CN106220654A - Stable bivalence silver complex and synthetic method thereof - Google Patents
Stable bivalence silver complex and synthetic method thereof Download PDFInfo
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- CN106220654A CN106220654A CN201610590531.XA CN201610590531A CN106220654A CN 106220654 A CN106220654 A CN 106220654A CN 201610590531 A CN201610590531 A CN 201610590531A CN 106220654 A CN106220654 A CN 106220654A
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- stable
- silver complex
- bivalence
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- 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
- C07F1/10—Silver compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a kind of stable bivalence silver complex and synthetic method thereof, organic ligand therein uses pyridine and aminopyridine, includes but are not limited to 2 aminopyridines, 2 amino 4 picolines, 2 amino 6 picolines；Using persulfate, including sodium peroxydisulfate, potassium peroxydisulfate and Ammonium persulfate. etc., as oxidant, react 1～3 hour, refrigerator cool overnight, sucking filtration under room temperature, washing is dried.This bivalence silver complex has good antibacterial ability, and colibacillary minimal inhibitory concentration (MIC) is 5 ppm, and the MIC of staphylococcus aureus is 20 ppm；Reaction is to carry out at normal temperatures, and makees solvent with water, synthesizes relatively simple, consumes energy low, environmental protection.
Description
Technical field
The present invention relates to a kind of complexes of the high oxidation states silver belonging to organic and Inorganic synthese technical field and preparation method thereof with
Antibacterial applications.
Background technology
Silver, as effective anti-biotic material, is known a long time ago, and silver had wide spectrum due to it in recent years
Anti-microbial property and be widely used, such as extensively utilize silver nitrate solution and silver sulfadiazine to treat the wound of burn and scald now
Face is infected.Silver ion has the strongest toxicity to a variety of microorganisms, and has the lowest toxicity to mammalian cell, safety
Nontoxic, nonirritant.And other conventional antibacterial have certain zest to human body, and some has certain toxicity.
The most chloride antibacterial sodium hypochlorite or calcium hypochlorite, although sterilizing ability is relatively strong, but the mucosa of skin is had thorn
Swash property, and for organochlorine antibacterial, it may have generate the probability of carcinogenic chloramination compound；Oxirane has wide spectrum
Bactericidal properties, and sterilizing ability is the strongest, but but there is bigger toxicity；For another example peroxide antibacterial peracetic acid, although
Bactericidal effect is relatively good, but has zest tart flavour, and character is the most unstable.
The antibacterial of unit price silver class is little to human body zest, will not cause some side reactions, the most friendly to environment.So
And unit price silver compound is under the effect of light and heat, it is easy to occur rotten and decompose and sensitive to halide ion, it is easily generated
Precipitation, is substantially reduced its anti-microbial property.
For the antibacterial activity order of the ion of different metal, Horsfal is summarized as: Ag > Hg > Cu > Cd > Pb > Co > Au >
Zn > Fe > Mn > Mo > Sn, and give also silver different valence state ion antibacterial activity order be: Ag (III) > Ag (II) > > >
>Ag(I).Visible high valency silver ion has higher activity, can be the most more efficient kill antibacterial, and antibacterial will not produce
Drug resistance.
The main component of current domestic existing argentic antibacterial mostly is Ag2O3With silver oxide (AgO), CN
101857262A reports a kind of method that synthetizing micro-nano contains trivalent silver iron oxide, but due to these argentic oxygen
Compound has the strongest oxidisability, it is easy to react with the base material of medicine.And Ag2O3The most unstable, at the medium of water
In be quickly decomposed into AgO, AgO continue decompose, generate Ag2O.Although so they have the highest antibacterial activity, but being difficult to
Preserve.The antibacterial containing bivalence silver of United States Patent (USP) US5017295 report, but it is only capable of in the phosphoric acid of 85% stable guarantor
Depositing, therefore, this, in transport, all can have a lot of troubles and potential danger during operating and using.
Summary of the invention
It is contemplated that overcome the deficiencies in the prior art, it is provided that a kind of stable novel bivalence silver complex is as antibacterial material
Material, is carried out at normal temperatures, and energy consumption is low, easy and simple to handle, cost is little.
A kind of stable bivalence silver complex that the present invention provides, this employing organic ligand stablizes bivalence silver ion.Use
Persulfate is as oxidant.
Described organic ligand is pyridine or aminopyridine.
Described organic ligand is PA, 2-AMINO-4-PICOLINE, 2-amino-6-picoline.
Described persulfate is sodium peroxydisulfate, potassium peroxydisulfate or Ammonium persulfate..
A kind of stable bivalence silver complex synthetic method, the method comprises the following steps: (1) claims 1～2 part of mol ratio
Silver nitrate is dissolved in deionized water, adds excess pyridine, adds ammonia and makes pH value 9～10；(2) 5～15 parts of mol ratios are claimed
Persulfate is dissolved in deionized water, is stirred continuously, be added to described in state silver solution in, solution has precipitation produce；(3) reaction 2
～after 3 hours, put into refrigerator freezing, sucking filtration, respectively with deionized water and washing with acetone, be finally vacuum dried.
Solution is put into freezing 8 to 16 hours in refrigerator.
A kind of stable bivalence silver complex synthetic method, the method comprises the following steps: (1) claims 4～8 parts of mol ratios 2-
Aminopyridine adds in deionized water, stirring and dissolving；(2) by silver nitrate 1～2 parts of mol ratios and persulfate 4～8 parts of mol ratios
Being dissolved in respectively in deionized water, be simultaneously introduced above two solution under being stirred continuously, solution produces brown color precipitation；(3) anti-
After answering 1～2 hour, put into refrigerator freezing, sucking filtration, respectively with cold deionized water and washing with acetone, be finally vacuum dried.
Solution is put into freezing 8 to 16 hours in refrigerator.
The present invention uses above technical scheme compared with prior art, has following technical effect that
1, the bivalence silver complex of preparation does not produces any irritating abnormal smells from the patient.Detect through anti-microbial property, find that it has
There is good antibacterial ability.Colibacillary minimal inhibitory concentration (MIC) is 5ppm, and the MIC of staphylococcus aureus is equal
For 20ppm.
2, the bivalence silver complex that prepared by the present invention has certain water solublity.Reaction is to carry out at normal temperatures, and with
Water makees solvent, synthesizes relatively simple, consumes energy low, environmental protection.
3, the bivalence silver complex that prepared by the present invention has good stability, can long period existence in aqueous.
Light stability detection is carried out under the fair weather of 22 ± 5 DEG C of ambient temperatures.Sunlight is exposed to the sun 2 days, the anti-microbial property of its material
The most significantly change.
Accompanying drawing explanation
Below with reference to accompanying drawing, the invention will be further described:
Fig. 1 is the synthetic reaction equation of pyridine dinitrogen bivalence silver complex；
Fig. 2 is the synthetic reaction equation of aminopyridine bivalence silver complex；
Fig. 3 is the XPS figure of Ag in PA bivalence silver complex；
Fig. 4 is the XPS figure of Ag in aminopyridine bivalence silver complex；
Fig. 5 is that the pyridine dinitrogen bivalence silver complex of variable concentrations is to colibacillary growth inhibited curve；
Fig. 6 is that the PA bivalence silver complex of variable concentrations is to colibacillary growth inhibited curve；
Fig. 7 is the pyridine dinitrogen bivalence silver complex of the variable concentrations growth inhibited curve to staphylococcus aureus；
Fig. 8 is the PA bivalence silver complex of the variable concentrations growth inhibited curve to staphylococcus aureus.
Detailed description of the invention
The present invention implements a kind of stable bivalence silver complex of offer and synthetic method thereof, for making those skilled in the art
It is more fully understood that technical scheme, makees to retouch the most in detail to the present invention with detailed description of the invention below in conjunction with the accompanying drawings
State.It is exemplary by the embodiment being described with reference to the drawings, is only used for explaining the present invention, and can not be construed to the present invention
Restriction.
The present invention as depicted in figs. 1 and 2, below in conjunction with specific embodiment, is done and explains further by synthetic reaction equation
State.
A kind of stable bivalence silver complex, this employing organic ligand stablizes bivalence silver ion.Use persulfate conduct
Oxidant.
Described organic ligand is pyridine or aminopyridine；Organic ligand is PA, 2-amino-4-methyl pyrrole
Pyridine, 2-amino-6-picoline.
Described persulfate is sodium peroxydisulfate, potassium peroxydisulfate or Ammonium persulfate..
A kind of stable bivalence silver complex synthetic method, the method comprises the following steps: (1) claims 1～2 part of mol ratio
Silver nitrate is dissolved in deionized water, adds excess pyridine, adds ammonia and makes pH value 9～10；(2) 5～15 parts of mol ratios are claimed
Persulfate is dissolved in deionized water, is stirred continuously, be added to described in state silver solution in, solution has precipitation produce；(3) reaction 2
～after 3 hours, put into refrigerator freezing, sucking filtration, respectively with deionized water and washing with acetone, be finally vacuum dried.
Solution is put into freezing 8 to 16 hours in refrigerator.
A kind of stable bivalence silver complex synthetic method, the method comprises the following steps: (1) claims 4～8 parts of mol ratios 2-
Aminopyridine adds in deionized water, stirring and dissolving；(2) by silver nitrate 1～2 parts of mol ratios and persulfate 4～8 parts of mol ratios
Being dissolved in respectively in deionized water, be simultaneously introduced above two solution under being stirred continuously, solution produces brown color precipitation；(3) anti-
After answering 1～2 hour, put into refrigerator freezing, sucking filtration, respectively with cold deionized water and washing with acetone, be finally vacuum dried.
Solution is put in refrigerator freezing 8 to hour.
It is noted that embodiment is only used to the present invention is more clearly described rather than limits by any way
The scope of the present invention processed.
Embodiment 1:[Ag (py)2(N2)2](OH)2Preparation.
By AgNO3(1mmol, 0.17g) is dissolved in 50mL deionized water, and adds the ammonia of 5mL pyridine and 5mL25%,
Final pH value is 9～10.(NH4)2S2O8(4mmol, 0.91g) is dissolved in 50mL deionized water, under stirring at normal temperature, by (NH4)2S2O8Solution adds above-mentioned AgNO3In solution.Solution turns yellow rapidly, subsequently becomes brown color, begins with precipitation after ten a few minutes
Produce.After reacting 3 hours, filter.Product with deionized water and washing with acetone three times, vacuum drying, obtains 0.16g brown respectively
The pyridine dinitrogen bivalence silver complex (C of color10H12AgN6O2), productivity 44% is (based on AgNO3).Product is through infrared, elementary analysis
Test with x-ray photoelectron power spectrum (XPS).
Infrared (KBr, cm-1): 3421 (s), 2157 (m), 1624 (m), 1580 (s), 1541 (m), 1468 (s), 1431
(m), 1179 (s), 1048 (s), 766 (s), 669 (m).
Elementary analysis: by C10H12AgN6O2Calculate (%), theoretical value: C, (33.73)；H,(3.37)；N,(23.59).Real
Actual value: C, (33.21)；H,(3.35)；N,(24.02).
XPS tests: the narrow of middle Ag if Fig. 3 is PA bivalence silver complex sweeps spectrum.
Embodiment 2:[Ag (2-Apy)3(OH)](HSO4)·H2The preparation of O.
Weigh 0.38g PA and be dissolved in 20mL deionized water, under stirring at normal temperature, be simultaneously introduced 25mL AgNO3
(1mmol, 0.17g) aqueous solution and 25mL (NH4)2S2O8(4mmol, 0.91g) aqueous solution.Solution turns yellow rapidly, subsequently becomes palm fibre
Color, and have precipitation to start to generate.After reacting 2 hours, reactant liquor is put into refrigerator freezing overnight, filter.Product spend respectively from
Sub-water and washing with acetone three times, vacuum drying, obtain the PA bivalence silver complex of 0.24g brown color
(C15H22AgN6O6S).Productivity 55.7% is (based on AgNO3).Product is through infrared, elementary analysis and x-ray photoelectron power spectrum (XPS)
Test.
Infrared (KBr, cm-1), 3422 (s), 3226 (s), 3088 (m), 1664 (m), 1636 (m), 1384 (m), 1261
(s), 1121 (s), 1048 (s), 801 (m), 619 (s).
Elementary analysis: by C15H22AgN6O6S calculates (%), theoretical value: C, (34.49)；H,(4.21)；N,(16.08)；S,
(6.14).Actual value: C, (34.17)；H,(3.98)；N,(16.52)；S,(6.04).
XPS tests: the narrow of middle Ag if Fig. 4 is pyridine dinitrogen bivalence silver complex sweeps spectrum.
Embodiment 3: Antimicrobial test.
1, experiment material
Bacterial strain: it is biological that escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC 25923) are purchased from the auspicious Chu in Shanghai
Science and Technology Ltd..
2, the preparation of series concentration medicinal liquid
Precise 4mg pyridine dinitrogen bivalence silver complex and PA bivalence silver complex, be heated to 40 respectively
DEG C, ultrasonic disperse is dissolved in 10mL MH meat soup, obtains the liquid storage that concentration is 400 μ g/mL, after serial dilution, respectively obtains 40 μ g/
ML, 20 μ g/mL, 10 μ g/mL, 5 μ g/mL, 2 μ g/mL and the medicinal liquid of 1 μ g/mL.
3, antibacterial culturing and counting
On inclined-plane, picking E. coli clones and S. aureus Inoculate are in MH meat soup, after cultivating 8～12 hours,
Pass on again once, continue to cultivate 8～12 hours.Centrifugal, abandoning supernatant, with the PBS solution serial dilution of 0.02M.Hemocytometer
Number plate counting, MH broth dilution obtains the bacterium solution that concentration is about 105-106cfu/mL, and cold preservation is stand-by.
4, microbionation and the detection of optical density value (OD value)
The medicinal liquid taking 125 μ L 6 kinds of concentration obtained above respectively is added in 96 orifice plates, and each concentration of every kind of medicine sets three
Group parallel control, arranges blank.Taking 125 μ L bacterium solution and add in each hole, now the concentration of each medicine is all diluted 2
Times.The orifice plate inoculated is put into incubator, 37 DEG C of cultivations, examine every 30min BIO-RAD Model 680 type microplate reader
Survey each hole optical density value at 630nm.
5, the drafting of growth inhibited curve and the determination of minimal inhibitory concentration (MIC)
Take OD meansigma methods, draw curve, as shown in Figure 3, Figure 4.Antibacterial culturing 24～after 36 hours, detects by an unaided eye, not
See the concentration of contained drug in the hole of bacterial growth as this medicine MIC to tested bacterium, result is as shown in table 1.
6, the light stability test of coordination compound
Three kinds of complexes of the high oxidation states silvers are placed in transparent centrifuge tube, from 7 conditions being initially placed at direct sunlight in morning
Lower irradiation 12h, irradiates 12h next day again.Ambient temperature is 22 ± 4 DEG C, intensity of illumination scope 2500～36000lx (by light intensity
Degree measurement measures).Each coordination compound after being irradiated by sunlight carries out above-mentioned anti-microbial property test again, detects MIC, is shown in Table
1。
The table 1 bivalence silver complex minimal inhibitory concentration (μ g/mL) to different bacterium
Claims (9)
1. a stable bivalence silver complex, it is characterised in that: use organic ligand to stablize bivalence silver ion.
A kind of stable bivalence silver complex the most according to claim 1, it is characterised in that: this coordination compound uses persulfuric acid
Salt is as oxidant.
A kind of stable bivalence silver complex the most according to claim 1, it is characterised in that: described organic ligand is pyridine
Or aminopyridine.
A kind of stable bivalence silver complex the most according to claim 3, it is characterised in that: described organic ligand is 2-ammonia
Yl pyridines, 2-AMINO-4-PICOLINE, 2-amino-6-picoline.
A kind of stable bivalence silver complex the most according to claim 2, it is characterised in that: described persulfate is over cure
Acid sodium, potassium peroxydisulfate or Ammonium persulfate..
6. a stable bivalence silver complex synthetic method, it is characterised in that: the method comprises the following steps: (1) claims 1～2
The silver nitrate of part mol ratio is dissolved in deionized water, adds excess pyridine, adds ammonia and makes pH value 9～10；(2) 5～15 are claimed
The persulfate of part mol ratio is dissolved in deionized water, is stirred continuously, be added to described in state in silver solution, solution has precipitation produce
Raw；(3) after reacting 2～3 hours, putting into refrigerator freezing, sucking filtration, respectively with deionized water and washing with acetone, last vacuum is done
Dry.
A kind of stable bivalence silver complex synthetic method the most according to claim 6, it is characterised in that: solution is put into
Freezing 8 to 16 hours in refrigerator.
8. a stable bivalence silver complex synthetic method, it is characterised in that: the method comprises the following steps: (1) claims 4～8
Part mol ratio PA adds in deionized water, stirring and dissolving；(2) by silver nitrate 1～2 parts of mol ratios and persulfate 4
～8 parts of mol ratios are dissolved in deionized water respectively, being simultaneously introduced above two solution under being stirred continuously, solution produces brown color
Precipitation；(3) after reacting 1～2 hour, putting into refrigerator freezing, sucking filtration, respectively with cold deionized water and washing with acetone, the most very
Empty dry.
A kind of stable bivalence silver complex synthetic method the most according to claim 8, it is characterised in that: solution is put into
Freezing 8 to 16 hours in refrigerator.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5017295A (en) * | 1990-05-01 | 1991-05-21 | N. Jonas & Co., Inc. | Divalent silver bactericide for water treatment |
| CN1214867A (en) * | 1997-10-21 | 1999-04-28 | 蒋华德 | Process for preparing bactericide containing silver |
| US6436420B1 (en) * | 2000-01-05 | 2002-08-20 | Marantech Holding, Llc | High performance silver (I,III) oxide antimicrobial textile articles |
-
2016
- 2016-07-25 CN CN201610590531.XA patent/CN106220654B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5017295A (en) * | 1990-05-01 | 1991-05-21 | N. Jonas & Co., Inc. | Divalent silver bactericide for water treatment |
| CN1214867A (en) * | 1997-10-21 | 1999-04-28 | 蒋华德 | Process for preparing bactericide containing silver |
| US6436420B1 (en) * | 2000-01-05 | 2002-08-20 | Marantech Holding, Llc | High performance silver (I,III) oxide antimicrobial textile articles |
Non-Patent Citations (5)
| Title |
|---|
| H.N. PO: "HETEROCYCLIC AND MACROCYCLIC AMINE COUPLETS OF SILVER(II) AND SiLVER(II1)", 《COORDINATION CHEMISTRY REVIEWS》 * |
| JANELLE L. PIERCE ET AL.: ""Secondary-Ion Mass Spectra of Nonvolatile Silver Complexes"", 《INORG. CHEM.》 * |
| SUKDEB PAL ET AL.,: ""A multifunctional composite of an antibacterial higher-valent silver metallopharmaceutical and a potent wound healing polypeptide: a combined killing and healing approach to wound care"", 《NEW.J.CHEM.》 * |
| T. J. SMITH ET AL.: ""STUDIES ON COORDINATION COMPLEXES OF SILVER(II). PART X. 1 DERIVATIVES WITH SUBSTITUTED PYRIDINE"", 《INORG. NUCL. CHEM. LETTERS》 * |
| WILLIAM LEVASON ET AL.: "THE CHEMISTRY OF COPPER AND SILVER IN THEIR HIGHER OXIDATION STATES", 《COORDINATION CHEMISTRY REVIEWS,》 * |
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