CN106432308A - Rare-earth cerium Schiff base complex and preparation method and application thereof - Google Patents
Rare-earth cerium Schiff base complex and preparation method and application thereof Download PDFInfo
- Publication number
- CN106432308A CN106432308A CN201610874416.5A CN201610874416A CN106432308A CN 106432308 A CN106432308 A CN 106432308A CN 201610874416 A CN201610874416 A CN 201610874416A CN 106432308 A CN106432308 A CN 106432308A
- Authority
- CN
- China
- Prior art keywords
- cerium
- preparation
- complex
- schiff bases
- tcptp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Rare-earth cerium Schiff base Chemical class 0.000 title claims abstract description 23
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 21
- 239000002262 Schiff base Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 title description 7
- 238000010668 complexation reaction Methods 0.000 title description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000000694 effects Effects 0.000 claims abstract description 15
- 101001087394 Homo sapiens Tyrosine-protein phosphatase non-receptor type 1 Proteins 0.000 claims abstract description 12
- 102100033001 Tyrosine-protein phosphatase non-receptor type 1 Human genes 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 1
- 102000002727 Protein Tyrosine Phosphatase Human genes 0.000 abstract description 16
- 108020000494 protein-tyrosine phosphatase Proteins 0.000 abstract description 16
- 150000000703 Cerium Chemical class 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- OHFIJHDYYOCZME-UHFFFAOYSA-N pyrazine-2-carbohydrazide Chemical compound NNC(=O)C1=CN=CC=N1 OHFIJHDYYOCZME-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 23
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 19
- 229910002651 NO3 Inorganic materials 0.000 description 18
- 239000000243 solution Substances 0.000 description 10
- 230000001629 suppression Effects 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical group N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 3
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 3
- 102000004877 Insulin Human genes 0.000 description 2
- 108090001061 Insulin Proteins 0.000 description 2
- 239000007993 MOPS buffer Substances 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 108091000080 Phosphotransferase Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 210000001185 bone marrow Anatomy 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 230000030609 dephosphorylation Effects 0.000 description 2
- 238000006209 dephosphorylation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229940125396 insulin Drugs 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- IDSXLJLXYMLSJM-UHFFFAOYSA-N morpholine;propane-1-sulfonic acid Chemical compound C1COCCN1.CCCS(O)(=O)=O IDSXLJLXYMLSJM-UHFFFAOYSA-N 0.000 description 2
- 230000026731 phosphorylation Effects 0.000 description 2
- 238000006366 phosphorylation reaction Methods 0.000 description 2
- 102000020233 phosphotransferase Human genes 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000019491 signal transduction Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- 0 CCC*(IC**(C)(C)N)[U] Chemical compound CCC*(IC**(C)(C)N)[U] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 101000852815 Homo sapiens Insulin receptor Proteins 0.000 description 1
- 101000617289 Homo sapiens Tyrosine-protein phosphatase non-receptor type 9 Proteins 0.000 description 1
- 102100036721 Insulin receptor Human genes 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 102000004022 Protein-Tyrosine Kinases Human genes 0.000 description 1
- 108090000412 Protein-Tyrosine Kinases Proteins 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 102100033019 Tyrosine-protein phosphatase non-receptor type 11 Human genes 0.000 description 1
- 101710116241 Tyrosine-protein phosphatase non-receptor type 11 Proteins 0.000 description 1
- 102100021657 Tyrosine-protein phosphatase non-receptor type 6 Human genes 0.000 description 1
- 101710128901 Tyrosine-protein phosphatase non-receptor type 6 Proteins 0.000 description 1
- 102100021722 Tyrosine-protein phosphatase non-receptor type 9 Human genes 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003178 anti-diabetic effect Effects 0.000 description 1
- 230000000118 anti-neoplastic effect Effects 0.000 description 1
- 230000003579 anti-obesity Effects 0.000 description 1
- 239000003472 antidiabetic agent Substances 0.000 description 1
- 206010003246 arthritis Diseases 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 210000003719 b-lymphocyte Anatomy 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 230000024245 cell differentiation 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
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 230000003828 downregulation Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003596 drug target Substances 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000010437 erythropoiesis Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 210000003958 hematopoietic stem cell Anatomy 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- FWFOFBMNMJJKEQ-UHFFFAOYSA-N n-(pyridin-2-ylmethylideneamino)pyrazine-2-carboxamide Chemical compound C=1N=CC=NC=1C(=O)NN=CC1=CC=CC=N1 FWFOFBMNMJJKEQ-UHFFFAOYSA-N 0.000 description 1
- 230000018791 negative regulation of catalytic activity Effects 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009822 protein phosphorylation Effects 0.000 description 1
- 239000003801 protein tyrosine phosphatase 1B inhibitor Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000022983 regulation of cell cycle Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000026683 transduction Effects 0.000 description 1
- 238000010361 transduction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides a rear-earth cerium Schiff base complex and a preparation method and application thereof. The molecular formula of the complex is [Ce(HL)2(NO3)3], wherein HL is N'-(pyridine-2-methylene)pyrazine-2-carbohydrazide. The preparation method of the complex comprises the steps that a methanol solution of rear earth cerium salt is dropwise added into a methanol solution placed in a ligand of a round-bottom flask, heating reflux is conducted at the temperature ranging from 40 DEG C to 60 DEG C for 6-9 h, deep green clear liquid is obtained, filtration is conducted, light yellow blocky crystals are dissolved out from a filtrate, and the yield is 45%-75% or above. The complex has a good inhibiting effect on the activity of protein tyrosine phosphatase (PTP1B and TCPTP) and can serve as an inhibitor of the protein tyrosine phosphatase (PTP1B and TCPTP) for use.
Description
Technical field
The present invention relates to metal complex field is and in particular to a kind of cerium schiff bases complex and preparation method thereof,
And this coordination compound is as the application of PTP1B and TCPTP activity inhibitor.
Background technology
Protein-tyrosine-phosphatase (PTPs) is to be widely present in the biological internal metal-free enzyme of a class, it and albumen
Kinases this reversible dynamic process of common modulin tyrosine phosphorylation.Wherein, protein-tyrosine makes protein phosphorylation, and egg
White kinases then makes albumen dephosphorylation.PTPs is capable of the transduction of cell cycle regulation and signal, in terms of the response of cell signal,
It can be by combining to come the effect degree of modulin tyrosine phosphorylation with protein tyrosine kinase.These signaling systeies
Abnormal regulation path is found relevant with numerous disease.Abnormal PTPs activity may result in including cancer, diabetes and rheumatism
Property arthritis etc. are in the generation of interior numerous disease.Because PTPs plays pivotal role in terms of disease control, therefore can conduct
Drug targets.Existing 107 kinds of the species of the PTPs that people's research at present finds, such as PTP1B, TCPTP, SHP-1, SHP-2, PTP-
MEG2 etc..
Wherein PTP1B is by making Insulin receptor INSR dephosphorylation, negative regulation insulin signal transduction.Biochemical research
Show, PTP1B clpp gene deratization is not only developed normally, and the sensitivity of insulin is increased, cancer morbidity and getting fat
Probability also has no raising.Therefore, PTP1B is the Effective target site for the treatment of type Ⅱdiabetes mellitus and obesity.The research of PTP1B inhibitor
It is expected to filter out the novel drugs of the anti-diabetic of high-efficiency low-toxicity and anti-obesity.
TCPTP is distributed more widely in cell body, have expression with each stage of cell in a organized way.Participate in a plurality of thin
The regulation of born of the same parents' signal transduction path, adjusts cell differentiation, propagation.Research to TCPTP deficient mice shows, TCPTP is to cell
Factor response and erythropoiesis have regulating and controlling effect, the fall of B cell number in the serious minimizing of cell quantity and bone marrow in bone marrow
Low prompting TCPTP has important effect in hematopoietic cell development.Therefore, the searching of TCPTP inhibitor and screening are possible to
Become the important channel of new type antineoplastic medicine research and development.
Content of the invention
A kind of it is an object of the invention to provide cerium schiff bases complex and preparation method thereof, and this coordination compound work
Application for PTP1B and TCPTP activity inhibitor.
A kind of cerium schiff bases complex that the present invention provides, its molecular formula is [Ce (HL)2(NO3)3], wherein HL is
N'- (pyridine -2- methylene) pyrazine -2- carbohydrazide (N'- (pyridin-2-ylmethylene) pyrazine-2-
Carbohydrazide, chemical formula C11H9N5O), structural formula is：
The preparation method of the cerium schiff bases complex that the present invention provides, comprises the steps：
(1) by Ce (NO3)3It is dissolved in methanol solution with N'- (pyridine -2- methylene) pyrazine -2- carbohydrazide respectively；
(2) above two solution is placed in mixing in reactor, 40-60 DEG C is heated to reflux 6-9h, obtains blackish green clear liquid, mistake
Filter, separates out faint yellow bulk crystals in filtrate.
Step (1) Ce (NO3)3Mol ratio with N'- (pyridine -2- methylene) pyrazine -2- carbohydrazide is 2：1.
The crystal of the cerium schiff bases complex of present invention preparation belongs to monoclinic C2/CSpace group, cell parameter： α=90 °, β=126.447 (1) °, γ=90 °.Should
In coordination compound, cerium ion and part form 1：2 mol ratio, two parts all with three tooth chelating ligands to cerium ion, simultaneously cerium from
Son also reaches electric neutrality with three nitrate ion coordinations.From methanol, the coordination compound of the present invention of crystallization contains the molten of two molecules
Agent.
The cerium schiff bases complex of the present invention has to the activity of Protein-tyrosine-phosphatase (PTP1B and TCPTP)
Inhibitory action, the half-inhibition concentration (IC to PTP1B50) be：5.21 μM, the half-inhibition concentration (IC to TCPTP50) be：
2.02μM.It can be applied as the inhibitor of Protein-tyrosine-phosphatase (PTP1B and TCPTP).
Advantages of the present invention and effect：
The cerium schiff bases complex of the present invention is rare-earth salts Ce (NO3)3React in a heated condition with schiff base ligand
Obtain, preparation method is convenient and simple, product purity is high, yield is high, up to 75%.
The cerium schiff bases complex that the present invention provides passes through half-inhibition concentration (IC50) mensure learn it to albumen
The activity of tyrosine phosphatase has inhibitory action, different to the rejection ability of different PTPs, and coordination compound shows selection to TCPTP
Property.
Brief description
Fig. 1 rare earth of the present invention cerium complexes [Ce (HL)2(NO3)3]·2CH3The crystal structure figure of OH
Fig. 2 rare earth of the present invention cerium complexes [Ce (HL)2(NO3)3] Electrospray Mass Spectrometry figure
Fig. 3 rare earth of the present invention cerium complexes [Ce (HL)2(NO3)3] the active IC of suppression PTP1B50Value measures curve
Fig. 4 rare earth of the present invention cerium complexes [Ce (HL)2(NO3)3] the active IC of suppression TCPTP50Value measures curve
Specific embodiment
Embodiment 1. coordination compound of the present invention [Ce (HL)2(NO3)3] preparation and crystal cultural method.
Weigh 0.434g Ce (NO3)3It is dissolved in 2ml methanol, 0.114g N'- (pyridine -2- methylene) pyrazine -2- carbohydrazide
It is dissolved in 50ml methanol, above two solution is placed in mixing in reactor, 55 DEG C are heated to reflux 8h, obtain blackish green clear liquid, filters,
Separate out faint yellow bulk crystals in filtrate, collect crystal and respectively washed three times with water, methanol respectively, vacuum drying, yield is 65%.
Elementary analysiss [Ce (C11H9N5O)2(NO3)3]·2CH3OH：Theoretical value：C 33.53H 2.70N 22.03；Experiment value：C
33.99, H 2.73, N 22.41.
Embodiment 2. coordination compound of the present invention [Ce (HL)2(NO3)3]·2CH3The monocrystalline X-ray diffraction experimental condition knot of OH
Really.
Under high power microscope, picking rule, transparent yellow bulk-shaped monocrystal granule.Selected crystal glass fiber is cemented,
And be fixed on Bruker SMART 1000CCD face spy diffractometer.With graphite monochromator Mo-K α as radiating light source, collect sample
To wavelength it isX-ray diffraction data.With ω scan mode, diffraction data is through the LP factor and empirical absorption correction.
After all X-ray diffraction figure is reduced to diffraction index data, solve crystal structure with SHELXL-97 direct method, hydrogen atom adopts
Theoretical hydrogenation, and make anisotropy refine, finally draw corresponding molecular structure.Some other detailed information about crystal
It is listed in table 1.
Table 1 coordination compound [Ce (C11H9N5O)2(NO3)3]·2CH3The crystallographic data of OH
Embodiment 3. coordination compound [Ce (HL)2(NO3)3] Electrospray Mass Spectrometry：
In order to study coordination compound existence form in the solution, a small amount of coordination compound pressed powder is dissolved in methanol, centrifugation
Obtain clear transparent solutions, be loaded to electrospray mass spectrometer, using electric spray ion source, detected with positive ion mode and record number
According to.Fig. 2 is the positive ionization electrospray mass spectrum of coordination compound.The molecular ion of corresponding coordination compound can be observed in all collection of illustrative plates
Peak.Table 2 is the positive ionization electrospray mass spectrum ownership of coordination compound.Result shows, experiment value is consistent with theoretical value, and coordination compound is in solution
In be to be existed with synthesizing the form stable that obtains.
Table 2 coordination compound [Ce (HL)2(NO3)3] (1) positive ionization electrospray mass spectrum ownership
Embodiment 4. rare earth compounding of the present invention [Ce (HL)2(NO3)3] PTP1B and TCPTP inhibition is detected.
IC50Measuring principle：
Protein-tyrosine-phosphatase (PTPs) can make reaction substrate 4-NPP salt (pNPP) decompose yellowly
Paranitrophenol, this product has very strong absorption at 405nm.After PTPs is acted on coordination compound, inhaled at 405nm by detecting
The change of shading value carrys out the situation of change of indirect detection enzymatic activity.
IC50The meaning of value：
IC50Refer to enzyme activity be reduced to former activity half when, inhibitor concentration now, suppression is weighed with this
The inhibition of agent, IC50Numerical value is less, illustrates that inhibitor suppresses the effect of PTPs activity better, detects on this basis
Suppression ratio.
IC50Assay method：
The mensure of inhibition of enzyme activity experiment is to be in pH for reaction substrate with 0.1M 4-NPP salt (pNPP)
Carry out in 6.00 MOPS buffer system [30mM morpholinepropanesulfonic acid (MOPS), 50mM NaCl].
Coordination compound dimethyl sulfoxide (DMSO) is dissolved, is made into 10-2The mother solution of M, then it is diluted to variable concentrations with DMSO
Solution (10-3M、10-4M、10-5M、10-6M、10-7M、10-8M、10-9M).With MOPS buffer solution, PTPs to be used is diluted
To finite concentration (matching while using).In 96 orifice plates, every hole sequentially adds 83 μ l and contains enzyme buffer solution, the joining of 10 μ l variable concentrations
Polymer solution, after 37 DEG C of constant temperature 30min of water-bath, starts reaction with the pNPP of 2 μ l (0.1M), after 30min, plus 5 μ l (2M)
NaOH terminating reaction, measures the catabolite paranitrophenol (pNP) of substrate at wavelength X=405nm by microplate reader
Absorption intensity.Using the logarithm of coordination compound concentration as abscissa, suppression ratio, as vertical coordinate, using the mapping of Origin program, is intended
Close and obtain the curve to enzyme level ability for the coordination compound, try to achieve suppression ratio corresponding coordination compound concentration when 50%, that is, IC50
Value.
All continuous modes are designed with blank and control experiment, to exclude the interference of solvent interference, coordination compound intrinsic colour.
Every time with the new complex solution prepared, and above parallel laboratory test in triplicate.
Testing result 1：Coordination compound [Ce (HL)2(NO3)3] half-inhibition concentration (IC to PTP1B50) be：5.21 μM (see
Fig. 3).
Testing result 2：Coordination compound [Ce (HL)2(NO3)3] half-inhibition concentration (IC to TCPTP50) be：2.02 μM (see
Fig. 4).
Claims (7)
1. a kind of cerium schiff bases complex, its structural formula is：
2. as claimed in claim 1 a kind of preparation method of cerium schiff bases complex it is characterised in that including following walking
Suddenly：
(1) by Ce (NO3)3It is dissolved in methanol solution with N'- (pyridine -2- methylene) pyrazine -2- carbohydrazide respectively；
(2) above two solution is placed in mixing in reactor, 40-60 DEG C is heated to reflux 6-9h, obtains blackish green clear liquid, filters,
Faint yellow bulk crystals are separated out in filtrate.
3. as claimed in claim 2 a kind of preparation method of cerium schiff bases complex it is characterised in that described step
(1)Ce(NO3)3Mol ratio with N'- (pyridine -2- methylene) pyrazine -2- carbohydrazide is 1：2.
4. as claimed in claim 2 a kind of preparation method of cerium schiff bases complex it is characterised in that described reaction temperature
Spend and be heated to reflux for 50-60 DEG C.
5. as claimed in claim 2 a kind of preparation method of cerium schiff bases complex it is characterised in that during described reaction
Between be 7-9h.
6. as claimed in claim 1 a kind of cerium schiff bases complex as the application of PTP1B activity inhibitor.
7. as claimed in claim 1 a kind of cerium schiff bases complex as the application of TCPTP activity inhibitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610874416.5A CN106432308B (en) | 2016-09-30 | 2016-09-30 | A kind of cerium schiff bases complex and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610874416.5A CN106432308B (en) | 2016-09-30 | 2016-09-30 | A kind of cerium schiff bases complex and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106432308A true CN106432308A (en) | 2017-02-22 |
| CN106432308B CN106432308B (en) | 2017-12-05 |
Family
ID=58171893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610874416.5A Expired - Fee Related CN106432308B (en) | 2016-09-30 | 2016-09-30 | A kind of cerium schiff bases complex and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106432308B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107266478A (en) * | 2017-07-19 | 2017-10-20 | 山西大学 | A kind of cerium complexes and its preparation method and application |
| CN107602413A (en) * | 2017-09-13 | 2018-01-19 | 哈尔滨理工大学 | Binol diform contractings o-aminophenol class schiff bases and its synthetic method and application |
| CN114573608A (en) * | 2022-03-18 | 2022-06-03 | 蚌埠医学院 | Schiff base pyridine metal complex and preparation method and application thereof |
| CN115491003A (en) * | 2022-09-14 | 2022-12-20 | 包头稀土研究院 | Application of rare earth amino acid complex, polylactic acid composition and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910212A (en) * | 2015-05-07 | 2015-09-16 | 山西大学 | Platinum schiff base complex and preparation method and application thereof |
| CN105037402A (en) * | 2015-06-19 | 2015-11-11 | 山西大学 | Schiff base and zinc coordination compound and preparation method and application thereof |
-
2016
- 2016-09-30 CN CN201610874416.5A patent/CN106432308B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910212A (en) * | 2015-05-07 | 2015-09-16 | 山西大学 | Platinum schiff base complex and preparation method and application thereof |
| CN105037402A (en) * | 2015-06-19 | 2015-11-11 | 山西大学 | Schiff base and zinc coordination compound and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| AGARWAL SURESH K.: "Spectral and biocidal studies on some mixed ligand complexes of lanthanides", 《JOURNAL OF ULTRA CHEMISTRY》 * |
| AGARWAL SURESH K.: "Synthesis and spectral studies of some mixed ligand complexes of Mn(III) and screening of their biological activity", 《INTERNATIONAL JOURNAL OF CHEMICAL SCIENCES》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107266478A (en) * | 2017-07-19 | 2017-10-20 | 山西大学 | A kind of cerium complexes and its preparation method and application |
| CN107602413A (en) * | 2017-09-13 | 2018-01-19 | 哈尔滨理工大学 | Binol diform contractings o-aminophenol class schiff bases and its synthetic method and application |
| CN107602413B (en) * | 2017-09-13 | 2019-08-20 | 哈尔滨理工大学 | Binol-diform contracting o-aminophenol class schiff bases and its synthetic method and application |
| CN114573608A (en) * | 2022-03-18 | 2022-06-03 | 蚌埠医学院 | Schiff base pyridine metal complex and preparation method and application thereof |
| CN114573608B (en) * | 2022-03-18 | 2024-04-16 | 蚌埠医学院 | Schiff base pyridine metal complex and preparation method and application thereof |
| CN115491003A (en) * | 2022-09-14 | 2022-12-20 | 包头稀土研究院 | Application of rare earth amino acid complex, polylactic acid composition and preparation method thereof |
| CN115491003B (en) * | 2022-09-14 | 2023-08-15 | 包头稀土研究院 | Application of rare earth amino acid complex, polylactic acid composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106432308B (en) | 2017-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106432308B (en) | A kind of cerium schiff bases complex and its preparation method and application | |
| Wu et al. | V-shaped ligand bis (2-benzimidazolylmethyl) amine containing three copper (II) ternary complexes: Synthesis, structure, DNA-binding properties and antioxidant activity | |
| CN107523291B (en) | It is a kind of while identifying phosphate radical and the fluorescence probe complex of copper ion, preparation method and application in water body | |
| CN103232486B (en) | Vanadium oxide complex as well as preparation method and application thereof | |
| CN107880277A (en) | A kind of two-dimentional zinc coordination polymer and preparation method thereof | |
| CN105384770A (en) | 2-oxo-propionic acid salicyloyl hydrazone and di(p-methylbenzyl)tin complex as well as preparation method and application of 2-oxo-propionic acid salicyloyl hydrazone and di(p-methylbenzyl)tin complex | |
| CN105503965A (en) | Rare earth (III)-transition (II) mixed metal fluorescence complex and preparing method and application thereof | |
| CN109233814A (en) | A kind of Zn-MOFs metal organic crystalline material, synthetic method and its application in sensing identification antibiotic | |
| CN104829635B (en) | Metal copper complexes of serine N derivant and its preparation method and application | |
| CN101735798A (en) | Rare earth organic framework material having sensing function to acetone, preparation method and application thereof | |
| Yraola et al. | [{Cu (pzPh)(Opo)} 2 (μ-Cl) 2]: A new dinuclear copper (II) complex with a chloride bridge and mixed blocking ligands | |
| CN105037187A (en) | Metal zinc complex of serine N derivatives as well as preparation method and application thereof | |
| Mathur et al. | Study of CLSI-M44-A Disk Diffusion method for determining the susceptibility of candida species against novel complexes derived from copper stearate with 2-amino benzothiazoles | |
| CN107266478B (en) | A kind of cerium complexes and its preparation method and application | |
| CN106749393A (en) | Picoline hydrazonic acid derivative dioxygen vanadium（V）Complex and preparation method thereof | |
| CN109627210B (en) | Gallium fluorescent probe, preparation method, application and application product thereof | |
| CN106589000B (en) | 2- hydroxy-n '-(1- (pyrazine -2-yl) ethylidene) benzoyl hydrazone palladium chloride complex | |
| CN110317218B (en) | Preparation method and application of high-activity tetranuclear polymer | |
| CN109666047B (en) | Ruthenium fluorescent probe, and preparation method, application and application product thereof | |
| Wang et al. | Synthesis, X-ray crystallographic analysis and BSA interaction of a new α-aminophosphonate | |
| Wei et al. | The structure of hycanthone methanesulfonate,[C20H24N2O2S][CH3SO3H]: an antischistosomal agent | |
| CN100422732C (en) | Method of measuring the molecular weight of phosphoric acid monoester compound and additive for mass spectrum measurement | |
| CN109796505B (en) | Preparation method and application of amide compound with antitumor activity | |
| CN110305147B (en) | Benzoic acid derivative zinc complex and preparation method and application thereof | |
| CN110483558A (en) | A kind of synthetic method and its application of the micropore cadmium compound with anion frame |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171205 Termination date: 20200930 |