CN105440059B

CN105440059B - Copper complex of amino acid and phenanthroline or derivatives thereof and its preparation method and application

Info

Publication number: CN105440059B
Application number: CN201410258273.6A
Authority: CN
Inventors: 鲁晓明; 张波; 张伟川; 程峰; 程一峰; 孙小静
Original assignee: Capital Normal University
Current assignee: Capital Normal University
Priority date: 2014-06-11
Filing date: 2014-06-11
Publication date: 2018-06-12
Anticipated expiration: 2034-06-11
Also published as: CN105440059A

Abstract

A series of copper complex the present invention provides amino acid and phenanthroline or derivatives thereof and its preparation method and application is the complex combined by amino acid, phenanthroline or derivatives thereof and other smaller ligands with copper ion.The preparation method of complex of the present invention, be by series of amino acids and phenanthroline or derivatives thereof with mantoquita and other small molecules are organic is stirred to react in a solvent, obtain the complex.Complex synthesis material of the present invention is easy to get, and at low cost, product is precipitated with crystal form, and purity is big, and yield is high；Moreover, the complex can be stabilized in its natural state, the introducing of amino acid in addition has good water-soluble and fat-soluble and biological amalgamation.In addition, complex of the present invention shows excellent inhibiting effect to kinds cancers cells such as lung cancer, gastric cancer, liver cancer, colon gland, leukaemia, nasopharyngeal carcinoma, action spectrum is wide, has wide range of applications.

Description

Copper complex of amino acid and phenanthroline or derivatives thereof and preparation method thereof and Using

Technical field

Copper complex the present invention relates to series of amino acids and phenanthroline or derivatives thereof and preparation method thereof and should Application of the class complex in the drug of prevention and treatment cancer and tumor disease is prepared.

Background technology

Amino acid is the basic structural unit for forming the large biological molecules such as biological vivo protein, enzyme.Due to amino and carboxylic The presence of base makes amino acid have chelant performance and cushion performance, and existing hydrophily has hydrophobicity again so that amino acid has There are some other unexistent special performances of organic compound.Copper is the indispensable important trace element of human body, research shows that, Copper shortage rises the incidence such as gastric cancer, nasopharyngeal carcinoma, liver cancer.1912, Germany a kind of chloride by copper and lecithin group Into patient of the mixture treatment with facial cancer.The research explanation of Liverpool University in 1913：By subcutaneously and intravenously Injection mantoquita and electrocuprol can soften or eliminate the carcinoma being implanted in mouse body.Nineteen thirty France research shows that：Copper is adjacent Ferrosin complex can be as the candidate of anticancer drug, to treat the growth and transfer that inhibit tumour.But the adjacent luxuriant and rich with fragrance hello of copper For quinoline complex as drug molecule, solubility is low, it is difficult to effectively play a role into life system.Therefore, other match is assisted Body, it is of crucial importance with the solubility for improving copper phenanthroline complex and for the amalgamation of life system.And amino acid with Life system has good amalgamation, there is better easy absorbability, thus as the auxiliary of drug molecule or drug molecule Group has unique advantage.2002, MaktoChikiraa collaboration persons devised serial complex [Cu (phen) Xaa] (Xaa represents certain amino acid, including alanine, leucine, serine, threonine, half skin propylhomoserin, lysine etc.), And by EPR (electron paramagnetic resonance) technology, analysis complex is combined front and rear complex co-ordination state variation with DNA；With with from Capture technique detection oxidation-reduction quality is revolved, inference different aminoacids complex there are different combinations from DNA.Major way is It is inserted into the small irrigation canals and ditches of DNA by the phenanthroline parallel with DNA double helical structure.L-arginine, L-Glutamine and bad ammonia The electron paramagnetic resonance spectrum of sour copper complex is similar.Aspartic acid and glutamine merely because the methylene in side group not Together, to the effect of DNA difference.So as to infer the size of amino acid chain, shape and polarity can all make ternary copper complex and DNA phases Interaction has a certain impact.But their complex lacks accurate chemical molecular formula and chemical constitution.Guo Zi in 2004 It builds and reports complex [Cu (phen) (L-Thr) (H₂O)(ClO₄) (L-Thr is L-threonine), anticancer the experimental results showed that its To HL-60, the supression rate more than 90% is presented in gastric cancer SGC-7901, but to liver cancer BEL-7402 and lung cancer A-549 without too Multiaction.It thanks to rhythm, Zhang Lei et al. within 2006 and passes through fluorescence spectrum, electronic, viscosimetric analysis and agargel electrophoresis etc. Experimental method detects phenanthroline-copper-glycine, phenanthroline-copper-isoleucine and phenanthroline-three kinds of copper-methionine The interaction of complex and DNA, experiment show that the effect of three kinds of complexs and DNA are all partial insertion.And auxiliary is matched Body amino acid steric hindrance crosses conference and hinders complex and the Insertion action of DNA, too small to be also unfavorable for Insertion action, but does not have It is related to the research of anticancer drug effect.Chetana has synthesized copper complex [Cu (L-pro) (B) (H in 2007₂O)](NO₃)(1, 2), L-pro is L-PROLINE, and B is respectively 2,2- bipyridyls and phenanthroline.It is matched by DNA electronic technologies The effect for closing object and calf thymus (CT) DNA is studied.The experimental results showed that the plane aromatic rings due to phenanthroline is deposited Make phenanthroline complex that there is higher combination DNA than bipyridyl analog.But also it is not involved with anticarcinogen The research of effect.Hoi-Ling Seng, Wai-San Wang designs in 2012 have synthesized a series of copper (II) complex 1-4 [Cu (phen)(aa)(H₂O)]NO₃·xH₂O, wherein phen are phenanthroline, and aa is glycine extremely derivative, comprising glycine, Dl- alanine, 2,2- dimethyl substitution glycine and sarcosine.And pass through electron paramagnetic resonance, and gel electrophoresis, fluorescent quenching Experiment is inhibited to detect these four complexs to the mutual of tetra- chain of different types of B-form DNA double-strand and G- with restriction enzyme Effect.The experimental results showed that these four complexs under 5 μM of concentration, can induce nasopharyngeal carcinoma HK1 Apoptosis 41-60%, but There is no apparent cell death to nasopharyngeal carcinoma cell NP69 cells.Moreover, the inhibition of other cancer cells is not reported.

Although scientists have accumulated one in terms of the anticarcinogenic effect of amino acid copper phenanthroline or derivatives thereof complex A little researchs, still, different amino acid has different physiological actions.And find in our study, first, amino acid sheet There is no apparent active anticancers for body；Second, significant anticancer effect is not presented yet for simple amino acid copper complex；Third, The difference that the mixture of amino acid and phenanthroline is presented in terms of active anticancer, and not all phenanthroline copper complex has There are the mononuclear copper complex and the cooperation of double-core copper that the glutamic acid in active anticancer, such as the application is formed with phenanthroline mixture The object reaction equal to cancer cell is weaker.For another example leucine copper complex shows superior anticancer than isoleucine copper complex Activity.Fourth, different difference, such as Hoi-Ling are presented for different cancers with monoamino-acid phenanthroline copper complex The glycine and its derivative of the synthesis such as Seng, Wai-San Wang can induce nasopharyngeal carcinoma HK1 Apoptosis 41-60%, but There is no apparent cell death to nasopharyngeal carcinoma cell NP69 cells.The threonine phenanthroline copper complex that Guo Zi is built is to HL-60 The supression rate more than 90% is presented with gastric cancer SGC-7901, but liver cancer BEL-7402 and lung cancer A-549 are not acted on too much. So the application is formed the active anticancer basis of phenanthroline copper complex in scrutiny using different amino acid as ligand On, apply for prepared by copper complex of amino acid and phenanthroline or derivatives thereof and preparation method thereof and such complex Prevent and treat the application in the drug of cancer and tumor disease.

Invention content

The object of the present invention is to provide the complex of series of amino acids and phenanthroline or derivatives thereof, specifically amino The complex that acid, phenanthroline or derivatives thereof and other small molecules are combined with mantoquita, and preparation method thereof and prepare prevent With the application in the drug for the treatment of cancer and tumor disease.

In order to achieve the above objectives, the present invention adopts the following technical scheme that：

The complex of amino acid phenanthroline provided by the present invention or derivatives thereof, by amino acid and phenanthroline or its Derivative and other small molecules are combined with copper ion.Its molecular formula and molecular structural formula difference are as follows：

(1) [(amino) Cu (n-Phen) (X)], (2) [(amino) Cu (n-Phen) (X) (Y)],

(3)[(n-Phen)Cu(amino(X)]_m, (4) [(n-Phen) Cu (amino) (X) (Y)]_m,

(5)[(n-Phen)Cu(amino)(X)]_m, (6) [(n-Phen) Cu (amino) (X) (Y)]_m,

Wherein：Amino is amino acid, n-Phen 1, and 10- ferrosins or derivatives thereof, Cu is bivalent cupric ion, X and Y It is respectively selected from H₂O, NO₃ ^-, ClO₄ ^-, SO₄ ^2-,CI^-Or Br^-, R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Be respectively selected from hydrogen, alkyl, nitro, Amino or halogen, m are more than 1 positive integer.

Wherein described amino acid is selected from glycine, alanine, glutamic acid, phenylalanine, aspartic acid, tyrosine, silk ammonia Acid, leucine, isoleucine, valine, methionine, lysine, tryptophan, threonine, methionine, proline, histidine, Cystine, cysteine, arginine or glutamine.

A kind of complex for preparing amino acid copper phenanthroline or derivatives thereof, it is characterised in that include the following steps：

By mantoquita, sodium salt, alkali, the amino acid is stirred continuously in a solvent to abundant dissolving, adds the adjacent luxuriant and rich with fragrance hello Quinoline or derivatives thereof reaction, filtering later, it stands or is spread with the mixed solvent of ether, isopropanol or a variety of organic solvents Afterwards, it stands, finally obtains the complex.

Wherein described mantoquita for inorganic mantoquita, organic copper salt, Inorganic Copper salt hydrate, organic copper salt hydrate or they in Any one or two or more mixtures.

Wherein described mantoquita is selected from copper nitrate, copper sulphate, cupric perchlorate, copper acetate, copper chloride, copper bromide, nitric acid copper water It closes in object, copper sulfate hydrate, cupric perchlorate hydrate, acetic acid copper hydrate, chlorination copper hydrate or bromination copper hydrate It is one or more kinds of.

Wherein described sodium salt is appointing in inorganic sodium, Organic Sodium Salt, inorganic sodium hydrate or Organic Sodium Salt hydrate The mixture for one or more of anticipating.

Wherein described sodium salt is selected from sodium nitrate, sodium sulphate, sodium perchlorate, sodium acetate, sodium chloride, sodium bromide, sodium nitrate water It closes in object, sulfuric acid sodium hydrate, sodium perchlorate hydrate, acetic acid sodium hydrate, chlorination sodium hydrate or bromination sodium hydrate It is one or more kinds of.

Wherein described solvent is single organic solvent or the mixed solvent of a variety of organic solvents or single inorganic solvent or more The kind mixed solvent of inorganic solvent or the mixed solvent of organic solvent and inorganic solvent.

Wherein described solvent be selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, methanol, ethyl alcohol, One or more of ethylene glycol, propylene glycol, glycerine, acetone, acetonitrile, acetylacetone,2,4-pentanedione or water.

Wherein described alkali is sodium hydroxide, potassium hydroxide or ammonium hydroxide.

The cell experiment commission China Medical institute of complex of the present invention carries out and provides Activity Results, is demonstrate,proved by testing Real, described amino acid copper phenanthroline or derivatives thereof complex is for leukaemia, gastric cancer, liver cancer, nasopharyngeal carcinoma, lung cancer and knot The cell of the cancers such as enteraden cancer has good growth inhibition effect, can be widely applied to preparation and prevents and treats these cancers Drug.

The complex of series of amino acids copper phenanthroline of the present invention or derivatives thereof, synthesis material are easy to get, into This is low, and product is precipitated with crystal form, and purity is big, and yield is high；Moreover, the complex can be stabilized in its natural state, and With good water-soluble and fat-soluble and biological amalgamation；In addition, complex of the present invention is for leukaemia, gastric cancer, liver cancer, nose The kinds cancers cell such as pharynx cancer, lung cancer and adenocarcinoma of colon leukaemia, gastric cancer, liver cancer, nasopharyngeal carcinoma, lung cancer and adenocarcinoma of colon is presented Go out excellent inhibiting effect, action spectrum is wide, has wide range of applications.

Description of the drawings：Figure 1A -35A are the infrared spectrogram of complex Z1-Z35 of the present invention；Figure 1B -35B match for the present invention Close the molecular structure of object Z1-Z29；Fig. 1 C are the structure cell accumulation graph of complex Z1 of the present invention；Figure 10 C are complex of the present invention The structure cell accumulation graph of Z10；Figure 16 C are the structure cell accumulation graph of complex Z16 of the present invention；Figure 18 C are the crystalline substance of complex Z18 of the present invention Born of the same parents' accumulation graph；Figure 33 C are the structure cell accumulation graph of complex Z33 of the present invention.

Specific embodiment

With reference to embodiment, the invention will be further described, it should be understood that these embodiments are only used for illustration Purpose, be never limited in protection scope of the present invention.

Embodiment 1-1, the preparation of complex Z1：Glycine (0.5mmol, 0.038g) and NaOH (0.5mmol, 0.02g) Mixing is dissolved in the mixed solvent (1 of 30ml second alcohol and waters:1) Cu (NO, are added₃)₂·3H₂O (0.5mmol, 0.119g), stirring To abundant dissolving；1,10- ferrosins (0.5mmol, 0.100g) are added, are stirred 8 hours.Then it filters and contains filtrate into 20ml Small test tube in, add diethyl ether to (volume ratio 1-3) above filtrate, stand, obtain blue colored crystal within 20 days or so.Elemental analysis (%)：Calculated value (experiment value):C 39.53(39.60)；H 4.00(4.01)；N 13.18(13.15).Its infrared spectrum and X- Diffraction mono-crystalline structures figure is shown in attached drawing 1A, 1B and 1C respectively.Z1 compound molecule formulas are：{[Cu^II(phen)(Gly)(H₂O)]· NO₃ ^-·2H₂O}_n, i.e. 11,10-Phen, 1 glycine, 1 H₂O and 1 Cu coordination, forms a repetitive unit (Figure 1B). This repetitive unit forms the structure (Fig. 1 C) of one-dimensional chain by Cu bridgings.Each repetitive unit is also containing there are one NO₃ ^-With two Crystallize H₂O。

The cell experiment of complex Z1：Select the attached tumor cells of exponential phase：A-549 (lung cancer), Bel-7402 After (liver cancer), HCT (adenocarcinoma of colon), HL-60 (leukaemia), BGC-823 (gastric cancer), KB (nasopharyngeal carcinoma) are digested with pancreatin, use The RPM11640 culture solutions of 10% calf serum are made into the cell suspension of 5000/mL, are seeded in 96 well culture plates, are connect per hole Kinds 100 μ L, 37 DEG C, 5%CO₂Culture is for 24 hours.Experimental group：1 gained sample solution of embodiment, 10 μ L is added (to use physiological saline solution Embodiment 1 gained complex crystal Z1, a concentration of 5mg/mL), it is 200 μ L per hole final volume, is supplied with 1640 culture medium.37 DEG C, 5%CO₂Cultivate 3d.Supernatant is abandoned after culture 3d, the 0.5mg/mL MTT (tetrazolium bromide) of 100 μ L Fresh are added in per hole Serum-free medium, 37 DEG C are continued to cultivate 4h, carefully abandon supernatant, and are added in 200 μ L DMSO dissolvings MTT formazon and sunk It forms sediment, with miniature ultrasonic oscillator mixing, the OD value at wavelength 544nm is measured in microplate reader.It is calculated according to equation below Growth of tumour cell inhibiting rate：Growth of tumour cell inhibiting rate (%)=(OD_Control- OD_Experiment)/(OD_Control- OD_Blank) × 100%. The result shows that Z1 is 79.71% to A-549 (lung cancer) inhibitory rate of cell growth, to Bel-7402 (liver cancer) cell growth inhibition Rate is 76.71%, is 79.71% to HCT (adenocarcinoma of colon) inhibitory rate of cell growth, HL-60 (leukaemia) cell growth is pressed down Rate processed is 79.12%, is 78.61% to BGC-823 (gastric cancer) inhibitory rate of cell growth, KB (nasopharyngeal carcinoma) cell growth is pressed down Rate processed is 79.80%, conclusion：Z1 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 1-2：Experiment is same as 1-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 1-3：It is real It tests and is same as 1-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.5mmol).Embodiment 1-4：Experiment is same as 1-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) replaces Cu(NO₃)₂3H₂O(0.5mmol).Embodiment 1-5：Experiment is same as 1-1, only CuCl₂·2H₂O (0.5mmol) and NaNO₃ (0.5mol) substitution Cu (NO₃)₂·3H₂O(0.5mmol).Embodiment 1-6：Experiment is same as 1-1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.5mmol)。

Embodiment 1-7：Experiment is same as 1-1, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.5mmol)。

Embodiment 2-1, the preparation of complex Z2, L-phenylalanine (0.5mmol, 0.083g) and NaOH (0.5mmol, 0.02g) mixing is dissolved in the mixed solvent (1 of 30ml second alcohol and waters:1) in；Add CuCl₂·2H₂O(0.5mmol, 0.0874g), it then stirs to abundant dissolving；1,10- ferrosins (0.5mmol, 0.099g) are added, are stirred 12 hours；It crosses It filters, in the small test tube that filtrate is contained to 20ml, adds diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue after a week Crystal.Elemental analysis (%)：Calculated value (experiment value):C 50.71(50.74)；H 4.86(4.77)；N 8.45(8.54).Its Infrared spectrum is shown in attached drawing 2A and 2B respectively with X- diffraction mono-crystalline structures figures.Z2 compound molecule formulas are：[Cu^II(phen)(L-Phe) (Cl)]₂·6H₂O, i.e. 11,10-Phen, 1 phenylalanine and 1 Cl and 1 Cu coordination, form a cis- complex； Another 11,10-Phen, 1 phenylalanine and 1 Cl and 1 Cu coordination, form a trans- complex (Fig. 2 B).This is a pair of Complex crystallizes H there are six also containing₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z2 is same as Z1, and sample Z1 only is changed to sample Z2, the results showed that, Z2 is to A-549 (lungs Cancer) inhibitory rate of cell growth be 88.93%, to Bel-7402 (liver cancer) inhibitory rate of cell growth be 88.936%, to HCT (knot Enteraden cancer) inhibitory rate of cell growth be 88.35%, to HL-60 (leukaemia) inhibitory rate of cell growth be 88.89%, it is right BGC-823 (gastric cancer) inhibitory rate of cell growth is 88.83%, and KB (nasopharyngeal carcinoma) inhibitory rate of cell growth is tied for 88.89%. By：Complex Z2 of the present invention can be used to prepare the drug of prevention and treatment cancer.

Embodiment 2-2：Experiment is same as 2-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 2-3：It is real It tests and is same as 2-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaCl (0.25mmol) substitutions CuCl₂·2H₂O(0.5mmol)。 Embodiment 2-4：Experiment is same as 2-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaCl (0.25mmol) substitutions CuCl₂· 2H₂O(0.5mmol).Embodiment 2-5：Experiment is same as 2-1, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaCl (0.25mmol) replaces CuCl₂·2H₂O(0.5mmol).Embodiment 2-6：Experiment is same as 2-1, only CuCl₂·2H₂O (0.5mmol) and NaCl (0.25mmol) replace CuCl₂·2H₂O(0.5mmol).Embodiment 2-7：Experiment is same as 2-1, only CuBr₂(0.5mmol) and NaCl (0.25mmol) replace CuCl₂·2H₂O(0.5mmol)。

Embodiment 3-1, the preparation of complex Z3：L-Aspartic acid (0.5mmol, 0.067g) and NaOH (0.75mmol, 0.03g) mixing is dissolved in the mixed solvent (arbitrary proportion) of 30ml second alcohol and waters；Add CuCl₂·2H₂O(0.5mmol, 0.0874g), it then stirs to abundant dissolving；1,10- ferrosins (0.5mmol, 0.099g) are added, are stirred 12 hours；It crosses It filters, in the small test tube that filtrate is contained to 20ml, adds diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue after a week Crystal.Elemental analysis (%)：Calculated value (experiment value):C 42.98(43.03)；H 4.40(3.98)；N 9.40(9.44).Its Infrared spectrum is shown in attached drawing 3A, 3B respectively with X- diffraction mono-crystalline structures figures.Z3 compound molecule formulas are：[Cu^II(phen)(L-Asn) (Cl)][Cu^II(Phen)(L-HAsn)(H₂O)]·5H₂O, i.e. 11,10-Phen, 1 aspartic acid and 1 Cl and 1 Cu Coordination forms a complex；Another 11,10-Phen, 1 aspartic acid and 1 H₂O and 1 Cu coordination, forms one and matches Close object (Fig. 3 B).This pair of of complex crystallizes H there are five also containing₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z3 is same as Z1, and sample Z1 only is changed to sample Z3.The result shows that Z3 is to A-549 (lungs Cancer) inhibitory rate of cell growth be 80.63%, to Bel-7402 (liver cancer) inhibitory rate of cell growth be 80.63%, to HCT (colons Gland cancer) inhibitory rate of cell growth be 80.30%, to HL-60 (leukaemia) inhibitory rate of cell growth be 80.86%, to BGC- 823 (gastric cancer) inhibitory rate of cell growth are 80.73%, are 80.76% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Conclusion：This Invention complex Z3 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 3-2：Experiment is same as 3-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 3-3：It is real It tests and is same as 3-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaCl (0.25mmol) substitutions CuCl₂·2H₂O(0.5mmol)。 Embodiment 3-4：Experiment is same as 3-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaCl (0.25mmol) substitution Cu (NO₃)₂· 3H₂O(0.5mmol).Embodiment 3-5：Experiment is same as 3-1, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaCl (0.25mmol) replaces CuCl₂·2H₂O(0.5mmol).Embodiment 3-6：Experiment is same as 3-1, only CuCl₂·2H₂O (0.5mmol) and NaCl (0.25mmol) replace CuCl₂·2H₂O(0.5mmol)。

Embodiment 3-7：Experiment is same as 3-1, only CuBr₂(0.5mmol) and NaCl (0.25mmol) replace CuCl₂· 2H₂O(0.5mmol)。

Embodiment 4-1, the preparation of complex Z4：L-tyrosine (0.5mmol, 0.091g) and NaOH (0.75mmol, 0.03g) mixing is dissolved in the mixed solvent (1 of 30ml second alcohol and waters:1.3) in；Add CuCl₂·2H₂O(0.5mmol, 0.0874g), it then stirs to abundant dissolving；1,10- ferrosins (0.5mmol, 0.099g) are added, are stirred 16 hours；It crosses It filters, in the small test tube that filtrate is contained to 20ml, adds diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue after a week Crystal.Elemental analysis (%)：Calculated value (experiment value):C 50.00(44.95)；H 4.60(4.68)；N 8.33(8.41).Its Infrared spectrum is shown in attached drawing 4A, 4B respectively with X- diffraction mono-crystalline structures figures.Z4 compound molecule formulas are：[Cu^II(phen)(L- Tyrosine)(Cl)]₂·5H₂O, i.e. 11,10-Phen, 1 tyrosine and 1 Cl and 1 Cu coordination, composition one are cis- Complex；Another 11,10-Phen, 1 tyrosine and 1 Cl and 1 Cu coordination, form a trans- complex (Fig. 4 B). This pair of of complex crystallizes H there are five also containing₂O (in order to which picture is clear, omission is not drawn).

The cell experiment complex of complex Z4 is same as Z1, and sample Z1 only is changed to sample Z4.The result shows that Z4 is to A- 549 (lung cancer) inhibitory rate of cell growth are 89.03%, are 89.09% to Bel-7402 (liver cancer) inhibitory rate of cell growth, right HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 89.25%, is to HL-60 (leukaemia) inhibitory rate of cell growth 89.179%, it is 89.188% to BGC-823 (gastric cancer) inhibitory rate of cell growth, to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth It is 89.09%.Conclusion：Z4 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 4-2：Experiment is same as 4-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 4-3：It is real It tests and is same as 4-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaCl (0.25mmol) substitutions CuCl₂·2H₂O(0.5mmol)。 Embodiment 4-4：Experiment is same as 4-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaCl (0.25mmol) substitution Cu (NO₃)₂· 3H₂O(0.5mmol).Embodiment 4-5：Experiment is same as 4-1, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaCl (0.25mmol) replaces CuCl₂·2H₂O(0.5mmol)。

Embodiment 5-1, the preparation of complex Z5：Serine (0.5mmol, 0.058g) and NaOH (0.5mmol, 0.024g) mixing is dissolved in 30ml mixed solvents (ratio is arbitrary), adds Cu (ClO₄)₂·6H₂O (0.5mmol, 0.180g), is stirred It mixes to abundant dissolving；1,10- ferrosins (0.5mmol, 0.095g) are added, are stirred 8 hours.Then it filters and contains filtrate into small In beaker, volatilization is stood, obtains blue colored crystal within 15 days or so.Elemental analysis (%)：Calculated value (experiment value):C 50.00 (44.95)；H 4.60(4.68)；N 8.33(8.41).Its infrared spectrum and X- diffraction mono-crystalline structures figures see respectively attached drawing 5A and 5B.Z5 compound molecule formulas are：[Cu^II(phen)(L-Ser)(H₂O)]·ClO₄ ^-, i.e. 11,10-Phen, 1 serine and 1 H₂O and 1 cis- complex of Cu coordinations；Another 11,10-Phen, 1 tyrosine and 1 Cl and 1 Cu coordination, structure Into a trans- complex (Fig. 5 B).Complex also contains a ClO₄ ^-(in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z5 is same as Z1, and sample Z1 only is changed to sample Z5.The result shows that Z5 is to A-549 (lungs Cancer) inhibitory rate of cell growth be 73.71%, to Bel-7402 (liver cancer) inhibitory rate of cell growth be 91.01%, to HCT (colons Gland cancer) inhibitory rate of cell growth be 90.38%, to HL-60 (leukaemia) inhibitory rate of cell growth be 89.79%, to BGC- 823 (gastric cancer) inhibitory rate of cell growth are 88.88%, are 89.69% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Conclusion：Z5 The drug of prevention and treatment cancer can be used to prepare.

Embodiment 5-2：Experiment is same as 5-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 5-3：It is real It tests and is same as 5-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and Na (ClO₄) (0.5mmol) substitution Cu (ClO₄)₂·6H₂O (0.5mmol).Embodiment 5-4：Experiment is same as 5-1, only CuCl₂·2H₂O (0.5mmol) and Na (ClO₄) (0.5mmol) take For Cu (NO₃)₂·3H₂O(0.5mmol).Embodiment 5-5：Experiment is same as 5-1, only Cu (CH₃COOH)₂·H₂O(0.5mmol) With Na (ClO₄) (0.5mmol) substitution Cu (NO₃)₂·3H₂O(0.5mmol)。

Embodiment 6-1, the preparation of complex Z6：L-Leu (0.5mmol, 0.068g) and NaOH (0.5mmol, 0.02g) mixing is dissolved in 30ml mixed solvents (V_C2H5OH：V_H2O=5：1) Cu (NO, are added₃)₂·3H₂O(0.5mmol, 0.119g), it stirs to abundant dissolving；1,10- ferrosins (0.5mmol, 0.100g) are added, are stirred 10 hours.Then it filters It in the small test tube that filtrate is contained to 20ml, adds diethyl ether to (volume ratio 1-3) above filtrate, stands, obtain within 20 days or so blue crystalline substance Body.Elemental analysis (%)：Calculated value (experiment value):C 47.63(47.64)；H4.88(4.88)；N 12.34(12.32).Its is red External spectrum is shown in attached drawing 6A and 6B with X- diffraction mono-crystalline structures figures.Z6 compound molecule formulas are：[Cu^II(phen)(L-Leucine) (H₂O)]·NO₃ ^-, i.e. 11,10-Phen, 1 leucine and 1 H₂O and 1 Cu coordination forms complex (Fig. 6 B).Cooperation Object also contains a NO₃ ^-(in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z6 is same as Z1, and sample Z1 only is changed to sample Z6.The result shows that Z6 is to A-549 (lungs Cancer) inhibitory rate of cell growth be 92.02%, to Bel-7402 (liver cancer) inhibitory rate of cell growth be 92.16%, to HCT (colons Gland cancer) inhibitory rate of cell growth be 92.36%, to HL-60 (leukaemia) inhibitory rate of cell growth be 91.79%, to BGC- 823 (gastric cancer) inhibitory rate of cell growth are 91.88%, are 91.69% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Conclusion：Z6 The drug of prevention and treatment cancer can be used to prepare.

Embodiment 6-2：Experiment is same as 6-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 6-3：It is real It tests and is same as 6-1, only Cu (ClO4) 26H2O (0.5mmol) and NaNO3 (0.5mol) substitution Cu (NO₃)₂·3H₂O (0.5mmol).Embodiment 6-4：Experiment is same as 6-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) replaces Cu(NO₃)₂·3H₂O(0.5mmol).Embodiment 6-5：Experiment is same as 6-1, only CuCl₂·2H₂O (0.5mmol) and NaNO₃ (0.5mol) substitution Cu (NO₃)₂·3H₂O(0.5mmol).Embodiment 6-6：Experiment is same as 6-1, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) replaces NaNO₃(0.5mol)。

Embodiment 7-1, the preparation of complex Z7：L-Isoleucine (0.5mmol, 0.068g) and NaOH (0.5mmol, 0.02g) mixing is dissolved in 35ml mixed solvents (V_C2H5OH：V_H2O=6：1) Cu (ClO, are added₄)₂·6H₂O(0.5mmol, 0.186g), it stirs to abundant dissolving；1,10- ferrosins (0.5mmol, 0.098g) are added, are stirred 11 hours.Then it filters It in the small test tube that filtrate is contained to 20ml, adds diethyl ether to (volume ratio 1-3) above filtrate, stands, obtain within 20 days or so blue crystalline substance Body.Elemental analysis (%)：Calculated value (experiment value):C 43.99(44.00)；H 4.51(4.52)；N 8.55(8.55).Its is red External spectrum is shown in attached drawing 7A and 7B respectively with X- diffraction mono-crystalline structures figures.Z7 compound molecule formulas are：[Cu^II(phen)(L- Isoleucine)(H₂O)]₂·2ClO₄ ^-, i.e. 11,10-Phen, 1 leucine and 1 H₂O and 1 Cu coordination forms cooperation Object (Fig. 7 B).Complex also contains a ClO₄ ^-(in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z7 is same as Z1, and sample Z1 only is changed to sample Z7.The result shows that Z7 is to A-549 (lungs Cancer) inhibitory rate of cell growth be 36.73%, to Bel-7402 (liver cancer) inhibitory rate of cell growth be 47.04%, to HCT (colons Gland cancer) inhibitory rate of cell growth be 47.53%, to HL-60 (leukaemia) inhibitory rate of cell growth be 47.79%, to BGC- 823 (gastric cancer) inhibitory rate of cell growth are 45.88%, are 42.69% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Conclusion：Z7 It is possibly used for preparing the drug of prevention and treatment cancer.

Embodiment 7-2：Experiment is same as 7-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 7-3：It is real It tests and is same as 7-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (ClO₄)₂·6H₂O (0.5mmol).Embodiment 7-4：Experiment is same as 7-1, only CuBr₂(0.5mmol) and Na (ClO₄) (0.5mmol) substitution Cu (ClO₄)₂·6H₂O(0.5mmol).Embodiment 7-5：Experiment is same as 7-1, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and Na (ClO₄) (0.5mmol) substitution Cu (ClO₄)₂·6H₂O(0.5mmol).Embodiment 7-6：Experiment is same as 7-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (ClO₄)₂·6H₂O(0.5mmol)。

Embodiment 8-1, the preparation of complex Z8：Valine (0.5mmol, 0.058g) and NH₃·H₂O (25%, 0.15ml) Mixing is dissolved in 30ml mixed solvents (V_C2H5OH：V_H2O=5：1) in；Add Cu (ClO₄)₂·6H₂O (0.5mmol, 0.18g), so After stir to abundant dissolving；1,10- ferrosins (0.5mmol, 0.099g) are added, are stirred 12 hours；Filtering, by filtrate contain into In the small test tube of 20ml, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue colored crystal after a week.Elemental analysis (%)：Calculated value (experiment value):C 42.85(42.88)；H 3.99(3.96)；N 8.82(8.78).Its infrared spectrum spreads out with X- It penetrates mono-crystalline structures figure and sees attached drawing 8A and 8B respectively.Z8 compound molecule formulas are：[Cu^II(phen)(L-Val)(H₂O)]·ClO₄ ^-, That is 11,10-Phen, 1 leucine and 1 H₂O and 1 Cu coordination forms complex (Fig. 8 B).Complex also contains one ClO₄ ^-(in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z8 is same as Z1, and sample Z1 only is changed to sample Z8.The result shows that Z8 is to A-549 (lungs Cancer) inhibitory rate of cell growth be 89.39%, to Bel-7402 (liver cancer) inhibitory rate of cell growth be 89.76%, to HCT (colons Gland cancer) inhibitory rate of cell growth be 89.25%, to HL-60 (leukaemia) inhibitory rate of cell growth be 89.79%, to BGC- 823 (gastric cancer) inhibitory rate of cell growth are 89.88%, are 89.69% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Conclusion：Z8 The drug of prevention and treatment cancer can be used to prepare.

Embodiment 8-2：Experiment is same as 8-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 8-3：It is real It tests and is same as 8-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (ClO₄)₂·6H₂O (0.5mmol).Embodiment 8-4：Experiment is same as 8-1, only CuBr₂(0.5mmol) and Na (ClO₄) (0.5mmol) substitution Cu (ClO₄)₂·6H₂O(0.5mmol).Embodiment 8-5：Experiment is same as 8-1, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and Na (ClO₄) (0.5mmol) substitution Cu (ClO₄)₂·6H₂O(0.5mmol).Embodiment 8-6：Experiment is same as 8-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (ClO₄)₂·6H₂O(0.5mmol)。

Embodiment 9-1, the preparation of complex Z9：L-methionine (0.5mmol, 0.075g) and HAC (37%, 0.15ml) Mixing is dissolved in 30ml mixed solvents (V_C2H5OH：V_H2O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.5mmol, 0.12g), so After stir to abundant dissolving；1,10- ferrosins (0.5mmol, 0.099g) are added, are stirred 12 hours；Filtering, by filtrate contain into In the small test tube of 20ml, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue whiskers after a week.Element It analyzes (%)：Calculated value (experiment value):C 37.50(37.56)；H 3.88(3.85)；N 12.07(12.09).Its infrared spectrum Attached drawing 9A and 9B are seen respectively with X- diffraction mono-crystalline structures figures.Z9 compound molecule formulas are：[Cu^II(phen)(L-Meth)(H₂O)] [Cu^II(Phen)(NO₃ ^-)(2H₂O)]·2NO₃ ^-·2H₂O, i.e. 11,10-Phen, 1 methionine and 1 H₂O and 1 Cu Coordination forms complex；Another 1,10-Phen, 1 H₂O and NO₃Form a complex (Fig. 9 B).Complex also contains Two NO₃ ^-With two H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z9 is same as Z1, and sample Z1 only is changed to sample Z9.The result shows that Z9 is to A-549 (lungs Cancer) inhibitory rate of cell growth be 95.42%, to Bel-7402 (liver cancer) inhibitory rate of cell growth be 82.95%, to HCT (colons Gland cancer) inhibitory rate of cell growth be 86.25%, to HL-60 (leukaemia) inhibitory rate of cell growth be 87.79%, to BGC- 823 (gastric cancer) inhibitory rate of cell growth are 86.88%, are 89.69% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Conclusion：Z9 The drug of prevention and treatment cancer can be used to prepare.

Embodiment 9-2：Experiment is same as 9-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 9-3：It is real It tests and is same as 9-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.5mmol).Embodiment 9-4：Experiment is same as 9-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.5mmol).Embodiment 9-5：Experiment is same as 9-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.5mmol).Embodiment 9-6：Experiment is same as 9-1, only CuCl₂·2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.5mmol).Embodiment 9-7：Experiment is same as 9-1, only Cu(CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.5mmol)。

Embodiment 10-1, the preparation of complex Z10：Lysine (0.5mmol, 0.073g) and NH₃·H₂O (25%, 0.15ml) mixing is dissolved in 30ml mixed solvents (V_C2H5OH：V_H2O=5：1) in；Add Cu (ClO₄)₂·6H₂O(0.5mmol, 0.18g), it then stirs to abundant dissolving；1,10- ferrosins (0.5mmol, 0.099g) are added, are stirred 12 hours；Filtering, It in the small test tube that filtrate is contained to 20ml, adds diethyl ether to (volume ratio 1-3) above filtrate, stands, about obtain blue crystalline substance after a week Body.Elemental analysis (%)：Calculated value (experiment value):C 42.68(42.71)；H 4.54(4.52)；N 11.07(11.10).Its Infrared spectrum is shown in attached drawing 10A, 10B and 10C with X- diffraction mono-crystalline structures figures.The molecular formula of Z10 is：{[Cu^II(phen)(Lys) (NO₃ ^-)]·ClO₄ ^-·H₂O}_n, i.e. 11,10-Phen, 1 lysine and 1 NO₃ ^-A repetition is formed with 1 Cu coordination Unit (Figure 10 B), repetitive unit form one-dimensional catenary structure (Figure 10 C) by Cu bridgings.Each repetitive unit also contains one ClO₄ ^-With a H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z10 is same as Z1, and sample Z1 only is changed to sample Z10.The result shows that Z10 is to A-549 (lung cancer) inhibitory rate of cell growth is 81.88%, is 82.77% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 82.16%, is 81.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 81.88%, is 82.69% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z10 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 10-2：Experiment is same as 10-1, only Cu (NO₃)₂·3H₂O (0.5mmol) and Na (ClO₄)(0.5mmol) Replace Cu (ClO₄)₂·6H₂O(0.5mmol).Embodiment 10-3：Experiment is same as 10-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and Na (ClO₄) (0.5mmol) and NaNO₃(0.5mol) substitution Cu (ClO₄)₂·6H₂O(0.5mmol).Embodiment 10-4：Experiment is same as 10-1, only CuCl₂·2H₂O (0.5mmol) and Na (ClO₄) (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O (0.5mmol) and Na (ClO₄)(0.5mmol)。

Embodiment 10-5：Experiment is same as 10-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) replaces Cu(NO₃)₂·3H₂O(0.5mmol).Embodiment 10-6：Experiment is same as 10-1, only Cu (CH₃COOH)₂·H₂O(0.5mmol) With Na (ClO₄) (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.5mmol) and Na (ClO₄) (0.5mmol).Embodiment 10-7：Experiment is same as 10-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).

Embodiment 11-1, the preparation of complex Z11：L-Trp (0.5mmol, 0.10g) and NaOH (0.5mmol, 0.02g) mixing is dissolved in 30ml mixed solvents (V_C2H5OH：V_H2O=5：1) in；Add Cu (NO₃)₂·3H₂O(0.5mmol, 0.12g), it then stirs to abundant dissolving；1,10- ferrosins (0.5mmol, 0.099g) are added, are stirred 12 hours；Filtering, In the small test tube that filtrate is contained to 20ml, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue-green after a week Whiskers 4.Elemental analysis (%)：Calculated value (experiment value):C 49.86(49.88)；H 4.37(4.33)；N 12.64 (12.61).Its infrared spectrum is shown in attached drawing 11A and 11B respectively with X- diffraction mono-crystalline structures figures.Z11 compound molecule formulas are：[Cu^II (phen)(L-Trp)(H₂O)]₂·2NO₃·3H₂O, i.e. 11,10-Phen, 1 tryptophan and 1 H₂O and 1 Cu coordination Form complex, another 11,10-Phen, 1 tryptophan and 1 H₂O and 1 Cu, which is coordinated, forms another complex, two Not equivalent (Figure 10 B) of complex.A pair of of complex also contains two 2NO₃With three H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z11 is same as Z1, and sample Z1 only is changed to sample Z11.The result shows that Z11 is to A-549 (lung cancer) inhibitory rate of cell growth is 72.20%, is 72.70% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 72.25%, is 72.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 72.88%, is 72.69% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z11 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 11-2：Experiment is same as 11-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.5mmol).Embodiment 11-3：Experiment is same as 11-1, only CuCl₂·2H₂O(0.5mmol, 0.0874g) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.5mmol).Embodiment 11-4：Experiment is same as 11-1, only It is Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.5mmol)。

Embodiment 11-5：Experiment is same as 11-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).

Embodiment 12

The preparation of complex Z12

L-Trp (0.5mmol, 0.10g) and NaOH (0.5mmol, 0.02g) mixing are dissolved in 30ml mixed solvents (V_C2H5OH：V_H2O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.5mmol, 0.12g) is then stirred to abundant dissolving；Again plus Enter 1,10- ferrosins (0.5mmol, 0.099g), stir 12 hours；It filters, in the small test tube that filtrate is contained to 20ml, adds diethyl ether Above to filtrate (volume ratio 1-3), stand, about obtain blue-green square crystal after a week.Elemental analysis (%)：Calculated value (experiment value):C 49.60(49.58)；H 4.40(4.43)；N 12.57(12.61).Its infrared spectrum and X- diffraction monocrystalline knots Composition is shown in attached drawing 12A, 12B respectively.Z12 compound molecule formulas are：[Cu^II(phen)(L-Trp)(H₂O)]₂[Cu^II(phen)(L- Trp)(NO₃)]·2NO₃·6H₂O, i.e. 11,10-Phen, 1 tryptophan and 1 H₂O and 1 Cu coordination forms cooperation Object, there are two types of (because not equivalent) for such complex；Another 11,10-Phen, 1 tryptophan and 1 NO₃Match with 1 Cu Position forms another complex (Figure 12 B).Also contain two 2NO₃With six H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z12 is same as Z1, and sample Z1 only is changed to sample Z12.The result shows that Z12 is to A-549 (lung cancer) inhibitory rate of cell growth is 76.26%, is 76.76% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 76.25%, is 75.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 75.88%, is 76.69% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z12 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 12-2：Experiment is same as 12-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.5mmol).Embodiment 12-3：Experiment is same as 12-1, only Cu (SO₄)₂·5H₂O(0.5mmol, 0.1248g) and NaNO₃(0.5mol, 0,0425g substitution Cu (NO₃)₂·3H₂O(0.5mmol).Embodiment 12-4：Experiment is same as 12-1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.5mmol)。

Embodiment 13-1, the preparation of complex Z13：L-threonine (0.5mmol, 0.060g) and NaOH (0.5mmol, 0.022g) mixing is dissolved in 30ml mixed solvents (V_CH3OH：V_H2O=5：1) Cu (ClO, are added₄)₂·6H₂O (0.5mmol), stirring To abundant dissolving；1,10- ferrosins (0.5mmol, 0.095g) are added, are stirred 8 hours.Then it filters and contains filtrate into 20ml Small test tube in, add diethyl ether to (volume ratio 1-3) above filtrate, stand, obtain blue bulk crystals within 15 days or so.Elemental analysis (%)：Calculated value (experiment value):C 37.10(37.09)；H5.45(5.44)；N29.74(29.74).Its infrared spectrum spreads out with X- It penetrates mono-crystalline structures figure and sees attached drawing 13A and 13B respectively.Z13 compound molecule formulas are：[Cu^II(phen)(L-Trp)(H₂O)]₂· ClO₄·10H₂O, i.e. 11,10-Phen, 1 threonine and 1 H₂O and 1 Cu coordination forms complex, such cooperation There are two types of (because not equivalent) (Figure 13 B) for object.Also 1 ClO₄With 10 H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z13 is same as Z1, and sample Z1 only is changed to sample Z13.The result shows that Z13 is to A-549 (lung cancer) inhibitory rate of cell growth is 87.26%, is 87.76% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 87.25%, is 87.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 87.88%, is 87.69% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z13 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 13-2：Experiment is same as 13-1, only Cu (NO₃)₂·3H₂O (0.5mmol) and Na (ClO₄)(0.5mmol) Replace Cu (ClO₄)₂·6H₂O(0.5mmol)。

Embodiment 14-1, the preparation of complex Z14：D- methionine (0.5mmol, 0.075g) and HAC (37%, 0.15ml) Mixing is dissolved in 30ml mixed solvents (V_C2H5OH：V_H2O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.5mmol, 0.12g), so After stir to abundant dissolving；1,10- ferrosins (0.5mmol, 0.099g) are added, are stirred 12 hours；Filtering, by filtrate contain into In the small test tube of 20ml, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue whiskers after a week.Element It analyzes (%)：Calculated value (experiment value):C 41.63(41.68)；H 4.48(4.44)；N 11.43(11.41).Its infrared spectrum Attached drawing 14A and 14B are seen respectively with X- diffraction mono-crystalline structures figures.Z14 compound molecule formulas are：[Cu^II(phen)(D-Meth) (H₂O)]·NO₃ ^-·H₂O, i.e. 11,10-Phen, 1 methionine and 1 H₂O and 1 Cu coordination forms complex (figure 14B).An also NO₃ ^-With a H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z14 is same as Z1, and sample Z1 only is changed to sample Z14.The result shows that Z14 is to A-549 (lung cancer) inhibitory rate of cell growth is 86.16%, is 86.73% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 86.15%, is 85.48% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 86.83%, is 86.579% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z14 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 15, the preparation of complex Z15：L-PROLINE (0.5mmol, 0.087g) and NaOH (0.5mmol, 0.02g) mixing is dissolved in 30ml mixed solvents (V_C2H5OH：V_H2O=5：1) Cu (NO, are added₃)₂·3H₂O(0.5mmol, 0.117g), it stirs to abundant dissolving；1,10- ferrosins (0.5mmol, 0.094g) are added, are stirred 8 hours.Then filtering will Filtrate is contained in small beaker, is stood volatilization, is obtained blue colored crystal within 20 days or so.Elemental analysis (%)：Calculated value (experiment value):C 45.69(45.68)；H4.29(4.28)；N 12.54(12.53).Its infrared spectrum is shown in attached respectively with X- diffraction mono-crystalline structures figures Figure 15 A and 15B.Z15 compound molecule formulas are：[Cu^II(phen)(L-Pro)(H₂O)]₂·2NO₃ ^-·H₂O, i.e., 11,10- Phen, 1 methionine and 1 H₂O and 1 Cu coordination forms complex；Another 11,10-Phen, 1 methionine and 1 H₂O Another complex is formed with 1 Cu coordination；Two complexs are not equivalent (Figure 15 B).Also 2 NO₃ ^-With 1 H₂O is (for picture Clearly, it omits and does not draw).

The cell experiment of complex Z15 is same as Z1, and sample Z1 only is changed to sample Z15.The result shows that Z15 is to A-549 (lung cancer) inhibitory rate of cell growth is 75.88%, is 88.596% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 88.88%, is 88.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 82.88%, is 80.69% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z15 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 16-1, the preparation of complex Z16：Glycine (0.4mmol, 0.038g) and NaOH (0.2mmol) mixing It is dissolved in 30ml mixed solvents (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol), then stir to Fully dissolving；3,4,7,8- tetramethyl -1,10- ferrosins (0.2mmol) are added, are stirred 12 hours；Filtering, by filtrate contain into In the small test tube of 6 20ml, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue acicular crystal after a week. Elemental analysis (%)：Calculated value (experiment value):C49.55(49.57)；H 4.59(4.58)；N 12.85(12.86).Its is infrared Spectrum is shown in attached drawing 16A, 16B and 16C respectively with X- diffraction mono-crystalline structures figures.Z16 compound molecule formulas are：{[Cu(3,4,7,8- Tetramethyl-1,10-phen)(gly)(H₂O)](NO₃ ^-)}_n, i.e. 13,4,7,8- tetramethyl -1,10-Phen, 1 sweet ammonia Acid and 1 H₂O and 1 Cu coordination forms a repetitive unit, and repetitive unit forms one-dimensional chain knot by the bridging of Cu Structure；One-dimensional catenary structure arranged in parallel is crystal.Each repetitive unit also contains 1 NO₃ ^-(in order to which picture is clear, omission does not have It draws).

The cell experiment of complex Z16 is same as Z1, and sample Z1 only is changed to sample Z16.The result shows that Z16 is to A-549 (lung cancer) inhibitory rate of cell growth is 90.81%, is 91.526% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 91.32%, is 91.61% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 92.26%, is 90.67% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z16 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 16-2：Experiment is same as 16-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.2mmol).Embodiment 16-3：Experiment is same as 16-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.2mmol).Embodiment 16-4：Experiment is same as 16-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.2mmol).Embodiment 16-5：Experiment is same as 16- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.2mmol).Embodiment 16-6：Experiment 16-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.2mmol).Embodiment 16-7:Experiment is same as 16-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).

Embodiment 17, the preparation of complex Z17:Glycine (0.4mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml Mixed solvent (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol) is then stirred to abundant dissolving； 3,4,7,8- tetramethyl -1,10- ferrosins (0.2mmol) are added, are stirred 12 hours；Filtering, filtrate is contained into 6 20ml Small test tube in, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue bulk crystals after a week.Elemental analysis (%)：Calculated value (experiment value):C 47.58(47.59)；H 4.85(4.84)；N 12.33(12.34).Its infrared spectrum and X- Diffraction mono-crystalline structures figure is shown in attached drawing 17A and 17B respectively.Z17 molecular formula are：[Cu(3,4,7,8-Tetramethyl-1,10- phen)(gly)(H₂O)]·NO₃ ^-, i.e. 13,4,7,8- tetramethyl -1,10-Phen, 1 glycine and 1 H2O and 1 Cu Coordination forms complex (Figure 17 B)；Complex also contains 1 NO₃ ^-(in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z17 is same as Z1, and sample Z1 only is changed to sample Z17.The result shows that Z17 is to A-549 (lung cancer) inhibitory rate of cell growth is 90.82%, is 90.56% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 90.82%, is 90.71% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 91.83%, is 90.63% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z17 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 17-2：Experiment is same as 17-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.2mmol).Embodiment 17-3：Experiment is same as 17-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.2mmol).Embodiment 17-4：Experiment is same as 17-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.2mmol).Embodiment 17-5：Experiment is same as 17- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.2mmol).Embodiment 17-6：Experiment 17-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.2mmol).Embodiment 17-7:Experiment is same as 17-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).

Embodiment 18-1, the preparation of complex Z18:Alanine (0.4mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml Mixed solvent (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.3mmol) is then stirred to abundant dissolving； 3,4,7,8- tetramethyl -1,10- ferrosins (0.2mmol) are added, are stirred 12 hours；Filtering, filtrate is contained into 6 20ml Small test tube in, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue strip monocrystalline after a week.Elemental analysis (%)：Calculated value (experiment value):C 48.72(48.73)；H 5.13(5.12)；N 11.97(11.98).Its infrared spectrum and X- Diffraction mono-crystalline structures figure is shown in attached drawing 18A, 18B and 18C respectively.Z18 compound molecule formulas are：{[Cu(3,4,7,8- Tetramethyl-1,10-phen)(Ala)][Cu(3,4,7,8-Tetramethyl-1,10-phen)(Ala)(H₂O)] (2NO₃ ^-(H₂O)}_n, i.e. 13,4,7,8- tetramethyl -1,10-Phen, 1 alanine and 1 H₂O and 1 Cu coordination, another 1 3,4,7,8- tetramethyls -1,10-Phen, 1 alanine and 1 Cu are coordinated, and two Cu coordinating groups form a repetitive unit, Its repetitive unit forms one-dimensional catenary structure by the bridging of Cu；One-dimensional catenary structure arranged in parallel is crystal.Each repeat list Member also contains 2 NO₃ ^-With 1 H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z18 is same as Z1, and sample Z1 only is changed to sample Z18.The result shows that 18 institute of embodiment It is 85.26% to A-549 (lung cancer) inhibitory rate of cell growth to obtain complex Z18, to Bel-7402 (liver cancer) cell growth inhibition Rate is 82.596%, is 82.13% to HCT (adenocarcinoma of colon) inhibitory rate of cell growth, to HL-60 (leukaemia) cell growth Inhibiting rate is 82.19%, is 81.88% to BGC-823 (gastric cancer) inhibitory rate of cell growth, to KB (nasopharyngeal carcinoma) cell growth Inhibiting rate is 81.69%.Conclusion：Complex Z18 of the present invention can be used to prepare the drug of prevention and treatment cancer.

Embodiment 18-2：Experiment is same as 18-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 18-3：Experiment is same as 18-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 18-4：Experiment is same as 18-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 18-5：Experiment is same as 18- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 18-6：Experiment 18-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 18-7:Experiment is same as 18-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).

Embodiment 19-1, the preparation of complex Z19：Tyrosine (0.2mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml Mixed solvent (the VC of second alcohol and water₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol), is then stirred To abundant dissolving；3,4,7,8- tetramethyl -1,10- ferrosins (0.2mmol) are added, are stirred 12 hours；Filtering, by filtrate It in the small test tube for containing 6 20ml, adds diethyl ether to (volume ratio 1-3) above filtrate, stands, it is blocky single about to obtain navy blue after a week It is brilliant.Elemental analysis (%)：Calculated value (experiment value):C50.46(50.47)；H 5.92(5.91)；N 8.22(8.20).Infrared light Spectrum is shown in attached drawing 19A and 19B with X- diffraction mono-crystalline structures figures.Z19 compound molecule formulas are：{[Cu(3,4,7,8- Tetramethyl-1,10-phen)(Tyr)(H₂O)]Cu(3,4,7,8-Tetramethyl-1,10-phen)(Tyr)]}· 2NO₃ ^-·5H₂O·CH₃CH₂OH, i.e. 13,4,7,8- tetramethyl -1,10-Phen, 1 tyrosine and 1 H₂O matches with 1 Cu Position forms a complex；Another 13,4,7,8- tetramethyl -1,10-Phen, 1 tyrosine and 1 H₂O and 1 Cu coordination Another complex is formed, two complexs are not equivalent.A pair of of complex also contains 2 NO₃ ^-With 5 H₂O and 1 CH₃CH₂OH (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z19 is same as Z1, and sample Z1 only is changed to sample Z19.The result shows that Z19 is to A-549 (lung cancer) inhibitory rate of cell growth is 90.28%, is 90.56% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 90.82%, is 91.19% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 91.38%, is 89.69% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z19 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 19-2：Experiment is same as 19-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 19-3：Experiment is same as 19-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 19-4：Experiment is same as 19-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 19-5：Experiment is same as 19- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 19-6：Experiment 19-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 19-7:Experiment is same as 19-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 19- 8:Experiment is same as 19-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 20-1, the preparation of complex Z20:Valine (0.2mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml Mixed solvent (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol) is then stirred to fully molten Solution；3,4,7,8- tetramethyl -1,10- ferrosins (0.2mmol) are added, are stirred 12 hours；Filtering, filtrate is contained into 6 In the small test tube of 20ml, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue bulk-shaped monocrystal after a week.Element It analyzes (%)：Calculated value (experiment value):C 50.80(50.81)；H 5.65(5.64)；N 11.29(11.30).Its infrared spectrum Attached drawing 20A and 20B are seen respectively with X- diffraction mono-crystalline structures figures.Z20 compound molecule formulas are：[Cu(3,4,7,8- Tetramethyl-1,10-phen)(Val)(NO₃ ^-)]·H₂O, i.e. 13,4,7,8- tetramethyl -1,10-Phen, 1 figured silk fabrics ammonia Acid and 1 NO₃ ^-Complex is formed with 1 Cu coordination.Complex also contains 1 H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z20 is same as Z1, and sample Z1 only is changed to sample Z20.The result shows that Z20 is to A-549 (lung cancer) inhibitory rate of cell growth is 90.32%, is 91.87% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 91.85%, is 91.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 92.68%, is 90.31% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z20 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 20-2：Experiment is same as 20-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 20-3：Experiment is same as 20-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 20-4：Experiment is same as 20-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 20-5：Experiment is same as 20- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 20-6：Experiment 20-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 20-7:Experiment is same as 20-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 20- 8:Experiment is same as 20-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 21-1, the preparation of complex Z21:Threonine (0.2mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml Mixed solvent (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol) is then stirred to fully molten Solution；3,4,7,8- tetramethyl -1,10- ferrosins (0.2mmol) are added, are stirred 12 hours；Filtering, filtrate is contained into 6 In the small test tube of 20ml, add diethyl ether to (volume ratio 1-3) above filtrate, stand, it is needle-shaped about to obtain blue after a week.Elemental analysis (%)：Calculated value (experiment value):C 47.33(47.35)；H 5.32(5.32)；N 11.05(11.07).Its infrared spectrum and X- Diffraction mono-crystalline structures figure is shown in attached drawing 21A and 21B respectively.Z21 compound molecule formulas are：[Cu(3,4,7,8-Tetramethyl-1, 10-phen)(Thr)(NO₃ ^-)]·3H₂O, i.e. 13,4,7,8- tetramethyl -1,10-Phen, 1 threonine and 1 NO₃ ^-With 1 A Cu coordinations form complex.Complex also contains 3 H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z21 is same as Z1, and sample Z1 only is changed to sample Z21.The result shows that 21 institute of embodiment It is 86.88% to A-549 (lung cancer) inhibitory rate of cell growth to obtain complex Z21, to Bel-7402 (liver cancer) cell growth inhibition Rate is 88.34%, is 88.26% to HCT (adenocarcinoma of colon) inhibitory rate of cell growth, HL-60 (leukaemia) cell growth is pressed down Rate processed is 88.31%, is 88.88% to BGC-823 (gastric cancer) inhibitory rate of cell growth, KB (nasopharyngeal carcinoma) cell growth is pressed down Rate processed is 88.12%.Conclusion：Complex Z21 of the present invention can be used to prepare the drug of prevention and treatment cancer.

Embodiment 21-2：Experiment is same as 21-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 21-3：Experiment is same as 21-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 21-4：Experiment is same as 21-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 21-5：Experiment is same as 21- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 21-6：Experiment 21-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 21-7:Experiment is same as 21-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 21- 8:Experiment is same as 21-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 22-1, the preparation of complex Z22：Glycine (0.4mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml Mixed solvent (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)2·3H₂O (0.2mmol) is then stirred to fully molten Solution；4,7- dimethyl -1,10- ferrosin (0.2mmol) is added, is stirred 12 hours；Filtering contains filtrate into 6 20ml's In small test tube, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue bulk-shaped monocrystal after a week.Elemental analysis (%)：Calculated value (experiment value):C 43.25(43.258)；H 4.51(4.50)；N 12.16(12.59).Its infrared spectrum with X- diffraction mono-crystalline structures figures are shown in attached drawing 22A and 22B respectively.Z22 compound molecule formulas are：[Cu(4,7-dimethyl-1,10- phen)(Gly)(NO₃ ^-)(H₂O)]·H₂O, i.e. 14,7- dimethyl -1,10-Phen, 1 glycine and 1 NO₃ ^-And 1 A H₂O and 1 Cu coordination forms complex.Complex also contains 1 H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z22 is same as Z1, and sample Z1 only is changed to sample Z22.The result shows that Z22 is to A-549 (lung cancer) inhibitory rate of cell growth is 75.23%, is 76.12% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 76.46%, is 76.21% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 76.43%, is 76.29% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z22 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 22-2：Experiment is same as 22-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 22-3：Experiment is same as 22-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 22-4：Experiment is same as 22-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 22-5：Experiment is same as 22- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 22-6：Experiment 22-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 22-7:Experiment is same as 22-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 22- 8:Experiment is same as 22-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 23-1, the preparation of complex Z23:Methionine (0.2mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml mixed solvents (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol), is then stirred to abundant Dissolving；4,7 are added,-dimethyl -1,10- ferrosin (0.2mmol) stirs 12 hours；Filtering, filtrate is contained into 6 In the small test tube of 20ml, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue bulk-shaped monocrystal after a week.Element It analyzes (%)：Calculated value (experiment value):C 51.36(51.39)；H 5.86(5.85)；N 94.16(94.18).Its infrared spectrum Attached drawing 23A and 23B are seen respectively with X- diffraction mono-crystalline structures figures.Z23 compound molecule formulas are：[Cu(4,7-dimethyl-1,10- phen)(Met)(H₂O)₂]·(NO₃ ^-), i.e. 14,7- dimethyl -1,10-Phen, 1 methionine and 1 H₂O and 1 Cu Coordination forms complex.Complex also contains 1 NO₃ ^-(in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z23 is same as Z1, and sample Z1 only is changed to sample Z9.The result shows that Z21 is to A-549 (lung cancer) inhibitory rate of cell growth is 86.63%, is 86.21% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 86.33%, is 86.27% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 86.518%, is 80.32% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z23 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 23-2：Experiment is same as 23-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 23-3：Experiment is same as 23-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 23-4：Experiment is same as 23-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 23-5：Experiment is same as 23- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 23-6：Experiment 23-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 23-7:Experiment is same as 23-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 23- 8:Experiment is same as 23-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 24-1, the preparation of complex Z24:Methionine (0.2mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml mixed solvents (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol), is then stirred to abundant Dissolving；5,6 are added,-dimethyl -1,10- ferrosin (0.2mmol) stirs 12 hours；Filtering, filtrate is contained into 6 In the small test tube of 20ml, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue bulk-shaped monocrystal after a week.Element It analyzes (%)：Calculated value (experiment value):C 51.36(51.39)；H 5.86(5.85)；N 9.42(9.46).Its infrared spectrum with X- diffraction mono-crystalline structures figures are shown in attached drawing 24A and 24B respectively.Z24 compound molecule formulas are：[Cu(5,6-dimethyl-1,10- phen)(Met)(H₂O)₂]·(NO₃ ^-), i.e., 15,6,-dimethyl -1,10-Phen, 1 methionine and 1 H₂O and 1 Cu coordinations form complex.Complex also contains 1 NO₃ ^-(in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z24 is same as Z1, and sample Z1 only is changed to sample Z9.The result shows that 24 institute of embodiment It is 86.63% to A-549 (lung cancer) inhibitory rate of cell growth to obtain complex Z21, to Bel-7402 (liver cancer) cell growth inhibition Rate is 86.21%, is 86.33% to HCT (adenocarcinoma of colon) inhibitory rate of cell growth, HL-60 (leukaemia) cell growth is pressed down Rate processed is 86.27%, is 86.518% to BGC-823 (gastric cancer) inhibitory rate of cell growth, KB (nasopharyngeal carcinoma) cell growth is pressed down Rate processed is 80.32%.Conclusion：Complex Z24 of the present invention can be used to prepare the drug of prevention and treatment cancer.

Embodiment 24-2：Experiment is same as 24-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 24-3：Experiment is same as 24-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 24-4：Experiment is same as 24-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 24-5：Experiment is same as 24- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 24-6：Experiment 24-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 24-7:Experiment is same as 24-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 24- 8:Experiment is same as 24-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 25-1, the preparation of complex Z25:Methionine (0.2mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml mixed solvents (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol), is then stirred to abundant Dissolving；3,8 are added,-dimethyl -1,10- ferrosin (0.2mmol) stirs 12 hours；Filtering, filtrate is contained into 6 In the small test tube of 20ml, add diethyl ether to (volume ratio 1-3) above filtrate, stand, about obtain blue bulk-shaped monocrystal after a week.Element It analyzes (%)：Calculated value (experiment value):C 51.36(51.39)；H 5.86(5.85)；N 9.42(9.46).Its infrared spectrum with X- diffraction mono-crystalline structures figures are shown in attached drawing 25A and 23B respectively.

Z25 compound molecule formulas are：[Cu(3,8-dimethyl-1,10-phen)(Met)(H₂O)₂]·(NO₃ ^-), i.e., 1 A 3,8,-dimethyl -1,10-Phen, 1 methionine and 1 H₂O and 1 Cu coordination forms complex.Complex also contains There is 1 NO₃ ^-(in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z25 is same as Z1, and sample Z1 only is changed to sample Z9.The result shows that 25 institute of embodiment It is 86.63% to A-549 (lung cancer) inhibitory rate of cell growth to obtain complex Z25, to Bel-7402 (liver cancer) cell growth inhibition Rate is 86.21%, is 86.33% to HCT (adenocarcinoma of colon) inhibitory rate of cell growth, HL-60 (leukaemia) cell growth is pressed down Rate processed is 86.27%, is 86.518% to BGC-823 (gastric cancer) inhibitory rate of cell growth, KB (nasopharyngeal carcinoma) cell growth is pressed down Rate processed is 80.32%.Conclusion：Complex Z25 of the present invention can be used to prepare the drug of prevention and treatment cancer.

Embodiment 25-2：Experiment is same as 25-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 25-3：Experiment is same as 25-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 25-4：Experiment is same as 25-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 25-5：Experiment is same as 25- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 25-6：Experiment 25-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 25-7:Experiment is same as 25-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 25- 8:Experiment is same as 25-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 26

The preparation of complex Z26

Methionine (0.2mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml mixed solvents (VC₂H₅OH：VH₂O=5： 1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol) is then stirred to abundant dissolving；2,9 are added,-dimethyl -1,10- Ferrosin (0.2mmol) stirs 12 hours；It filters, in the small test tube that filtrate is contained to 6 20ml, adds diethyl ether to above filtrate (volume ratio 1-3) stands, about obtains blue bulk-shaped monocrystal after a week.Elemental analysis (%)：Calculated value (experiment value):C 51.36 (51.39)；H 5.86(5.85)；N 9.42(9.46).Its infrared spectrum and X- diffraction mono-crystalline structures figures see respectively attached drawing 26A and 26B。

Z26 compound molecule formulas are：[Cu(2,9-dimethyl-1,10-phen)(Met)(H₂O)₂]·(NO₃ ^-), i.e., 1 A 2,9,-dimethyl -1,10-Phen, 1 methionine and 1 H₂O and 1 Cu coordination forms complex.Complex also contains There is 1 NO₃ ^-(in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z26 is same as Z1, and sample Z1 only is changed to sample Z9.The result shows that 26 institute of embodiment It is 86.63% to A-549 (lung cancer) inhibitory rate of cell growth to obtain complex Z26, to Bel-7402 (liver cancer) cell growth inhibition Rate is 86.21%, is 86.33% to HCT (adenocarcinoma of colon) inhibitory rate of cell growth, HL-60 (leukaemia) cell growth is pressed down Rate processed is 86.27%, is 86.518% to BGC-823 (gastric cancer) inhibitory rate of cell growth, KB (nasopharyngeal carcinoma) cell growth is pressed down Rate processed is 80.32%.Conclusion：Complex Z26 of the present invention can be used to prepare the drug of prevention and treatment cancer.

Embodiment 26-2：Experiment is same as 26-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 26-3：Experiment is same as 26-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 26-4：Experiment is same as 26-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 26-5：Experiment is same as 26- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 26-6：Experiment 26-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 26-7:Experiment is same as 26-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 26- 8:Experiment is same as 26-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 27-1, the preparation of complex Z27:Valine (0.2mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml Mixed solvent (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol) is then stirred to fully molten Solution；3- methyl-1s are added, 10- ferrosins (0.2mmol) stir 12 hours；Filtering, the lab scale into 6 20ml is contained by filtrate Guan Zhong adds diethyl ether to (volume ratio 1-3) above filtrate, stands, about obtain blue bulk-shaped monocrystal after a week.Elemental analysis (%)： Calculated value (experiment value):C 47.47(47.98)；H 5.05(5.01)；N 12.31(12.19).Its infrared spectrum and X- diffraction Mono-crystalline structures figure is shown in attached drawing 27A and 27B respectively.

Z27 compound molecule formulas are：[Cu(3-methyl-1,10-phen)(Val)(NO₃ ^-)]·H₂O, i.e. 1 3- first Base -1,10-Phen, 1 valine and 1 NO₃ ^-Complex is formed with 1 Cu coordination.Complex also contains 1 H₂O (in order to Picture is clear, and omission is not drawn).

The cell experiment of complex Z27 is same as Z1, and sample Z1 only is changed to sample Z9.The result shows that 27 institute of embodiment It is 90.32% to A-549 (lung cancer) inhibitory rate of cell growth to obtain complex Z27, to Bel-7402 (liver cancer) cell growth inhibition Rate is 91.87%, is 91.85% to HCT (adenocarcinoma of colon) inhibitory rate of cell growth, HL-60 (leukaemia) cell growth is pressed down Rate processed is 91.79%, is 92.68% to BGC-823 (gastric cancer) inhibitory rate of cell growth, KB (nasopharyngeal carcinoma) cell growth is pressed down Rate processed is 90.31%.Conclusion：Complex Z27 of the present invention can be used to prepare the drug of prevention and treatment cancer.

Embodiment 27-2：Experiment is same as 27-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 27-3：Experiment is same as 27-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 27-4：Experiment is same as 27-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 27-5：Experiment is same as 27- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 27-6：Experiment 27-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 27-7:Experiment is same as 27-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 27- 8:Experiment is same as 27-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 28-1, the preparation of complex Z28:Valine (0.2mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml Mixed solvent (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol) is then stirred to fully molten Solution；4- methyl-1s are added, 10- ferrosins (0.2mmol) stir 12 hours；Filtering, the lab scale into 6 20ml is contained by filtrate Guan Zhong adds diethyl ether to (volume ratio 1-3) above filtrate, stands, about obtain blue bulk-shaped monocrystal after a week.Elemental analysis (%)： Calculated value (experiment value):C 47.47(47.98)；H 5.05(5.01)；N 12.31(12.19).Its infrared spectrum and X- diffraction Mono-crystalline structures figure is shown in attached drawing 28A and 28B respectively.Z28 compound molecule formulas are：[Cu(4-methyl-1,10-phen)(Val) (NO₃ ^-)]·H₂O, i.e. 1 4- methyl-1,10-Phen, 1 valine and 1 NO₃ ^-Complex is formed with 1 Cu coordination.Match It closes object and also contains 1 H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z28 is same as Z1, and sample Z1 only is changed to sample Z9.The result shows that Z28 is to A-549 (lung cancer) inhibitory rate of cell growth is 90.32%, is 91.87% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 91.85%, is 91.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 92.68%, is 90.31% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z28 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 28-2：Experiment is same as 28-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 28-3：Experiment is same as 28-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 28-4：Experiment is same as 28-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 28-5：Experiment is same as 28- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 28-6：Experiment 28-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 28-7:Experiment is same as 28-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 28- 8:Experiment is same as 28-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 29-1, the preparation of complex Z29:Valine (0.2mmol) and NaOH (0.2mmol) mixing are dissolved in 30ml Mixed solvent (VC₂H₅OH：VH₂O=5：1) in；Add Cu (NO₃)₂·3H₂O (0.2mmol) is then stirred to fully molten Solution；7- methyl-1s are added, 10- ferrosins (0.2mmol) stir 12 hours；Filtering, the lab scale into 6 20ml is contained by filtrate Guan Zhong adds diethyl ether to (volume ratio 1-3) above filtrate, stands, about obtain blue bulk-shaped monocrystal after a week.Elemental analysis (%)： Calculated value (experiment value):C 47.47(47.98)；H 5.05(5.01)；N 12.31(12.19).Its infrared spectrum and X- diffraction Mono-crystalline structures figure is shown in attached drawing 29A and 29B respectively.Z29 compound molecule formulas are：[Cu(7-methyl-1,10-phen)(Val) (NO₃ ^-)]·H₂O, i.e. 1 7- methyl-1,10-Phen, 1 valine and 1 NO₃ ^-Complex is formed with 1 Cu coordination.Match It closes object and also contains 1 H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z29 is same as Z1, and sample Z1 only is changed to sample Z9.The result shows that Z29 is to A-549 (lung cancer) inhibitory rate of cell growth is 90.32%, is 91.87% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 91.85%, is 91.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 92.68%, is 90.31% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z29 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 29-2：Experiment is same as 29-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 29-3：Experiment is same as 29-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 29-4：Experiment is same as 29-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 29-5：Experiment is same as 29- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 29-6：Experiment 29-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 29-7:Experiment is same as 29-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 29- 8:Experiment is same as 29-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 30-1, the preparation of complex Z30:Methionine (0.3mmol) and NaOH (0.3mmol) are dissolved in 30ml and mix Bonding solvent (VC2H5OH：VH2O=5：1) in；Stirring 5 hours, makes it fully dissolve；Add CuCl₂(0.3mmol), stirring 24 hours；Then 3,4,7,8- tetramethyl -1,10- ferrosins (0.3mmol) are added in, are stirred 48 hours；Filtering takes its clear liquid to contain In the small test tube for entering 20ml, ether is added to above filtrate, the volume ratio of filtrate and ether is about 1:2.5, it stands, about one Blue colored crystal is obtained after week.Elemental analysis (%)：Calculated value (experiment value):C 51.36(53.71)；H 6.22(6.51)；N 8.17(8.54).Its infrared spectrum is shown in attached drawing 30A and 30B with X- diffraction mono-crystalline structures figures.Z30 molecular formula are：[Cu^II(3,4,7, 8-Tetramethyl-1,10-phen)(D-Meth)(H₂O)]·Cl^-·2H₂O, i.e. 13,4,7,8- tetramethyl -1,10- Phen, 1 methionine and 1 H₂O and 1 Cu coordination forms complex.Complex also contains and 1 Cl^-With 2 H₂O (in order to Picture is clear, and omission is not drawn).

The cell experiment of complex Z30 is same as Z1, and sample Z1 only is changed to sample Z30.The result shows that Z30 is to A-549 (lung cancer) inhibitory rate of cell growth is 91.32%, is 91.34% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 91.26%, is 91.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 91.68%, is 91.31% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z30 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 30-2：Experiment is same as 30-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaCl (0.5mol) substitutions CuCl₂(0.3mmol).Embodiment 30-3：Experiment is same as 30-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaCl (0.5mol) replaces CuCl₂(0.3mmol).Embodiment 30-4：Experiment is same as 30-1, only CuCl₂·2H₂O (0.5mmol) and NaCl (0.5mol) replaces CuCl₂(0.3mmol).Embodiment 30-5：Experiment is same as 30-1, only CuBr₂(0.5mmol) and NaCl (0.5mol) replaces CuCl₂(0.3mmol).Embodiment 30-6：Experiment is same as 30-1, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaCl (0.5mol) replace CuCl₂(0.3mmol).Embodiment 30-7:Experiment is same as 30-1, only KOH (0.5mmol) substitution NaOH (0.5mmol).Embodiment 30-8:Experiment is same as 30-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 31-1, the preparation of complex Z31:Methionine (0.3mmol) and NaOH (0.3mmol) are dissolved in 30ml and mix Bonding solvent (VCH₃OH：VH₂O=5：1) in；Stirring 5 hours, makes it fully dissolve；Add in Cu (NO₃)₂·3H₂O (0.3mmol), Stirring 24 hours；Then 3,4,7,8- tetramethyl -1,10- ferrosins (0.3mmol) are added in, are stirred 48 hours；Filtering takes it clear Liquid is contained in the test tube of 20ml, and ether is added to above filtrate, and the volume ratio of filtrate and ether is about 1:2.5, it stands, about Dark blue crystals are obtained after a week.Elemental analysis (%)：Calculated value (experiment value):C 44.68(44.69)；H 5.67(5.67)； N 9.92(9.93).Its infrared spectrum is shown in attached drawing 31A and 31B respectively with X- diffraction mono-crystalline structures figures.Z31 compound molecule formulas For：[Cu^II(3,4,7,8-Tetramethyl-1,10-phen)(D-Meth)(H₂O)]·H₂O·NO₃ ^-, i.e., 13,4,7,8- Tetramethyl -1,10-Phen, 1 methionine and 1 H₂O and 1 Cu coordination forms complex.Complex also contains 1 NO₃ ^- (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z31 is same as Z1, and sample Z1 only is changed to sample Z31.The result shows that Z31 is to A-549 (lung cancer) inhibitory rate of cell growth is 90.99%, is 91.67% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 91.88%, is 91.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 91.68%, is 91.31% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z31 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 31-2：Experiment is same as 31-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaNO₃(0.5mol) takes For Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 31-3：Experiment is same as 31-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 31-4：Experiment is same as 31-1, only CuCl₂· 2H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 31-5：Experiment is same as 31- 1, only CuBr₂(0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O(0.3mmol).Embodiment 31-6：Experiment 31-1 is same as, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaNO₃(0.5mol) substitution Cu (NO₃)₂·3H₂O (0.3mmol).Embodiment 31-7:Experiment is same as 31-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 31- 8:Experiment is same as 31-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 32-1, the preparation of complex Z32:Serine (0.4mmol) and NaOH (0.3mmol) are dissolved in 30ml and mix Bonding solvent (VCH₃OH：VH₂O=5：1) in；Stirring 5 hours, makes it fully dissolve；Add CuBr₂(0.3mmol), stirring 24 Hour；Then 3,4,7,8- tetramethyl -1,10- ferrosins (0.3mmol) are added in, are stirred 48 hours；Then it filters, takes its clear liquid In the test tube for containing 20ml, ether is taken to be added to above filtrate, the volume ratio of filtrate and ether is about 1:2.5, it stands, about one Dark blue crystals are obtained after week.Elemental analysis (%)：Calculated value (experiment value):C46.256(46.252)；H 4.666 (4.665)；N 8.521(8.520).Its infrared spectrum is shown in attached drawing 32A and 32B respectively with X- diffraction mono-crystalline structures figures.Z32 chemical combination Object molecular formula is：[Cu^II(3,4,7,8-Tetramethyl-1,10-phen)(Ser)(Br^-)]₂·H₂O, i.e., 13,4,7,8- Tetramethyl -1,10-Phen, 1 serine and 1 Br^-A complex, two complex compositions one are formed with 1 Cu coordination It is right.A pair of of complex also contains 1 H₂O (in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z32 is same as Z2, and sample Z1 only is changed to sample Z32.The result shows that Z32 is to A-549 (lung cancer) inhibitory rate of cell growth is 92.32%, is 92.87% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 92.85%, is 92.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 92.88%, is 92.31% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z32 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 32-2：Experiment is same as 32-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and NaBr (0.5mol) substitutions CuBr₂(0.3mmol).Embodiment 32-3：Experiment is same as 32-1, only Cu (SO₄)₂·5H₂O (0.5mmol) and NaBr (0.5mol) replaces CuBr₂(0.3mmol).Embodiment 32-4：Experiment is same as 32-1, only CuCl₂·2H₂O (0.5mmol) and NaBr (0.5mol) replaces CuBr₂(0.3mmol).Embodiment 32-5：Experiment is same as 32-1, only Cu (CH₃COOH)₂·H₂O (0.5mmol) and NaCl (0.5mol) replace CuBr₂(0.3mmol).Embodiment 32-6:Experiment is same as 32-1, only KOH (0.5mmol) substitution NaOH (0.5mmol).Embodiment 32-7:Experiment is same as 32-1, only NH₃·H₂O (concentration, 25%, 0.2mL) substitution NaOH (0.5mmol).

Embodiment 33-1, the preparation of complex Z33:Glutamic acid (0.6mmol) and NaOH (0.6mmol) are dissolved in 30ml and mix Bonding solvent (VCH₃CH₂OH：VH₂O=5：1) in；Stirring 5 hours, makes it fully dissolve；Cu (Ac) 2 (0.6mmol) is added, is stirred It mixes 24 hours；Then 3,4,7,8- tetramethyl -1,10- ferrosins (0.6mmol) are added in, are stirred 48 hours；Filtering, takes its clear liquid In the test tube for containing 20ml, ether is taken to be added to above filtrate, it is about 1 to make the volume ratio of filtrate and ether:2.5, it stands, about Blue colored crystal is obtained after a week.Elemental analysis (%)：Calculated value (experiment value):C 50.574(50.579)；H 6.131 (6.130)；N 8.045(8.046).Its infrared spectrum is shown in attached drawing 33A and 33B and 33C respectively with X- diffraction mono-crystalline structures figures. Z33 compound molecule formulas are：{[Cu^II(3,4,7,8-Tetramethyl-1,10-phen)(Clu)]·3H₂O}_n, i.e., 13, 4,7,8- tetramethyls -1,10-Phen, 1 glutamic acid and 1 Cu coordination form a repetitive unit (33B), this repetitive unit leads to Cu bridgings are crossed, form the structure (Figure 33 C) of one-dimensional chain.Complex also contains 3 H₂O and 0.5 CH₃CH₂OH is (for picture Clearly, it omits and does not draw).

The cell experiment of complex Z33 is same as Z1, and sample Z1 only is changed to sample Z33.The result shows that Z33 is to A-549 (lung cancer) inhibitory rate of cell growth is 90.12%, is 91.11% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 91.23%, is 91.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 91.68%, is 90.31% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z33 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 33-2：Experiment is same as 33-1, only Cu (ClO₄)₂·6H₂O (0.5mmol) and Na Ac (0.5mol) take For Cu (Ac)₂(0.6mmol).Embodiment 33-3：Experiment is same as 33-1, only CuCl₂·2H₂O (0.5mmol) and Na Ac (0.5mol) substitution Cu (Ac)₂(0.6mmol).Embodiment 33-4：Experiment is same as 33-1, only CuBr₂(0.5mmol) and Na Ac (0.5mol) substitution Cu (Ac)₂(0.6mmol).Embodiment 33-5:Experiment is same as 33-1, and only KOH (0.5mmol) replaces NaOH (0.5mmol).Embodiment 33-6:Experiment is same as 33-1, only NH₃·H₂O (concentration, 25%, 0.2mL) replaces NaOH (0.5mmol)。

Embodiment 34-1, the preparation of complex Z34:Glutamic acid (0.6mmol) and NaOH (0.6mmol) are dissolved in 30ml and mix Bonding solvent (VCH₃OH：VH₂O=5：1) in；Stirring 5 hours, makes it fully dissolve；Add Cu (ClO₄)₂(0.6mmol), is stirred It mixes 24 hours；Then 3,4,7,8- tetramethyl -1,10- ferrosins (0.6mmol) are added in, are stirred 48 hours；Filtering, takes its clear liquid In the test tube for containing 20ml, it is added to above filtrate along test tube wall with dropper absorption ether is careful, makes the body of filtrate and ether Product is than being about 1:2.5, it stands, about obtains blue colored crystal after a week.Elemental analysis (%)：Calculated value (experiment value):Calculated value (experiment value):C 41.658(40.682)；H 3.664(3.578)；N 10.800(10.547).Its infrared spectrum and X- diffraction Mono-crystalline structures figure is shown in attached drawing 34A and 34B respectively.Z34 compound molecule formulas are：[Cu^II(3,4,7,8-Tetramethyl-1,10- phen)(Clu)(H₂O)]·ClO₄ ^-, i.e. 13,4,7,8- tetramethyl -1,10-Phen, 1 glutamic acid and 1 H₂O and 1 Cu Form complex (34B).Complex also contains 1 ClO₄ ^-(in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z34 is same as Z1, and sample Z1 only is changed to sample Z34.The result shows that Z34 is to A-549 (lung cancer) inhibitory rate of cell growth is 90.32%, is 90.87% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 90.85%, is 90.79% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 90.68%, is 90.11% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z34 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 34-2：Experiment is same as 34-1, only Cu (NO₃)₂·6H₂O (0.5mmol) and NaClO₄(0.5mol) takes For Cu (ClO₄)₂(0.6mmol).Embodiment 34-3：Experiment is same as 34-1, only CuCl₂·2H₂O (0.5mmol) and NaClO₄ (0.5mol) substitution Cu (ClO₄)₂(0.6mmol).Embodiment 34-4：Experiment is same as 34-1, only CuBr₂(0.5mmol) and NaClO₄(0.5mol) substitution Cu (ClO₄)₂(0.6mmol).Embodiment 34-5:Experiment is same as 34-1, only KOH (0.5mmol) Replace NaOH (0.5mmol).Embodiment 34-6:Experiment is same as 34-1, only NH₃·H₂O (concentration, 25%, 0.2mL) replaces NaOH(0.5mmol)。

Embodiment 35-1, the preparation of complex Z35:Phenylalanine (0.6mmol) and NaOH (0.6mmol) mixing are dissolved in 30ml mixed solvents (VCH₃OH：VH₂O=5：1) in；Stirring 5 hours, makes it fully dissolve；Add Cu (ClO₄)₂ (0.6mmol) is stirred 24 hours；Then 3,4,7,8- tetramethyl -1,10- ferrosins (0.6mmol) are added in, continue stirring 48 Hour；Then filter, its clear liquid taken to contain respectively in the small test tube of 6 20ml, with dropper draw ether it is careful along test tube wall It is added to above filtrate, it is about 1 to make the volume ratio of filtrate and ether:2.5, it stands, about obtains dark blue crystals after a week.Member Element analysis (%)：Calculated value (experiment value):C 57.777(57.401)；H 4.814(4.783)；N 7.777(7.727).Its is red External spectrum is shown in attached drawing 35A and 35B respectively with X- diffraction mono-crystalline structures figures.Z35 compound molecule formulas are：{[Cu^II(3,4,7,8- Tetramethyl-1,10-phen)(Phe)(ClO₄)][Cu^II(3,4,7,8-Tetramethyl-1,10-phen)(Phe)]· 2(ClO₄ ^-), i.e. 13,4,7,8- tetramethyl -1,10-Phen, 1 phenylalanine and a ClO₄ ^-, formed with 1 Cu coordination One trans- complex；Another 13,4,7,8- tetramethyl -1,10-Phen, 1 phenylalanine form one with 1 Cu coordination Trans- complex, two complexs form a pair of.A pair of of complex also contains 2 ClO₄ ^-(in order to which picture is clear, omission is not drawn).

The cell experiment of complex Z35 is same as Z1, and sample Z1 only is changed to sample Z35.The result shows that Z35 is to A-549 (lung cancer) inhibitory rate of cell growth is 90.32%, is 90.57% to Bel-7402 (liver cancer) inhibitory rate of cell growth, to HCT (adenocarcinoma of colon) inhibitory rate of cell growth is 90.25%, is 90.19% to HL-60 (leukaemia) inhibitory rate of cell growth, right BGC-823 (gastric cancer) inhibitory rate of cell growth is 90.18%, is 90.21% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth.Knot By：Z35 can be used to prepare the drug of prevention and treatment cancer.

Embodiment 35-2：Experiment is same as 35-1, only Cu (NO₃)₂·6H₂O (0.5mmol) and NaClO₄(0.5mol) takes For Cu (ClO₄)₂(0.6mmol).Embodiment 35-3：Experiment is same as 35-1, only CuCl₂·2H₂O (0.5mmol) and NaClO₄ (0.5mol) substitution Cu (ClO₄)₂(0.6mmol).Embodiment 35-4：Experiment is same as 35-1, only CuBr₂(0.5mmol) and NaClO₄(0.5mol) substitution Cu (ClO₄)₂(0.6mmol).Embodiment 35-5:Experiment is same as 35-1, only KOH (0.5mmol) Replace NaOH (0.5mmol).Embodiment 35-6:Experiment is same as 35-1, only NH₃·H₂O (concentration, 25%, 0.2mL) replaces NaOH(0.5mmol)。

The foregoing is merely presently preferred embodiments of the present invention, is merely illustrative for the purpose of the present invention, and not restrictive 's.Those skilled in the art understands, many changes can be carried out to it in the spirit and scope limited in the claims in the present invention, It changes or even equivalent, but falls in protection scope of the present invention.

Claims

A series of 1. copper complex of amino acid and phenanthroline or derivatives thereof, it is characterised in that the molecular formula of the complex It is with molecular structural formula：

[Cu^II(phen)(L-Asn)(Cl)][Cu^II(Phen)(L-HAsn)(H₂O)]·5H₂O、

[Cu^II(phen)(L-Tyrosine)(Cl)]₂·5H₂O、

[Cu^II(phen)(L-Ser)(H₂O)]·ClO₄ ^-、

[Cu^II(phen)(L-Leucine)(H₂O)]·NO₃ ^-、

[Cu^II(phen)(L-Isoleucine)(H₂O)]₂·2ClO₄ ^-、

[Cu^II(phen)(L-Val)(H₂O)]·ClO₄ ^-、

[Cu^II(phen)(L-Meth)(H₂O)][Cu^II(Phen)(NO₃ ^-)(2H₂O)]·2NO₃ ^-·2H₂O、

{[Cu^II(phen)(Lys)(NO₃ ^-)]·ClO₄ ^-·H₂O}_n、

[Cu^II(phen)(L-Trp)(H₂O)]₂[Cu^II(phen)(L-Trp)(NO₃)]·2NO₃·6H₂O、

[Cu^II(phen)(D-Meth)(H₂O)]·NO₃ ^-·H₂O、

{[Cu(3,4,7,8-Tetramethyl-1,10-phen)(Ala)][Cu(3,4,7,8-Tetramethyl-1,10- phen)(Ala)(H₂O)](2NO₃ ^-(H₂O)}_n、

{[Cu(3,4,7,8-Tetramethyl-1,10-phen)(Tyr)(H₂O)][Cu(3,4,7,8-Tetramethyl-1, 10-phen)(Tyr)]}·2NO₃ ^-·5H₂O·CH₃CH₂OH、

[Cu(3,4,7,8-Tetramethyl-1,10-phen)(Val)(NO₃ ^-)]·H₂O、

[Cu(3,4,7,8-Tetramethyl-1,10-phen)(Thr)(NO₃ ^-)]·3H₂O、

[Cu(4,7-dimethyl-1,10-phen)(Met)(H₂O)₂]·(NO₃ ^-)、

[Cu(5,6-dimethyl-1,10-phen)(Met)(H₂O)₂]·(NO₃ ^-)、

[Cu(3,8-dimethyl-1,10-phen)(Met)(H₂O)₂]·(NO₃ ^-)、

[Cu(2,9-dimethyl-1,10-phen)(Met)(H₂O)₂]·(NO₃ ^-)、

[Cu(3-methyl-1,10-phen)(Val)(NO₃ ^-)]·H₂O、

[Cu(4-methyl-1,10-phen)(Val)(NO₃ ^-)]·H₂O、

[Cu(7-methyl-1,10-phen)(Val)(NO₃ ^-)]·H₂O、

[Cu^II(3,4,7,8-Tetramethyl-1,10-phen)(D-Meth)(H₂O)]·Cl^-·2H₂O、

[Cu^II(3,4,7,8-Tetramethyl-1,10-phen)(D-Meth)(H₂O)]·H₂O·NO₃ ^-、

[Cu^II(3,4,7,8-Tetramethyl-1,10-phen)(Ser)(Br^-)]₂·H₂O、

{[Cu^II(3,4,7,8-Tetramethyl-1,10-phen)(Clu)]·3H₂O}_n、

[Cu^II(3,4,7,8-Tetramethyl-1,10-phen)(Clu)(H₂O)]·ClO₄ ^-、

{[Cu^II(3,4,7,8-Tetramethyl-1,10-phen)(Phe)(ClO₄)][Cu^II(3,4,7,8-Tetramethyl- 1,10-phen)(Phe)]·2(ClO₄ ^-)}。
2. a kind of method for the copper complex for preparing amino acid described in claim 1 and phenanthroline or derivatives thereof, feature It is to include the following steps：

By mantoquita, sodium salt, alkali, the amino acid is stirred continuously in a solvent to abundant dissolving, add the phenanthroline or Its derivatives reaction filters, stands a couple of days or with after the mixed solvent diffusion of ether, isopropanol or a variety of organic solvents later A couple of days is stood, finally obtains the complex.
3. the preparation method of the copper complex of amino acid according to claim 2 and phenanthroline or derivatives thereof, special Sign is：The mantoquita is inorganic mantoquita, organic copper salt, Inorganic Copper salt hydrate, organic copper salt hydrate or appointing in them The mixture for one or more of anticipating.
4. the preparation method of the copper complex of amino acid according to claim 3 and phenanthroline or derivatives thereof, special Sign is：The mantoquita be selected from copper nitrate, copper sulphate, cupric perchlorate, copper acetate, copper chloride, copper bromide, nitric acid copper hydrate, Copper sulfate hydrate, cupric perchlorate hydrate, acetic acid copper hydrate, chlorination copper hydrate or one kind in bromination copper hydrate or It is two or more.
5. the preparation method of the copper complex of amino acid according to claim 2 and phenanthroline or derivatives thereof, special Sign is：The sodium salt is any one in inorganic sodium, Organic Sodium Salt, inorganic sodium hydrate or Organic Sodium Salt hydrate Or two or more mixture.
6. the preparation method of the copper complex of amino acid according to claim 5 and phenanthroline or derivatives thereof, special Sign is：The sodium salt be selected from sodium nitrate, sodium sulphate, sodium perchlorate, sodium acetate, sodium chloride, sodium bromide, nitric acid sodium hydrate, Sulfuric acid sodium hydrate, sodium perchlorate hydrate, acetic acid sodium hydrate, chlorination sodium hydrate or one kind in bromination sodium hydrate or It is two or more.
7. the preparation method of the copper complex of amino acid according to claim 2 and phenanthroline or derivatives thereof, special Sign is：Mixed solvent or single inorganic solvent or a variety of nothing of the solvent for single organic solvent or a variety of organic solvents The mixed solvent or organic solvent of solvent and the mixed solvent of inorganic solvent.
8. the preparation method of the copper complex of amino acid according to claim 7 and phenanthroline or derivatives thereof, special Sign is：The solvent for N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, methanol, ethyl alcohol, ethylene glycol, One or more of propylene glycol, glycerine, acetone, acetonitrile, acetylacetone,2,4-pentanedione or water.
9. the preparation method of the copper complex of amino acid according to claim 2 and phenanthroline or derivatives thereof, special Sign is：The alkali is sodium hydroxide, potassium hydroxide or ammonium hydroxide.
10. the copper complex of amino acid described in claim 1 and phenanthroline or derivatives thereof is preparing prevention and treatment in vain Application in blood disease, gastric cancer, liver cancer, nasopharyngeal carcinoma, lung cancer and adenocarcinoma of colon drug.