CN112321617B - Binuclear zinc complex with biological activity and preparation method and application thereof - Google Patents
Binuclear zinc complex with biological activity and preparation method and application thereof Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 18
- 230000004071 biological effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 10
- -1 (2-hydroxybenzylidene) propyl Chemical group 0.000 claims abstract description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000011592 zinc chloride Substances 0.000 claims abstract description 4
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 4
- 235000014469 Bacillus subtilis Nutrition 0.000 claims abstract description 3
- 241000588724 Escherichia coli Species 0.000 claims abstract description 3
- 239000000022 bacteriostatic agent Substances 0.000 claims abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 14
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 claims description 3
- BOKSKTADHYXBBM-UHFFFAOYSA-L [Cl-].[Cl-].[Zn+2].OC Chemical compound [Cl-].[Cl-].[Zn+2].OC BOKSKTADHYXBBM-UHFFFAOYSA-L 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims 1
- 229960000074 biopharmaceutical Drugs 0.000 claims 1
- 230000003993 interaction Effects 0.000 abstract description 7
- 108091003079 Bovine Serum Albumin Proteins 0.000 abstract description 4
- 229940098773 bovine serum albumin Drugs 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 238000004467 single crystal X-ray diffraction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 244000063299 Bacillus subtilis Species 0.000 abstract description 2
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- UVLSCMIEPPWCHZ-UHFFFAOYSA-N 3-piperazin-1-ylpropan-1-amine Chemical compound NCCCN1CCNCC1 UVLSCMIEPPWCHZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000003385 bacteriostatic effect Effects 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000002798 spectrophotometry method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 6
- 239000002262 Schiff base Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000004753 Schiff bases Chemical class 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 125000004193 piperazinyl group Chemical group 0.000 description 3
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- BHZZEOGTGMUITC-UHFFFAOYSA-N 2-[4-[4-[4-(2-hydroxyphenyl)but-3-enyl]piperazin-1-yl]but-1-enyl]phenol Chemical compound OC1=C(C=CCCN2CCN(CC2)CCC=CC2=C(C=CC=C2)O)C=CC=C1 BHZZEOGTGMUITC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
Abstract
The invention discloses a binuclear zinc complex with biological activity and a preparation method and application thereof; taking salicylaldehyde, N' -di (aminopropyl) piperazine and zinc chloride as raw materials, heating for reaction, cooling to room temperature, filtering, standing, precipitating a bright yellow target product, and determining the crystal structure of the target product by single crystal X-ray diffraction, wherein the chemical formula of the target product is Zn2(bbpp)2(Cl)2·(Sal)2Wherein bbpp represents N, N' -bis [ (2-hydroxybenzylidene) propyl group]Piperazine, Sal represents salicylaldehyde. The complex has good bacteriostatic activity on escherichia coli, staphylococcus aureus and bacillus subtilis. The interaction between the target product and bovine serum albumin BSA is conveniently tested by using an ultraviolet spectrophotometry, and the strong interaction is found. And further deducing that the complex has good biological activity and can be applied to the aspects of novel bacteriostatic agents, biological medicine detection and the like.
Description
Technical Field
The invention relates to a binuclear zinc complex with biological activity and a preparation method and application thereof, in particular to a Zn-containing complex Zn2(bbpp)2(Cl)2·(Sal)2Wherein bbpp represents deprotonated N, N' -bis [ (2-hydroxybenzylidene) propyl ] group]Piperazine, Sal represents salicylaldehyde. The invention also relates to the crystal structure of the complex.
Background
Schiff base and complexes thereof have excellent biological activity, catalysis, optics and other performances and are concerned, and especially polydentate salicylaldehyde Schiff ligands have good biological activity and strong metal ion chelating capacity, so that the Schiff base and the metal complexes thereof have wide application prospects in the fields of catalysis, optical materials, analysis, biomedicine, environment and the like, and are research hotspots in the field.
N, N' -di [ (2-hydroxybenzylidene) propyl ] piperazine is a bis-salicylaldehyde Schiff base hexadentate ligand containing a piperazine ring, the coordination atoms of the ligand are 4N atoms and 2O atoms, and the ligand can be chelated and coordinated with various metal ions such as iron, cobalt, manganese, nickel, copper and the like to generate a mononuclear, dinuclear or polynuclear complex, wherein the piperazine ring is usually a dinuclear complex in a chair conformation and a mononuclear complex in a boat conformation. The complexes show certain characteristics of fluorescence, catalysis, antimicrobial activity, interaction with CT-DNA and bovine serum albumin macromolecules and the like.
The invention synthesizes a compound which is N, N' -di [ (2-hydroxybenzylidene) propyl group]Unreported binuclear zinc complex Zn with piperazine as ligand2(bbpp)2(Cl)2·(Sal)2And the crystal structure of the complex is analyzed through single crystal X-ray diffraction, the antibacterial activity, the interaction with bovine serum albumin and the thermal stability of the complex are researched, and the complex is found to have good thermal stability and biological activity and to be expected to be used in the aspects of biological drug detection, novel antibacterial agents and the like. The preparation of the ligand metal complex and the performance research of the ligand metal complex are carried out, and the ligand metal complex has important significance for enriching subject contents of coordination chemistry, pharmaceutical chemistry, analytical chemistry and the like and promoting the development and application of salicylaldehyde Schiff base.
Disclosure of Invention
The invention aims to provide a binuclear zinc complex with biological activity and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a binuclear zinc complex with bioactivity has a molecular formula of Zn2(bbpp)2(Cl)2·(Sal)2Wherein bbpp represents deprotonated N, N' -bis [ (2-hydroxybenzylidene) propyl ] group]Piperazine, Sal represents salicylaldehyde.
The invention further discloses a crystal of the binuclear zinc complex with biological activity, and a piece of binuclear zinc complex Zn with the size of about 0.31mm multiplied by 0.17mm multiplied by 0.14mm is selected2(bbpp)2(Cl)2·(Sal)2Single crystals were placed on a BRUKER SMART 1000 CCD diffractometer and monochromated Mo-K with graphiteα(λ -0.071073 nm) at 1.83 °<θ<In the 25.02 degree range, in the omega-2 theta scanning mode, at 298(2) K. All intensity data reduction was performed on the Bruker SAINT program. To be provided withLpFactor correction data, crystal structure is solved by direct method by adopting SHELESS 97 software, theoretical hydrogenation is carried out, and coordinates and anisotropic thermal parameters of all non-hydrogen atoms are corrected and converged by a full matrix least square method. Detailed crystallographic data are shown in table 1; partial key length and key angle data are shown in table 2;
TABLE 1 Complex Zn2(bbpp)2(Cl)2·(Sal)2Crystallographic data of
TABLE 2 Complex Zn2(bbpp)2(Cl)2·(Sal)2Partial bond length of
Angle of harmony key (°)
Symmetry transformations used to generate equivalent atoms:#1:-x+1,-y+1,-z+2
Complex Zn2(bbpp)2(Cl)2·(Sal)2Is monoclinic system, P2(1)/c space group,
α＝90°,β＝92.3810(10)°,γ＝90°,
the single crystal X-ray diffraction analysis result shows that the complex contains a binuclear zinc Zn2(bbpp)2(Cl)2And two free salicylaldehyde molecules. Wherein the binuclear zinc structure is formed by a deprotonated N, N' -bis [ (2-hydroxybenzylidene) propyl ] group]Piperazine ligand, two Cl-With two Zn2+Are each connected to form2+Adopting a four-coordinate coordination mode, and respectively reacting with Cl-Two nitrogen atoms, one oxygen atom from one bbpp ligand. The ORTEP diagram and the atom number are shown in the attached figure 1 of the specification.
The invention further discloses a preparation method of the complex, which comprises the steps of mixing N, N' -di (3-aminopropyl) piperazine (AP for short) and Sal according to the mass ratio of 1: 2-50, taking ethanol and ethyl acetate as solvents, stirring and reacting at 50-80 ℃ for 2-5 h, then adding a zinc chloride methanol solution, continuing to react for 1-3 h, cooling to room temperature, filtering, standing the filtrate in a beaker for 3-10 days to obtain bright yellow blocky crystals, filtering, washing with ethanol to obtain a target product Zn2(bbpp)2(Cl)2·(Sal)2。
Further, the preparation method of the complex is characterized in that the solvent is a mixed solution of ethanol and ethyl acetate, and the volume ratio of the ethanol to the ethyl acetate is 1: 2-5.
Further, according to the preparation method of the complex, the amount of the substance added with the zinc chloride is 0.5-4 times of that of the substance added with the AP.
The invention further discloses application prospects of the binuclear zinc complex with biological activity in the aspects of bacteriostat, biological medicine detection and the like. Experiments prove that: the complex has good inhibition effect on escherichia coli, staphylococcus aureus and bacillus subtilis, has strong interaction with bovine serum albumin, and has good thermal stability.
Drawings
FIG. 1 is a crystal structure diagram of a target complex.
FIG. 2 is a graph showing ultraviolet absorption spectra of a target complex, BSA, and a target complex-BSA mixture.
FIG. 3 is a graph of the UV absorption spectrum of the target complex interacting with BSA.
FIG. 4 is an infrared spectrum of a target complex.
FIG. 5 is a differential thermal-thermogravimetric analysis plot of a target complex.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples. Various changes or modifications may be made to the invention by those skilled in the art, and equivalents may be made thereto without departing from the scope of the invention defined in the claims set forth herein.
Example 1:
a100 mL round-bottom flask was charged with 0.6g (3mmol) of N, N' -bis (3-aminopropyl) piperazine, 1.83g (15mmol) of salicylaldehyde and 8mL of ethanol and 25mL of ethyl acetate, stirred at 55 ℃ for 3h, and then 6mL of 0.5mmol was added-1(3mmol) zinc chloride methanol solution, continuously reacting for 2h, cooling to room temperature, filtering, washing filter residue with ethanol, placing the filtrate in a 50mL beaker, sealing with a preservative film, symmetrically pricking the preservative film with a needle, placing in a cool and quiet place, obtaining bright yellow blocky crystals after 5 days, filtering, washing with ethanol to obtain the target complex Zn2(bbpp)2(Cl)2·(Sal)2. The yield was about 67% (in Zn) and the melting point was greater than 300 ℃. Elemental analysis found (%, theoretical): c53.17 (53.55), H5.13 (4.97), N6.82 (6.57).
FIG. 2 shows the equimolar concentration (1.25X 10)-5mol.L-1) The ultraviolet absorption spectrum of the target complex (3 #), BSA solution and mixed solution of 3#: BSA with the molar ratio of 1: 1. By comparison with the BSA, 3# profile, it was found that: the peak of the mixed solution at 278nm is attributed to the characteristic peak of BSA, and the intensity becomes strong; the other three peaks (258, 321 and 391nm) are from pi-pi and n-pi transition of ligand molecule, the peak at 255nm of ligand red-shifts 3nm to become shoulder peak, and the intensity is increased; the peak at 321nm was red-shifted by 6nm and the peak at 391nm was blue-shifted by 3nm, and the intensity was reduced, indicating that 3# had an effect on BSA.
FIG. 3 is a graph showing the UV absorption spectrum of the interaction between # 3 and BSA. Dissolving # 3 in a small amount of N, N-dimethylformamide, and then adding a solution having a pH of 7.37Tris-HCl buffer solution diluted to a concentration of 4.7X 10-6mol.L-1. The Tris-HCl buffer solution is used for preparing different concentrations (0, 0.5, 1, 2, 2.5, 3.5 and 4 multiplied by 10)-6mol.L-1) BSA solution (1). Adding 2ml of Tris-HCl buffer solution into a colorimetric tube, adding 3# and BSA solution respectively by using a micropipette, fixing the volume by using secondary distilled water, uniformly mixing, reacting for 30min at 25 ℃, and testing the ultraviolet spectrum by using a UV-2550 ultraviolet spectrophotometer (Shimadzu, Japan). As can be seen from the figure: with the increase of BSA concentration, the peak of the complex at 255nm is red-shifted by 3nm to 258nm, and the intensity of the complex is continuously increased, which indicates that the two have stronger interaction.
FIG. 4 is an infrared spectrum of the target complex. The main infrared characteristic peaks of the target complex can be seen from the figure as follows: 3450,3040,2932,2863,1680,1632,1604,1543,1460,1442,1397,1376,1315,1294,1277,1242,1190,1155,1123,762 (cm)-1). 3450 and 1680cm-1The peak attribution is hydroxyl and aldehyde carbonyl of free salicylaldehyde molecules in the target complex; 1632cm-1The peak is a stretching vibration peak generated by coordination of N and Zn in a Schiff base C ═ N bond. Meanwhile, the infrared spectrogram also shows peaks of corresponding functional groups such as a benzene ring, a piperazine ring and the like.
FIG. 5 is a graph of differential thermal-thermogravimetric analysis of a target complex. As can be seen from the figure, the target complex Zn2(bbpp)2(Cl)2·(Sal)2The first weight loss occurs within the temperature range of 100-150 ℃, and 2 free Sal molecules in the complex are correspondingly lost along with an endothermic process at 139 ℃. Heating is continued, and the complex Zn2(bbpp)2(Cl)2The decomposition is started at about 300 ℃, the weight loss is slow, the decomposition is not completed until 900 ℃, and finally, the residues are zinc oxide and zinc chloride. The target complex has good thermal stability.
Claims (4)
1. A binuclear zinc complex with biological activity is characterized in that: mixing N, N' -di (3-aminopropyl) piperazine (AP for short) and Sal at a mass ratio of 1: 2-50, and stirring and reacting at 50-80 ℃ for 2-5 by using ethanol and ethyl acetate as solventsh, then adding a zinc chloride methanol solution, continuing to react for 1-3 h, cooling to room temperature, filtering, standing the filtrate in a beaker for 3-10 days to obtain bright yellow blocky crystals, filtering, washing with ethanol to obtain a target product Zn2(bbpp)(Cl)2·(Sal)2；
Wherein bbpp represents deprotonated N, N' -bis [ (2-hydroxybenzylideneamino) propyl ] group]Piperazine, Sal represents salicylaldehyde; the complex contains a binuclear zinc Zn2(bbpp)(Cl)2Structure and two free salicylaldehyde molecules; wherein the binuclear zinc structure is formed by a deprotonated N, N' -bis [ (2-hydroxybenzylideneamino) propyl ] group]Piperazine ligand, two Cl- With two Zn2+Are each connected to form2+Adopting a four-coordinate coordination mode, and respectively reacting with Cl-Two nitrogen atoms and one oxygen atom from bbpp ligand are coordinated, and the binuclear zinc complex Zn2(bbpp) (Cl)2·(Sal)2Is monoclinic system, P2(1)/c space group, and the unit cell parameters are:a = 10.8774(12) Å, b = 7.8640(9) Å, c = 22.255(2) Å, α = 90°, β = 92.3810(10)°, γ = 90°, V = 1902.1(4) Å3, Z = 2, Dc = 1.488 Mg.m-3, F(000) = 880, I > 2 σ(I) The data of (a): final deviation factorR 1 = 0.0383, wR 2= 0.0792; all data are as follows:R 1 = 0.0595, wR 2 = 0.0866。
2. the binuclear zinc complex with biological activity according to claim 1, wherein the solvent is a mixture of ethanol and ethyl acetate, and the volume ratio of the two is 1: 2-5.
3. The biologically active dinuclear zinc complex according to claim 1, wherein the amount of zinc chloride added is 0.5 to 4 times the amount of AP.
4. The use of a biologically active dinuclear zinc complex according to claim 1 for the preparation of bacteriostatic agents or biopharmaceutical assays, wherein said bacteriostatic agent is a bacteriostatic agent for E.coli, S.aureus or B.subtilis.
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