CN103125483B - Green double active center antibacterial agent and preparation method thereof - Google Patents
Green double active center antibacterial agent and preparation method thereof Download PDFInfo
- Publication number
- CN103125483B CN103125483B CN201210345117.4A CN201210345117A CN103125483B CN 103125483 B CN103125483 B CN 103125483B CN 201210345117 A CN201210345117 A CN 201210345117A CN 103125483 B CN103125483 B CN 103125483B
- Authority
- CN
- China
- Prior art keywords
- antibacterial agent
- solution
- pmo
- preparation
- active center
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
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, substituted metal ion is arranged in corproporphyrin environment, has higher chemism than classic acid.Have the quaternary ammonium salt absorption thalline and different from cell membrane binding ability after different functional groups producing high-molecular, antibiotic property and stability are also different.Quaternary ammonium cation, because containing hydrophobic grouping, can form salt with heteropolyacid anions, becomes super molecular compound.During heteropoly acid quaternary ammonium salt can entirety regard that body that the ion pair of an organic matter and inorganic matter, quaternary ammonium cation be inserted into polyacid securely mutually as.
At present by heteropoly acid (being mainly classical polyacid) and quaternary ammonium salt composite supramolecular compound mainly as phase transfer catalyst, the more oxidation system that is applied to olefin oxidation and epoxidation systems and alcohol.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 by 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 to 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 strengthen the anti-microbial property of quaternary ammonium salt, thereby promote the range of application of heteropoly acid in 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, under hydrothermal condition, carry out self-assembling reaction with DTAB and obtained a kind of new for Keggin type polyoxoanion and organic antibacterial agent.The decomposition temperature of this antibacterial agent has improved 200 ℃ compared with 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, at 70～80 ℃ after 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, to be now yellow green transparent for solution, reacts with this understanding 0.5～1h;
3. add wherein again 0.88～1.32gNH
4vO
3, continuing after reaction 1～2h, it is orange red that solution is.Be cooled to room temperature, divide and add 18～28gKCl solid 3～5 times, static layering, lower floor's crocus precipitation, puts into refrigerator;
4. after 3～5 days, separate out orange crystal, suction filtration, dry, bottle and post label, note-PMo
11v;
5. 10～the 20g-PMo taking
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 V salting liquid;
6. 40～60 ℃ of magnetic agitation reaction 2～3h, obtain 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, proves after tested: the decomposition temperature of this antibacterial agent has improved 200 ℃ compared with quaternary ammonium salt, is conducive at high temperature kill virus.
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
11v x-ray diffraction pattern)
Fig. 4 is the XRD figure (C after antibacterial agent of the present invention synthesizes
15h
34nBrPMo
11v 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, with 1mol/L hydrochloric acid solution adjusting pH=1～2, after temperature constant magnetic stirring 40～50min, continues to drip wherein the KH of 0.50mol/L at 70～80 ℃
2pO
4solution 5mL, and keep pH of mixed=1, to be now yellow green transparent for solution, reacts with this understanding 0.5～1h, then add wherein 0.293gNH
4vO
3, continuing after reaction 1h, it is orange red that solution is.Be cooled to room temperature, divide and add several times 6.250gKCl solid, static layering, lower floor's crocus precipitation, puts into refrigerator.After 3 days, separate out orange crystal, suction filtration, dry, bottle and post 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 V salting liquid, normal temperature magnetic force stirring reaction 1h, solution is crocus.Stop reaction, suction filtration, is placed in dry 1h at 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 represents that title compound still keeps Keggin skeleton.At C
15h
34in NBr molecule, saturated C-H stretching vibration appears at 3000cm
-1below ,-CH
2-absworption peak at 2930 ± 5cm
-1near antisymmetric stretching vibration, at 2850 ± 10cm
-1near symmetrical stretching vibration, when after itself and polyacid chemical combination, all there are displacement in various degree, wherein P-O in all absworption peak positions
akey and Mo-O
dkey blue shift 20cm
-1left and right, Mo-O
b-Mo key red shift 2-3cm
-1, Mo-O
c-Mo key red shift 3-15cm
-1show to form after title compound, chemical bond in heteropolyanion has weakening or strengthening in various degree owing to being subject to the effect of quaternary ammonium salt cationic, quaternary ammonium salt specific surface area is large, between quaternary ammonium salt and polyacid ion because the effect of electrostatic attraction is combined, heteropoly acid is attached in the long-chain of quaternary ammonium salt, and organic ammonium cation is compared with H
+radius is large, and cationic bulk effect has weakened the interaction between anion and anion, thereby metal-oxygen key in heteropolyanion is weakened, and makes 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 further to determine that synthesized compound is noval chemical compound, investigates the variation of its structure, and title compound is carried out to X-ray powder diffraction material phase analysis.Result shows, title compound is 2
θbe to have absorption within the scope of 0 °～7 °, obviously different from heteropolyacid salt and quaternary ammonium salt, show to obtain new thing phase.
Accompanying drawing 5 and 6 is respectively the TG figure of the synthetic front and back of antibacterial agent, and TG curve is the powerful of research heteropoly compound heat endurance.-PMo
11shown in the TG curve of V, only have two step weightlessness, 20～400 ℃ lose adsorbed water, and 484 ℃ of samples start to decompose, and may be because heteropoly acid molecular structure changes, C
15h
34nBr-PMo
11shown in the TG curve of V, there are three step weightlessness.First stage 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 subject to the impact of heteropolyacid anions, and heat endurance improves.The 3rd step weightlessness is 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 occurred 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 being made up 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 micron bar form as seen from Figure 7, is mostly rule cylindrical, is evenly distributed.Target product has certain rigidity, is aggregated to after certain length, and because the effect of gravity is ruptured, therefore 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, in the form of sheets, particle diameter is even for material grains, and good dispersion, and particle size is greatly about 100nm left and right.
Claims (1)
1. a preparation method for green double activity center antibacterial agent, this product adopts following methods to prepare:
step 1,take Na
2moO
4 ˙2H
2o20～30g, after ultrasonic dissolution, regulates pH=1～2 with 4～6mol/L hydrochloric acid solution, at 70～80 ℃ after temperature constant magnetic stirring 40～50min;
step 2,continue to drip wherein the KH of 0.50mol/L
2pO
4solution 15～22mL, and keep pH of mixed=1～2, to be now yellow green transparent for solution, reacts with this understanding 0.5～1h;
step 3,add wherein again 0.88～1.32gNH
4vO
3, continuing after reaction 1～2h, it is orange red that solution is, and is cooled to room temperature, and divide and add 18～28gKCl solid 3～5 times, static layering, lower floor's crocus precipitation, puts into refrigerator;
step 4,after 3～5 days, separate out orange crystal, suction filtration, dry, bottle and post label, note-PMo
11v;
step 5,10～the 20g-PMo taking
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 V salting liquid;
step 6,40～60 ℃ of magnetic agitation reaction 2～3h, obtain 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210345117.4A CN103125483B (en) | 2012-09-18 | 2012-09-18 | Green double active center antibacterial agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210345117.4A CN103125483B (en) | 2012-09-18 | 2012-09-18 | Green double active center antibacterial agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103125483A CN103125483A (en) | 2013-06-05 |
| CN103125483B true CN103125483B (en) | 2014-05-14 |
Family
ID=48486431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210345117.4A Expired - Fee Related CN103125483B (en) | 2012-09-18 | 2012-09-18 | Green double active center antibacterial agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103125483B (en) |
Families Citing this family (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 |
| 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 |
| 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 |
| 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 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344597C (en) * | 2005-12-28 | 2007-10-24 | 浙江工业大学 | Process for preparing cyclohexone by catalyzing oxidating cyclohexol |
| CN101302147B (en) * | 2008-06-13 | 2011-05-25 | 浙江工业大学 | Method for preparing hexane diacid by liquid-phase catalytic oxidation of cyclohexanol |
| CN101811768B (en) * | 2010-04-02 | 2012-01-25 | 东北师范大学 | Method for degrading phenol in sewage by using vanadium-molybdenum polyoxometallate-contained catalyst |
| CN101870658B (en) * | 2010-05-14 | 2013-02-13 | 东北师范大学 | Keggin polyoxometallate-based ion liquid and synthesis method thereof |
| CN102614930B (en) * | 2012-03-16 | 2013-10-09 | 西南石油大学 | Metal quaternary ammonium oxyphosphate dispersoid and application of metal quaternary ammonium oxyphosphate dispersoid in exploitation of thickened oil |
-
2012
- 2012-09-18 CN CN201210345117.4A patent/CN103125483B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103125483A (en) | 2013-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103125483B (en) | Green double active center antibacterial agent and preparation method thereof | |
| Liu et al. | Preparation and testing of cementing and coating nano-subnanocomposites of slow/controlled-release fertilizer | |
| Lin et al. | A review on the synthesis and applications of mesostructured transition metal phosphates | |
| CN104030314B (en) | A kind of ZSM-5 Quito level porous molecular sieve material and preparation method thereof | |
| CN102838129B (en) | Mesoporous molecular sieves with crystal structures and preparation method of mesoporous molecular sieves | |
| CN102795610B (en) | Amorphous calcium phosphate nanoball and preparation method thereof | |
| Mothé-Esteves et al. | How Keggin-Type polyoxometalates self-organize into crystals | |
| CN106000287A (en) | Ion sieve material and preparing and using methods thereof | |
| CN101898155B (en) | Preparation method and application of sandwich type polyacid intercalated hydrotalcite composite material | |
| CN102500407A (en) | Preparation method of bimetal-doped mesoporous material SBA-15 catalyst and bimetal-doped SBA-15 catalyst | |
| Wang et al. | Phosphomolybdate assembly as a low-cost catalyst for the reduction of toxic Cr (vi) in aqueous solution | |
| CN102897737A (en) | Method for preparation of pillared zirconium phosphate material by self-assembly technology | |
| CN104445263A (en) | SCM-3 molecular sieve and preparation method thereof | |
| CN107161970A (en) | It is a kind of that there is magnesium phosphate nano material of flourishing mesopore orbit structure and preparation method thereof | |
| Lee et al. | Catalytic and sorption applications of porous nickel phosphate materials | |
| CN105061810B (en) | A kind of antibacterial electronic cigarette appearance material and its preparation method and application | |
| Peng et al. | Heteropolyoxometalates which are included in microporous silica, CsxH3− xPMo12O40/SiO2 and CsyH5− yPMo10V2O40/SiO2, as insoluble solid bifunctional catalysts: synthesis and selective oxidation of benzyl alcohol in liquid–solid systems | |
| Abu-Zied et al. | Preparation of caesium-substituted phosphomolybdic acid via solid-state ion exchange method | |
| CN106167254A (en) | A kind of metal phosphate and preparation method thereof | |
| CN102935381A (en) | Amphiphilic type rare earth polyacid catalytic material and preparation method and application thereof | |
| Zhang et al. | Controlled synthesis of hierarchical beta zeolite through design template to enhance gas-phase beckmann rearrangement performance | |
| CN108816179A (en) | A kind of porous, high-specific surface area amorphous MnPO material and its preparation method and application | |
| US11434140B2 (en) | Hierarchical zeolites and preparation method therefor | |
| CN103834197A (en) | Preparation method of organic montmorillonite modified by supermolecular liquid crystal polymer | |
| CN114620698B (en) | Large-particle zirconium phosphate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140514 Termination date: 20180918 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |