CN106496258B - A kind of preparation method and application of the more nitrogen dysprosium complexs of nanometer - Google Patents
A kind of preparation method and application of the more nitrogen dysprosium complexs of nanometer Download PDFInfo
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- CN106496258B CN106496258B CN201610816144.3A CN201610816144A CN106496258B CN 106496258 B CN106496258 B CN 106496258B CN 201610816144 A CN201610816144 A CN 201610816144A CN 106496258 B CN106496258 B CN 106496258B
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- IBIOTXDDKRNYMC-UHFFFAOYSA-N azanylidynedysprosium Chemical compound [Dy]#N IBIOTXDDKRNYMC-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical class CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001514 detection method Methods 0.000 claims abstract description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 230000005518 electrochemistry Effects 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 5
- 239000000499 gel Substances 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- RQEUFEKYXDPUSK-SSDOTTSWSA-N (1R)-1-phenylethanamine Chemical compound C[C@@H](N)C1=CC=CC=C1 RQEUFEKYXDPUSK-SSDOTTSWSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 239000003599 detergent Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000013384 organic framework Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001903 differential pulse voltammetry Methods 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 238000001548 drop coating Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 150000003939 benzylamines Chemical class 0.000 claims description 2
- 239000003115 supporting electrolyte Substances 0.000 claims description 2
- 229940075397 calomel Drugs 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 230000006837 decompression Effects 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 (+)-Alpha-Methyl benzyl Chemical group 0.000 description 3
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005557 chiral recognition Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ASJSAQIRZKANQN-CRCLSJGQSA-N 2-deoxy-D-ribose Chemical compound OC[C@@H](O)[C@@H](O)CC=O ASJSAQIRZKANQN-CRCLSJGQSA-N 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 229940126534 drug product Drugs 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
- 238000003821 enantio-separation Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000037323 metabolic rate Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to belong to nano metal organic coordination compound and chiral sensing detection technical field, the preparation of specifically a kind of more nitrogen dysprosium complexs of nanometer and its method in detection trace chiral enantiomer electrochemical sensing technology.(1) Dy (NO are used3)3·6H2O, part, N methyl pyrrolidones and the LiOH aqueous solution are raw material, and using sol-gal process, the nanocrystalline more nitrogen dysprosium complexs formed for 30 50nm by particle diameter are made；（2）More nitrogen dysprosium complexs are modified in glassy carbon electrode surface, prepare more nitrogen dysprosium complex chiral sensor working electrodes；（3）More nitrogen dysprosium complex electrochemistry chiral sensors are prepared, detect the content of R (+) α methylbenzylamines or S () α methylbenzylamine enantiomers.Beneficial effects of the present invention are：The preparation method of more nitrogen dysprosium complexs is easy, and energy consumption is low；It is simple, easy to operate based on the electrochemistry chiral sensor of more nitrogen dysprosium complexs, preparation method；Detection to R (+) α methylbenzylamines and S () α methylbenzylamine chiral enantiomer contents, quick response, the good, high sensitivity of selectivity.
Description
Technical field
A kind of preparation method and application of the more nitrogen dysprosium complexs of nanometer of the present invention, belong to nano material, metal organic complexes
Thing and chiral sensing detection technical field.
Background technology
The property that the molecular structure of one compound molecular structure corresponding with its mirror image can not overlap, it is referred to as chirality, this
Relation between two stereoisomers, i.e. referred to as enantiomter（enantiomers）, abbreviation enantiomer.Chirality is life
Material is different from the important symbol of non-living matter, and the property and our daily life are closely bound up, such as DNA and RNA
Ribose and deoxyribose are D configurations, and form 20 kinds of natural amino acids of protein, except glycine exception is L-configuration, institute
There is life chemistry to be carried out in chiral environment.When two or more enantiomers are in chiral environment, would indicate that different
Chemical property and bioactivity, by the phenomenon of selectively acting between chiral environment and enantiomer chiral Recognition.
Physical-chemical property between chiral enantiomer is in addition to optical activity difference, other equal indistinctions, but chipal compounds
Into internal, its physiological action by by internal macromolecular, between such as chiral acceptor, enzyme, carrier strict chiral matching and
Identify and realize, in many cases, absorption, distribution, metabolism and excretion of the chiral enantiomer in life entity have very big
Difference, that is to say, that activity, metabolic process, metabolic rate and the toxicity of chiral enantiomer in life entity etc. exists significant
Difference.The behavior of chiral enantiomer significant difference in vivo is mainly manifested in:1. may be only a kind of in two enantiomers
Enantiomer has physiologically active, and another kind is then without significant physiologically active;2. the physiologically active of two kinds of configurations of chiral enantiomer
It is different；3. a kind of configuration of enantiomer mainly has physiologically active, and another kind produces serious side effect；4. two mappings
Body has same or like physiologically active.
At present, the production of chipal compounds and application percentage increasingly increase, this require to have to look for it is effective, quick simultaneously
The method of convenient detection and identification chiral enantiomer.In recent years, asked to solve caused by racemic modification medicine some
Topic, many developed countries constantly promulgate the guidance quality guide or policy of relevant chiral drug exploitation.In the U.S., the food of chiral drug
Product and Drug Administration (FICA) require that the chiral component and enantiomer that contain in applicant's mandatory declaration novel drugs are respective
Pharmacological action, clinical effectiveness and toxicity, and attempt to separate stereoisomer therein.Canada, European Community etc. have also formulated phase
The policy of pass.Therefore, the identification of chipal compounds, reasonably accurate use and control chiral drug to studying chiral drug
The problems such as quality, has great importance.
At present, the method for chiral Recognition mainly includes chiral chromatogram and spectrum.Wherein chiral chromatography methods are extensive
Chipal compounds are analyzed for separating, but the method instrument cost is high, analysis time is long, cumbersome, and technical requirements are high, and are difficult to
Realize in situ and on-line checking etc..Using the chiral detection enantiomer of electrochemical techniques and its content, play Electrochemical Detection and prepare
Simply, the advantages that cost is low, recognition efficiency is high, there is important application value.
The content of the invention
One of technical assignment of the present invention is to make up the deficiencies in the prior art, there is provided a kind of more nitrogen dysprosiums of achirality nanometer
The preparation method of complex, the raw materials used cost of this method is low, and preparation technology is simple, and energy consumption of reaction is low, before having commercial Application
Scape.
The two of the technical assignment of the present invention are to provide the purposes of the more nitrogen dysprosium complexs of the achirality nanometer, will the complex
For the content of efficient detection R (+)-Alpha-Methyl benzylamine and S (-)-Alpha-Methyl benzylamine enantiomer, the chiral detecting instrument cost
It is low, analysis efficiency is high, easy to operate, operating technology require it is low.
Technical scheme is as follows：
1. a kind of preparation method of the more nitrogen dysprosium complexs of nanometer, preparation process are as follows：
By 45.6mg Dy (NO3)3·6H2O and 9.7mg part H3L and 0.3-0.9mL 1-METHYLPYRROLIDONE
NMP is blended, and the obtained settled solution of room temperature ultrasound, 0.12-0.16mL, 3mol/L the LiOH aqueous solution is added dropwise in 10-30s and shakes
Blending is shaken, more nitrogen dysprosium complex DyL gels are made, the gel is inverted still without mobility；After DyL gel detergents, what is obtained consolidates
Body powder is dried overnight in 40-50 DEG C, and the more nitrogen dysprosium complexs of nanometer are made；Yield is 70-76%.
（1）The H3L, structural formula are as follows：
（2）The H3L, preparation process are as follows：
Into 13-15 mmol PABA, under agitation, 20mL, mmol containing 15-17 are sequentially added
The aqueous solution and 5mL of sodium hydroxide, the dioxane solution of the cyanuric trichloride containing 3mmol, are heated to reflux 10-12h, are adjusted with hydrochloric acid
PH is 2-3, and decompression filters, and the solid filtered out is washed with water three times, H is made3L, yield 85-88%；
（3）The L, structural formula are as follows：
（4）It is described that DyL gel detergents, step is as follows：
Centrifuged after DyL gels and 4-10mL ethanol are blended into uniform mixed liquor, obtained solid powder divides again
Do not washed 2 times with 4-10mL ethanol；
（5）The more nitrogen dysprosium complexs of nanometer, belong to 3D porous metals organic frameworks, its chemical formula is { [Dy3L
(H2O)6](NO3)6(NMP)17(H2O)5}；
（6）The more nitrogen dysprosium complexs of nanometer, it is that the nanocrystalline of 30-50nm forms by particle diameter.
2. the more nitrogen dysprosium complexs of nanometer prepared by preparation method as described above, for chirality detection R (+)-Alpha-Methyl benzyl
The content of amine or S (-)-Alpha-Methyl benzylamine enantiomer；
The content of chiral detection R (+)-Alpha-Methyl benzylamine or S (-)-Alpha-Methyl benzylamine enantiomer, step are as follows：
（1）In the more nitrogen dysprosium complexs of surface modification that basal electrode is glass-carbon electrode, the chiral biography of more nitrogen dysprosium complexs is prepared
The working electrode of sensor；
The more nitrogen dysprosium complexs of surface modification, be polished in alumina powder glassy carbon electrode surface drop coating 6uL,
The more nitrogen dysprosium complex solutions of nanometer, room temperature are dried；
The more nitrogen dysprosium complex solutions of nanometer, be by the more nitrogen dysprosium complexs of 3mg nanometer and 0.25mL isopropanols and
The blending ultrasound 15min of 0.75mL water is made；
（2）Prepare more nitrogen dysprosium complex electrochemistry chiral sensors, detection R (+)-Alpha-Methyl benzylamine or S (-)-Alpha-Methyl
The content of benzylamine enantiomer；
The preparation electrochemistry chiral sensor, is by reference electrode, to electrode and above-mentioned steps（1）The work electricity of preparation
Pole is connected on electrochemical workstation, forms the electrochemistry chiral sensor based on more nitrogen dysprosium complexs, and the reference electrode is
Saturated calomel electrode, it is platinum electrode to electrode；
The content of detection R (+)-Alpha-Methyl benzylamine or S (-)-Alpha-Methyl benzylamine enantiomer, it is to contain 0.1 with pH 5.5
MolL-1 KCl as supporting electrolyte PBS cushioning liquid as bottom liquid, using differential pulse voltammetry, respectively
R (+)-Alpha-Methyl benzylamine of various concentrations or the current value of S (-)-Alpha-Methyl benzylamine are determined, draws R (+)-Alpha-Methyl benzylamine and S
The working curve based on the more nitrogen dysprosium complex sensors of nanometer of (-)-Alpha-Methyl benzylamine molecule.
The beneficial technique effect of the present invention：
（1）The preparation method of more nitrogen dysprosium complexs is easy, and energy consumption is low
The preparation generally use solvent-thermal method of metal organic complex, this method be by metal salt, organic ligand and water or
Other solvent seals are heated to certain temperature (80-300 DEG C), because in kettle in the stainless steel cauldron of inner liner polytetrafluoroethylene
Pressure can reach hundreds of atmospheric pressure, cause many compounds to dissolve reaction in the supercritical state, after maintaining a period of time, delay
Slow cooling, reactant mixture crystallize to obtain the crystal of sizeable systematicness.It is limited in that preparation time is longer, and needs
HTHP step is wanted, the application of method in the industrial production is hindered to challenge of production equipment and high energy consumption etc..This
Invention uses gel method, is only blended by raw material, and using the difference of usual vehicle solubility, one-step method, a few minutes are made
The more nitrogen dysprosium complexs of nanometer, process is simple, is easy to industrialize.
（2）The invention provides a kind of electrochemistry chiral sensor based on more nitrogen dysprosium complexs, the sensor is will be more
Nitrogen dysprosium complex decorating is made in glassy carbon electrode surface, and preparation method is simple, easy to operate.Particular note is that more nitrogen dysprosiums are matched somebody with somebody
Compound, and achiral material, but because in the material nano size and molecule the avtive spot of more nitrogen-atoms and metal have machine frame
The synergy of porous grade in frame so that the sensor of material modification successfully detects R (+)-Alpha-Methyl benzylamine and S (-)-α-first
The content of base benzylamine chiral enantiomer, and there is quick response, the good, high sensitivity of selectivity；Detection operation letter
It is single, time saving.Experiment shows that the chiral sensor is 0.01-1.0 × 10 to R (+)/S (-)-Alpha-Methyl benzylamine detection range-13g/
mL。
Embodiment
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not only limited to implement
Example, the change that professionals in the field is made to technical solution of the present invention, all should belong in protection scope of the present invention.
Embodiment 1 prepares H3L parts
Into 13 mmol PABA, under agitation, 20mL is sequentially added, containing 15 mmol hydroxides
The aqueous solution and 5mL of sodium, the dioxane solution of the cyanuric trichloride containing 3mmol, are heated to reflux 10 h, and it is 2- to adjust pH with hydrochloric acid
3, decompression is filtered, and the solid filtered out is washed with water three times, H is made3L, yield 85%.
Embodiment 2 prepares H3L parts
Into 15 mmol PABA, under agitation, 20mL is sequentially added, containing 17 mmol hydroxides
The aqueous solution and 5mL of sodium, the dioxane solution of the cyanuric trichloride containing 3mmol, are heated to reflux 12h, and it is 2-3 to adjust pH with hydrochloric acid,
Decompression is filtered, and the solid filtered out is washed with water three times, H is made3L, yield 88%.
Embodiment 3 prepares H3L parts
Into 14 mmol PABA, under agitation, 20mL is sequentially added, containing 16 mmol hydroxides
The aqueous solution and 5mL of sodium, the dioxane solution of the cyanuric trichloride containing 3mmol, are heated to reflux 11 h, and it is 2- to adjust pH with hydrochloric acid
3, decompression is filtered, and the solid filtered out is washed with water three times, H is made3L, yield 86%.
Embodiment 4
By H made from embodiment 1-33L parts, warp1HNMR and12CNMR is detected, and its structural formula is as follows：
Embodiment 5 prepares the more nitrogen dysprosium complexs of nanometer
By 45.6mg Dy (NO3)3·6H2O and 9.7mg part H3L and 0.3 mL 1-METHYLPYRROLIDONE NMP
Blending, the obtained settled solution of room temperature ultrasound, 0.12mL, 3mol/L the LiOH aqueous solution are added dropwise in 10s and shakes blending, is made
More nitrogen dysprosium complex DyL gels, the gel are inverted still without mobility；After DyL gel detergents, obtained solid powder is in 40 DEG C
It is dried overnight, the more nitrogen dysprosium complexs of obtained nanometer, nitrogen dysprosium complex more than this nanometer, belongs to 3D porous metals organic frameworks, it is changed
Formula is { [Dy3L (H2O)6](NO3)6(NMP)17(H2O)5}；It is that the nanocrystalline of 30-50nm forms by particle diameter.Yield is 70%.
Embodiment 6 prepares the more nitrogen dysprosium complexs of nanometer
By 45.6mg Dy (NO3)3·6H2O and 9.7mg part H3L and 0.9mL 1-METHYLPYRROLIDONE NMP is total to
It is mixed, the obtained settled solution of room temperature ultrasound, 0.16mL, 3mol/L the LiOH aqueous solution are added dropwise in 30s and shakes blending, is made more
Nitrogen dysprosium complex DyL gels, the gel are inverted still without mobility；After DyL gel detergents, obtained solid powder is dry in 50 DEG C
It is dry overnight, the more nitrogen dysprosium complexs of nanometer are made；The dysprosium complex of nitrogen more than this nanometer, belong to 3D porous metals organic frameworks, its chemistry
Formula is { [Dy3L (H2O)6](NO3)6(NMP)17(H2O)5}；It is that the nanocrystalline of 30-50nm forms by particle diameter.Yield is 76%.
Embodiment 7 prepares the more nitrogen dysprosium complexs of nanometer
By 45.6mg Dy (NO3)3·6H2O and 9.7mg part H3L and 0.6mL 1-METHYLPYRROLIDONE NMP is total to
It is mixed, the obtained settled solution of room temperature ultrasound, 0.14 mL, 3mol/L LiOH aqueous solution is added dropwise in 10-30s and shakes blending, makes
Much nitrogen dysprosium complex DyL gels, the gel are inverted still without mobility；After DyL gel detergents, obtained solid powder is in 45
DEG C it is dried overnight, is made the more nitrogen dysprosium complexs of nanometer, nitrogen dysprosium complex more than this nanometer, belongs to 3D porous metals organic frameworks, its
Chemical formula is { [Dy3L (H2O)6](NO3)6(NMP)17(H2O)5}；It is that the nanocrystalline of 30-50nm forms by particle diameter；Yield is
73%。
Embodiment 8
The more nitrogen dysprosium complexs of nanometer prepared by embodiment 5 or embodiment 6 or embodiment 7, chirality detection R (+)-Alpha-Methyl benzyl
The content of amine or S (-)-Alpha-Methyl benzylamine enantiomer；
（1）Prepare more nitrogen dysprosium complex chiral sensor working electrodes
Glass-carbon electrode is clear with 1.0,0.3,0.05 μm of alundum (Al2O3) polishing powder polishing, EtOH Sonicate
Wash, then it is clean with ultrapure water, dry；In the more nitrogen dysprosium complex solutions of glassy carbon electrode surface drop coating 6uL nanometer, room temperature is dried in the air
It is dry, the working electrode of more nitrogen dysprosium complex chiral sensors is made；
The more nitrogen dysprosium complex solutions of nanometer, be by the more nitrogen dysprosium complexs of 3mg nanometer and 0.25mL isopropanols and
The blending ultrasound 15min of 0.75 mL water is made；
（2）Prepare more nitrogen dysprosium complex electrochemistry chiral sensors
By reference electrode, to electrode and above-mentioned steps（1）The working electrode of preparation is connected on electrochemical workstation, is formed
Based on the electrochemistry chiral sensor of more nitrogen dysprosium complexs, the reference electrode is saturated calomel electrode, is platinum filament electricity to electrode
Pole；
（3）Detect the content of R (+)-Alpha-Methyl benzylamine or S (-)-Alpha-Methyl benzylamine enantiomer
Contain 0.1 molL using 10mL, pH as 5.5-1KCl PBS cushioning liquid is distinguished as bottom liquid in the liquid of bottom
It is continuously added to 10uL, containing 0.5mgmL-1R (+)-Alpha-Methyl benzylamine or S (-)-Alpha-Methyl benzylamine pH be 5.5 PBS buffering it is molten
Liquid, using differential pulse voltammetry, R (+)-Alpha-Methyl benzylamine of various concentrations or the current value of S (-)-Alpha-Methyl benzylamine are determined,
Draw the working curve of R (+)-Alpha-Methyl benzylamine and S (-)-Alpha-Methyl benzylamine molecule；
Measurement result shows that R (+)-Alpha-Methyl benzylamine and S (-)-Alpha-Methyl benzylamine are in 0.01-1.0 × 10-13G/mL scopes
Interior linear, the chiral sensor is limited to 0.1 × 10 to R (+)/S (-)-Alpha-Methyl benzylamine detection-11g/L。
Claims (3)
1. a kind of preparation method of the more nitrogen dysprosium complexs of nanometer, it is characterised in that preparation process is as follows：
By 45.6mg Dy (NO3)3·6H2O and 9.7mg part H3L and 0.3-0.9mL 1-METHYLPYRROLIDONE NMP blendings,
The obtained settled solution of room temperature ultrasound, 0.12-0.16mL, 3mol/L the LiOH aqueous solution are added dropwise in 10-30s and shakes blending,
More nitrogen dysprosium complex DyL gels are made, the gel is inverted still without mobility；After DyL gel detergents, obtained solid powder in
40-50 DEG C is dried overnight, and the more nitrogen dysprosium complexs of nanometer are made；Yield is 70-76%；
The H3L, structural formula are as follows：
The H3L, preparation process are as follows：
Into 13-15mmol PABA, under agitation, 20mL, sodium hydroxide containing 15-17mmol are sequentially added
The aqueous solution and 5mL, the dioxane solution of the cyanuric trichloride containing 3mmol, be heated to reflux 10-12h, with hydrochloric acid adjust pH be 2-3, subtract
Pressure is filtered, and the solid filtered out is washed with water three times, H is made3L, yield 85-88%；
The L, structural formula are as follows：
It is described that DyL gel detergents, step is as follows：
Centrifuged after DyL gels and 4-10mL ethanol are blended into uniform mixed liquor, obtained solid powder is used respectively again
4-10mL ethanol washs 2 times；
The more nitrogen dysprosium complexs of nanometer, belong to 3D porous metals organic frameworks, its chemical formula is { [Dy3L(H2O)6](NO3)6
(NMP)17(H2O)5}；
The more nitrogen dysprosium complexs of nanometer, it is that the nanocrystalline of 30-50nm forms by particle diameter.
2. the more nitrogen dysprosium complexs of nanometer prepared by preparation method as claimed in claim 1 are used for chiral detection R (+)-Alpha-Methyl
The purposes of the content of benzylamine or S (-)-Alpha-Methyl benzylamine enantiomer.
3. purposes as claimed in claim 2, it is characterised in that chiral detection R (+)-Alpha-Methyl benzylamine or S (-)-α-first
The content of base benzylamine enantiomer, step are as follows：
(1) in the more nitrogen dysprosium complexs of surface modification that basal electrode is glass-carbon electrode, more nitrogen dysprosium complex chiral sensors are prepared
Working electrode；
The more nitrogen dysprosium complexs of surface modification, it is the glassy carbon electrode surface drop coating 6uL polished in alumina powder nanometer
More nitrogen dysprosium complex solutions, room temperature are dried；
The more nitrogen dysprosium complex solutions of nanometer, it is by the more nitrogen dysprosium complexs of 3mg nanometer and 0.25mL isopropanols and 0.75mL
The blending ultrasound 15min of water is made；
(2) more nitrogen dysprosium complex electrochemistry chiral sensors, detection R (+)-Alpha-Methyl benzylamine or S (-)-Alpha-Methyl benzylamine are prepared
The content of enantiomer；
The preparation electrochemistry chiral sensor, it is to connect reference electrode, the working electrode prepared to electrode and above-mentioned steps (1)
It is connected on electrochemical workstation, forms the electrochemistry chiral sensor based on more nitrogen dysprosium complexs, the reference electrode is saturation
Calomel electrode, it is platinum electrode to electrode；
The content of detection R (+)-Alpha-Methyl benzylamine or S (-)-Alpha-Methyl benzylamine enantiomer, is to contain 0.1mol with pH 5.5
L-1KCl as supporting electrolyte PBS cushioning liquid as bottom liquid, using differential pulse voltammetry, measure is different dense respectively
The current value of the R (+) of degree-Alpha-Methyl benzylamine and S (-)-Alpha-Methyl benzylamine, draw based on the more nitrogen dysprosium complex sensors of nanometer
R (+)-Alpha-Methyl benzylamine and S (-)-Alpha-Methyl benzylamine enantiomer working curve.
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| Synthesis, Characterization and Photoluminescence of Lanthanide Metal-organic Frameworks, Constructed from Triangular 4,4,4-s-triazine-1,3,5-triyl-p-aminobenzoate Ligands;Ju-Hsiou Liao et al.;《J. Chin. Chem. Soc.》;20140707;第61卷;第1115-1120页 * |
| Versatile Mesoporous DyIII Coordination Framework for Highly Efficient Trapping of Diverse Pollutants;Miao Du et al.;《Inorg. Chem.》;20140702;第53卷;第7074-7076页 * |
| 手性金属有机框架材料的构建及其在分离与识别中的应用研究;匡轩;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20150915(第9期);第B014-40页 * |
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