CN104262366A - Amino acid schiff base ligand silver complexes, and preparation method and antibacterial application thereof - Google Patents

Amino acid schiff base ligand silver complexes, and preparation method and antibacterial application thereof Download PDF

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CN104262366A
CN104262366A CN201410488711.8A CN201410488711A CN104262366A CN 104262366 A CN104262366 A CN 104262366A CN 201410488711 A CN201410488711 A CN 201410488711A CN 104262366 A CN104262366 A CN 104262366A
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histidine
silver
schiff base
preparation
salicylidene
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CN104262366B (en
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刘海燕
黄守磊
王广慧
赵东江
孙红梅
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Xinghua runhai Cultural Tourism Development Co.,Ltd.
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Suihua University
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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
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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  • General Health & Medical Sciences (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract

The invention provides two complexes formed by a salicylaldehyde L-histidine schiff base ligand, a reduced ligand of the salicylaldehyde L-histidine schiff base ligand and silver, and a preparation method and an antibacterial application of the complexes. The two silver complexes can be represented by general formulas {Ag(L<1>)}n and Ag2(L<2>)2.3H2O, wherein the structural formulas of L<1> and L<2> are as shown in the figure. The preparation method comprises the following steps: firstly, restoring C=N double bonds in the salicylaldehyde L-histidine schiff base ligand (HL<1>) into a C-N single bond by using NaBH4 to obtain a reduced ligand (HL<2>); and then enabling the two ligands to respectively act together with AgNO3 to obtain two silver complexes. The amino acid schiff base ligand silver complexes provided by the invention are brand new in structure and simple in preparation method, have significant antibacterial activity, and are expected to be applied to antibacterial materials and antibacterial medicines.

Description

Amino-acid schiff base part silver complex and preparation method thereof and antibacterial applications
Technical field
The present invention relates to transition metal complex Material Field, be specifically related to silver system anti-microbial type title complex and preparation method and application, two kinds of described silver complexes have stronger anti-microbial activity, are expected to be applied in anti-biotic material and antibacterials.
Technical background
Along with the raising of people's living standard and the reinforcement of health perception, antimicrobial prod has become an indispensable part in people's life.Because silver ions is to human body cell and immunity system safety non-toxic, and anti-microbial property is splendid, so, prepare inorganic antiseptic and usually use silver ions and compound thereof.Current silver-based inorganic antibacterial agent is widely used in the every field such as chemical fibre, plastic articles, building materials, glass, pottery, coating, water treatment, makeup.Difference according to silver ions Releasing Mechanism can be divided into two classes: a class is for depending on certain carrier, and in use procedure, silver ions parses from carrier; Another kind of is containing silver in compound own, touches other media such as water, discharge silver ions by solvency action in the process used.But because silver ions is stable not, argent or silver suboxide generation variable color can be transformed into, reduce its antibacterial ability, limit its application to a certain extent.
Result of study both domestic and external shows, substituting silver ions with the complexing ion of silver is the effective way addressed this problem, the research tendency forward silver complex direction of silver-series antibacterial agent is expanded, improve the stability of silver ions by coordination, due to coordination ion, there is good slow releasing function thus make it have the advantages such as efficient, lasting, broad-spectrum antimicrobial.And amino-acid schiff base part has O atom and the atom N of strong electronegativity, easily form stronger coordination with the silver ions as soft acid, thus form stable silver system title complex.Simultaneously in order to overcome amino-acid schiff base compound due to the rigidity of C=N double bond the weakness of poor stability, when ensureing active group, be C-N singly-bound by the C=N reduction in schiff base ligand.Amino-acid schiff base part after reduction, will have better snappiness, more be conducive to and silver ions coordination, thus obtain a series of corresponding reduced form amino-acid schiff base silver complex.It is expected to the silver ions by having excellent anti-bacterium capability and the amino-acid schiff base ligand binding with good biological activity, both combinations among the strong ones, thus synthesize high, the active strong antibacterial metal title complex of stability, for the development & application of silver system anti-biotic material and inorganic antibacterial medicine provides Research foundation.
Summary of the invention
The object of this invention is to provide two kinds of silver system antibacterial metal title complexs and preparation method thereof and application.
Compound chemistry formula provided by the present invention is { Ag (L 1) nand Ag 2(L 2) 23H 2o, wherein L 1with L 2structural formula is as follows.
The present invention relates generally to following two reactions.
1) reduced form salicylidene l-Histidine schiff base ligand HL 2preparation method: by salicylidene l-Histidine schiff base ligand (HL 1) be dissolved in methyl alcohol, stir under condition of ice bath, add solid NaBH in batches 4after reaction 1 ~ 1.5h, after wanting underpressure distillation to remove most methyl alcohol, under the solution room temperature of gained, after adding a large amount of distilled water, dropwise adding HCl solution adjust ph is again 3 ~ 4, separates out a large amount of white precipitate, after filtration, washs and obtains reduced form salicylidene Histidine schiff base ligand HL after drying 2.
2) preparation method of two kinds of silver complexes: under room temperature, by AgNO 3the aqueous solution join and be dissolved with HL 1stir in the methanol solution of part, produce white precipitate, after filtration, washing, obtain { Ag (L after vacuum-drying 1) n; By AgNO 3the aqueous solution join and be dissolved with HL 2after stirring 0.5h in the methanol solution of part, have yellow mercury oxide to generate, drip ammoniacal liquor, after dissolving completely to be precipitated, filter, filtrate is Ag at the yellow bulk crystals of normal temperature dark place volatilization precipitation 2(L 2) 23H 2o.
Described reactant A gNO 3be 1:1 with amino-acid schiff base part mol ratio; The volume ratio of reaction soln methyl alcohol and water is 4:1.
The invention provides salicylidene l-Histidine Schiff's base silver complex { Ag (L 1) npreparation method provided by embodiment 1, corresponding title complex is characterized by infrared; Reduced form salicylidene l-Histidine Schiff's base silver complex Ag 2(L 2) 23H 2the preparation method of O is provided by embodiment 2, and corresponding title complex has carried out characterizing (Ag respectively by infrared, ultimate analysis and x-ray crystal structure analysis 2(L 2) 23H 2o crystalline structure figure is shown in accompanying drawing 1).
The Antimicrobial test research of above-mentioned two kinds of silver complexes is provided by embodiment 3.Have detected two kinds of silver complexes to Serratia marcescans, Bacillus subtillis, M. smegmatics and saccharomycetic bacteriostatic action by agar diffusion method and micro-dilution method.Experimental result shows, two kinds of title complexs all show good anti-microbial activity, is suitable for the application as anti-biotic material or antibacterials.
Accompanying drawing explanation
Fig. 1 is reduced form salicylidene l-Histidine Schiff's base silver complex Ag 2(L 2) 23H 2the crystalline structure figure of O.
Embodiment
For a better understanding of the present invention, technical scheme of the present invention is illustrated below by specific embodiment.
Embodiment 1: salicylidene l-Histidine Schiff's base silver complex { Ag (L 1) npreparation.
Salicylidene l-Histidine schiff base ligand HL 1(1 mmol, 0.26g) is dissolved in 40 mL methyl alcohol, in this solution, add AgNO 3the aqueous solution 10 mL of (1 mmol, 0.17g), stirs about 10 min, and adularescent precipitation generates, and then filter, after washing with water, vacuum-drying, obtains salicylidene l-Histidine Schiff's base silver complex (productive rate 68%): IR (KBr, cm -1) 3463 (ms), 3380 (s), 3220 (s), 3030 (s), 1786 (s), 1650 (vs), 1530 (s), 1297 (s), 1211 (s), 1098 (s), 1004 (s), 967 (s), 886 (s), 583 (s).
Embodiment 2: reduced form salicylidene l-Histidine Schiff's base silver complex Ag 2(L 2) 23H 2the preparation of O.
Step 1: by salicylidene l-Histidine schiff base ligand HL 1(2 mmol, 0.52g) is dissolved in 50mL methyl alcohol, under condition of ice bath, adds solid NaBH in batches 4(3 mmol, 0.11g), until do not have gas to release after reaction 1 ~ 1.5h, after then underpressure distillation removes 4/5 solvent.Under the solution room temperature of gained, after adding 50 mL distilled water, more dropwise add 6 mol/L HCl solution adjust ph red to be about 3 ~ 4, to separate out a large amount of white precipitate, after filtration, after washing and drying reduced form salicylidene l-Histidine schiff base ligand HL 2(productive rate 63%).
Step 2: again by reduced form salicylidene l-Histidine schiff base ligand HL 2(0.2 mmol, 0.026g) is dissolved in 20 mL methyl alcohol, in this solution, add AgNO 3the aqueous solution 5 mL of (0.2 mmol, 0.017g), after stirring 0.5h, has yellow mercury oxide to generate, and drips ammoniacal liquor, after dissolving completely to be precipitated, filters, and filtrate, room temperature dark place's placement 5 days, has faint yellow bulk crystals to separate out (productive rate 42%).C 26h 30ag 2n 6o 9ultimate analysis (%) theoretical value: C 39.72, H 3.85, N 10.69; Actual value: C 40.30, H 3.76, N 10.77.IR(KBr,?cm -1)?3450(ms),?3329(s),?3180(s),?1833(s),?1710(vs),?1644(s),?1345(s),?1230(s),?1175(s),?1070(s),?980(s),?805(s),?650(s)。
Step 3: reduced form salicylidene lthe crystal structure determination of-Histidine Schiff's base silver complex, the monocrystalline of suitable size is chosen with microscope, carry out collecting with Oxford Diffraction Gemini R CCD diffractometer, when temperature is 293K, graphite monochromator Mo K alpha-ray is adopted to be source of radiation (λ=0.71073).Crystalline structure resolves (Sheldrick, 1997) by SHELXS-97 program with direct method, uses SHELXL-97 software package, and uses range battle array method of least squares f 2refine.Non-hydrogen atom anisotropic temperature factor correction.Except the hydrogen atom on water molecules determines position by difference Fourier figure, other all hydrogen atom coordinate is determined by Theoretical Calculation.Title complex Ag 2(L 2) 23H 2the crystallographic data of O is in table 1, and crystalline structure figure is shown in accompanying drawing 1.
Table 1. title complex Ag 2(L 2) 23H 2the crystallographic data of O and structure refinement data.
Title complex Ag 2(L 2) 2·3H 2O
Molecular weight 786.30
Crystallographic system Orthogonal
Spacer P2 12 1 ?2 1
a [? ] 11.9148(2)
b [? ] 14.0598(3)
c [? ] 17.4528(4)
α [ ? ] 90
β [ ? ] 90
γ [ ? ] 90
Volume [? 3 ] 2923.69(10)
Z 4
Theoretical density (g/cm 3） 1.786
GOF 1.044
R int 0.0317
R1 [I>2σ(I)] 0.0323
wR2 (all data) 0.0763
Embodiment 3: Antimicrobial test.
Step 1: experiment material.
1.1 bacterial strains: Serratia marcescans (jn01), yeast (jn05), Bacillus subtillis (JN-16) are preserved by Jilin Agriculture University's animal medicine laboratory; M. smegmatics (mc 2155) purchased from China Veterinery Drug Inspection Office.
The preparation of 1.2 liquids
Take 12.8mg solid pharmaceutical, dissolve with 12.5 μ L dimethyl formamides (DMF), when adding 300 μ L sterilizing distilled waters to be again diluted to concentration be 40960 μ g/mL, the liquid 10 μ L getting dissolving adds 90 μ L distilled waters and dilutes 10 times, and now concentration is 4096 μ g/mL.
1.3 microbial culture and counting
By tested bacterium access respective liquid substratum, after growing to logarithmic phase, take a morsel with spread plate counting, all the other bacterium liquid are for subsequent use under being placed in 4 DEG C of conditions.
Step 2: agar diffusion method detects the bacteriostatic action of two kinds of title complexs
Draw 100 μ L and be diluted to 5 × 10 4~ 5 × 10 5the bacterium liquid of CFU/mL puts into the flat board containing solid medium, even with aseptic spreading rod coating, after bacterium liquid absorbs completely, drawing 5 μ L concentration is that the liquid of 4096 μ g/mL drops in designated area, after cultivating certain hour, observes antibacterial situation, and measure antibacterial circle diameter, the results are shown in Table 2.
Table 2. two kinds of silver complexes are to the antibacterial circle diameter (unit: mm) of different microorganisms.
? Serratia marcescans Bacillus subtillis M. smegmatics Yeast
{Ag(L 1)} n? 17 20 8.5 8
Ag 2(L 2) 2·3H 2O 10.5 20 8 9
Step 3: micro-dilution method detects the minimum inhibitory concentration (MIC) of two kinds of title complexs.
1) method
1. 24 autoclaved 0.5mLEP pipes are got, numbering;
2. 2nd ~ 23 pipes add 25 μ L substratum respectively, the 1st, 2,24 pipes add the liquid that 25 μ L concentration are 4096 μ g/mL respectively;
3. from the 2nd pipe, doubling dilution, to the 21st pipe, discards the liquid in the 21st pipe after 25 μ L mixings;
4. 1st ~ 22 pipes add the corresponding bacterium liquid of 175 μ L (concentration are 5 × 10 4~ 5 × 10 5cFU/mL), the 23rd, 24 pipes add 175 μ L substratum, in contrast.Cultivate certain hour in suitable temp incubator, observe microorganism growth situation in EP pipe.
2) the results are shown in Table 3.
Table 3. two kinds of silver complexes are to the minimal inhibitory concentration (unit: μ g/mL) of different microorganisms
? Serratia marcescans Bacillus subtillis M. smegmatics Yeast
{Ag(L 1)} n? 0.016 0.004 0.016 4
Ag 2(L 2) 2·3H 2O 0.008 0.002 0.031 8

Claims (4)

1. salicylidene ltwo kinds of title complexs that-Histidine schiff base ligand and reduced form part thereof are formed with silver, is characterized in that their useful chemical formula { Ag (L 1) nand Ag 2(L 2) 23H 2o represents, wherein L 1with L 2structural formula is as follows.
2. salicylidene according to claim 1 lthe preparation method of-Histidine Schiff's base and reduced form part silver complex thereof, is characterized in that it comprises the steps: salicylidene l-Histidine schiff base ligand HL 1be dissolved in methyl alcohol, stir under condition of ice bath, add NaBH in batches 4reduction, question response completely after, remove most of solvent, add suitable quantity of water, then drip HCl solution and be adjusted to acidity, adularescent Precipitation is HL 2part, then by HL 1part and reduced form HL 2part respectively with AgNO 3effect, with first alcohol and water for reaction medium, thus obtains two kinds of silver complexes.
3. preparation method according to claim 2, is characterized in that: described regulates pH to be about 3 ~ 4, reactant A gNO with HCl solution 3be 1:1 with amino-acid schiff base part mol ratio; The volume ratio of reaction medium methyl alcohol and water is 4:1.
4. salicylidene according to claim 1 l-Histidine Schiff's base and reduced form part silver complex thereof are in the application of antibiosis as anti-biotic material or antibacterials.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107118127A (en) * 2017-06-28 2017-09-01 哈尔滨理工大学 Amino-acid schiff base and its synthetic method and application
CN107325117A (en) * 2017-07-07 2017-11-07 常州大学 Structure of chiral silver complex of N pyridines threonine derivatives and preparation method thereof
CN107960533A (en) * 2016-10-20 2018-04-27 湖南晶天科技实业有限公司 A kind of amino acid aldehyde schiff bases feed addictive and a kind of feed
CN108424467A (en) * 2018-04-16 2018-08-21 陕西科技大学 A kind of preparation method of cellulose base composite antibacterial material
CN110563654A (en) * 2019-09-30 2019-12-13 大连民族大学 AHL structural analogue based on histidine and preparation method thereof
CN114410296A (en) * 2022-03-15 2022-04-29 贵州医科大学 Preparation method and application of MOF composite material based on isoleucine derivative ligand
CN115322390A (en) * 2022-08-26 2022-11-11 厦门稀土材料研究所 Antibacterial silver complex crystal, preparation method and application thereof
CN115413918A (en) * 2022-09-03 2022-12-02 希诺股份有限公司 Titanium metal vacuum thermos cup and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1926141A (en) * 2003-09-05 2007-03-07 阿克伦大学 Metal complexes of N-heterocyclic carbenes as radiopharmaceuticals and antibiotics

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1926141A (en) * 2003-09-05 2007-03-07 阿克伦大学 Metal complexes of N-heterocyclic carbenes as radiopharmaceuticals and antibiotics

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107960533A (en) * 2016-10-20 2018-04-27 湖南晶天科技实业有限公司 A kind of amino acid aldehyde schiff bases feed addictive and a kind of feed
CN107118127B (en) * 2017-06-28 2019-01-04 哈尔滨理工大学 Amino-acid schiff base and its synthetic method and application
CN107118127A (en) * 2017-06-28 2017-09-01 哈尔滨理工大学 Amino-acid schiff base and its synthetic method and application
CN107325117A (en) * 2017-07-07 2017-11-07 常州大学 Structure of chiral silver complex of N pyridines threonine derivatives and preparation method thereof
CN108424467A (en) * 2018-04-16 2018-08-21 陕西科技大学 A kind of preparation method of cellulose base composite antibacterial material
CN110563654B (en) * 2019-09-30 2022-10-18 大连民族大学 AHL structural analogue based on histidine and preparation method thereof
CN110563654A (en) * 2019-09-30 2019-12-13 大连民族大学 AHL structural analogue based on histidine and preparation method thereof
CN114410296A (en) * 2022-03-15 2022-04-29 贵州医科大学 Preparation method and application of MOF composite material based on isoleucine derivative ligand
CN114410296B (en) * 2022-03-15 2023-08-22 贵州医科大学 Preparation method and application of MOF composite material based on isoleucine derivative ligand
CN115322390A (en) * 2022-08-26 2022-11-11 厦门稀土材料研究所 Antibacterial silver complex crystal, preparation method and application thereof
CN115322390B (en) * 2022-08-26 2023-06-13 厦门稀土材料研究所 Antibacterial silver complex crystal, preparation method and application thereof
CN115413918A (en) * 2022-09-03 2022-12-02 希诺股份有限公司 Titanium metal vacuum thermos cup and preparation method thereof
CN115413918B (en) * 2022-09-03 2024-04-19 希诺股份有限公司 Titanium metal vacuum thermos cup and preparation method thereof

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