CN111205312B - Antibacterial rare earth complex material and preparation method thereof - Google Patents
Antibacterial rare earth complex material and preparation method thereof Download PDFInfo
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- CN111205312B CN111205312B CN202010243356.3A CN202010243356A CN111205312B CN 111205312 B CN111205312 B CN 111205312B CN 202010243356 A CN202010243356 A CN 202010243356A CN 111205312 B CN111205312 B CN 111205312B
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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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
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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
- 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
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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
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
Abstract
The invention provides an antibacterial rare earth complex and a preparation method thereof, which are characterized in that the complex is LaXCeyAgZ(A) m (B) n, wherein x: y: z =1:0.01-0.05:0.01-0.05, A is stearate, B is sulfosalicylate, and m: n =2:1 or 1: 2. The invention provides an antibacterial rare earth complex and a preparation method thereof, and finds that stearic acid and sulfosalicylic acid are used as ligands according to a certain proportion, and a certain amount of Ce and Ag are added at the same time, so that the antibacterial property can be enhanced, and the thermal decomposition temperature can be increased at the same time.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an antibacterial rare earth complex material and a preparation method thereof.
Background
Rare earth is an effective bactericide, often used as a bioactive agent to improve the performance of drugs, but has an oxidative damage effect on organisms or cells by directly utilizing rare earth oxides or rare earth ions. In recent years, the field of public health safety of human beings faces increasingly serious challenges, a world-level food panic is caused by a European 'poisonous cucumber' event in 2011, the 'superbacteria' in 2010 has a global impact, the 'bird flu' in southeast Asia in 2004 is spread globally, the 'atypical pneumonia' in 2003 is spread globally, and the panic brought to human beings by European 'mad cow disease' and 'foot-and-mouth disease' cannot be resolved until now. Although the problems facing the field of human public health and safety are alleviated by a wide call for world health organizations and a continuous effort in the field of global medicine and health, the threat to human health and hygiene remains serious.
Research shows that the rare earth ions have special electron layer structure, so that the rare earth ions can inhibit the metabolic activity of fungi and have an antibacterial effect. China is a large country with rare earth resources, and rare earth is known as industrial gold, is an indispensable raw material for many high-precision industries, is the most abundant strategic resource in China, and is widely applied to the fields of materials, energy, medicine, aviation, electronics, agriculture and the like, so that the rare earth elements and the complexes thereof are widely applied to life science and become one of the hotspots of current research. Related researches show that compared with a plurality of organic synthetic drugs or transition metal complexes, the rare earth complex has lower toxicity, and meanwhile, the rare earth complex is not found to accumulate in vivo through oral administration or external application, so that the rare earth complex has wider application prospect.
However, the rare earth complex has the defect of poor stability, and the bioactivity of the rare earth complex is improved aiming at the problem that rare earth oxide or rare earth ions have oxidative damage on organisms or cells. Therefore, it is one of the research hotspots to further improve the antibacterial property and stability by doping other elements.
Disclosure of Invention
The invention provides an antibacterial rare earth complex and a preparation method thereof, and the prepared antibacterial rare earth complex has good antibacterial effect and improved stability.
The purpose of the invention is realized by the following technical scheme:
an antibacterial rare earth complex material is characterized in that the complex is LaXCeyAgZ(A) m (B) n, wherein x: y: z =1:0.01-0.05:0.01-0.05, A is stearate, B is sulfosalicylate, and m: n =2:1 or 1: 2.
Preferably, x: y: z =1:0.02: 0.02.
The invention also provides a preparation method of the antibacterial rare earth complex material, which is characterized by comprising the following steps:
(1) preparing lanthanum oxide, cerium oxide and silver oxide, placing the materials into a small beaker, and dropwise adding 1: 1HNO3Heating in water bath for dissolving, then continuing heating, steaming to be viscous, and adding absolute ethyl alcohol for dissolving;
(2) dissolving stearic acid in an ethanol solution, then adding sulfosalicylic acid, fully dissolving, and adding an alkali liquor to adjust the pH value to 6.5-7.0;
(3) and (3) slowly adding the solution obtained in the step (2) into the solution obtained in the step (1) at the temperature of 30-60 ℃, reacting for 2-10 hours under a stirring state, standing and aging for 5-24 hours, filtering, washing and drying.
Preferably, the lye comprises one of sodium hydroxide, potassium hydroxide or an aqueous ammonia solution.
Preferably, the concentration of the alkali liquor is 0.5-5 mol/L.
Sulfosalicylic acid and stearic acid are used as coordination groups of the La ternary complex, after the rare earth ions with the antibacterial effect are combined with the chelating effect organic ligand of the ligand and the rare earth metal ions to form the complex, the positive charge of the rare earth ions is transferred to the organic ligand, electrons on a chelate ring generate a delocalization effect, so that the polarity of the metal ions is reduced, the lipid solubility of the complex is enhanced, and the complex can better penetrate through a lipid layer of a biological cell membrane, thereby influencing the normal metabolism of cells. The sulfosalicylic acid has sulfo group, can be used as a bactericidal effect reinforcing agent of rare earth elements, has aromatic ring and has the characteristic of stabilizing electron delocalization effect. Meanwhile, stearic acid with a certain proportion is coordinated, the stearic acid has a longer carbon chain, and the thermal stability of the complex is enhanced by utilizing the space effect. Meanwhile, after the coordination of stearic acid, the complex can have better biocompatibility by utilizing the lipophilic property of the complex.
The rare earth elements have more various electronic energy levels and spectral lines than other elements, can absorb or emit in ultraviolet light, visible light and infrared light regions, and are very good substances with wide chromatograms. The La element is used as a coordination main body in the complex, and the Ce and Ag elements are used as auxiliaries, so that the photoelectron effect of the rare earth element can be further improved, the excitation energy barrier is reduced, and meanwhile, Ag atoms also have certain biological antibacterial property and good biocompatibility. Meanwhile, after a small amount of Ag element is added, Ag atoms can be used as another coordination center, and the polar group of sulfosalicylic acid of the coordination part plays a role in complexing the rare earth ternary complex, so that the stability is enhanced.
The invention has the beneficial technical effects that:
the invention provides an antibacterial rare earth complex and a preparation method thereof, and the prepared antibacterial rare earth complex has good antibacterial effect and improved stability by selecting a ligand and adding a small amount of other metal elements.
Detailed Description
The present invention is further described below with reference to examples, but the scope of the present invention is not limited by these examples. The scope of the invention is set forth in the claims.
Example 1
The preparation method of the antibacterial rare earth complex comprises the following steps:
(1) putting 1mmol of lanthanum oxide, 0.02mmol of cerium oxide and 0.02mmol of silver oxide into a small beaker, dropwise adding 1: 1HNO3, heating in a water bath for dissolving, then continuously heating, steaming to be viscous, adding absolute ethyl alcohol for dissolving, transferring into a 100mL volumetric flask, and fixing the volume.
(2) Dissolving 2mmol of stearic acid in an ethanol solution, then adding 1mmol of sulfosalicylic acid, fully dissolving, adding an alkali liquor, and adjusting the pH value to 6.5-7.0;
(3) slowly adding the solution obtained in the step (2) into the solution obtained in the step (1) at the temperature of 30-60 ℃, reacting for 2-10 hours under a stirring state, standing and aging for 5-24 hours, filtering, washing for a plurality of times by using 95% ethanol, washing for 3 times by using acetone to obtain a ternary complex, and drying in a vacuum drier.
Example 2
The preparation method of the antibacterial rare earth complex comprises the following steps:
(1) putting 1mmol of lanthanum oxide, 0.05mmol of cerium oxide and 0.05mmol of silver oxide into a small beaker, dropwise adding 1: 1HNO3, heating in a water bath for dissolving, then continuously heating, steaming to be viscous, adding absolute ethyl alcohol for dissolving, transferring into a 100mL volumetric flask, and fixing the volume.
(2) Dissolving 2mmol of stearic acid in an ethanol solution, then adding 1mmol of sulfosalicylic acid, fully dissolving, adding an alkali liquor, and adjusting the pH value to 6.5-7.0;
(3) slowly adding the solution obtained in the step (2) into the solution obtained in the step (1) at the temperature of 30-60 ℃, reacting for 2-10 hours under a stirring state, standing and aging for 5-24 hours, filtering, washing for a plurality of times by using 95% ethanol, washing for 3 times by using acetone to obtain a ternary complex, and drying in a vacuum drier.
Example 3
The preparation method of the antibacterial rare earth complex comprises the following steps:
(1) putting 1mmol of lanthanum oxide, 0.01mmol of cerium oxide and 0.01mmol of silver oxide into a small beaker, dropwise adding 1: 1HNO3, heating in a water bath for dissolving, then continuously heating, steaming to be viscous, adding absolute ethyl alcohol for dissolving, transferring into a 100mL volumetric flask, and fixing the volume.
(2) Dissolving 2mmol of stearic acid in an ethanol solution, then adding 1mmol of sulfosalicylic acid, fully dissolving, adding an alkali liquor, and adjusting the pH value to 6.5-7.0;
(3) slowly adding the solution obtained in the step (2) into the solution obtained in the step (1) at the temperature of 30-60 ℃, reacting for 2-10 hours under a stirring state, standing and aging for 5-24 hours, filtering, washing for a plurality of times by using 95% ethanol, washing for 3 times by using acetone to obtain a ternary complex, and drying in a vacuum drier.
Example 4
The preparation method of the antibacterial rare earth complex comprises the following steps:
(1) putting 1mmol of lanthanum oxide, 0.02mmol of cerium oxide and 0.02mmol of silver oxide into a small beaker, dropwise adding 1: 1HNO3, heating in a water bath for dissolving, then continuously heating, steaming to be viscous, adding absolute ethyl alcohol for dissolving, transferring into a 100mL volumetric flask, and fixing the volume.
(2) Dissolving 1mmol of stearic acid in an ethanol solution, then adding 2mmol of sulfosalicylic acid, fully dissolving, adding an alkali liquor, and adjusting the pH value to 6.5-7.0;
(3) slowly adding the solution obtained in the step (2) into the solution obtained in the step (1) at the temperature of 30-60 ℃, reacting for 2-10 hours under a stirring state, standing and aging for 5-24 hours, filtering, washing for a plurality of times by using 95% ethanol, washing for 3 times by using acetone to obtain a ternary complex, and drying in a vacuum drier.
Comparative example 1
Prepared in the same manner as in example 1, except that cerium oxide and silver oxide were not added.
Comparative example 2
Prepared in the same manner as in example 1, except that no cerium oxide was added.
Comparative example 3
Prepared in the same manner as in example 1, except that 0.1mmol of cerium oxide was added.
Comparative example 4
Prepared in the same manner as in example 1, except that silver oxide was not added.
Comparative example 5
Prepared in the same manner as in example 1, except that 0.1mmol of silver oxide was added.
Comparative example 6
Prepared in the same manner as in example 1 except that stearic acid was not added and sulfosalicylic acid was 3 mmol.
Comparative example 7
Prepared in the same manner as in example 1 except that sulfosalicylic acid was not added and stearic acid was 3 mmol.
And (3) testing and evaluating antibacterial performance:
a medium diffusion method:
the principle of the medium diffusion method is as follows: the antibacterial agent is continuously dissolved and diffused by agar to form different concentration gradients so as to show the antibacterial effect.
The method comprises the following operation steps: the rare earth complex prepared by the invention is dissolved by secondary distilled water or a small amount of DMF to prepare 0.005mol/L solution, and the bacteriostatic action on escherichia coli and staphylococcus aureus is respectively tested. Culturing at 37 deg.C for 18-24 hr by medium diffusion method, and measuring the diameter of the zone of inhibition with vernier caliper.
And (3) carrying out judgment regulation on the result of the bacteriostatic zone and evaluation on the antibacterial performance: the negative control group of the 3 repeated experiments should not generate a bacteriostatic zone, and the antibacterial agent sample pieces have bacteriostatic effects and are judged to be qualified; otherwise the experiment is not valid. And judging whether the antibacterial agent has antibacterial capacity or not according to the diameter of the antibacterial zone. According to the chemical industry standard of the people's republic of China: performance and evaluation of inorganic antibacterial agent, and judging that the antibacterial ring diameter is less than or equal to 7mm has no antibacterial effect; the diameter of the bacteriostatic zone is larger than 7mm, and the bacteriostatic action is weak; the bacteriostatic circle is 10-20mm, and has moderate bacteriostatic action; the diameter of the bacteriostatic circle is larger than 20mm, and the bacteriostatic action is strong.
Thermogravimetric analysis of the complex in an air atmosphere with a flow-1-1 speed of 50mL & min, with alpha-Al 2O3 as a reference, a temperature rise rate of 10 ℃ & min, TG-DTA (instrument model: TG/DTA-6300) measurement at 25 ℃ to 1000 ℃ and a thermal decomposition temperature thereof.
TABLE 1 antibacterial Properties of examples and comparative examples
| Diameter of bacteriostatic circle (mm) | Thermal decomposition temperature C | |
| Example 1 | 26 | 355 |
| Example 2 | 26 | 352 |
| Example 3 | 23 | 350 |
| Example 4 | 26 | 334 |
| Comparative example 1 | 15 | 320 |
| Comparative example 2 | 19 | 348 |
| Comparative example 3 | 24 | 352 |
| Comparative example 4 | 18 | 328 |
| Comparative example 5 | 25 | 350 |
| Comparative example 6 | 25 | 312 |
| Comparative example 7 | 12 | 356 |
By comparing the performances, it is found that stearic acid and sulfosalicylic acid are used as ligands according to a certain proportion, and a certain amount of Ce and Ag are added at the same time, so that the antibacterial property can be enhanced, the thermal decomposition temperature can be increased at the same time, and no more excellent effect can be realized by excessive addition, so that the optimal performance effect can be realized by the formula of example 1.
Those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.
Claims (5)
1. An antibacterial rare earth complex material is characterized in that the complex is LaXCeyAgZ(A) m (B) n, wherein x: y: z =1:0.01-0.05:0.01-0.05, A is stearate, B is sulfosalicylate, and m: n =2:1 or 1: 2.
2. The antimicrobial rare earth complex material of claim 1, wherein x: y: z =1:0.02: 0.02.
3. A method for preparing the antibacterial rare earth complex material according to claim 1, characterized by comprising the steps of:
(1) preparing lanthanum oxide, cerium oxide and silver oxide, placing the materials into a small beaker, and dropwise adding 1: 1HNO3Heating in water bath for dissolving, then continuing heating, steaming to be viscous, and adding absolute ethyl alcohol for dissolving;
(2) dissolving stearic acid in an ethanol solution, then adding sulfosalicylic acid, fully dissolving, and adding an alkali liquor to adjust the pH value to 6.5-7.0;
(3) and (3) slowly adding the solution obtained in the step (2) into the solution obtained in the step (1) at the temperature of 30-60 ℃, reacting for 2-10 hours under a stirring state, standing and aging for 5-24 hours, filtering, washing and drying.
4. The method for preparing the antibacterial rare earth complex material as claimed in claim 3, which is characterized in that: the alkali liquor is selected from one of sodium hydroxide, potassium hydroxide or ammonia water solution.
5. The method for preparing the antibacterial rare earth complex material as claimed in claim 4, which is characterized in that: the concentration of the alkali liquor is 0.5-5 mol/L.
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| US6426093B1 (en) * | 1998-02-09 | 2002-07-30 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Synergistic biocidal activity if ternary complexes of negatively-charged biocides (component A), transition metal ions (component B), and neutral chelators (component C) |
| WO2000027390A1 (en) * | 1998-11-09 | 2000-05-18 | Ira Jay Newman | Ionic silver complex |
| CN101041666A (en) * | 2006-12-29 | 2007-09-26 | 上海师范大学 | Antibiosis rare earth ternary complexes and preparation method and application thereof |
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| US8399028B2 (en) * | 2008-08-14 | 2013-03-19 | Exciton Technologies Inc. | Antimicrobial silver solutions |
| CN101723962A (en) * | 2008-10-31 | 2010-06-09 | 华东理工大学 | Simple pyridinedicarboxylic acid rare earth complex and preparation method thereof |
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| JP5603702B2 (en) * | 2010-08-02 | 2014-10-08 | 株式会社Ｊ−ケミカル | Antibacterial composition and use thereof |
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