CN102746842A - Rare earth complex fluorescent probe, its preparation method and application in methanol impurity detection - Google Patents
Rare earth complex fluorescent probe, its preparation method and application in methanol impurity detection Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 57
- 239000012535 impurity Substances 0.000 title claims abstract description 56
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 55
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001514 detection method Methods 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- -1 hydroxyl Whitfield's ointment Chemical compound 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 10
- 239000000356 contaminant Substances 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- 230000005284 excitation Effects 0.000 claims description 5
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- WHSXTWFYRGOBGO-UHFFFAOYSA-N 3-methylsalicylic acid Chemical compound CC1=CC=CC(C(O)=O)=C1O WHSXTWFYRGOBGO-UHFFFAOYSA-N 0.000 claims description 2
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 229960004889 salicylic acid Drugs 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 229910009112 xH2O Inorganic materials 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- 239000013558 reference substance Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a rare earth complex fluorescent probe, its preparation method and application in methanol impurity detection. The fluorescent probe is a compound of the following chemical formula: [Ln2(L)6(H2O)4].xH2O, wherein Ln is Tb or Eu, L as an electron-donating ligand, is salicylic acid or its derivative, and x ranges from 0 to 8. The preparation method consists of: dissolving the electron-donating ligand in water, adjusting the pH to 5-6.5, mixing the solution with a rare earth salt solution, standing or heating the obtained mixed solution till precipitation of a crystal, and filtering, washing, as well as drying the crystal so as to obtain the rare earth complex fluorescent probe. The binuclear complex synthesized in the invention as a fluorescent probe can effectively detect whether methanol is polluted by impurity solvents. And the detection method is simple, can be realized by employment of a relatively simple fluorometer, and needs no gas chromatograph and other complicated and expensive instruments, thus achieving the detection purposes of convenience and fastness.
Description
Technical field
The present invention relates to a kind of rare earth coordination compound fluorescent probe and preparation method thereof, also relate to this rare earth coordination compound fluorescent probe and in detecting methyl alcohol, whether contain impurity and impurity is carried out quantitative application.
Background technology
A metal-organic complex has had huge development at nearest 20 years, and their applied research receives much concern.But how therefore the nearest new rarely found report of application of for some time make a metal-organic complex become novel and functional materials that be convenient to use has caused a lot of researchists' interest.
Methyl alcohol is of many uses, is the Organic Chemicals and the high-grade fuel on basis.It also is one of important source material of agricultural chemicals, medicine.For chemical industry, methyl alcohol is also through being commonly used to do the solvent or the reaction medium of various reactions.Below mostly the purity of methyl alcohol there is higher requirement.Therefore detecting methanol solution, whether impurity is arranged also is a vital problem.The method whether present monitoring methyl alcohol contains impurity generally is to realize through vapor-phase chromatography, but this method need be used large-scale gas chromatography mass spectrometry instrument, and test process is complicated and time-consuming, on efficient and benefit, all haves much room for improvement.
Summary of the invention
The object of the present invention is to provide a kind of rare earth coordination compound fluorescent probe and preparation method thereof and its application in methanol contaminant detects.
For overcoming the above problems, the technical scheme that the present invention adopts is:
A kind of rare earth coordination compound fluorescent probe, it is the compound of following chemical formula: [Ln
2(L)
6(H
2O)
4] xH
2O, wherein, Ln=Tb or Eu, L is the Whitfield's ointment or derivatives thereof for to the electronics part, the value of x is 0～8.
Preferably, salicyclic acid derivatives is selected from cresotinic acid, hydroxyl Whitfield's ointment, aminosallcylic acid, halo Whitfield's ointment, sulphosalicylic acid.Give the structural formula of electronics part following:
In the formula, R is 3,4,5 or 6 H, NH
2, CH
3, OH, F, Cl, Br, I or SO
3H.
Preferably, Ln=Tb, L are the 4-cresotinic acid, and x is 6.The structural unit of this rare earth coordination compound fluorescent probe belongs to triclinic(crystalline)system, P-1 spacer, unit cell parameters a=12.675 (2); B=14.612 (2); C=17.035 (3), α=107.915 (2) °, β=104.265 (2) °; γ=106.165 (2) °, unit cell volume V=2686.3 (7)
3
The preparation method of above-mentioned rare earth coordination compound fluorescent probe may further comprise the steps:
1) will be water-soluble to the electronics part, regulate pH to 5～6.5, get solution A;
2) rare-earth salts is water-soluble, get rare earths salt, the rare earth in the said rare-earth salts is Tb or Eu;
3) solution A, rare earths salt are mixed, the gained mixed solution leaves standstill or is heated to separates out crystal, filter, and washing crystal, drying gets rare earth coordination compound fluorescent probe.
Preferably, rare-earth salts is 1:1～3 with the mol ratio of giving the electronics part.
Preferably, rare-earth salts is selected from nitrate salt, muriate or the phosphoric acid salt of Tb, or the nitrate salt of Eu, muriate or phosphoric acid salt.
Preferably, rare-earth salts is a Terbium trinitrate, and giving the electronics part is the 4-cresotinic acid.
The method that a kind of methanol contaminant detects may further comprise the steps:
1) above-mentioned rare earth coordination compound fluorescent probe is dissolved in the methyl alcohol, gets mother liquor;
2) in methyl alcohol to be checked, add mother liquor, get mixed solution;
3) mixed solution is left standstill, detect the fluorescence intensity of mixed solution, judge the content whether impurity in impurity and the methyl alcohol is arranged in the methyl alcohol to be checked according to fluorescence intensity.
Preferably, step 2) concentration of mixed solution middle-weight rare earths coordination compound fluorescent probe is 0.1～5 μ mol/L.The concentration of controlling fluorescent probe in the mixed solution is 0.1～5 μ mol/L, because fluorescent probe content is few in the mixed solution, if directly fluorescent probe is joined in the mixed solution; Can be because the fluorescent probe amount be few; And balance can't accurately be measured, so earlier fluorescent probe is made into mother liquor, is convenient to take by weighing.
Preferably, step 2) concentration of mixed solution middle-weight rare earths coordination compound fluorescent probe is 3～5 μ mol/L.
Preferably, during fluorescence intensity, the excitation wavelength that uses is 328nm.Repeatedly experiment proof excites in the excitation wave strong point of 328nm, and the fluorescence of generation is the strongest, and just this wavelength detects the sensitiveest down.
Whether the present invention judges has the method for impurity to be in the methyl alcohol to be checked: when detecting the fluorescence intensity of mixed solution; Set up reference substance simultaneously, reference substance replaces methyl alcohol to be checked with standard methyl alcohol, is mixed with reference substance solution by isodose; Similarity condition detects the fluorescence intensity of reference substance solution down; Compare with the fluorescence intensity of reference substance solution, the fluorescence intensity of mixed solution reduces or extinguishes, and just representing has impurity in the methyl alcohol to be checked; Impurity is many more, and fluorescence reduces obvious more.
Impurity is specific impurities in the methyl alcohol, and specific impurities is at least a in DMF, THF, acetone and four kinds of compounds of chloroform, and the volume ratio of its content of specific impurities and methyl alcohol can realize quantitatively determined 0～25%.The present invention judges that the method for specific impurities content in the methyl alcohol to be checked is:
1) set up the judgment standard of specific impurities: preparation contains the methanol solutions of different amount specific impurities respectively; The volume ratio of specific impurities is distributed in 0～25%; Impure methanol solution is mixed with mother liquor; Make the concentration of mixed solution middle-weight rare earths coordination compound fluorescent probe identical, set up curve according to the volumetric concentration of impurity in the fluorescence intensity of gained and the methanol solution, and obtain the typical curve equation;
2) under the similarity condition, detect the fluorescence intensity of methyl alcohol to be checked,, can calculate the content of impurity in the methyl alcohol to be checked according to the typical curve equation.
The invention has the beneficial effects as follows:
The present invention is a raw material with salicylic acid part and rare earth metal salt, has synthesized rare earth coordination compound fluorescent probe, and whether it can effectively detect methyl alcohol by contaminating impurity as fluorescent probe, can carry out quantitatively determined to the impurity in the methyl alcohol simultaneously.
The method that rare earth compounding of the present invention is used for detecting methyl alcohol impurity is simple, and adopts fairly simple luminoscope to realize, need not use the instrument of complex and expensive such as gc, has therefore realized the mensuration to impurity in the methyl alcohol quickly and easily.
Synthetic rare earth coordination compound fluorescent probe of the present invention all is suitable for the following single or poly-doped impurity that contains in the methyl alcohol: benzene, oil of mirbane, toluene, aniline, ethanol, acetonitrile, terepthaloyl moietie, glycerine, butanols, methylene dichloride, chloroform, tetracol phenixin, acetone, methyl ethyl diketone, dioxane, N, DMSO 99.8MIN., THF, hexane, hexanaphthene, pyridine, ether, DIOXANE, ether, sherwood oil, single impurity or poly-doped impurities such as formaldehyde, trolamine, water.
Rare earth coordination compound fluorescent probe of the present invention is DMF for impurity in the methyl alcohol, THF, and at least a in four kinds of compounds of acetone and chloroform, and the volume ratio of its content and methyl alcohol can realize quantitatively determined 0～25%.
Description of drawings
Fig. 1 is the X-ray powder diffraction figure of rare earth coordination compound fluorescent probe I;
Fig. 2 is the crystalline structure ellipsoid figure of rare earth coordination compound fluorescent probe I;
Fig. 3 is the coordination mode figure of 4-cresotinic acid part among the embodiment 1;
Fig. 4 is that rare earth coordination compound fluorescent probe I detects the fluorescence intensity column diagram that contains 3% each impurity solvent methanol solution 547nm place;
Fig. 5 is the change curve of fluorescence intensity with impurity concentration.
Embodiment
Embodiment below in conjunction with concrete is further described the present invention, but does not limit to so.
A kind of rare earth coordination compound fluorescent probe I, chemical formula are [Tb
2(Msal)
6(H
2O)
4] 6H
2O, wherein, Msal is the 4-cresotinic acid, its preparation method may further comprise the steps:
1) 0.1533 g 4-cresotinic acid (Msal) is dissolved in 10mL water, regulates pH to 6, get solution A with 0.1M NaOH solution;
2) with 0.1519g Tb (NO
3)
36H
2O is dissolved in 10mL water, gets solution B;
3) solution A, solution B are mixed, the gained mixed solution leaves standstill in open container, slowly volatilizees a week, has separated out colourless bulk crystals, filters, and it is inferior that crystal water is given a baby a bath on the third day after its birth, and drying gets rare earth coordination compound fluorescent probe I, and its output is 0.2135g, and productive rate is 90.9%.
A crystal of getting among the gained rare earth coordination compound fluorescent probe I is done the X ray single crystal diffraction, and the monocrystalline analytical results shows this crystal structure of rare earth coordination compound fluorescent probe in triclinic(crystalline)system, the P-1 spacer; A=12.675 (2), b=14.612 (2), c=17.035 (3); α=107.915 (2) °; β=104.265 (2) °, γ=106.165 (2) °, V=2686.3 (7)
3, its molecular formula is [Tb
2(Msal)
6(H
2O)
4] 6H
2O (I).Simulate crystalline X ray crystalline diffraction collection of illustrative plates, and then get a large amount of rare earth coordination compound fluorescent probes of synthetic and do X-ray powder diffraction, the X-ray powder diffraction that obtains is seen Fig. 1, proved synthesize the phase purity of big quantity of material.
The rare earth coordination compound fluorescent probe I for preparing is done infrared test, the data of PXRD collection of illustrative plates infrared test:
IR?(cm
-1,?KBr):?3397?(s),?1638?(s),?1589(s),?1504?(s),?1438?(s),?1368?(s),?1308?(w),?1257?(s),?1225?(w),?1168?(m),950?(m),?855?(m),790?(m),737?(m),703?(m),628?(m)。
Analytical results is known; This rare earth coordination compound fluorescent probe I is a dinuclear complex; Wherein the coordination mode of two metals ions is the same, is 9 coordinations, and wherein two oxygen come from two coordinated water; All the other seven oxygen all come from the carboxyl of part Msal, and the bond distance of metal and oxygen is at 2.309-2.614.
The crystalline structure figure of present embodiment rare earth coordination compound fluorescent probe sees Fig. 2.Wherein, The coordination mode of metals ion and Msal part has three kinds, sees Fig. 3, and M represents the terbium metal ion; The mode of connection of M and Sauerstoffatom is followed successively by 5 kinds of mode of connection from scheming a left side to the right side; And each terbium ion and seven oxygen coordination modes from the carboxyl of Msal in the title complex are 5 kinds of above mode of connection, every kind of mode each once.
The application of rare earth coordination compound fluorescent probe of the present invention in methanol contaminant detects:
The detection of methanol contaminant:
1. preparation mother liquor
With 2.1mg rare earth coordination compound fluorescent probe I, be dissolved in the 50mL methyl alcohol, get 30 μ mol/L mother liquors.
2. preparation contains the methanol solution of the single impurity solvent of 3% (volume ratio)
The single impurity solvent that pipettes 300 μ L with liquid-transfering gun is in the 10mL volumetric flask, and methanol constant volume is to 10mL then, impure methanol solution.Single impurity is respectively: ETHYLE ACETATE, toluene, ethanol, THF, normal hexane, DMSO, methylene dichloride, terepthaloyl moietie, dioxane, acetonitrile, ether, acetone, DMF (N, dinethylformamide), chloroform, water, triethylamine.
3. preparation contains the methanol solution of the poly-doped impurity of 3% (volume ratio).
The poly-doped impurity methanol solution of preparation three kind 3% (volume ratio).Earlier in the 10mL volumetric flask, add various impurity, use methanol constant volume then.Hybrid plan is following:
A: chloroform, acetonitrile, each 100 μ L of DMSO;
B: chloroform, DMF, acetonitrile, dioxane, methylene dichloride, each 50 μ L of DMSO;
C:DMSO, methylene dichloride, THF, normal hexane, ethanol, each 50 μ L of toluene.
4. the mensuration of fluorescence spectrum.
The excitation wavelength of fluorometric investigation is 328nm; Slit is wide for being 1nm; Experimental group: get 1mL 30 μ M mother liquors in the 10mL volumetric flask, the methanol solvate that adds 3% different impurities solvent then respectively is settled to 10mL, and control group is set simultaneously at every turn; Get 1mL 30 μ M mother liquors in the 10mL volumetric flask, use pure methanol constant volume then to 10mL.The fluorescence spectrum of scanning solution behind the 37h.
5. rare earth coordination compound fluorescent probe of the present invention is as the response results of fluorescent probe to the different impurities solvent
The result sees table 1, and the result in the table 1 is represented to see Fig. 4 with column diagram, all can be known by table 1 or Fig. 4, and the rare earth coordination compound fluorescent probe I among the present invention all has an obvious response to kind of different impurities surplus ten, but degree is different.Wherein, Respond and more intense be: trolamine, acetone, water, chloroform, DMF, A, B; Respond and not too strong be: terepthaloyl moietie, DIOXANE, acetonitrile, ether respond more weak: methylene dichloride, dioxane, DMSO, THF, toluene, ethanol, hexane, C.
Can know by table 1 and Fig. 4, relatively excite and the peak height discovery of the fluorescence spectrum at the fluorescence highest peak 547nm place that launches that the fluorescence intensity that contains the impurity solvent solution is compared with control group and all reduced more than 50% by 328nm, some in addition fluorescence quenching has taken place.This possibly be in the title complex, and two functional groups of the hydroxyl of part and methyl and impurity solvent on every side bump, and therefore solvent around having passed to the energy of the photon of part absorption with radiationless mode passes to Tb
3+Energy cause fluorescence to reduce with regard to minimizing or extinguish.
The methanol contaminant detection by quantitative:
1. fluorescent probe is to the response of some impurity solvent and the relation of impurity concentration
Preparation contains DMF, THF, the acetone of different volumes amount, the methanol solution of four kinds of different impurities solvents of chloroform respectively; Mix with 30 μ mol/L mother liquors of above-mentioned preparation with impure methanol solution; The concentration that makes mixed solution middle-weight rare earths coordination compound fluorescent probe is 5 μ mol/L; Survey their fluorescence (excitation wavelength is 328nm) immediately, detected fluorescence intensity is with change curve such as Fig. 5 of impurity concentration.Four curve's equation and relative coefficient are following among the figure, the scope of foreign body volume concentrations in the said linearity range nail alcohol:
DMF:Y=2.15484-7.99997X, R=-0.99886 linearity range 0.00～21%;
THF:Y=2.07899-4.37541X, R=-0.99554 linearity range 0.01～18%;
C
3H
6O:Y=2.16596-2.99073X, R=-0.99799 linearity range 0.00～22%;
CHCl
3: Y=2.11328-3.17781X, R=-0.99781 linearity range 0.00～18%.
Can know that by Fig. 5 along with the increase of the amount of impurity solvent, fluorescence quenching is also many more, therefore in linearity range, can carry out quantitatively a certain specific impurity in the methyl alcohol.
Detection by quantitative: under the similarity condition; Methanol solution to be checked is mixed with mother liquor, and the concentration that makes mixed solution middle-weight rare earths coordination compound fluorescent probe is 5 μ mol/L, surveys fluorescence immediately; According to the curve's equation of above-mentioned correspondence, can calculate the content of the impurity solvent in the methanol solution to be checked.
Therefore, synthetic rare earth coordination compound fluorescent probe of the present invention, whether contaminated, to by the methyl alcohol of a certain specific contaminating impurity, can carry out quantitatively impurity within the specific limits if can detect methyl alcohol.When methanol contaminant is DMF, THF, at least a in four kinds of solvents of acetone and chloroform, and the volume ratio that this impurity solvent accounts for methyl alcohol is 0～25%, can realize the quantitatively determined of impurity.
Claims (10)
1. rare earth coordination compound fluorescent probe, it is the compound of following chemical formula: [Ln
2(L)
6(H
2O)
4] xH
2O, wherein, Ln=Tb or Eu, L is the Whitfield's ointment or derivatives thereof for to the electronics part, the value of x is 0～8.
2. rare earth coordination compound fluorescent probe according to claim 1 is characterized in that: salicyclic acid derivatives is selected from cresotinic acid, hydroxyl Whitfield's ointment, aminosallcylic acid, halo Whitfield's ointment, sulphosalicylic acid.
3. rare earth coordination compound fluorescent probe according to claim 1 is characterized in that: Ln=Tb, L are the 4-cresotinic acid, and x is 6.
4. rare earth coordination compound fluorescent probe according to claim 3 is characterized in that: the structural unit of this rare earth coordination compound fluorescent probe belongs to triclinic(crystalline)system, the P-1 spacer; Unit cell parameters a=12.675 (2), b=14.612 (2), c=17.035 (3); α=107.915 (2) °; β=104.265 (2) °, γ=106.165 (2) °, unit cell volume V=2686.3 (7)
3
5. the preparation method of each described rare earth coordination compound fluorescent probe of claim 1～4 may further comprise the steps:
1) will be water-soluble to the electronics part, regulate pH to 5～6.5, get solution A;
2) rare-earth salts is water-soluble, get rare earths salt, the rare earth in the said rare-earth salts is Tb or Eu;
3) solution A, rare earths salt are mixed, the gained mixed solution leaves standstill or is heated to separates out crystal, filter, and washing crystal, drying gets rare earth coordination compound fluorescent probe.
6. the preparation method of rare earth coordination compound fluorescent probe according to claim 5 is characterized in that: rare-earth salts is 1:1～3 with the mol ratio of giving the electronics part.
7. the preparation method of rare earth coordination compound fluorescent probe according to claim 5, it is characterized in that: rare-earth salts is selected from nitrate salt, muriate or the phosphoric acid salt of Tb, or the nitrate salt of Eu, muriate or phosphoric acid salt.
8. the method that detects of a methanol contaminant may further comprise the steps:
1) each described rare earth coordination compound fluorescent probe of claim 1～4 is dissolved in the methyl alcohol, gets mother liquor;
2) in methyl alcohol to be checked, add mother liquor, get mixed solution;
3) mixed solution is left standstill, detect the fluorescence intensity of mixed solution, judge the content whether impurity in impurity and the methyl alcohol is arranged in the methyl alcohol to be checked according to fluorescence intensity.
9. method according to claim 8 is characterized in that: step 2) concentration of mixed solution middle-weight rare earths coordination compound fluorescent probe is 0.1～5 μ mol/L.
10. method according to claim 8 is characterized in that: during fluorescence intensity, the excitation wavelength that uses is 328nm.
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| CN105062469A (en) * | 2015-08-26 | 2015-11-18 | 重庆理工大学 | Six-nuclear cyclotriphosphazene terbium complex light-emitting material and preparation method thereof |
| CN108593609A (en) * | 2018-03-27 | 2018-09-28 | 南昌大学 | A kind of method of highly sensitive highly selective fluoroscopic examination magnesium ion |
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| CN105062469A (en) * | 2015-08-26 | 2015-11-18 | 重庆理工大学 | Six-nuclear cyclotriphosphazene terbium complex light-emitting material and preparation method thereof |
| CN108593609A (en) * | 2018-03-27 | 2018-09-28 | 南昌大学 | A kind of method of highly sensitive highly selective fluoroscopic examination magnesium ion |
| CN108593609B (en) * | 2018-03-27 | 2020-10-20 | 江西省得鑫电子新材料有限公司 | Method for high-sensitivity and high-selectivity fluorescence detection of magnesium ions |
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