Ion has good selectivity.
Embodiment 4 (color reaction)
Take by weighing compound 0.0137 gram of embodiment 2, be dissolved in acetonitrile, be mixed with 5 * 10 with the 25ML volumetric flask
-4M gets 1.25 milliliters and is diluted to 25 milliliters and is made into 2.5 * 10
-5The standard inventory solution (L) of M.Take by weighing 4-butyl amine fluorine 0.1464 gram, be dissolved in acetonitrile, be mixed with 2.5 * 10 with the 10ML volumetric flask
-2The standard inventory solution (F) of M.Measure stock solution L2.5 milliliter, add the stock solution F of calculated amount, be mixed with standard testing solution, measure absorption value at the 582nm place.Test result such as Fig. 3 and Fig. 4.Calculate the compound of embodiment 2 and the binding constant of fluorion is log K=6.23+0.03 with nonlinear least square method.
Embodiment 5 (test)
With working curve at embodiment 4, add replacement stock solution F with sample to be tested (the our unit laboratory is water sample from the beginning), the 582nm place measures absorption value, calculates fluorine content from working curve, 2.5 * 10
-6Below the M (0.05 mg/litre).
Embodiment 6 (preparation of test paper)
2.0 * 10 of the compound of preparation embodiment 2
-3The acetonitrile solution of M is cut into 3 * 0.5 square centimeters with filter paper, immerses wherein 2 seconds, takes out airing in air.
Embodiment 7 (trying out of test paper)
Test paper dipped in get the aqueous solution that concentration is respectively blank, 10 milligrams, 0.1 milligram of every liter of fluoride ion and 1 gram.Colour-change is changed to gold (10 milligrams) respectively from golden rod (blank), and sap green (0.1 milligram) and naval's look (1 gram) be (color is because the black and white original text has become gray tone among the figure) as shown in Figure 5.
Claims (8)
1, a kind of title complex of formula 1,
[L
1]
a(L
2)
bM] A
cFormula 1,
In the formula 1, a=0-2, b=1-3, a+b=3, M are the thulium of divalence, and A is a negatively charged ion, and c gets 1,2, makes charge balance, L
1For nitrogen-atoms and/or Sauerstoffatom are the bitooth ligand of ligating atom, L
2Part for formula 2 exists with tautomerism,
2, a kind of title complex of claim 1, wherein L1 is selected from phenanthrolene, and 2, the 2-dipyridyl, ethamine a kind of, M is selected from a kind of positive divalent ion of ruthenium, europium, rhodium, palladium.
3, a kind of title complex of claim 2, wherein L
1Be 2,2-dipyridyl, M are divalent ruthenium, a=2, b=1.
4, a kind of title complex of claim 3, wherein A is hexafluoro-phosphate radical PF
6 -
5, the method for fluorion in a kind of complexes measuring solution that utilizes one of claim 1 to 4, may further comprise the steps: the title complex of one of claim 1 to 4 is made into organic solution, and its concentration is 1 * 10
-5To 1 * 10
-4M gets a certain amount ofly, and fluorine-containing solution to be measured is got a certain amount of adding, according to the colour-change visual colorimetric determination or measure the solution absorption degree, extrapolates fluorine content.
6, the method for fluorion in a kind of mensuration solution of claim 5, wherein organic solvent is selected from acetonitrile, dimethyl sulfoxide (DMSO), a kind of or mixed solvent of tetrahydrofuran (THF).
7, a kind of fluorion that soaks the title complex that contains one of right requirement 1 to 4 is measured test paper, makes by may further comprise the steps: the title complex of one of claim 1 to 4 is made into organic solution, paper is dipped in wherein, take out airing in air.
8, a kind of method of utilizing the test paper mensuration fluorinion concentration of claim 7 may further comprise the steps: the test paper of claim 7 contacted with solution to be tested, and airing in air, relatively colour-change is calculated fluorine content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100413537A CN100344641C (en) | 2005-08-05 | 2005-08-05 | Fluorion sensing test paper for visual colorimetry and its uses |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100413537A CN100344641C (en) | 2005-08-05 | 2005-08-05 | Fluorion sensing test paper for visual colorimetry and its uses |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1730485A true CN1730485A (en) | 2006-02-08 |
| CN100344641C CN100344641C (en) | 2007-10-24 |
Family
ID=35962910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100413537A Expired - Fee Related CN100344641C (en) | 2005-08-05 | 2005-08-05 | Fluorion sensing test paper for visual colorimetry and its uses |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100344641C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101806744A (en) * | 2010-03-29 | 2010-08-18 | 河海大学 | Method for rapid analysis of fluoride through flowing injection and device thereof |
| CN102466635A (en) * | 2010-11-17 | 2012-05-23 | 中国科学院化学研究所 | Application of oxazole compound in fluoride ion detection |
| CN104277065A (en) * | 2014-09-02 | 2015-01-14 | 北京师范大学 | Complex, preparation method thereof, fluorine ion sensor and method for detecting fluorine ion |
| CN104277010A (en) * | 2014-09-02 | 2015-01-14 | 北京师范大学 | Compound and preparation method thereof, fluoride ion sensor and fluorine ion detection method |
| CN105158181A (en) * | 2015-08-27 | 2015-12-16 | 晋江尚京富本环保科技有限公司 | Kit for detecting fluoride ions |
| CN105699342A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | A method of measuring an oxygen atom concentration by utilizing a titration technology |
| CN110006878A (en) * | 2018-01-04 | 2019-07-12 | 南京江原安迪科正电子研究发展有限公司 | A kind of calibrating Na18The coloration method and kit of fluorinion concentration limit in F injection |
-
2005
- 2005-08-05 CN CNB2005100413537A patent/CN100344641C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101806744A (en) * | 2010-03-29 | 2010-08-18 | 河海大学 | Method for rapid analysis of fluoride through flowing injection and device thereof |
| CN101806744B (en) * | 2010-03-29 | 2012-05-23 | 河海大学 | Method for rapid analysis of fluoride through flowing injection and device thereof |
| CN102466635A (en) * | 2010-11-17 | 2012-05-23 | 中国科学院化学研究所 | Application of oxazole compound in fluoride ion detection |
| CN102466635B (en) * | 2010-11-17 | 2013-08-21 | 中国科学院化学研究所 | Application of oxazole compound in fluoride ion detection |
| CN104277065B (en) * | 2014-09-02 | 2016-08-24 | 北京师范大学 | Coordination compound, its preparation method, fluorine ion sensing device and the method for detection fluorion |
| CN104277010A (en) * | 2014-09-02 | 2015-01-14 | 北京师范大学 | Compound and preparation method thereof, fluoride ion sensor and fluorine ion detection method |
| CN104277010B (en) * | 2014-09-02 | 2016-07-27 | 北京师范大学 | Compound, its preparation method, fluorine ion sensing device and the method for detection fluorion |
| CN104277065A (en) * | 2014-09-02 | 2015-01-14 | 北京师范大学 | Complex, preparation method thereof, fluorine ion sensor and method for detecting fluorine ion |
| CN105699342A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | A method of measuring an oxygen atom concentration by utilizing a titration technology |
| CN105699342B (en) * | 2014-11-28 | 2018-04-06 | 中国科学院大连化学物理研究所 | A kind of method that concentration of oxygen atoms is measured using titration technique |
| CN105158181A (en) * | 2015-08-27 | 2015-12-16 | 晋江尚京富本环保科技有限公司 | Kit for detecting fluoride ions |
| CN105158181B (en) * | 2015-08-27 | 2017-11-07 | 晋江尚京富本环保科技有限公司 | Detect the kit of fluorine ion |
| CN110006878A (en) * | 2018-01-04 | 2019-07-12 | 南京江原安迪科正电子研究发展有限公司 | A kind of calibrating Na18The coloration method and kit of fluorinion concentration limit in F injection |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100344641C (en) | 2007-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100344641C (en) | Fluorion sensing test paper for visual colorimetry and its uses | |
| Shellaiah et al. | Novel pyrene-and anthracene-based Schiff base derivatives as Cu 2+ and Fe 3+ fluorescence turn-on sensors and for aggregation induced emissions | |
| Cimerman et al. | The Schiff bases of salicylaldehyde and aminopyridines as highly sensitive analytical reagents | |
| Werner et al. | Novel optical pH-sensor based on a boradiaza-indacene derivative | |
| Prodi et al. | A fluorescent sensor for magnesium ions | |
| Rabenstein et al. | Nuclear magnetic resonance studies of the solution chemistry of metal complexes. 21. The complexation of zinc by glycylhistidine and alanylhistidine peptides | |
| Baglan et al. | Selective and sensitive turn-on fluorescent sensing of arsenite based on cysteine fused tetraphenylethene with AIE characteristics in aqueous media | |
| CN101135644B (en) | Mercury ion fluorescent color-developing agent and detecting method | |
| Farhi et al. | A quinoline-based fluorescent probe for selective detection and real-time monitoring of copper ions–a differential colorimetric approach | |
| Blaser et al. | Spectrofluorometric investigation of trace metal complexation by an aqueous chestnut leaf litter extract | |
| Kursunlu et al. | Cu (II) chemosensor based on a fluorogenic bodipy-salophen combination: sensitivity and selectivity studies | |
| CN103411943B (en) | Method for detecting Ag<+1>, Hg<2+> and Fe<3+> based on fluorescence quenching method or colorimetric method of erythrosine B | |
| Barghouthi et al. | Spectrophotometric determination of fluoride in drinking water using aluminium complexes of triphenylmethane dyes | |
| CN100483113C (en) | Visual colorimetric fluorine ion sensing test-paper and use thereof | |
| Nardo et al. | Spectroscopic evidence for the coordination of oxygen donor ligands to tetraphenylporphinatozinc | |
| Li et al. | A fluorescent chemosensor for cobalt ions based on a multi-substituted phenol-ruthenium (II) tris (bipyridine) complex | |
| CN107540681B (en) | Probe and its application used in a kind of multiple target ion detection | |
| Sarma et al. | A rapid and sensitive extractive spectrophotometric determination of palladium (II) in synthetic mixtures and hydrogenation catalysts using pyridoxal-4-phenyl-3-thiosemicarbazone | |
| CN103323443A (en) | Application of infinite coordination polymer with visual alcoholic strength sensing function | |
| de la Riva et al. | Determination of trace levels of mercury in water samples based on room temperature phosphorescence energy transfer | |
| Schuster et al. | N-Dansyl-N′-ethylthiourea for the fluorometric detection of heavy metal ions | |
| CN106967420B (en) | Cross-linked chitosan fluorescent probe material and preparation method and application thereof | |
| CN107727620B (en) | Kit for detecting nitrite ions and application thereof | |
| CN108822118B (en) | Fluorescein derivative ultraviolet sensor and method for detecting nickel ions | |
| CN106366087A (en) | 4-(dimethylamino)-benzaldehyde-rhodamine B acylhydrazone condensation product and its preparation method and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Hubei Neptune Environmental Engineering Co., Ltd. Assignor: Nanjing University Contract record no.: 2010320001116 Denomination of invention: Fluorion sensing test paper for visual colorimetry and its uses Granted publication date: 20071024 License type: Exclusive License Open date: 20060208 Record date: 20100908 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071024 Termination date: 20110805 |