CN103125483A - Green double active center antibacterial agent and preparation method thereof - Google Patents
Green double active center antibacterial agent and preparation method thereof Download PDFInfo
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- CN103125483A CN103125483A CN2012103451174A CN201210345117A CN103125483A CN 103125483 A CN103125483 A CN 103125483A CN 2012103451174 A CN2012103451174 A CN 2012103451174A CN 201210345117 A CN201210345117 A CN 201210345117A CN 103125483 A CN103125483 A CN 103125483A
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Abstract
The invention discloses a green double active center antibacterial agent and a preparation method of the green double active center antibacterial agent. Stereo choosing method synthesis in which a Keggin structure of using transition element V to replace atom replaces type phosphorus molybdenum heteropoly hydrochloric acid, self-assembly reaction with dodecyl trimethyl ammonium bromide under hydrothermal conditions is conducted, and the novel antibacterial agent based on Keggin type polyacid anion and organic matters. Decomposition temperature of the antibacterial agent increase 200 DEG C compared with quaternary ammonium salt, and thereby benefiting for sterilization under high temperature.
Description
Technical field
The present invention relates to a kind of green double activity center antibacterial agent and preparation method thereof.
Background technology
In the assorted poly-tungstate of Keggin structure substituted type, the substituted metal ion is arranged in the corproporphyrin environment, has higher chemism than classic acid.Have quaternary ammonium salt absorption thalline after the different functional groups producing high-molecular and different from the cell membrane binding ability, antibiotic property and stability is difference also.Quaternary ammonium cation can form salt with heteropolyacid anions because containing hydrophobic grouping, becomes super molecular compound.The heteropoly acid quaternary ammonium salt can whole be regarded the ion pair of an organic matter and inorganic matter as, the body that quaternary ammonium cation is inserted into polyacid securely mutually in.
At present with heteropoly acid (being mainly classical polyacid) and quaternary ammonium salt composite supramolecular compound mainly as phase transfer catalyst, more olefin oxidation and epoxidation systems and the Alcohol oxidation system of being applied to.In order to develop new functional area, the strategy of a feasibility is exactly to improve the activity of polyacid, adopts the novel vacant polyacid that replaces, and gives different functional groups with quaternary ammonium salt, make the antibacterial effect of both compound generation high-efficiency low-toxicities, thus the new functional area of developing green polyacid.
According to MOLECULE DESIGN thought, green polyacid is introduced quaternary ammonium salt with different functional groups to prepare more effective environmentally friendly double activity center high-efficiency low-toxicity antibacterial agent.The higher chemism of vacant substituted type heteropoly acid can be strengthened the anti-microbial property of quaternary ammonium salt, thereby promote the range of application of heteropoly acid in the anti-biotic material field.In the exploitation of functionalization material, the efficient utilization of material will be a breakthrough.
Summary of the invention
The invention discloses a kind of green double activity center antibacterial agent and preparation method thereof, take the synthetic Keggin structure substituted type phosphato-molybdic heteropolyacid salt that replaces atom with transition elements V of Stereoselective process, carry out self-assembling reaction with DTAB and obtained a kind of new for Keggin type polyoxoanion and organic antibacterial agent under hydrothermal condition.The decomposition temperature of this antibacterial agent has improved 200 ℃ than quaternary ammonium salt, is conducive at high temperature kill virus.
A kind of green double activity center of the present invention antibacterial agent is to adopt following methods synthetic:
1. take Na
2MoO
4 ˙2H
2O20～30g after ultrasonic dissolution, regulates pH=1～2 with 4～6mol/L hydrochloric acid solution, after 70～80 ℃ of lower temperature constant magnetic stirring 40～50min;
2. continue to drip wherein the KH of 0.50mol/L
2PO
4Solution 15～22mL, and keep pH of mixed=1～2, this moment solution to be yellow green transparent, react with this understanding 0.5～1h;
3. add wherein again 0.88～1.32gNH
4VO
3, after continuing reaction 1～2h, it is orange red that solution is.It is cooled to room temperature, divides to add 18～28gKCl solid 3～5 times, static layering, lower floor's crocus precipitation is put into refrigerator;
4. after 3～5 days, separate out the orange crystal, suction filtration, drying is bottled and posts label, note-PMo
11V；
5. 10～the 20g-PMo that takes
11V salt is dissolved in 20～30mL distilled water; Get again 9～18gC
15H
34NBr is dissolved in a small amount of distilled water wiring solution-forming, drips hydrochloric acid solution to-PMo
11In the V salting liquid;
6. 40～60 ℃ of magnetic agitation reaction 2～3h, get a large amount of crystal.Stop reaction, suction filtration is placed in the dry 1～2h of 50～70 ℃ of vacuum desiccators, obtains antibacterial agent;
Advantage of the present invention: synthetic method is simple, adopts IR, UV, and TG, XRD, SEM, TEM characterizes product, after tested proof: the decomposition temperature of this antibacterial agent has improved 200 ℃ than quaternary ammonium salt, is conducive at high temperature kill virus.
Description of drawings
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Fig. 1 is the synthetic front IR figure of antibacterial agent of the present invention (PMo
11V IR spectrogram)
Fig. 2 is the IR figure (C after antibacterial agent of the present invention synthesizes
15H
34NBrPMo
11V IR spectrogram)
Fig. 3 is the synthetic front XRD figure of antibacterial agent of the present invention (PMo
11The V x-ray diffraction pattern)
Fig. 4 is the XRD figure (C after antibacterial agent of the present invention synthesizes
15H
34NBrPMo
11The V x-ray diffraction pattern)
Fig. 5 is the synthetic front TG figure of antibacterial agent of the present invention (PMo
11V TG collection of illustrative plates)
Fig. 6 is the TG figure (C after antibacterial agent of the present invention synthesizes
15H
34NBrPMo
11V TG collection of illustrative plates)
Fig. 7 is the SEM figure (C after antibacterial agent of the present invention synthesizes
15H
34NBr-PMo
11The SEM figure of V)
Fig. 8 is the TEM figure (C after antibacterial agent of the present invention synthesizes
15H
34NBr-PMo
11The TEM figure of V)
Embodiment
Embodiment 1:K
3[PMo
11V(H
2O)O
39] synthetic
Accurately take Na
2MoO
4 ˙2H
2O 6.654g after ultrasonic dissolution, regulates pH=1～2 with the 1mol/L hydrochloric acid solution, after 70～80 ℃ of lower temperature constant magnetic stirring 40～50min, continues to drip wherein the KH of 0.50mol/L
2PO
4Solution 5mL, and keep pH of mixed=1, this moment solution to be yellow green transparent, react with this understanding 0.5～1h, then add wherein 0.293gNH
4VO
3, after continuing reaction 1h, it is orange red that solution is.It is cooled to room temperature, divides and add several times the 6.250gKCl solid, static layering, lower floor's crocus precipitation is put into refrigerator.After 3 days, separate out the orange crystal, suction filtration, drying is bottled and posts label, note-PMo
11V。
Embodiment 2: double activity center's green antibacterial agent synthetic
Get 0.500g-PMo
11V salt is dissolved in wiring solution-forming in 8mL distilled water, then gets 0.081gC
15H
34NBr is dissolved in 2mL distilled water wiring solution-forming, after ultrasonic dissolution, drips C
15H
34NBr solution is to-PMo
11In the V salting liquid, normal temperature magnetic force stirring reaction 1h, solution is crocus.Stop reaction, suction filtration is placed in dry 1h under 50 ℃ of vacuum desiccators, takes out and bottles and post label.Be denoted as C
15H
34NBrPMo
11V。
Attached Fig. 1 and 2 is respectively the IR figure of the synthetic front and back of antibacterial agent, and as can be seen from the figure, the eigen vibration frequency of heteropolyanion IR spectrum is substantially constant, and this expression title compound still keeps the Keggin skeleton.At C
15H
34In the NBr molecule, saturated C-H stretching vibration appears at 3000cm
-1Below ,-CH
2-absworption peak at 2930 ± 5cm
-1Near antisymmetric stretching vibration is at 2850 ± 10cm
-1Near symmetrical stretching vibration, after itself and polyacid chemical combination, all there are displacement in various degree, wherein P-O in all absworption peaks positions
aKey and Mo-O
dKey blue shift 20cm
-1The left and right, Mo-O
b-Mo key red shift 2-3cm
-1, Mo-O
c-Mo key red shift 3-15cm
-1After showing the formation title compound, chemical bond in heteropolyanion is because the effect that is subject to quaternary ammonium salt cationic has weakening or strengthening in various degree, the quaternary ammonium salt specific surface area is large, quaternary ammonium salt effect due to electrostatic attraction between the polyacid ion is combined, heteropoly acid is attached in the long-chain of quaternary ammonium salt, and the organic ammonium cation is than H
+Radius is large, and cationic bulk effect has weakened the interaction between anion and anion, and in heteropolyanion, the metal-oxygen key weakens thereby make, and makes the absworption peak red shift.
Accompanying drawing 3 and 4 is respectively the XRD figure of the synthetic front and back of antibacterial agent, in order to determine that further institute's synthetic compound is noval chemical compound, investigates the variation of its structure, and title compound is carried out X-ray powder diffraction material phase analysis.Result shows, title compound is 2
θBe in 0 °～7 ° scopes, absorption to be arranged, obviously different from heteropolyacid salt and quaternary ammonium salt, show to have obtained new phase.
Accompanying drawing 5 and 6 is respectively the TG figure of the synthetic front and back of antibacterial agent, and the TG curve is the powerful of research heteropoly compound heat endurance.-PMo
11Only had for two steps weightless shown in the TG curve of V, 20～400 ℃ lose adsorbed water, and 484 ℃ of samples begin to decompose, and may be because the heteropoly acid molecular structure changes, C
15H
34NBr-PMo
11Shown in the TG curve of V, there were three steps weightless.Phase I weightlessness is 20～180 ℃, and weight-loss ratio is 3.21%, and this is because material has lost adsorbed water and water of crystallization.The weightlessness of second stage is 200～430 ℃, and weight-loss ratio is 41.64%, shows that in this temperature range organic ammonium cation may be subjected to the impact of heteropolyacid anions, and heat endurance improves.The 3rd step is weightless since 490～698 ℃ of C
15H
34NBr-PMo
11The structure of V changes and decomposed, and weight-loss ratio is 4.72%, thinks that decomposition has occured heteropoly acid, loses constitution water.After 2 to 3 step weightlessness, ammonium heteropoly acids has lost all ammonium ions substantially, and the end product of its decomposition is the oxide that is comprised of heteropolyanion.Initial decomposition temperature between contrast title compound and quaternary ammonium salt, 200 ℃ of the highest raisings of decomposition temperature of discovery title compound, illustrate that the stability of title compound is much higher than the stability of quaternary ammonium salt, the explanation title compound that this conclusion is conducive to can at high temperature be brought into play antibacterial functions.
Accompanying drawing 7 and 8 is respectively SEM and the TEM figure after antibacterial agent synthesizes, and material shows as the micron bar form as seen from Figure 7, mostly is the regular circle cylindricality, is evenly distributed.Target product has certain rigidity, and after being aggregated to certain-length, due to the action of gravitation fracture, so electromicroscopic photograph demonstrates short bar-shaped form.As seen from Figure 8, the micron bar diameter of material is more or less the same.By the transmission electron microscope graph discovery of object observing product, material grains in the form of sheets, particle diameter is even, and good dispersion, particle size is greatly about about 100nm.
Claims (1)
1. green double activity center antibacterial agent and preparation method thereof, this product are to adopt the following methods preparation:
1. take Na
2MoO
4 ˙2H
2O20～30g after ultrasonic dissolution, regulates pH=1～2 with 4～6mol/L hydrochloric acid solution, after 70～80 ℃ of lower temperature constant magnetic stirring 40～50min;
2. continue to drip wherein the KH of 0.50mol/L
2PO
4Solution 15～22mL, and keep pH of mixed=1～2, this moment solution to be yellow green transparent, react with this understanding 0.5～1h;
3. add wherein again 0.88～1.32gNH
4VO
3, after continuing reaction 1～2h, it is orange red that solution is.It is cooled to room temperature, divides to add 18～28gKCl solid 3～5 times, static layering, lower floor's crocus precipitation is put into refrigerator;
4. after 3～5 days, separate out the orange crystal, suction filtration, drying is bottled and posts label, note-PMo
11V；
5. 10～the 20g-PMo that takes
11V salt is dissolved in 20～30mL distilled water; Get again 9～18gC
15H
34NBr is dissolved in a small amount of distilled water wiring solution-forming, drips hydrochloric acid solution to-PMo
11In the V salting liquid;
6. 40～60 ℃ of magnetic agitation reaction 2～3h, get a large amount of crystal.Stop reaction, suction filtration is placed in the dry 1～2h of 50～70 ℃ of vacuum desiccators, obtains antibacterial agent.
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| CN103125483B CN103125483B (en) | 2014-05-14 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106342890A (en) * | 2016-08-25 | 2017-01-25 | 齐齐哈尔大学 | Heteropoly acid and amino acid compound antibacterial agent, and preparation method and application thereof |
| CN111916722A (en) * | 2020-07-08 | 2020-11-10 | 旌德君创科技发展有限公司 | Preparation method of manganese vanadium molybdenum phosphorus heteropoly acid and application of manganese vanadium molybdenum phosphorus heteropoly acid in lithium battery |
| CN115041228A (en) * | 2022-07-22 | 2022-09-13 | 西安石油大学 | Organic-inorganic hybrid material based on Waugh type manganese molybdenum heteropoly acid and synthetic method thereof |
| CN115538195A (en) * | 2022-09-30 | 2022-12-30 | 浙江越新印染有限公司 | Color fixing finishing method and application thereof in pure cotton printing and dyeing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106342890A (en) * | 2016-08-25 | 2017-01-25 | 齐齐哈尔大学 | Heteropoly acid and amino acid compound antibacterial agent, and preparation method and application thereof |
| CN111916722A (en) * | 2020-07-08 | 2020-11-10 | 旌德君创科技发展有限公司 | Preparation method of manganese vanadium molybdenum phosphorus heteropoly acid and application of manganese vanadium molybdenum phosphorus heteropoly acid in lithium battery |
| CN111916722B (en) * | 2020-07-08 | 2022-02-25 | 旌德君创科技发展有限公司 | Preparation method of manganese vanadium molybdenum phosphorus heteropoly acid and application of manganese vanadium molybdenum phosphorus heteropoly acid in lithium battery |
| CN115041228A (en) * | 2022-07-22 | 2022-09-13 | 西安石油大学 | Organic-inorganic hybrid material based on Waugh type manganese molybdenum heteropoly acid and synthetic method thereof |
| CN115041228B (en) * | 2022-07-22 | 2024-03-26 | 西安石油大学 | Organic-inorganic hybrid material based on Waugh type manganese-molybdenum heteropoly acid and synthesis method thereof |
| CN115538195A (en) * | 2022-09-30 | 2022-12-30 | 浙江越新印染有限公司 | Color fixing finishing method and application thereof in pure cotton printing and dyeing |
| CN115538195B (en) * | 2022-09-30 | 2023-11-03 | 浙江越新印染有限公司 | Color fixation finishing method and application thereof in pure cotton printing and dyeing |
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|---|---|
| CN103125483B (en) | 2014-05-14 |
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