CN100483113C - Visual colorimetric fluorine ion sensing test-paper and use thereof - Google Patents
Visual colorimetric fluorine ion sensing test-paper and use thereof Download PDFInfo
- Publication number
- CN100483113C CN100483113C CNB2006100382548A CN200610038254A CN100483113C CN 100483113 C CN100483113 C CN 100483113C CN B2006100382548 A CNB2006100382548 A CN B2006100382548A CN 200610038254 A CN200610038254 A CN 200610038254A CN 100483113 C CN100483113 C CN 100483113C
- Authority
- CN
- China
- Prior art keywords
- fluorine
- solution
- test paper
- testing
- fluorine ion
- 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.)
- Expired - Fee Related
Links
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 36
- 230000000007 visual effect Effects 0.000 title claims abstract description 6
- 238000012360 testing method Methods 0.000 claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- 239000011737 fluorine Substances 0.000 claims abstract description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 238000010998 test method Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 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
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 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
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- 238000002835 absorbance Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 35
- 238000001514 detection method Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000003651 drinking water Substances 0.000 abstract description 5
- 238000004737 colorimetric analysis Methods 0.000 abstract description 2
- 235000020188 drinking water Nutrition 0.000 abstract description 2
- 238000002845 discoloration Methods 0.000 abstract 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 abstract 1
- 238000011835 investigation Methods 0.000 abstract 1
- 238000005375 photometry Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- -1 4-butyl Chemical group 0.000 description 4
- YKWHBPOLZPQBPG-UHFFFAOYSA-N C1(C=CC=C2C3=CC=CC=C3C=C12)=O.[N] Chemical class C1(C=CC=C2C3=CC=CC=C3C=C12)=O.[N] YKWHBPOLZPQBPG-UHFFFAOYSA-N 0.000 description 4
- 206010016818 Fluorosis Diseases 0.000 description 4
- 208000004042 dental fluorosis Diseases 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- 239000012327 Ruthenium complex Substances 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000012206 bottled water Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 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
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 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 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 208000002064 Dental Plaque Diseases 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage 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
- 238000009826 distribution Methods 0.000 description 1
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 208000014674 injury Diseases 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
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000003908 quality control method Methods 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
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Landscapes
- 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
Present Invention discloses high efficiency selected development compound fluorine ion detection method and test paper based on identifying naked eye visual investigation combination. Said compound use 2, 4-binitro phenylhydrazones-4, 5-dihetero fluorenone ligand coordination as characteristic coordination compound, said compound selectivity detection to fluorine ion in 10-5concentration range, capable of using absorption photometry and naked eye visual colorimetry to detect. Discoloration test paper made from compound can detect fluorine ion concentration low to 1 ppm. Said inventive test paper has simple making, convenient detect, visual, in favor of habitualness detect of fluorine content in drinking water.
Description
Technical field
The invention belongs to the identification combination and be used for the ion detection technical field that the anionic compound of optical detection constitutes, be specifically related to utilize compound for discerning the fluorine ion test paper of colour developing with metal-complexing functional group.
Background technology
In the environment particularly the Trace Fluoride element in the water have grievous injury people's health.Fluorine in the drinking-water, low fluorine water area children caries rate uprises, and high-fluorine water area crowd's fluorine dental plaque, fluorosis of bone morbidity rate increase.The severe fluorosis can cause allowing the very painful fluorosis of bone of people.
Fluorinion concentration can use the fluoride ion selective electrode test more conveniently, but for the normal low developed area that takes place of fluorosis, is not suitable for the daily use of general citizen.The inventor is on the basis of carrying out a series of researchs, invented and contained the detection test paper that a kind of metal complex that has the phenazo group is made, can detect the detection test paper (Chinese patent application number: 200510041353.7) of 10ppm concentration, particularly obtain progress aspect the use of rural area suitable general citizen, but be difficult to detect the 1ppm concentration requirement of the security reference water quality standard defined of World Health Organization's regulation.
The inventor finds to utilize the another kind of metal complex that has azo group again through research with keen determination, can and can make test paper in lower detectable concentration work, and the selectivity that is used for fluorine ion detects.
Summary of the invention
Purpose of the present invention provides a kind of color-developing compounds that utilizes selectivity to detect fluorine ion to detect the method for fluorine ion and easy fluorine ion test paper, and can be directly used in the detection that water sample is used in particular for potable water.
The objective of the invention is to be achieved through the following technical solutions:
Find that at first a kind of coordination compound by formula 1 expression has high efficiency selected colour developing character to fluorine ion.
[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 negative ion, and c gets 1,2, makes charge balance, L
1For nitrogen-atoms and/or oxygen atom are the bidentate ligand of coordination atom, L
2Be the part of formula 2,,
This metal complexes, wherein L
1As long as metallic ion coordination is formed the part of more stable coordination compound, can be the part of bidentate, three teeth or four teeth, bidentate ligand is better usually, and coordination atom can nitrogen-atoms, sulphur atom, oxygen atom, and what common market can get gets final product.Consider stability, absorption and the fluorescence intensity of complex, part can select to have the part of aromatic ring, and for example 2,2-dipyridine, parts such as phenanthrolene.Central metallic ions M be usually as long as can form stable complex, because the formation complex promotes sensitivity that fluorine ion 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 bivalent metal ion of palladium etc., wherein the OPTICAL PROPERTIES of the complex of ruthenium is detailed, selects ruthenium better.As long as negative ion A wherein satisfies charge balance and the colour developing of later fluorine ion is not produced harmful effect, consider the synthetic and purifying that in organic solvent, carries out compound, it is better to be chosen in the salt anionoid that dissolves in the organic solvent, 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
2Part for formula 2.
This compounds is when interacting colour developing with fluorine ion, mainly in ligand L
2Last generation proton and fluorine ion (F
-) fluorine ion interact to form hydrogen bond, causes the variation of electron distributions in the molecule and change color takes place, and reaches the purpose that detects fluorine ion.Chlorion, bromide ion, iodide ion, hydrogen sulfate ion, nitrate ion etc. can not cause change color with its effect, and dihydrogen phosphate ions and its effect easily form precipitation.
Itself can synthesize part and complex according to bibliographical information.Ligand L
2Can be according to document from 4,5-two assorted nitrogen Fluorenones synthetic (Chemistry Letters (2004), 33 (1), 78-79., structural chemistry (2002), 21 (3), 249-251) or from supplier for example Aldrich obtain ligand L
1Can for example Aldrich acquisition from market.Complex can be according to document, the synthetic complex that contains 4,5-two assorted nitrogen Fluorenones and other parts, for example 2,2 '-dipyridine, 1,10-phenanthrolene-5, the 6-diketone (natural science newspaper (1996), 35 (6), 19-22.) close ruthenium, with 2, the 4-dinitrophenylhydrazine reacts direct acquisition coordination compound of the present invention with it, for example, and 2 L
1Be 2,2 '-dipyridine and the ruthenium complex that L2 is a formula 2.This moments 4,5-two, assorted nitrogen Fluorenone and 2,4 dinitrophenyl hydrazine reaction generated feature ligand L used in the present invention
2
The structure of synthetic coordination compound usually can be by ultimate analysis, mass spectrum, nuclear magnetic resonance, and ultraviolet-visible absorption spectroscopy characterizes.
The present invention has found that such complex has good selective coloration effect to fluorine ion.
The second, the developer coordination compound that the present invention finds can be made into organic solution, and the selectivity colorimetric that is used for fluorine ion detects.General coordination compound, for example 2 L in the formula 1 with indication of the present invention
1Be two (2,2 '-dipyridine) and a L
2Ruthenium complex 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 acetonitrile (MeCN) easily, dimethyl sulfoxides (DMSO) etc. are as solvent.Concentration can determine according to test condition and change color degree, for method of the present invention, and coordination compound, can be made into volumetric molar concentration is 10
-3-10
-6M, the concentration of conventional method of testing can be made into 10
-4-10
-5M.In this solution, add the acidity stabilizing agent for well, for example add p-methyl benzenesulfonic acid, common concentration be adjusted at complex in L
2The concentration molar ratio be 0.8-1.1:1 for well, 1:1 is better.Test concentrations after the sample of fluoride ion to be measured 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 absorptiometry, fluorophotometric method to test.
The 3rd, utilize the present invention to find the coordination compound of indication, can make the test paper of testing fluorine ion easily.The coordination compound of indication 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 acetonitrile (MeCN) easily, dimethyl sulfoxide (DMSO) etc. are as solvent, and solution concentration can be prepared according to the variable color degree of the test paper of making, and is generally 5 x 10
-4-10
-2M is preferably 1 x 10
-3-9 x 10
-3M, infiltrating time needn't limit especially, and the general several seconds gets final product, and airing or additive method make solvent evaporates then.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 change color the content of fluorine is better as pH test paper test water solution.
The fluorine of the potable water of World Health Organization's regulation allows that amount is 1ppm.Use the test paper of fluorine ion of the present invention, when the fluorine amount was 1ppm in the water outlet to be detected, having tangible colour developing to send out should.Therefore the quality control that utilizes test paper of the present invention can carry out potable water easily detects.
In sum, technique effect of the present invention is tangible.The used coordination compound of the present invention has good selectivity identification to fluorine ion, 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 sensitiveer 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 of the result of Fig. 1 embodiment 2: embodiment 1 coordination compound and p-toluenesulfonic acid (1:1) (5 x 10
-5M) change color that adds various anionic 4-butyl amine salt solusions in.Anionic kind from left to right order is: blank, 1 equivalent fluorine ion, 10 equivalent H
2PO
4 -, 20 equivalent Cl
-, Br
-, I
-, HSO
4 -, NO
3 -Equivalent refers to the equivalent with coordination compound.
The acetonitrile solution of the result of Fig. 2 embodiment 2: embodiment 1 coordination compound and p-toluenesulfonic acid (1:1) (5 x 10
-5M) absorption spectrum that adds various anionic 4-butyl amine salt solusions in.Wherein anionic kind concentration is respectively: fluorine ion 1 equivalent, H
2PO
4 -Ion 10 equivalents, Cl
-, Br
-, I
-, HSO
4 -, NO
3 -Ion 20 equivalents.Equivalent refers to the equivalent with coordination compound.
The acetonitrile solution of the result of Fig. 3 embodiment 2: embodiment 1 coordination compound and p-toluenesulfonic acid (1:1) (5 x 10
-5M) fluorescence spectrum that adds various anionic 4-butyl amine salt solusions in.Wherein anionic kind concentration is respectively: fluorine ion 1 equivalent, H
2PO
4 -Ion 10 equivalents, Cl
-, Br
-, I
-, HSO
4 -, NO
3 -Ion 20 equivalents.Equivalent refers to the equivalent with coordination compound.
The acetonitrile solution of the result of Fig. 4 embodiment 3: embodiment 1 coordination compound and p-toluenesulfonic acid (1:1) (2.5 x 10
-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 acetonitrile solution of the result of Fig. 5 embodiment 3: embodiment 1 coordination compound and p-toluenesulfonic acid (1:1) (2.5 x 10
-5Fluorescence spectrum when dripping 4-butyl amine fluorine solution (the other numeral equivalents of arrow among the figure) M) changes.
The fluorine ion equivalent of the adding of Fig. 6 Fig. 4 correspondence and the variation of absorption value.
Fig. 7 embodiment 6 test paper are tested the change color 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, the synthetic method of the present invention's improvement)
With 2 of 0.238 gram (1.2 mM), 4-dinitrophenylhydrazine, two (dipyridine) (4,5-two assorted nitrogen Fluorenones) ruthenium complex 0.88 gram (1 mM) joins in the mixed solution of ethanol of 25 milliliters acetonitrile containing 5 milliliters of phosphoric acid and 25 milliliters, in nitrogen atmosphere, refluxed 8 hours, and be concentrated into 5 milliliters, add 100 milliliters of ethanolic solutions, separate out the brown precipitation, filter and wash three times with ethanol.Precipitation is dissolved in 5 ml waters, adds KPF
6Aqueous solution, separate out furvous precipitation, leach ethanol washing final vacuum drying, productive rate 60%.Ultimate analysis (C
10H
8N
2)
2Ru (C
17H
10N
6O
5) (PF
6)
2Value is C, 41.6; H, 2.6; N, 13.2%, theoretical value is C, 41.7; H, 2.4; N, 13.1%.Nuclear magnetic resonance spectroscopy
1H NMR (500MHz, CD
3CN, T-toluene sulfonic acid), δ (ppm): 8.96 (s, 1H), 8.46 (m, 6H), 8.29 (d, 2H), 8.02 (m, 6H), 7.83 (m, 2H), 7.63 (d, 1H), 7.61 (t, 2H), 7.49 (t, 1H), 7.37 (m, 4H).Electrospray ionization mass spectrum m/z=388.3 and 775.3..
Embodiment 2 (selectivity experiment)
The complex compound of preparation embodiment 1 and acetonitrile solution (5 x 10 of p-toluenesulfonic acid (1:1)
-5M), the F that adds 1 equivalent respectively
-, the H of 10 equivalents
2PO
4 -, the Cl of 20 equivalents
-, Br
-, I
-, HSO
4 -, NO
3 -The 4-butyl amine salt solusion, obtain change color (accompanying drawing 1) and also measure absorption spectrum (accompanying drawing 2) and fluorescence spectrum (accompanying drawing 3): have obvious color to change to fluorine ion, measure H 10 times
2PO
4 -Certain variation is arranged, to the Cl of 20 times of amounts
-, Br
-, I
-, HSO
4 -, NO
3 -Do not see significant change color.
Embodiment 3 (chromogenic reaction)
The coordination compound of preparation embodiment 1 and the acetonitrile solution of p-toluenesulfonic acid (1:1), preparation 4-butyl amine fluorine solution mixes two solution, and the concentration that makes coordination compound solution is 1 x 10
-5M, the fluorine concentration change records visible ultraviolet spectrum (Fig. 4) and fluorescence spectrum (Fig. 5).Measure absorption value at the 580nm place and change (Fig. 6).Calculate the coordination compound of embodiment 1 and the binding constant of fluorine ion is log K=6.71 ± 0.04 with nonlinear least square method.
Embodiment 4 (test)
With working curve at embodiment 3, add replacement stock solution F with sample to be tested (the our unit laboratory is water sample from the beginning), the 580nm place measures absorption value, calculates fluorinated volume from working curve, at 2.5 x 10
-6Below the M (0.05 mg/litre).
Embodiment 5 (preparation of test paper)
The compound of preparation embodiment 1 and 2.0 x 10 of p-toluenesulfonic acid (1:1)
-3The acetonitrile solution of M with filter paper (0.5 square centimeter of 3 x), immersed wherein 2 seconds, took out airing in air.
Embodiment 6 (trying out of test paper)
Test paper is immersed concentration to be respectively in the aqueous solution of blank, every liter of fluoride ion 1 gram, 0.1 gram, 10 milligrams and 1 milligram and to take out airing after 5 seconds.Change color is changed to peace green (1 milligram) respectively from bright green (blank), and green (10 milligrams), celadon (0.1 gram) and light color (1 gram) are shown (color is because the black and white original text has become gray tone among the figure) as Fig. 7.
Claims (8)
1, the colour developing method of testing of fluorine ion in a kind of solution is characterized in that developer is the 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 negative ion, and c gets 1,2, makes charge balance, L
1For nitrogen-atoms and/or oxygen atom are the bidentate ligand of coordination atom, L
2Be the part of formula 2,
2, a kind of method of testing of claim 1, wherein L
1Be selected from phenanthrolene, 2, the 2-dipyridine, ethamine a kind of, M is selected from a kind of positive divalent ion of ruthenium, europium, rhodium, palladium.
3, a kind of method of testing of claim 2, wherein L
1Be 2,2-dipyridine, M are divalent ruthenium, a=2, b=1.
4, a kind of method of testing of claim 3, wherein A is hexafluoro-phosphate radical PF
6 -
5, the method for testing of one of a kind of claim 1 to 4 may further comprise the steps: the developer complex of one of claim 1 to 4 is made into organic solution, and its concentration is 1 x 10
-5To 1 x 10
-4M gets a certain amount ofly, and fluorine-containing solution to be measured is got a certain amount of adding, according to the change color visual colorimetric determination or measure the solution absorbance log, extrapolates fluorine content.
6, a kind of method of testing of claim 5, wherein organic solvent is selected from acetonitrile, dimethyl sulfoxide (DMSO), a kind of or mixed solvent of tetrahydrofuran.
7, the colour developing of fluorine ion test is made by may further comprise the steps with measuring test paper in a kind of solution: the developer complex of one of claim 1 to 4 is made into organic solution, paper is dipped in wherein, take out dry.
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 drying, relatively change color is calculated fluorine content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100382548A CN100483113C (en) | 2006-02-13 | 2006-02-13 | Visual colorimetric fluorine ion sensing test-paper and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100382548A CN100483113C (en) | 2006-02-13 | 2006-02-13 | Visual colorimetric fluorine ion sensing test-paper and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1815201A CN1815201A (en) | 2006-08-09 |
| CN100483113C true CN100483113C (en) | 2009-04-29 |
Family
ID=36907490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100382548A Expired - Fee Related CN100483113C (en) | 2006-02-13 | 2006-02-13 | Visual colorimetric fluorine ion sensing test-paper and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100483113C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102507548B (en) * | 2011-10-12 | 2016-10-12 | 江南大学 | A kind of method and application of relevant reagent paper thereof preparing detection of heavy metal ion sensing test-paper based on inkjet technology |
| CN103743737B (en) * | 2014-01-17 | 2018-07-13 | 陕西理工学院 | A method of F- is detected based on aluminum-eriochrome cyanine R color development systems |
| CN105651743A (en) * | 2014-09-11 | 2016-06-08 | 华东师范大学 | Method for selective fluorescence recognition and colorimetric recognition of fluorine ions by using perimidine onium anion receptor |
| CN105891164A (en) * | 2014-09-11 | 2016-08-24 | 华东师范大学 | Method for perimidinium anion receptor selective fluorescent identification and color discrimination of fluoride ions |
| JP7002774B2 (en) * | 2020-03-24 | 2022-01-20 | 国立大学法人信州大学 | Fluorine ion concentration detection test paper, fluorine ion concentration measuring method and fluorine ion concentration measuring device |
-
2006
- 2006-02-13 CN CNB2006100382548A patent/CN100483113C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 钌(II)多吡啶配合物的合成及表征. 杨光，王雷，邹永德，吴建中，计亮年.中山大学学报(自然科学版)，第35卷第6期. 1996 |
| 钌(II)多吡啶配合物的合成及表征. 杨光，王雷，邹永德，吴建中，计亮年.中山大学学报(自然科学版)，第35卷第6期. 1996 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1815201A (en) | 2006-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100483113C (en) | Visual colorimetric fluorine ion sensing test-paper and use thereof | |
| Elleouet et al. | Determination of trace amounts of chromium (VI) in water by electrochemical methods | |
| Barghouthi et al. | Spectrophotometric determination of fluoride in drinking water using aluminium complexes of triphenylmethane dyes | |
| CN100344641C (en) | Fluorion sensing test paper for visual colorimetry and its uses | |
| CN105038766A (en) | Visible and reversible ratiometric fluorescent probe as well as preparation method and application thereof | |
| CN103411943B (en) | Method for detecting Ag<+1>, Hg<2+> and Fe<3+> based on fluorescence quenching method or colorimetric method of erythrosine B | |
| Ghaedi et al. | A novel PVC-membrane optical sensor for high sensitive and selective determination of Cu2+ ion based on synthesized (E)-N′-(pyridin-2-ylmethylene) isonicotin-ohydrazide | |
| Nagy et al. | Isocyanonaphthalenes as extremely low molecular weight, selective, ratiometric fluorescent probes for Mercury (II) | |
| Munshi et al. | Spectrophotometric Determination of Rare Earth Metals with 4-(2-Pyridylazo) resorcinol. | |
| Karaböcek et al. | A new spectrophotometric reagent for copper: 3, 3′-(1, 3-propanediyldiimine) bis-[3-methyl-2-butanone] dioxime | |
| Musagala et al. | A spectrophotometric method for quantification of sulphite ions in environmental samples | |
| Bonifácio et al. | Chemiluminescent determination of sulfite traces based on the induced oxidation of Ni (II)/tetraglycine complex by oxygen in the presence of luminol: mechanistic considerations | |
| de la Riva et al. | Determination of trace levels of mercury in water samples based on room temperature phosphorescence energy transfer | |
| CN105985291B (en) | A kind of colorimetric fluorescence probe of quick high-selectivity analysis fluorine ion | |
| CN109053709B (en) | For detecting Al3+Fluorescent probe and kit | |
| Ovenston et al. | Notes on the spectrophotometric determination of copper as diethyldithiocarbamate | |
| CN106967420B (en) | Cross-linked chitosan fluorescent probe material and preparation method and application thereof | |
| Tagashira | Distribution equilibria of aluminum-pyrocatechol violet-quaternary onium salt ion-pairs in micellar systems: Spectrophotometric Determination of Aluminum | |
| CN114544613A (en) | Method for detecting high-concentration copper ions by spectrophotometry | |
| Zhu et al. | A fluorometric method for the determination of iron (II) with fluorescein isothiocyanate and iodine | |
| Kola et al. | The influence of some chemical and physical parameters of water samples on spectral determinations of fluorescent dyes | |
| CN105987892B (en) | Measure the method and its kit of fluorine ion | |
| CN100387608C (en) | Glycosyl quinoline and its mercury ion detecting method | |
| Dass et al. | An Extractive Spectrophotometric Method of Determination of Molybdenum (VI) Using 3-Hydroxy-2-(4-methoxyphenyl)-6-methyl-4H-chromen-4-one. | |
| Raju et al. | LIQUID-LIQUID EXTRACTION SYSTEM INCLUDING 4-(2-THIAZOLYLAZO) RESORCINOL AND 2, 3, 5-TRIPHENYL-2H-TETRAZOLIUM CHLORIDE FOR SPECTROPHOTOMETRIC DETERMINATION OF COBALT (II) |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090429 Termination date: 20130213 |