CN107056686A - A kind of water-soluble Mononuclear nickel complex and preparation method and applications - Google Patents
A kind of water-soluble Mononuclear nickel complex and preparation method and applications Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
- G01N2001/386—Other diluting or mixing processes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention provides a kind of water-soluble Mononuclear nickel complex and preparation method and applications, chemical formula is [Ni (bpma)2](ClO4)2, wherein bpma is N methyl Ns, N bipyridine methyl amine, by NiCl2·6H2O is dissolved in the mixed solution of acetonitrile and water, is added the acetonitrile solution containing bpma, is heated to reflux, NaClO is added dropwise after cooling4Saturated aqueous solution, after stirring filter;Filtrate is placed under room temperature condition, is obtained being suitable to the purple bulk crystals that X single crystal diffractions are analyzed after volatilization, after being washed through ether, is dried.Monocrystalline of the invention by being heated to reflux can obtain complex under the conditions of stirring, the slow volatilization of room temperature, complex has preferable water-soluble, its bioactivity can be studied in physiological conditions, it was found that complex can be interacted with the bonding pattern and DNA of partial insertion, potential nucleic acid recognizing reagent can be used as, and it was found that obvious interaction can also occur with BSA for complex, it may be possible to be used as potential medicine.
Description
Technical field
The invention belongs to nickel complex field, more particularly, to a kind of water-soluble Mononuclear nickel complex and preparation method and its
Using.
Background technology
Since the nineties in last century, the own warp of research of Medicine small molecule and large biological molecule DNA, protein interaction
Common concern and problem interested as numerous scientific research personnel because carry out Medicine small molecule (including potential drug) with
Repercussion study not only facilitates people and medicine and biological big point is appreciated and understood by from molecular level between DNA, protein
The mode and its mechanism of action, and in vivo significant to the in-vitro screening of cancer therapy drug of son interaction, simultaneously
Also theoretical direction and valuable information are provided for the lower PTS of design better efficacy, toxicity.
Cancer is serious threat human health even a class disease of life, and active prevention, diagnosis and treatment are vast scientific research scholars
Common objective.And small molecule and DNA interaction are that, using DNA as target molecule, on the one hand its bond styles may cause
Canceration, mutation and cell death, such as some carcinogenic substances can be with DNA formation adducts, and this DNA adduct is possible canceration
The marker of early-warning, is on the other hand also likely to be clinically wide variety of cancer therapy drug, and such as tumor tissues are that cell division is lived
The position of jump, and many cancer therapy drugs are all using DNA as action target spot, by occurring interaction destruction with the DNA of cancer cell
Its structure, and then gene regulation and expressive function are influenceed, show active anticancer.In addition, micromolecular compound and DNA specificity
Positioning combination, it is extremely important in the research of the mode of action in the regulation process and many cancer therapy drug bodies of gene expression.Cause
The research of this small molecule and DNA interaction not only contributes to explore and develops new nucleic acid probe, and contribute to from point
The mechanism of action of cancer therapy drug is understood in sub- level, carcinogenic, teratogenesis the molecular biological mechanism of Toxic is illustrated, faced for design
More effectively cancer therapy drug provides theoretical direction on bed.
It is part using N- methyl-N, N- bipyridine methyl amine (bpma), using metallic nickel ions as activated centre, by adding
The synthetic method of hot return stirring, design has synthesized a new water-soluble Mononuclear nickel complex;And use elementary analysis, infrared
The means such as spectrum, the analysis of x- single crystal diffractions, ultraviolet-visible spectrum, fluorescence spectrum are characterized and property research to complex, hair
Existing complex can be interacted with inserted mode with calf thymus DNA, and can occur phase interaction strongly with BSA
With.
The content of the invention
In view of this, the present invention is directed to propose a kind of water-soluble Mononuclear nickel complex and preparation method and applications, are used
It is heated to reflux stirring at ambient temperature, target product is obtained using the synthetic method slowly volatilized, preparation method is simple and reliable.
To reach above-mentioned purpose, the technical proposal of the invention is realized in this way:
A kind of water-soluble Mononuclear nickel complex, chemical formula is [Ni (bpma)2](ClO4)2, wherein bpma is N- methyl-N,
N- bipyridine methyl amine.
Further, the structural formula of the complex is:
Further, the described complex belongs to rhombic system, P212121Space group, cell parameter isα=β=γ=90 °, unit-cell volume is
Further, the described complex be mononuclear structure, Ni1 metal ions respectively with the nitrogen from two bpma parts
Atom N1, N2, N3, N4, N5, N6 are coordinated, and form the octoploids structure of a distortion, and wherein N2, N3, N4, N5 composition is octahedra
Equatorial plane, N1 and N6 occupy octahedral axial location;Ni1-N1、Ni1-N2、Ni1-N3、Ni1-N4、Ni1-N5、Ni1-
N6 bond distance is respectively Ni1-N average bond length isThe distance of Ni1 metal ions to equatorial plane is
Present invention also offers a kind of method for preparing water-soluble Mononuclear nickel complex as described above, including following step
Suddenly:
By NiCl2·6H2O is dissolved in the mixed solution of acetonitrile and water composition, is added in above-mentioned solution containing bpma's
Acetonitrile solution, is then heated to reflux stirring, is cooled to after room temperature;NaClO is added dropwise4Saturated aqueous solution, continue to stir, then mistake
Filter;Filtrate is placed under room temperature condition, after slow volatilization several weeks, obtains being suitable to the purple bulk crystals that X- single crystal diffractions are analyzed, warp
After ether washing, dry.
Further, the NiCl2·6H2The amount ratio of O and bpma material is (0.2~0.5mmol):(0.4~
1.0mmol)。
Further, the reaction time for being heated to reflux stirring is 2~6 hours, and temperature is 82~100 DEG C.
Further, the volume ratio of acetonitrile and water is 1.0 in the mixed solution of acetonitrile and the water composition:1.0~2.0.
Further, the rate of addition of the acetonitrile solution containing bpma is 0.05ml/s.
Invention also provides a kind of water-soluble Mononuclear nickel complex as described above or preparation method as described above
Application of the water-soluble Mononuclear nickel complex of preparation in nucleic acid recognizing reagent and potential drug is prepared.
Product elemental analysis experiment value be respectively:C 45.63%, H 4.40%, N 12.30%.Wherein elementary analysis
Theoretical value be respectively:C 45.60%, H 4.38%, N 12.28%.
With the infrared spectrum analysis of KBr tablettings, the complex is in 1607cm-1There is very sharp strong absworption peak in place, is bpma
On C-N stretching vibrations produce absorption;In 2964cm-1And 2901cm-1The sharp absworption peaks of two moderate strengths can refer to
Send the C-H stretching vibrations for bpma;622~760cm-1Multiplet is the stretching vibration peak of pyridine ring;1081cm-1Strong peak and
622cm-1In strong peak be believed that perchlorate is not engaged in coordination, be consistent with mono-crystalline structures.
The monokaryon nickel is confirmed by complex and the CT-DNA Absorption Spectrum Research interacted and fluorescent quenching experiment
Complex is interacted with the medium bonding pattern and DNA of partial insertion.
Confirm that the Mononuclear nickel complex can be sent out with BSA by complex and the BSA Absorption Spectrum Research interacted
Life interacts strongly.
Relative to prior art, water-soluble Mononuclear nickel complex of the present invention and preparation method and applications have with
Lower advantage:
Water-soluble Mononuclear nickel complex of the present invention and preparation method and applications, preparation process are simple, heat back
The monocrystalline of complex is can obtain under the conditions of stream stirring, the slow volatilization of room temperature, complex has preferable water solubility, so as to
Its bioactivity is studied in physiological conditions, it is found that with the bonding pattern of partial insertion and DNA phase interaction can occur for complex
With potential nucleic acid recognizing reagent can be used as, and it was found that obvious interaction can also occur with BSA for complex, can
So that potential medicine can be used as.
Brief description of the drawings
Fig. 1 is the crystal structure figure of the water-soluble Mononuclear nickel complex described in the embodiment of the present invention 1;
Fig. 2 is the ultraviolet-visible spectrogram of the water-soluble Mononuclear nickel complex described in the embodiment of the present invention 1;
Fig. 3 is electricity of the water-soluble Mononuclear nickel complex after different amounts of CT-DNA is added described in the embodiment of the present invention 1
Sub- abosrption spectrogram;
Fig. 4 is under 273K and 298K, to add the water-soluble monokaryon nickel described in the embodiment of the present invention 1 of various concentrations and coordinate
The EB-DNA of thing fluorescent quenching spectrogram;
Fig. 5 is for the water-soluble Mononuclear nickel complex described in the embodiment of the present invention 1 in 273K and 298K to EB-DNA compounds
The influence of fluorescence;
Fig. 6 is the Electron absorption that the water-soluble Mononuclear nickel complex described in the embodiment of the present invention 1 is added after different amounts of BSA
Spectrogram.
Embodiment
In addition to being defined, technical term used has universal with those skilled in the art of the invention in following examples
The identical meanings of understanding.Test reagent used, is routine biochemistry reagent unless otherwise specified in following examples;It is described
Experimental method, is conventional method unless otherwise specified.
The present invention is described in detail with reference to embodiment and accompanying drawing.
Embodiment 1
The synthesis of water-soluble Mononuclear nickel complex:
By 0.3mmol NiCl2·6H2O is dissolved in 15mL by acetonitrile and water according to volume ratio 1:The mixed solution of 1 composition
In, acetonitriles of the 1.00mL wherein containing 0.6mmol bpma is then added into above-mentioned solution with 0.05ml/s drop speed dropwise molten
Liquid, is subsequently heated return stirring 3 hours, is cooled to after room temperature, and 2.50ml NaClO are added dropwise4Saturated aqueous solution, at room temperature
Continue to stir after half an hour and filter, filtrate is placed under room temperature condition, after slow volatilization, obtain the purple block suitable for X- single crystal diffractions
Shape crystal, is dried after being washed with ether, and yield is:49%.
The test of water-soluble Mononuclear nickel complex:
1st, the experiment value of product elemental analysis is respectively:C 45.57%, H 4.46%, N 12.24%.Wherein element divides
The theoretical value of analysis is respectively:C 45.60%, H 4.38%, N 12.28%, elementary analysis result are consistent with crystal structure formula.
2nd, ultraviolet-visible light analysis of spectrum:
As shown in Fig. 2 from the uv-vis spectra it can be seen from the figure that of complex, model of the complex in 200~1200nm
There are three absorption bands in enclosing, be respectively:Absorption at 203nm, is π-π * transition, ε=6.5 × 103L·mol-1·cm-1, belong to
It is relatively strong to absorb;Absorption at 259nm, is that the n- π lotuses of part to metal ion move transition, ε=2.2 × 103L·mol-1·cm-1,
Belong to stronger to absorb;Absorption at 819nm, is the d-d transition of metal ion, ε=27.1Lmol-1·cm-1, belong to weak suction
Receive.
3、FT-IR(KBr):With the infrared spectrum analysis of KBr tablettings, complex is in 2964cm-1And 2901cm-1Appearance
Moderate strength, broad peak be assigned as bpma C-H stretching vibration peaks;In 1607cm-1There is point, Qiang Feng in place, is the C-N on bpma
Stretching vibration peak;622~760cm-1Multiplet is the stretching vibration peak of pyridine ring;1081cm-1Strong peak and 622cm-1In it is strong
Peak deduces perchlorate and is not engaged in coordination, is consistent with mono-crystalline structures.
4th, the crystal structure determination of nickel complex:
1) experimentation:
Under 296 (2) K, sizeable crystal is chosen, with the Mo-K α through graphite monochromator monochromatizationRay collects diffraction data as incident light source with ω -2 θ scan modes.Crystal structure direct method
Solve, first determine whole non-atomic hydrogen coordinates with difference function method and least square method, then hydrogen is obtained with the method for theory hydrogenation
Atom site, finally carries out refine with least square method to crystal structure.All calculating uses SHELXS-97 and SHELXL-
97 program bags are carried out.
2) experimental result:
As shown in figure 1, the complex is mononuclear structure, X-ray single crystal diffraction analyze data is shown, in complex, gold
The ligancy for belonging to ion Ni1 is six, respectively and nitrogen-atoms N1, N2, N3, N4, N5, the N6 coordination from two bpma parts, shape
Into distorted octahedron configuration.Wherein N2, N3, N4, N5 constitute octahedral equatorial plane, and N1 and N6 are occupied in octahedral axial direction
Position, Ni1-N1, Ni1-N2, Ni1-N3, Ni1-N4, Ni1-N5, Ni1-N6 bond distance is respectively Ni1-N's is averaged
Bond distance isThe distance of Ni1 metal ions to equatorial plane is
The key data of the crystal structure of the complex of table 1
The main bond distance of the complex crystal of table 2, bond angle
5th, implement to add different amounts of CT-DNA, the electronic change examination of the water-soluble Mononuclear nickel complex of observation
Test:
1) experimentation:
At room temperature, 2.0mL cushioning liquid is respectively added into sample cell and reference cell, cushioning liquid is prepared wherein with tri-distilled water
The Tris of NaCl and 5mM containing 50mM, are then adjusted to pH=7.4 with hydrochloric acid, then add a certain amount of volume to sample cell
Complex solution, complex concentration is 1.45 × 10-4M, and add into reference cell corresponding isometric cushioning liquid.With micro
Injector adds the CT-DNA storing solutions of a certain amount of same volume into sample cell and reference cell, makes the dense of CT-DNA and complex
Degree ratio is continuously increased, and CT-DNA concentration is 0~3.94 × 10-4M, observes the change of complex absworption peak.
2) experimental result:
As shown in figure 3, complex has strong UV absorption at 204nm, add, coordinate with CT-DNA gradually equivalent
There is obvious decline in the maximal ultraviolet absorption intensity of thing, that is, occurs in that obvious " hypochromic effect ", while showing with red shift
As red shift is 5nm apart from △ λ, and the rate that loses lustre is 39.2%, illustrates complex under this experiment condition, with the bonding of partial insertion
Mode and DNA interact.
6th, implement to add different amounts of nickel complex, observation EB-DNA fluorescent quenching experiment:
Nickel complex does not produce fluorescence in itself, the fluorescence of EB-DNA conjugates is quenched using complex, by studying EB-
The change of DNA conjugate fluorescence intensities comes indirect determination complex and DNA combination degree.
1) experimentation:
CT-DNA and EB mixed solution is prepared, its content is respectively 2.4 × 10-6M EB and 4.8 × 10-5M CT-DNA,
Lay in 4 DEG C of refrigerators, nickel complex is configured to 3.0 × 10-3M storing solutions.When titration experiments are quenched, added into sample cell
The EB-DNA mixed liquors of 2.0mL deposits, observe its fluorescence intensity, then with each body such as addition into sample cell of microsyringe
Long-pending complex storing solution, observes the change of emission spectrum and preserves data so as to process of fitting treatment.
2) experimental result:
As shown in figure 4, EB-DNA fluorescence spectrum is quenched in Mononuclear nickel complex, after nickel complex is added, EB-DNA's
There is obvious reduction in fluorescence intensity, and as the increase of complex concentration, its fluorescence intensity are gradually reduced, shows that nickel coordinates
Thing and CT-DNA competition binding instead of EB.
According to Stern-Volmer equations:I0/ I=1+K [Q], to add the glimmering of EB-DNA before and after Mononuclear nickel complex
Intensity ratio (I0/ I) it is ordinate, the concentration of nickel complex is abscissa, is made that Stern-Volmer schemes i.e. Fig. 5, matches somebody with somebody
The fluorescent quenching curve of compound linearly, substantially meets Stern-Volmer equations, it is nickel complex to show fluorescent quenching
It instead of the result for the EB for having inserted DNA.According to equation KEB[EB]=Kapp[complex], KEB=1.0 × 107M-1([EB]=
4.0 μM), the apparent binding constants for calculating nickel complex are respectively 1.40 × 105M-1.As a result in showing complex and DNA and being
Deng bonding pattern, less than ethidium bromide, the binding constants 10 of typical insertion reagent7M-1。
Further analyze under 298K and 273K, influence of the nickel complex to EB-DNA complex fluorescences.Such as Fig. 5 institutes
Show, nickel complex is raised with temperature, slope K increase, illustrate the nickel complex with the compound of EB-DNA formation with temperature
Rise increasingly stablize, fluorescent quenching is due to what diffusion was produced, its fluorescent quenching for dynamically mechanism is quenched.
7th, implement to add different amounts of BSA, the electronic change experiment of observation nickel complex:
UV-Vis Spectrophotometry mainly uses the amino such as tryptophan in seralbumin, phenylalanine, TYR
The change of sour residue absworption peak is analyzed, if absworption peak is before and after small molecule partner and seralbumin effect
Changed, then illustrate that small molecule partner and seralbumin are acted on.Thus, we pass through electronic
It has studied nickel complex and BSA interaction.
1) experimentation:
At room temperature, 2.0mL cushioning liquid is respectively added into sample cell and reference cell, it is dense that cushioning liquid is prepared with tri-distilled water
Spend for 10mM NaH2PO4/Na2HPO4, pH=7.4, then to sample cell add a certain amount of volume nickel complex solution and to
Corresponding isometric cushioning liquid is added in reference cell.Added with microsyringe into sample cell and reference cell a certain amount of identical
The BSA storing solutions of volume, are continuously increased the concentration proportion of BSA and nickel complex, observe the change of nickel complex absworption peak simultaneously
Data are preserved.
2) experimental result:
As shown in fig. 6, can be clearly seen that, with being continuously added for BSA, π-π transition of the nickel complex at 207nm
Obvious hypochromicity occurs for peak and with red shift, and the distance of red shift is 5nm;Lotus at 259nm moves transition peak almost not by BSA
The increased influence of concentration.Illustrate under this experiment condition, show to there occurs phase interaction strongly between the nickel complex and BSA
With.
Embodiment 2
Experimental procedure:
By 0.1mmol NiCl2·6H2O is dissolved in 15mL by acetonitrile and water according to volume ratio 2:The mixed solution of 3 compositions
In, acetonitriles of the 0.50mL wherein containing 0.2mmol bpma is then added into above-mentioned solution with 0.05ml/s drop speed dropwise molten
Liquid, is subsequently heated return stirring 5 hours, is cooled to after room temperature, and 2.50ml NaClO are added dropwise4Saturated aqueous solution, at room temperature
Continue to stir half an hour, filtering, filtrate is placed under room temperature condition, slow volatilization.
Experiment conclusion:
The crystallite of lilac is obtained after one month, is unsuitable for the analysis of X- single crystal diffractions, fine structure data is not obtained, second is used
Dried after ether washing, yield is:27%.
Embodiment 3
Experimental procedure:
By 0.6mmol NiCl2·6H2O is dissolved in 15mL by acetonitrile and water according to volume ratio 1:The mixed solution of 2 compositions
In, acetonitriles of the 2.00mL wherein containing 1.2mmol bpma is then added into above-mentioned solution with 0.05ml/s drop speed dropwise molten
Liquid, is heated to reflux stirring 4 hours, is cooled to after room temperature, and 2.50ml NaClO are added dropwise4Saturated aqueous solution, continue at room temperature
Stir half an hour, filtering, filtrate is placed in 4 DEG C of refrigerators, slow volatilization.
Experiment conclusion:
The solid powder of lilac is obtained after five weeks, does not obtain being adapted to the monocrystalline of structure elucidation, is dried after being washed with ether,
Yield is:51%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (10)
1. a kind of water-soluble Mononuclear nickel complex, it is characterised in that:Chemical formula is [Ni (bpma)2](ClO4)2, wherein bpma is
N- methyl-N, N- bipyridine methyl amine.
2. water-soluble Mononuclear nickel complex according to claim 1, it is characterised in that:The structural formula of the complex is:
3. water-soluble Mononuclear nickel complex according to claim 1, it is characterised in that:The complex belongs to rhombic system,
P212121Space group, cell parameter is α=β=
γ=90 °, unit-cell volume is
4. water-soluble Mononuclear nickel complex according to claim 1, it is characterised in that:The complex is mononuclear structure, Ni1
Metal ion is coordinated with nitrogen-atoms N1, N2, N3, N4, N5, N6 from two bpma parts respectively, forms the eight of a distortion
Face body configuration, wherein N2, N3, N4, N5 constitute octahedral equatorial plane, and N1 and N6 occupy octahedral axial location;Ni1-
N1, Ni1-N2, Ni1-N3, Ni1-N4, Ni1-N5, Ni1-N6 bond distance is respectively Ni1-N average bond length isThe distance of Ni1 metal ions to equatorial plane is
5. a kind of method of the water-soluble Mononuclear nickel complex prepared as described in any one of Claims 1 to 4, it is characterised in that:
Comprise the following steps:
By NiCl2·6H2O is dissolved in the mixed solution of acetonitrile and water composition, and the acetonitrile containing bpma is added in above-mentioned solution
Solution, is then heated to reflux stirring, is cooled to after room temperature;NaClO is added dropwise4Saturated aqueous solution, continue stir, then filter;
Filtrate is placed under room temperature condition, after slow volatilization several weeks, obtains being suitable to the purple bulk crystals that X- single crystal diffractions are analyzed, through ether
After washing, dry.
6. the preparation method of water-soluble Mononuclear nickel complex according to claim 5, it is characterised in that:The NiCl2·
6H2The amount ratio of O and bpma material is (0.2~0.5mmol):(0.4~1.0mmol).
7. the preparation method of water-soluble Mononuclear nickel complex according to claim 5, it is characterised in that:It is described to be heated to reflux
The reaction time of stirring is 2~6 hours, and temperature is 82~100 DEG C.
8. the preparation method of water-soluble Mononuclear nickel complex according to claim 5, it is characterised in that:The acetonitrile and water
The volume ratio of acetonitrile and water is 1.0 in the mixed solution of composition:1.0~2.0.
9. the preparation method of water-soluble Mononuclear nickel complex according to claim 5, it is characterised in that:It is described to contain bpma
Acetonitrile solution rate of addition be 0.05ml/s.
10. such as water-soluble Mononuclear nickel complex according to any one of claims 1 to 4 or such as any one of claim 5~9
The application of water-soluble Mononuclear nickel complex prepared by described preparation method in nucleic acid recognizing reagent and cancer therapy drug is prepared.
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