CN106342890A - Heteropoly acid and amino acid compound antibacterial agent, and preparation method and application thereof - Google Patents
Heteropoly acid and amino acid compound antibacterial agent, and preparation method and application thereof Download PDFInfo
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- CN106342890A CN106342890A CN201610720129.9A CN201610720129A CN106342890A CN 106342890 A CN106342890 A CN 106342890A CN 201610720129 A CN201610720129 A CN 201610720129A CN 106342890 A CN106342890 A CN 106342890A
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- heteropoly acid
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- 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
- A01N59/20—Copper
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- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
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Abstract
The invention discloses a heteropoly acid and amino acid compound antibacterial agent, and a preparation method and application thereof. A stereoscopic selection method is adopted for compounding a heteropoly acid isomer, and the heteropoly acid isomer carries out self-assembly reaction with amino acid under a hydrothermal condition, thereby obtaining a novel heteropoly acid-based amino acid compound antibacterial agent. The antibacterial agent has high safety, strong antibacterial activity, high water solubility and high heat stability; the decomposition temperature of the antibacterial agent is 300 DEG C higher than that of amino acid; and the antibacterial agent is beneficial to disinfection at high temperature.
Description
Technical field
The present invention relates to a kind of heteropoly acid aminoacid complex antimicrobials, its preparation method and application.
Background technology
Heteropoly acid has the structure of uniqueness and preferable oxidation-reduction quality, is good electron acceptor again；Aminoacid due to
Both sexes act on, and the growth to common bacteria has better inhibition effect, when aminoacid and polyoxoanion occur to interact, can
Formation awards-be subject to electron transporting compound, such compound have organic with inorganic component some characteristics, can also derive perhaps
How new property.The present invention combines the feature of heteropoly acid and aminoacid, prepares complex antimicrobials, thus simultaneously lifting heteropoly acid and
Aminoacid is in the range of application in anti-biotic material field.
Content of the invention
The invention discloses a kind of heteropoly acid aminoacid complex antimicrobials, its preparation method and application, take Stereoselective
Method synthesizes Heteroply acid isomer, carry out with aminoacid under hydrothermal conditions self-assembling reaction obtained a kind of new based on heteropoly acid
Aminoacid complex antimicrobials, and antibacterial application is carried out to common bacteria；
Advantages of the present invention:
Heteropoly acid aminoacid complex antimicrobials safe, biocidal property is strong, water solublity is big, heat stability is good, be conducive in height
Temperature is lower to kill virus.
The preparation method of above-mentioned heteropoly acid aminoacid complex antimicrobials, is carried out according to the following steps:
hn[x(h2o)mz11o39]·mh2(skeleton symbol is mz to o11The preparation of Heteroply acid isomer x): 0.11mol～0.15mol
Na2zo4·2h2O ultrasonic dissolution in 150ml～200ml distilled water, the salt containing m element for the 0.01mol～0.05mol
Ultrasonic dissolution, in 50ml～100ml distilled water, adds 50ml～100ml aqueous solution that 0.01mol～0.05mol contains x salt,
Stop stirring after 1h～1.5h, after cooling, additions mass concentration is 95% dehydrated alcohol, obtains oil product, settle 0.5h～
1h, the grease obtaining is dissolved in 50ml～100ml distilled water, resulting solution is passed to h+The amberliteir-120 of type
In cation exchange column, the ion exchange in solution be performed until ph be 0.5～1 till, with cooling method separation solid-state hpa；
The preparation of heteropoly acid aminoacid complex antimicrobials: accurately weigh hpa in molar ratio and aminoacid is dissolved in dilute hcl solution respectively
(1mol·l-1) in, in the hydrochloric acid solution under electromagnetic agitation, the hydrochloric acid solution of aminoacid being added drop-wise to hpa, slow precipitation is brilliant
Body, after continuing stirring 24h, puts into refrigerator standing, uses sintered glass funnel decompression separation, use 1mol l-1Hydrochloric acid solution washing crystal
3 times, drain, 30 DEG C about thermostat water baths are dried, and obtain product.
The reaction equation of the heteropoly acid aminoacid complex antimicrobials of present invention preparation is as follows:
(1)
(2)
X:al, ti, v, fe, co, ni, cu, zn；M:si, p, fe, co, ni, mn, zn, cu, cr；Z:mo, w.As above-mentioned reaction equation
Shown, first allow two kinds of simple ions be formed with one or several vacant unsaturated heteropolyanions by metering ratio in reaction,
It is subsequently adding x ion and makes it into omission, that is, obtain, containing x, the sodium salt of the heteropoly acid of m and z, exchanging through cation exchange resin
Afterwards, obtain final product corresponding heteropoly acid.
Brief description
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Fig. 1 is the uv figure of heteropoly acid aminoacid complex antimicrobials of the present invention.
Fig. 2 is the ir figure of heteropoly acid aminoacid complex antimicrobials of the present invention.
Fig. 3 is the tg figure of heteropoly acid aminoacid complex antimicrobials of the present invention.
Fig. 4 is the sem figure of heteropoly acid aminoacid complex antimicrobials of the present invention.
Fig. 5 is heteropoly acid aminoacid complex antimicrobials of the present invention to colibacillary antibacterial figure.
Fig. 6 is the antibacterial figure to bacillus cereuss of heteropoly acid aminoacid complex antimicrobials of the present invention.
Specific embodiment
Embodiment 1: α-siw11The synthesis of cu
Weigh na2sio3·9h2It is placed under o 5.631g room temperature in 80ml distilled water, ultrasonic dissolution, add in 500ml beaker
100.541g na2wo4·2h2O, with the dissolving of 150ml boiling water, under 100 DEG C of heated and stirred, is slowly added dropwise in boiling dissolving
The hcl solution of 4mol/l, adjusts ph=5 ~ 6, is stirred vigorously the sodium tungstate resolution of precipitate that lower local produces, pours rapidly na into2sio3
Aqueous solution, the hcl solution of Deca 4mol/l again, adjust ph=5 ~ 6, seethe with excitement 1h, is cooled to room temperature, sucking filtration, will not react sio2
Filter Deng insoluble matter, take 3.527gcuso4Solid dissolving is added drop-wise in above-mentioned solution, continues magnetic agitation 1h～1.5h, treats molten
Add 50ml alcohol flushing to obtain oily light green solid after pouring out supernatant five times after liquid cooling, be dissolved into 100ml water
In, resulting solution is passed to h+In the amberliteir-120 cation exchange column of type, the ion exchange in solution is carried out always
To ph is 0.5～1, is separated with cooling method and obtain pistac crystal, be placed in air drying, weigh, bottling is smooth good
Label, remembers α-siw11Cu,
Embodiment 2: heteropoly acid glycine hybrid material (hgly) α-siw11The liquid phase synthesis of cu.
Weigh gly2.2712g, α-siw11Cu8.4317g, is dissolved in 10ml dilute hcl solution (1mol l respectively-1) in,
Under electromagnetic agitation, the hydrochloric acid solution of 10mlgly is added drop-wise to the α-siw of same volume11In cu hydrochloric acid solution, slow precipitation is yellowish green
Color crystal, after continuing stirring 24h, puts into refrigerator standing, uses sintered glass funnel decompression separation, use 1mol l-1Hydrochloric acid solution washs
Crystal 3 times, drains, and 30 DEG C about thermostat water baths are dried, and obtain product (hgly) α-siw11cu.
Embodiment 3: Fig. 1 α-siw11Cu and (hgly) α-siw11The ultraviolet spectra of cu, the absorption of od → w as can be seen from Figure
Band blue shift (199nm → 194nm), and ob/oc → w red shift (253nm → 264nm), and glycine no substantially absorbs in ultra-violet (UV) band
Band.Illustrate that complex is not physical absorption, but chemical reaction, the new product obtaining occur.
Embodiment 4: Fig. 2 is α-siw11Cu, gly and (hgly) α-siw11The infrared spectrogram of cu.700cm-1~
1100cm-1For α-siw11The characteristic absorption band of cu, special α-siw as seen from the figure11It is 1094.28 cm that cu levies absorption peak position-1,
966.12 cm-1, 919.87 cm-1, 796.08cm-1；1300 cm-1~1750 cm-1Characteristic absorption band for gly, can by figure
Know that gly characteristic absorption peak position is 1333.68cm-1, 1413.17cm-1, 1591.68cm-1.(hgly)α-siw11The existing α of cu-
siw11The characteristic absorption band 1116.67cm of cu-1, 970.69cm-1, 925.99cm-1, 784.07cm-1, also have the feature of gly to inhale
Take-up 1430.50cm-1, 1495.54cm-1, 1618.62cm-1And several absworption peaks occur in that skew in complex, illustrate compound
Thing be produced by chemical bonds rather than physical absorption.
Embodiment 5: Fig. 3 is (hgly) α-siw11Cu is weightless big in the hot weightless picture of 25 ° of c to 700 ° of c, as can be seen from Figure its
Cause is divided into 25 ° of c ~ 300 ° c weight loss rates of three phases first stage very fast, may be for losing water of crystallization, in conjunction with water and part
The decomposition of glycine, weight-loss ratio is 87%；300 ° of c ~ 550 ° c weight loss rates of second stage are more slow, may be glycine enter one
It is 81% that step decomposes weight-loss ratio；550 ° of c ~ 700 ° c wt-lossing rates of phase III accelerate again it should be the decomposition of heteropoly acid, lose
Rate is 76% again.And the decomposition temperature of glycine is only 248 ° of c, illustrate that the addition of heteropoly acid makes the stability of sweet base acid improve
300°c.
Embodiment 6: Fig. 4 is (hgly) α-siw11The scanning electron microscope (SEM) photograph of cu, shows in image that the pattern of this compound is in
Flakey, particle diameter is more uniform, and form is more regular, and good dispersion, there is good pattern.
Embodiment 7: Fig. 5 α-siw11Cu, gly and (hgly) α-siw11Cu to colibacillary fungistatic effect figure, 1 is
Gly bacteriostatic diameter is 7mm, and 2 is α-siw11Cu bacteriostatic diameter is 14mm, and 3 is (hgly) α-siw11Cu bacteriostatic diameter is 17mm.
Can be seen that gly bacteriostasis are general by figure data, α-siw11Cu bacteriostasis are preferable, and (hgly) α-siw11Cu's is antibacterial
Ability is best.
Embodiment 8: Fig. 6 is α-siw11Cu, gly and (hgly) α-siw11The fungistatic effect to bacillus cereuss of cu
Figure, 1 gly bacteriostatic diameter is 7mm, and 2 is α-siw11Cu bacteriostatic diameter is 14mm, and 3 is (hgly) α-siw11Cu bacteriostatic diameter is
16mm.Can be seen that gly bacteriostasis are general by figure data, α-siw11Cu bacteriostasis are preferable, and (hgly) α-siw11Cu's
Bacteriostasis are best.
Claims (6)
1. a kind of heteropoly acid aminoacid complex antimicrobials are it is characterised in that structural formula is:
Wherein said x:al, ti, v, fe, co, ni, cu, zn；M:si, p, fe, co, ni, mn, zn, cu, cr；Z:mo, w.
2. as claimed in claim 1 a kind of heteropoly acid aminoacid complex antimicrobials preparation method it is characterised in that heteropoly acid ammonia
Base acid complex antimicrobials preparation method sequentially includes the following steps:
First, hn[x(h2o)mz11o39]·mh2(skeleton symbol is mz to o11The preparation of Heteroply acid isomer x): 0.11mol～
The na of 0.15mol2zo4·2h2O ultrasonic dissolution, in 150ml～200ml distilled water, contains m 0.01mol～0.05mol
The salt ultrasonic dissolution of element in 50ml～100ml distilled water, add 0.01mol～0.05mol contain the 50ml of x salt～
100ml aqueous solution, stops stirring after 1h～1.5h, and after cooling, addition mass concentration is 95% dehydrated alcohol, obtains oil product,
Sedimentation 0.5h～1h, the grease obtaining is dissolved in 50ml～100ml distilled water, resulting solution is passed to h+Type
In amberliteir-120 cation exchange column, the ion exchange in solution be performed until ph be 0.5～1 till, with cooling
Method separation solid-state hpa；
2nd, the preparation of heteropoly acid aminoacid complex antimicrobials: accurately weigh hpa in molar ratio and aminoacid is dissolved in dilute hcl respectively
Solution (1mol l-1) in, by aminoacid under electromagnetic agitation: in the hydrochloric acid solution that hydrochloric acid solution is added drop-wise to hpa, slow analysis
Go out crystal, after continuing stirring 24h, put into refrigerator standing, use sintered glass funnel decompression separation, use 1mol l-1Hydrochloric acid solution washs
Crystal 3 times, drains, and 30 DEG C about thermostat water baths are dried, and obtain product.
3. a kind of heteropoly acid aminoacid complex antimicrobials preparation method according to claim 2 it is characterised in that formed
Vacant heteropoly acids isomer is replaced with other metals, lifts its activity.
4. a kind of heteropoly acid aminoacid complex antimicrobials preparation method according to claim 2 is it is characterised in that selected
Aminoacid extensively, and there is certain biocidal property.
5. a kind of application of described heteropoly acid aminoacid complex antimicrobials according to claim 2 is it is characterised in that safety
Good, dissolubility is good, and good stability is it is adaptable to high temperature sterilization.
6. a kind of application of heteropoly acid aminoacid complex antimicrobials according to claim 2 is it is characterised in that scope of restraining fungi
It is all common antibacterials.
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Cited By (4)
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| CN109433266A (en) * | 2018-11-29 | 2019-03-08 | 东北师范大学 | Three center POMs catalysis oxidation glycerol of polylysine modification prepare the technology of lactic acid |
| CN112674111A (en) * | 2020-12-22 | 2021-04-20 | 安徽稞馨环境科技有限公司 | Heteropoly acid air bactericide and preparation method and application thereof |
| CN112876421A (en) * | 2021-02-07 | 2021-06-01 | 哈尔滨医科大学 | Heteropolyacid-sulfadiazine hybrid compound and preparation method and application thereof |
| CN114892278A (en) * | 2022-05-12 | 2022-08-12 | 齐齐哈尔大学 | Ciprofloxacin modified heteropoly acid isomer composite single crystal and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109433266A (en) * | 2018-11-29 | 2019-03-08 | 东北师范大学 | Three center POMs catalysis oxidation glycerol of polylysine modification prepare the technology of lactic acid |
| CN112674111A (en) * | 2020-12-22 | 2021-04-20 | 安徽稞馨环境科技有限公司 | Heteropoly acid air bactericide and preparation method and application thereof |
| CN112876421A (en) * | 2021-02-07 | 2021-06-01 | 哈尔滨医科大学 | Heteropolyacid-sulfadiazine hybrid compound and preparation method and application thereof |
| CN114892278A (en) * | 2022-05-12 | 2022-08-12 | 齐齐哈尔大学 | Ciprofloxacin modified heteropoly acid isomer composite single crystal and preparation method and application thereof |
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