CN106198600B - A kind of method of magnetic resonance detection solution concentration - Google Patents
A kind of method of magnetic resonance detection solution concentration Download PDFInfo
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- CN106198600B CN106198600B CN201510224685.2A CN201510224685A CN106198600B CN 106198600 B CN106198600 B CN 106198600B CN 201510224685 A CN201510224685 A CN 201510224685A CN 106198600 B CN106198600 B CN 106198600B
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- 238000001514 detection method Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 17
- 239000002086 nanomaterial Substances 0.000 claims abstract description 83
- 238000012986 modification Methods 0.000 claims abstract description 46
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 30
- 230000005298 paramagnetic effect Effects 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 46
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 39
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 36
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 33
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 32
- 239000002105 nanoparticle Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229910052691 Erbium Inorganic materials 0.000 claims description 17
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 17
- 235000010323 ascorbic acid Nutrition 0.000 claims description 17
- 239000011668 ascorbic acid Substances 0.000 claims description 17
- 229960005070 ascorbic acid Drugs 0.000 claims description 17
- 229960003638 dopamine Drugs 0.000 claims description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 239000001509 sodium citrate Substances 0.000 claims description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- WCZAXBXVDLKQGV-UHFFFAOYSA-N n,n-dimethyl-2-(7-oxobenzo[c]fluoren-5-yl)oxyethanamine oxide Chemical compound C12=CC=CC=C2C(OCC[N+](C)([O-])C)=CC2=C1C1=CC=CC=C1C2=O WCZAXBXVDLKQGV-UHFFFAOYSA-N 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 238000006011 modification reaction Methods 0.000 claims description 4
- 238000007796 conventional method Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 230000005408 paramagnetism Effects 0.000 claims 1
- 230000009021 linear effect Effects 0.000 abstract description 3
- 238000001574 biopsy Methods 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052689 Holmium Inorganic materials 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 229960004756 ethanol Drugs 0.000 description 12
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 10
- 238000012545 processing Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- -1 fluorine halide Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 229960004502 levodopa Drugs 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
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- 238000010792 warming Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002795 fluorescence method Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910003317 GdCl3 Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 239000002616 MRI contrast agent Substances 0.000 description 1
- 229910004064 NOBF4 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Compounds Of Iron (AREA)
Abstract
The present invention provides a kind of methods of magnetic resonance detection solution concentration, include the following steps: the nano material for 1) containing paramagnetic metal ion with superparamagnetic metal ion modification, obtain functionalized nano material；2) it is reacted respectively with series of standards product with the functionalized nano material, obtains a series of mixed liquors, and survey its relaxation time respectively, do the standard curve of relaxation time and concentration；3) solution to be measured of unknown concentration is reacted with the functionalized nano material, obtains mixed liquor, survey its relaxation time, compared with the standard curve to get the concentration of the solution to be measured is arrived.Method of the invention can carry out quick, sensitive, accurate quantitative detection to many kinds of substance, such as: the quantitative detection of food, drug and biopsy samples, and it is easy to operate, linear effects are good, at low cost.
Description
Technical field
The invention belongs to technical field of analysis and detection, and in particular to one kind is based on longitudinal (T1) and/or lateral (T2) relaxation when
Between change magnetic resonance detection solution concentration method.
Background technique
Analysis and detection technology is to be analyzed by the means of multiple technologies measurand, obtain measured object it is qualitative or
One technology of quantitative elemental composition composition result, it is commonly used for solving performance, quality problems and the failure analysis of product,
It is also used for the feature of environmental protection etc. of test product.Analysis method common at present has optical detection, Electrochemical Detection etc..But at present
There are many defects for common analysis method, such as: detecting slow speed, poor sensitivity or cannot accurately and effectively carry out quantitative inspection
Survey etc..
Summary of the invention
The purpose of the present invention is to provide a kind of method of magnetic resonance detection solution concentration, this method utilizes nano material
Quick, sensitive, the accurate quantitative detection to ingredient to be measured is realized in the variation of magnetic resonance signal.
The method of magnetic resonance detection solution concentration provided by the present invention, includes the following steps:
1) nano material for containing paramagnetic metal ion with superparamagnetic metal ion modification, obtains functionalized nano material
Material；
2) it is reacted respectively with series of standards product with the functionalized nano material, obtains a series of mixed liquors, and
Its relaxation time is surveyed respectively, does the standard curve of relaxation time and concentration；
3) solution to be measured of unknown concentration is reacted with the functionalized nano material, obtains mixed liquor, survey its relaxation
The Henan time compares with the standard curve, the concentration of the solution to be measured can be obtained.
In the method for above-mentioned magnetic resonance detection solution concentration, in step 1), the superparamagnetic metal ion is selected from Fe3+,
Co3+And Ni3+At least one of, but not limited to this, other superparamagnetic metal ions are also applicable in.
The nano material containing paramagnetic metal ion is selected from the fluorine that paramagnetic metal ion and rare earth element are formed
At least one of compound, oxide, oxyfluoride, fluorine halide, phosphate, vanadate and tungstates, but be not limited to
This.
In the nano material containing paramagnetic metal ion the mass fraction m of paramagnetic metal ion be 0 < m≤
100%.
The nano material containing paramagnetic metal ion can be nano particle and/or nanometer rods, wherein the nanometer
The diameter of particle is 5nm-999nm, and the length of the nanometer rods is 6nm-20 μm, diameter 5nm-999nm.
The nano material containing paramagnetic metal ion can be prepared by a conventional method to obtain, such as: solid phase method, liquid phase
Method, vapor phase method etc..
The paramagnetic metal ion is selected from Gd3+, Ho3+And Mn2+At least one of, but not limited to this.
The rare earth element is selected from following at least one: lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium
(Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and
Yttrium (Y).
The nano material containing paramagnetic metal ion concretely NaLuF4: Yb, Er, Gd nano particle,
NaGdF4: Dy nanometer rods, NaLuF4: Mn nano particle and NaLuF4: any one of Ho nano particle.
Wherein, the NaLuF4: the mass fraction of Gd is 10-80%, preferably 30-50% in Yb, Er, Gd nano particle
Concretely 40%.
The NaGdF4: in Dy nanometer rods the mass fraction of Gd be 15-100%, preferably 70-90%, concretely
80%.
The NaLuF4: in Mn nano particle the mass fraction of Mn be 10-100%, preferably 5-25%, concretely
15%.
The NaLuF4: the mass fraction of Ho is 10-100% in Ho nano particle, and preferably 20-40% specifically may be used
It is 30%.
The functionalized nano material can specifically be prepared as follows: by the nanometer containing paramagnetic metal ion
Material and NOBF4It is reacted, uses CH2Cl2After ethanol washing, reaction gains are dispersed in the aqueous solution of sodium citrate,
Stir process is eventually adding the substance containing superparamagnetic metal ion, carries out modification reaction, the functionalization can be obtained and receive
Rice material.
The nano material and NOBF containing paramagnetic metal ion4Mass ratio be (0.1-1): 1, concretely 1:
1。
The reaction temperature of the reaction is 10-40 DEG C, reaction time 5-60min, concretely 5min.
The mass fraction of the aqueous solution of the sodium citrate is 2.5%-61%, concretely 20%.
The temperature of the stir process is 10-40 DEG C, time 5-60min, concretely 60min.
The molar ratio of the superparamagnetic metal ion and the nano material containing paramagnetic metal ion is (0.5-
5): 1, concretely 0.5:1.
The reaction temperature of the modification reaction is 10-40 DEG C, reaction time 5-60min, concretely 60min.
The substance containing superparamagnetic metal ion concretely CoCl3、FeCl3And NiCl3In it is any.
In the method for above-mentioned magnetic resonance detection solution concentration, in step 2), the concentration range of the series of standards product is
50nM-8 μM, concretely 50nM, 100nM, 250nM, 500nM, 1 μM, 4 μM, 8 μM.
The functionalized nano material is that reaction, the functionalization are participated in the form of functionalized nano material aqueous solution
The molar concentration of nano material aqueous solution is 0.1mM-10mM, concretely 1mM；
The functionalized nano material aqueous solution is respectively (0.15-1.5) mL with the volume ratio of the series of standards product:
150 μ L, concretely 1.35mL:150 μ L.
In the method for above-mentioned magnetic resonance detection solution concentration, in step 2) and step 3), the standard items and solution to be measured
In ingredient to be measured be can with the superparamagnetic metals ion of surface modification occur complexing and/or redox reaction substance.
The standard items and solution to be measured specifically can be dopamine (DA) aqueous solution, ascorbic acid (AA) aqueous solution, iodine
Change any one of potassium (KI) aqueous solution and sodium fluoride (NaF) aqueous solution.
The functionalized nano material is that reaction, the functionalization are participated in the form of functionalized nano material aqueous solution
The molar concentration of nano material aqueous solution is 0.1mM-10mM, concretely 1mM.
The relaxation time is longitudinal relaxation time (T1) and/or lateral (T2) relaxation time.
In the method for above-mentioned magnetic resonance detection solution concentration, in step 2) and step 3), the reaction temperature of the reaction is
10-40 DEG C, reaction time 0.5-60min, concretely 5min.
The reaction time of step 2) and the reaction in step 3), reaction temperature, the functionalized nano in the present invention
The additional amount and addition concentration of material should be consistent, and guarantee identical test environment, in addition, the solution to be measured does not need
It is reacted completely with the functionalized nano material, but utilizes superparamagnetic ion and the institute of the functionalized nano material surface
The ingredient to be measured stated in solution to be measured reacts, the surface area for causing the reduction of surface superparamagnetic ion amount and kernel to be exposed
Increase, causes T2And T1Variation, therefore the amount for the functionalized nano material being added should be consistent.
The relaxation time is the detection carried out by mri contrast agent imaging analysis instrument, model MicroMR-
MOUSE is purchased from Niu Mai Electronic Science and Technology Co., Ltd..
The present invention is realized with the variation of the magnetic resonance signal of nano material to the quick, sensitive, accurate of ingredient to be measured
Quantitative detection.Especially by a series of longitudinal direction (T of the solution of the ingredient to be measured of the known concentrations measured1) and/or lateral (T2) relax
The value of Henan time and linear map (the regression coefficient R of concentration2>=0.99) normal linearity map, is obtained.Unknown concentration is surveyed again
The relaxation time of ingredient to be measured, with normal linearity map comparison it can be learnt that.
Compared with prior art, the invention has the following beneficial effects:
1) method of the invention quick, sensitive, accurately can carry out quantitative analysis to the component to be measured in testing liquid, mention
A kind of new analysis test method is supplied；
2) material used in the method for the present invention is simpler, and the price of required instrument is also cheaper, can be realized low
Quick, sensitive, the accurate quantitative analysis of cost.
3) analyzing detecting method of the present invention can be used for the detection of the samples such as food, drug and biopsy samples.
Detailed description of the invention
Fig. 1 is the Fe in embodiment 13+The NaLuF containing 40%Gd of modification4: the transmission electricity of Yb, Er, Gd nano particle
Sub- microscope photo.
Fig. 2 is the Fe in embodiment 13+The NaLuF containing 40%Gd of modification4: Yb, Er, Gd nano particle detect DOPA
The T of amine (DA)1Normal linearity map.
Fig. 3 is the Fe in embodiment 13+The NaLuF containing 40%Gd of modification4: Yb, Er, Gd nano particle detect DOPA
The T of amine (DA)2Normal linearity map.
Fig. 4 is the Co in embodiment 23+The NaGdF containing 80%Gd of modification4: the transmission electron microscope of Dy nanometer rods
Photo.
Fig. 5 is the Co in embodiment 23+The NaGdF containing 80%Gd of modification4: Dy nanometer rods detect ascorbic acid (AA)
T1Normal linearity map.
Fig. 6 is the Co in embodiment 23+The NaGdF containing 80%Gd of modification4: Dy nanometer rods detect ascorbic acid (AA)
T2Normal linearity map.
Fig. 7 is the Ni in embodiment 33+The NaLuF containing 15%Mn of modification4: the transmission electron microscopy of Mn nano particle
Mirror photo.
Fig. 8 is the Ni in embodiment 33+The NaLuF containing 15%Mn of modification4: Mn nano particle detects potassium iodide (KI)
T1Normal linearity map.
Fig. 9 is the Ni in embodiment 33+The NaLuF containing 15%Mn of modification4: Mn nano particle detects potassium iodide (KI)
T2Normal linearity map.
Figure 10 is the Fe in embodiment 43+The NaLuF containing 30%Ho of modification4: the transmission electron microscopy of Ho nano particle
Mirror photo.
Figure 11 is the Fe in embodiment 43+The NaLuF containing 30%Ho of modification4: Ho nano particle detects sodium fluoride
(NaF) T1Normal linearity map.
Figure 12 is the Fe in embodiment 43+The NaLuF containing 30%Ho of modification4: Ho nano particle detects sodium fluoride
(NaF) T2Normal linearity map.
Specific embodiment
Method of the invention is illustrated below by specific embodiment, but the present invention is not limited thereto, it is all at this
Any modifications, equivalent replacements, and improvements etc. done within the spirit and principle of invention, should be included in protection model of the invention
Within enclosing.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Nano material NaLuF used containing 40%Gd in following embodiments4: Yb, Er, Gd are to be prepared as follows
It obtains:
1) firstly, by 0.40mmol LuCl3、0.40mmol GdCl3、0.18mmol YbCl3With 0.02mmol ErCl3
It is added in the there-necked flask of 100mL, adds 6mL oleic acid and 15mL octadecylene；Then under the protection of nitrogen, by mixed solution
Being heated to 120 DEG C is completely dissolved rare earth-iron-boron, after forming transparent clear solution, stops heating, is cooled to room temperature；
2) after, 6mL NaOH (2.5mmol) and NH are added into clear solution4The methanol solution of F (4mmol), nitrogen
It is heated to 80 DEG C under protection except methanol, after about 30min, is warming up to 120 DEG C and vacuumizes water removal deoxygenation；It is finally anti-under nitrogen atmosphere
Answer 1h.After reaction, cooled to room temperature；Then suitable hexamethylene and ethyl alcohol is added, is centrifugated, removes supernatant
Liquid；Ultrasonic disperse after appropriate hexamethylene is added into solid, after adding ethanol in proper amount, then is centrifugated；Above step is repeated,
Continue with hexamethylene and ethanol washing several times after, the nano material NaLuF containing 40%Gd can be obtained4: Yb, Er, Gd (nanometer
Particle, diameter 7-9nm).
Nano material NaGdF as used in the following examples containing 80%Gd4: Dy is to be prepared as follows
It arrives:
1) firstly, by 0.80mmol GdCl3With 0.20mmol DyCl3It is added in the there-necked flask of 100mL, adds 6mL
Oleic acid and 15mL octadecylene；Then under the protection of nitrogen, mixed solution, which is heated to 120 DEG C, keeps rare earth-iron-boron completely molten
Solution after forming transparent clear solution, stops heating, is cooled to room temperature；
2) after, 6mL NaOH (2.5mmol) and NH are added into clear solution4The methanol solution of F (4mmol), nitrogen
It is heated to 80 DEG C under protection except methanol, after about 30min, is warming up to 120 DEG C and vacuumizes water removal deoxygenation；It is finally anti-under nitrogen atmosphere
Answer 1h.After reaction, then suitable hexamethylene and ethyl alcohol is added in cooled to room temperature, supernatant is removed in centrifuge separation
Liquid；Ultrasonic disperse after appropriate hexamethylene is added into solid, after adding ethanol in proper amount, then is centrifugated；Above step is repeated,
Continue with hexamethylene and ethanol washing several times after, the nano material NaGdF containing 80%Gd can be obtained4: Dy (nanometer rods, it is long
Degree is 30nm, diameter 7-9nm).
Nano material NaLuF as used in the following examples containing 15%Mn4: Mn is to be prepared by the following method
It arrives:
It takes 1.5mL deionized water, 5mL oleic acid and 10mL ethyl alcohol to stir in 100mL flask, 0.3g is added
NaOH is stirred to being completely dissolved；Then LuCl is added3(0.85mmol) and MnCl3(0.15mmol) is sufficiently stirred；By NaF
(4mmol) is dissolved in 2mL deionized water, and is slowly added in above-mentioned solution, and it is anti-to be transferred to high pressure after stir about 15min
Answer kettle, 200 DEG C of holding 10h；With ethyl alcohol, hexamethylene centrifugation, washing after cooling, sample is sealed in hexamethylene, spare, institute
State the nano material NaLuF containing 15%Mn4: Mn (nano particle, diameter 20-25nm).
Nano particle NaLuF as used in the following examples containing 30%Ho4: Ho is to be prepared as follows
It arrives:
1) firstly, by 0.70mmol LuCl3With 0.30mmol HoCl3It is added in the there-necked flask of 100mL, adds 6mL
Oleic acid and 15mL octadecylene.Then under the protection of nitrogen, mixed solution, which is heated to 120 DEG C, keeps rare earth-iron-boron completely molten
Solution after forming transparent clear solution, stops heating, is cooled to room temperature；
2) after, 6mL NaOH (2.5mmol) and NH are added into solution4The methanol solution of F (4mmol), nitrogen protection
Under be heated to 80 DEG C except methanol, after about 30min, be warming up to 120 DEG C and vacuumize water removal deoxygenation, finally react under nitrogen atmosphere
1h.After reaction, then suitable hexamethylene and ethyl alcohol is added in cooled to room temperature, supernatant is removed in centrifuge separation；
Ultrasonic disperse after appropriate hexamethylene is added into solid, after adding ethanol in proper amount, then is centrifugated；Above step is repeated, after
Continuous hexamethylene and ethanol washing several times after, the nano particle NaLuF containing 30%Ho can be obtained4: Ho (nano particle, directly
Diameter is 32-38nm).
Fe as used in the following examples3+The nano material NaLuF containing 40%Gd of modification4: Yb, Er, Gd be according to
Following method is prepared:
By the nano material NaLuF containing 40%Gd4: the solution and NOBF of Yb, Er, Gd4Ultrasound is mixed with mass ratio 1:1
Processing, the temperature of processing are 20 DEG C, time 5min, wash away the oil-soluble ligand on surface, then use CH respectively2Cl2With anhydrous second
Alcohol washs twice, is redispersed in the deionized water for the sodium citrate that mass fraction is 20%, the stir process 1h at 20 DEG C.Through
After crossing citric acid treatment, the FeCl of isometric 0.5mM is added3Solution continues to stir 1h, and centrifuge separation is washed with deionized water
It washs three times, obtains Fe3+The nano material NaLuF containing 40%Gd of modification4:Yb,Er,Gd。
Co as used in the following examples3+The nano material NaGdF containing 80%Gd of modification4: Dy is according to following sides
Method is prepared:
By the nano material NaGdF containing 80%Gd4: the solution and NOBF of Dy4It is mixed and is ultrasonically treated with mass ratio 1:1, place
The temperature of reason is 30 DEG C, time 5min, washes away the oil-soluble ligand on surface, then uses CH respectively2Cl2It is washed with dehydrated alcohol
Twice, being then dispersed in is the stir process 1h at 30 DEG C in the deionized water of 20% sodium citrate containing mass fraction.By
After citric acid treatment, the CoCl of isometric 0.5mM is added3Solution continues to stir 1h, and centrifuge separation is washed with deionized
Three times, Co is obtained3+The nano material NaGdF containing 80%Gd of modification4:Dy。
Ni as used in the following examples3+The nano material NaLuF containing 15%Mn of modification4: Mn is according to following sides
Method is prepared:
By the nano material NaLuF containing 15%Mn4: Mn be dispersed in containing mass fraction be 20% sodium citrate go from
In sub- water, the stir process 1h at 40 DEG C.After citric acid treatment, the NiCl of isometric 0.5mM is added3Solution continues
1h is stirred, centrifuge separation is washed with deionized three times, obtains Ni3+The nano material NaLuF containing 15%Mn of modification4:
Mn。
Fe as used in the following examples3+The nano material NaLuF containing 30%Ho of modification4: Ho is according to following
Method is prepared:
By the nano material NaLuF containing 15%Mn4: Ho be dispersed in containing mass fraction be 20% sodium citrate go from
In sub- water, the stir process 1h at 30 DEG C.After citric acid treatment, the FeCl of isometric 0.5mM is added3Solution continues
1h is stirred, centrifuge separation is washed with deionized three times, obtains Fe3+The nano material NaLuF containing 30%Ho of modification4:
Ho。
Embodiment 1, the concentration for detecting dopamine (DA) aqueous solution:
1) drafting of standard curve: respectively by 50nM, 100nM of 150 μ L, 250nM, 500nM, 1 μM, 4 μM, 8 μM more
Bar amine (DA) aqueous solution and 1.35mL 1mM Fe3+The nano material NaLuF containing 40%Gd of modification4: Yb, Er, Gd aqueous solution
Uniformly mixing after standing reaction 10min, reacts complete, measures the T of mixed liquor respectively1Time and/or T2Time handles data
Obtain T1And/or T2Linear map, obtain the standard curve in concentration and relaxation time.Minimum detection limit can reach 5nM.
2) detection of dopamine (DA) concentration of aqueous solution: by dopamine (DA) aqueous solution and 1.35mL of the 120nM of 150 μ L
1mM Fe3+The nano material NaLuF containing 40%Gd of modification4: Yb, Er, Gd aqueous solution uniformly mix, and stand reaction 10min
Afterwards, it reacts complete, measures T1Time and T2Time, to obtain △ T1/T1 be 21.65, △ T2/T2 is 2.83 for processing, substitution standard
Curve, respectively obtaining concentration is 119.67nM (T1 is calculated) and 119.11nM (T2 is calculated).
Fig. 1 is the Fe in embodiment 13+The nano material NaLuF containing 40%Gd of modification4: the transmission electricity of Yb, Er, Gd
Sub- microscope photo can be obtained from Fig. 1: of uniform size, the good dispersion of nano material.
Fig. 2 is the Fe in embodiment 13+The nano material NaLuF containing 40%Gd of modification4: Yb, Er, Gd detect DOPA
The T1 normal linearity map of amine (DA) aqueous solution, can obtain from Fig. 2: obtained standard diagram is linearly good.
Fig. 3 is the Fe in embodiment 13+The nano material NaLuF containing 40%Gd of modification4: Yb, Er, Gd detect DOPA
The T2 normal linearity map of amine (DA) aqueous solution, can obtain from Fig. 3: obtained standard diagram is linearly good.
In order to compare, the comparison of the present invention and existing detection method to the detection time and detection limit of aqueous dopamine solution
Table is as shown in table 1 below, as known from Table 1: detection limit of the invention is much better than existing detection method, and detection time is big better than absolutely
The existing detection method in part.Wherein, citation [1] BIOSENSORS&BIOELECTRONICS of fluorescence method, 2015,68,
27；Citation [2] JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY of electrochemical process, 2015,15 (7),
4855；Citation [3] MICROCHIMICA ACTA of colorimetric method, 2015,182 (5), 1003.
1 present invention of table is with existing detection method to the correlation data of the detection time of aqueous dopamine solution and detection limit
| Method | Detection limit | Detection time | Source |
| Fluorescence method | 2.02μM/L | 1-30min | [1] |
| Electrochemical process | 1μM/L | 0.5-5min | [2] |
| Colorimetric method | 33nM/L | 5-30min | [3] |
| The present invention | 5nM/L | 0.5-15min | — |
Embodiment 2, the concentration for detecting ascorbic acid (AA) aqueous solution:
1) drafting of standard curve: by 50nM, 100nM of 150 μ L, 250nM, 500nM, 1 μM, 4 μM, 8 μM of Vitamin C
Sour (AA) aqueous solution and 1.35mL, 1mM Co3+The nano material NaGdF containing 80%Gd of modification4: Dy aqueous solution uniformly mixes
It closes, after standing reaction 20min, reacts complete, measure the T of mixed liquor respectively1Time and/or T2Time, processing data obtain T1
And/or T2Linear map.Minimum detection limit can reach 5nM.
2) detection of ascorbic acid (AA) concentration of aqueous solution: by ascorbic acid (AA) aqueous solution of the 120nM of 150 μ L with
1.35mL 1mM Co3+The nano material NaGdF containing 80%Gd of modification4: Dy aqueous solution uniformly mixes, and stands reaction 10min
Afterwards, it reacts complete, measures T2Time, it is 4.90 that processing, which obtains △ T2/T2, substitutes into standard curve, obtaining concentration is
(118.97nM T2 is calculated).
Fig. 4 is the Co in embodiment 23+The nano material NaGdF containing 80%Gd of modification4: the transmission electron microscopy of Dy
Mirror photo can be obtained from Fig. 4: of uniform size, the good dispersion of nano material.
Fig. 5 is the Co in embodiment 23+The nano material NaGdF containing 80%Gd of modification4: Dy detects ascorbic acid
(AA) the T1 normal linearity map of aqueous solution, can obtain from Fig. 5: obtained standard diagram is linearly poor, it is impossible to be used in detection.
Fig. 6 is the Co in the embodiment of the present invention 23+The nano material NaGdF containing 80%Gd of modification4: Dy detection is anti-bad
The T2 normal linearity map of hematic acid (AA) aqueous solution, can obtain from Fig. 6: obtained standard diagram is linearly good.
Embodiment 3, the concentration for detecting potassium iodide (KI) aqueous solution:
1) drafting of standard curve: by 25nM, 50nM of 150 μ L, 100nM, 250nM, 500nM, 1 μM, 4 μM, 8 μM of iodine
Change potassium (KI) aqueous solution and 1.35mL 1mM Ni3+The nano material NaLuF containing 15%Mn of modification4: Mn aqueous solution uniformly mixes
It closes, after standing reaction 15min, reacts complete, measure the T of mixed liquor respectively1Time and/or T2Time, processing data obtain T1
And/or T2Linear map.Detection limit can reach 2.5nM.
2) detection of potassium iodide (KI) concentration of aqueous solution: by potassium iodide (KI) aqueous solution and 1.35mL of the 120nM of 150 μ L
1mM Ni3+The nano material NaLuF containing 15%Mn of modification4: Mn aqueous solution uniformly mixes, after standing reaction 10min, reaction
Completely, T is measured2Time, it is 3.09 that processing, which obtains △ T2/T2, substitutes into standard curve, and obtaining concentration is 122.18nM (T2 meter
It obtains).
Fig. 7 is Ni in embodiment 33+The nano material NaLuF containing 15%Mn of modification4: the transmission electron microscope of Mn
Photo can be obtained from Fig. 7: of uniform size, the good dispersion of nano material.
Fig. 8 is the Ni in embodiment 33+The nano material NaLuF containing 15%Mn of modification4: Mn detects potassium iodide (KI)
The T1 normal linearity map of aqueous solution, can obtain from Fig. 8: obtained standard diagram is linearly poor, it is impossible to be used in detection.
Fig. 9 is the Ni in embodiment 33+The nano material NaLuF containing 15%Mn of modification4: Mn detects potassium iodide (KI)
The T2 normal linearity map of aqueous solution, can obtain from Fig. 9: obtained standard diagram is linearly good.
Embodiment 4, the concentration for detecting sodium fluoride (NaF) aqueous solution:
1) drafting of standard curve: by 100nM, 250nM of 150 μ L, 500nM, 1 μM, 4 μM, 8 μM of sodium fluoride (NaF)
Aqueous solution and 1.35mL 1mM Fe3+The nano particle NaLuF containing 30%Ho of modification4: Ho aqueous solution uniformly mixes, and stands
After reacting 10min, reacts complete, measure the T of mixed liquor respectively1Time and/or T2Time, processing data obtain T1And/or T2
Linear map.Minimum detection limit can reach 10nM.
2) detection of sodium fluoride (NaF) concentration of aqueous solution: by sodium fluoride (NaF) aqueous solution of the 120nM of 150 μ L with
1.35mL 1mM Fe3+The nano particle NaLuF containing 30%Ho of modification4: Ho aqueous solution uniformly mixes, and stands reaction 10min
Afterwards, it reacts complete, measures T1Time and T2Time, to obtain △ T1/T1 be -2.64, △ T2/T2 is 3.52 for processing, substitution standard
Curve, respectively obtaining concentration is 121.65nM (T1 is calculated) and 118.04nM (T2 is calculated).
Figure 10 is the Fe in embodiment 43+The nano material NaLuF containing 30%Ho of modification4: the transmission electron microscopy of Ho
Mirror photo can be obtained from Figure 10: of uniform size, the good dispersion of nano material.
Figure 11 is the Fe in embodiment 43+The nano material NaLuF containing 30%Ho of modification4: Ho detects sodium fluoride
(NaF) T of aqueous solution1Normal linearity map can be obtained from Figure 11: obtained standard diagram is linearly good.
Figure 12 is the Fe in embodiment 43+The nano material NaLuF containing 30%Ho of modification4: Ho detects sodium fluoride
(NaF) T of aqueous solution2Normal linearity map can be obtained from Figure 12: obtained standard diagram is linearly good.
Claims (5)
1. a kind of method of magnetic resonance detection solution concentration, includes the following steps:
1) nano material for containing paramagnetic metal ion with superparamagnetic metal ion modification, obtains functionalized nano material；
2) it is reacted respectively with series of standards product with the functionalized nano material, obtains a series of mixed liquors, and respectively
Its relaxation time is surveyed, the standard curve of relaxation time and concentration is done；
3) solution to be measured of unknown concentration is reacted with the functionalized nano material, obtains mixed liquor, when surveying its relaxation
Between, it is compared with the standard curve to get the concentration of the solution to be measured is arrived；
In step 2) and step 3), the ingredient to be measured in the standard items and solution to be measured is the superparamagnetism with surface modification
The substance of complexing and/or redox reaction occurs for metal ion or surface coated superparamagnetic compound；It is described in step 1)
Superparamagnetic metal ion is selected from Fe3+, Co3+And Ni3+At least one of；
The nano material containing paramagnetic metal ion is nano particle and/or nanometer rods, wherein the nano particle
Diameter is 5nm-999nm, and the length of the nanometer rods is 6nm-20 μm, diameter 5nm-999nm；
The nano material containing paramagnetic metal ion is any in solid phase method, liquid phase method and vapor phase method by conventional method
And it is prepared；
In step 1), the nano material containing paramagnetic metal ion is NaLuF4: Yb, Er, Gd nano particle, NaGdF4:
Dy nanometer rods, NaLuF4: Mn nano particle and NaLuF4: it is any in Ho nano particle；
The NaLuF4: the mass fraction of Gd is 10-80% in Yb, Er, Gd nano particle；
The NaGdF4: the mass fraction of Gd is 15-100% in Dy nanometer rods；
The NaLuF4: the mass fraction of Mn is 10-100% in Mn nano particle；
The NaLuF4: the mass fraction of Ho is 10-100% in Ho nano particle；
The functionalized nano material is that reaction, the functionalized nano are participated in the form of functionalized nano material aqueous solution
The molar concentration of material aqueous solution is 0.1mM-10mM；
The relaxation time is longitudinal relaxation time and/or lateral relaxation time；
The reaction temperature of the reaction is 10-40 DEG C, reaction time 0.5-60min.
2. the method for magnetic resonance detection solution concentration according to claim 1, it is characterised in that: in step 1), the function
Nano material can be changed to be prepared as follows: by nano material and NOBF containing paramagnetic metal ion4It is reacted,
Reaction gains are dispersed in the aqueous solution of sodium citrate again, stir process is eventually adding containing superparamagnetic metal ion
Substance, carry out modification reaction to get arrive the functionalized nano material.
3. the method for magnetic resonance detection solution concentration according to claim 2, it is characterised in that: described to contain paramagnetism gold
Belong to the nano material and NOBF of ion4Mass ratio be (0.1-1): 1；
The reaction temperature of the reaction is 10-40 DEG C, reaction time 5-60min；
The mass fraction of the aqueous solution of the sodium citrate is 2.5%-61%；
The temperature of the stir process is 10-40 DEG C, time 5-60min；
The molar ratio of the superparamagnetic metal ion and the nano material containing paramagnetic metal ion is (0.5-5):
1；
The reaction temperature of the modification reaction is 10-40 DEG C, reaction time 5-60min；
The substance containing superparamagnetic metal ion is CoCl3、FeCl3And NiCl3In it is any.
4. the method for magnetic resonance detection solution concentration according to claim 1, it is characterised in that: in step 2), described one
The concentration range of serial standards is 50nM-8 μM；
The nano material aqueous solution that can change is respectively (0.15-1.5) mL:150 μ L with the volume ratio of the series of standards product.
5. the method for magnetic resonance detection solution concentration according to claim 1, it is characterised in that: step 2) and step 3)
In, the standard items and solution to be measured are aqueous dopamine solution, aqueous ascorbic acid, potassium iodide aqueous solution and sodium fluoride water
Any one of solution.
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