CN101456875A - Hydrogen bond type rare-earth metal complexes and preparation method thereof - Google Patents
Hydrogen bond type rare-earth metal complexes and preparation method thereof Download PDFInfo
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- CN101456875A CN101456875A CNA2008102021011A CN200810202101A CN101456875A CN 101456875 A CN101456875 A CN 101456875A CN A2008102021011 A CNA2008102021011 A CN A2008102021011A CN 200810202101 A CN200810202101 A CN 200810202101A CN 101456875 A CN101456875 A CN 101456875A
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Abstract
The invention provides a hydrogen-bonded rare earth metal complex and a method for preparing the same. The structural general formula of the hydrogen-bonded rare earth metal complex is RExM'yM'z.nH2O. The invention synthesizes and prepares the rare earth metal organic complex by molecular structures. The rare earth metal and the organic ligand complex have cooperative antibacterial function, thus the synthesized rare earth metal organic complex has the advantages of high antibacterial efficiency, wide antimicrobial spectrum, long antibacterial aging, and so on, and has better antibacterial function on colon bacillus, Staphylococcus aureus, and so on, and can be applied to industries of chemical antimicrobial. Moreover, the synthetic method has mild technological conditions, simple equipment and convenient operation.
Description
Technical field
The present invention relates to class hydrogen bond type rare-earth metal complexes and preparation method thereof, be meant a kind of hydrogen bond type rare-earth metal complexes that contains the dinicotinic acid part and preparation method thereof especially.
Background technology
Rare earth element comprises scandium, yttrium and group of the lanthanides totally 16 elements, because their ionic charges are identical, radius is approaching, so character is closely similar.
Materials such as that rare earth salts and title complex thereof can be used as is luminous, magnetic, catalysis, air-sensitive sensing, superconduction, be widely used in the various fields of industrial production and scientific research, and the application of rare earth compound at aspects such as medicine, agricultural, biological chemistry and environmental purification is a brand-new field, especially aspect anti-biotic material, rare earth salts and organic coordination compound thereof receive much concern because of having characteristics such as the strong and has a broad antifungal spectrum of germ resistance.
Antiseptic-germicide generally can be divided into several classes such as inorganic, organic and natural antibacterial agent according to forming.Inorganic antiseptic generally is made up of metal cation component such as argentiferous, zinc, copper and inorganic carrier, in order to improve antibacterial effect, has advantages such as security, thermotolerance, persistence by slow releasing function.But silver ions chemistry character is active, and is easy to change under effects such as illumination, heat, and use silver can cause cost to increase as antiseptic-germicide, seriously restricted its application.The organic antibacterial agent sterilizing ability is strong, antibiotic rapid, effective, but have that security is relatively poor, chemical stability is bad, poor heat resistance, work-ing life are short, easily produce resistance and can cause secondary pollution problems.Natural antibacterial material is mainly the extract of natural phant, and thermotolerance is relatively poor, and range of application is narrower.
Rare earth ion has intensive and is penetrated into the plysiochemical character of biological intravital uniqueness, can disclose Na in the organism as probe
+, K
+, Ca
2+Function Deng metal ion.Utilize this biological nature, rare earth salts and rare earth organic complex thereof have advantages such as germ resistance is strong, has a broad antifungal spectrum, good heat resistance as antiseptic-germicide, therefore become the focus of domestic and international research.
Chinese invention patent CN101020820 and CN101020819 have introduced a kind of by two kinds of rare earth ions and two kinds of metal-rare-earth title complexs that organic ligand forms, be mainly used in the plastics film of agriculture field as light-converting agent, be not suitable as antiseptic-germicide and use.
Chinese invention patent CN1803804 has introduced a kind of by two trivalent rare earth ionses and two rare earth metal complexs that part forms, can be used as photoelectric functional material and be applied to each field, but a kind of part 3 wherein, 5-two (4-carboxyl benzoic ether) the easy oxidation of methyl benzoate is restricted in application.
It is the rare earth metal complex of main part with the beta-diketon or derivatives thereof that Chinese invention patent CN1730522, CN1730454, CN101037390 and CN1687079 have introduced a kind of, this title complex is mainly used in the photoluminescence field of functional materials, have advantages such as good light stability, thermotolerance height, difficult generation bloom phenomenon as photostabilizer, but in title complex, contain more hydroxide ion or hydroxyl, under the irradiation of light, be easy to go bad.
Chinese invention patent CN101220060 relates to the novel single-indenyl rareearth complexes of a class, and this title complex is obtained by substituted indenyl part and the reaction of rare earth alkyl compound.This class title complex is mainly used in the polymerization of catalyzed ethylene, vinylbenzene, norbornylene and alhpa olefin, and is relatively poor as antiseptic-germicide Use Limitation fruit.
Chinese invention patent CN101019555 has introduced a kind of ternary RE-amino acid-vitamin complex as plant growth conditioning agent.It is the rare earth compounding of part with the kilnitamin that Chinese invention patent CN1044029 discloses a kind of, mainly as disinfectant use in agriculture and plant-growth regulator, but be kilnitamin just because of part, so its sterilization effect is not fine.
Chinese invention patent CN101235047 and CN101235048 disclose by sunaptic acid and 1, and the 10-phenanthroline is the rare earth compounding of part and the application aspect antimycotic thereof.Naphthoic acid is a monocarboxylic acid, be not very desirable aspect design molecular structure and the self-assembly formation super molecular complex.
Chinese invention patent CN101156589 discloses binary or the ternary complex that a kind of rare earth element and oxine and other organic ligands are formed, and this kind Caspase inhibitors is mainly used in the agricultural as agricultural bactericide control plant fungus damage.The defective of its existence is that thermostability is not high, easily decomposes.
Chinese invention patent CN101041666 has related to a kind of rare earth ternary complexes of being made up of Schiff's base and phenanthroline or pyridine, is applied to the environmental purification field as antibacterial agent.The performance of product was subjected to Effect of Environmental bigger when this rare earth ternary complexes was used as antiseptic-germicide.
Summary of the invention
The purpose of this invention is to provide a kind of hydrogen bond type rare-earth metal complexes and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
The general structure of hydrogen bond type rare-earth metal complexes of the present invention is:
RE
xM’
yM”
z·nH
2O
In the formula:
RE is a rare earth ion, preferably scandium, yttrium or lanthanide rare;
M ' is a pyridine-2,3-dioctyl phthalate, pyridine-2,4-dioctyl phthalate, pyridine-2,5-dioctyl phthalate, pyridine-2,6-dioctyl phthalate, pyridine-3,4-dioctyl phthalate or pyridine-3,5-dioctyl phthalate;
M " be 2,6-diamino-pyridine, 1,10-phenanthroline or other organic ligand; M ' and M " constituted the part of organic coordination compound;
X is 1～3, and y is 1～3, and z is 1～6, and n is 1～15 integer.
Preferably, described hydrogen bond type rare-earth metal complexes is Y
2(pydc)
4(pydaH)
2NH
2O;
Wherein: pyda is 2, and 6-diamino-pyridine, pydc are pyridine 2, the dianion in the 6-dioctyl phthalate after two proton ionization, n=10.
In the described hydrogen bond type rare-earth metal complexes, the effect of rare earth ion RE provides the metal center ion in the rare earth compounding, part is by M ' and M " form, part M ' is the pyridine derivate that contains two carboxyls, part M " for having the heterocyclic organic compounds of nitrogenous lone-pair electron.In the forming process of above-mentioned rare earth compounding, carboxyl hydrogen atom among the part M ' is as protophobe, part M " in the nitrogen-atoms of nitrogen-containing heterocycle compound as proton acceptor; under the effect of solvent, formed the hydrogen bond super molecular compound, further formed hydrogen bond type supramolecule metal complexes with the metal center ion.
One of said hydrogen bond type rare-earth metal complexes preparation method of the present invention is:
(1) the rare-earth salts dissolving is prepared the rare earth ion solution A;
Described rare-earth salts is selected from muriate, oxalate or the nitrate of rare earth, preferred Yttrium trichloride, Yttrium trinitrate or lanthanum nitrate;
Solution A middle-weight rare earths ionic concn is 0.01～0.20molL
-1
(2) with part M ' and part M " be dissolved in respectively in the solvent, obtain solution B and C;
Described solvent is selected from more than one in water, methyl-sulphoxide, acetone, butanone, ether, tetrahydrofuran (THF), chloroform, methylene dichloride, methyl alcohol or the ethanol;
In the solution B, the concentration of part M ' is 0.02～0.20molL
-1, part M in the solution C " concentration be 0.02～0.40molL
-1
(3) solution B is mixed with solution C, be heated to 50～80 ℃, stir 10～30min, add solution A, 50～80 ℃ of stirring reaction 4～6h collect rare earth metal complex then from reaction product;
Solute in the solution B and the solute mol ratio in the solution C are 1:1～1:3, and solute in the solution A and the solute mol ratio in the solution B are 1:1～1:3.
The preparation method's of the said hydrogen bond type rare-earth metal complexes of the present invention two is:
(1) the rare-earth salts dissolving is prepared the rare earth ion solution A;
Described rare-earth salts is selected from muriate, oxalate or the nitrate of rare earth, preferred Yttrium trichloride, Yttrium trinitrate, yttrium oxalate, Lanthanum trichloride or lanthanum nitrate;
Solution A middle-weight rare earths ionic concn is 0.01～0.20molL
-1
(2) with part M ' and part M " in solvent, 50～80 ℃ of reaction 12～24h, synthetic compound M '
aM "
b, then with compound M '
aM "
bHeating for dissolving obtains solution D in solvent;
Described solvent is selected from more than one in water, methyl-sulphoxide, acetone, butanone, ether, tetrahydrofuran (THF), chloroform, methylene dichloride, methyl alcohol or the ethanol;
Part M ' and part M " mol ratio be 1:1～1:3, in the solution D, M '
aM "
bConcentration be 0.02～0.20molL
-1
(3) solution A is mixed with solution D, be heated to 50～80 ℃ of stirring reaction 4～6h, from reaction product, collect rare earth metal complex then;
The solute in the solution A and the mol ratio of the solute in the solution D are 1:1～1:3.
The present invention can be applicable in the chemical antiseptic-germicide industry by the synthetic preparation of specific molecule structure design hydrogen bond type rare-earth metal complexes.Because rare earth metal and organic ligand compound have collaborative anti-microbial effect, thereby have important use value and wide application prospect at biochemical field.Can be applicable to aspects such as wrapping material, building coating, sports goods, furniture material, rubber plastic, tackiness agent, toy, biological medicine, agricultural, belong to the rare earth material chemical field.The synthetic method craft mild condition, required equipment is simple, and is easy to operate.The hydrogen bond type rare-earth metal complexes that is synthesized has advantages such as antimicrobial efficiency height, has a broad antifungal spectrum, antibiotic timeliness length, and intestinal bacteria, streptococcus aureus etc. are had anti-microbial effect preferably, can be widely used in the various anti-biotic materials.
Embodiment
Embodiment 1
Take by weighing Yttrium trichloride 0.1175g and be dissolved in and make solution (A1) in the 10mL water, with 0.3010g pyridine-2,6-dioctyl phthalate (pydcH
2) be dissolved in 80 ℃ the 30mL water and make solution (B1), with 2,6-diamino-pyridine (pyda) 0.1965g is dissolved in and makes solution (C1) in the 10mL water.
Solution (B1) is mixed with solution (C1), and behind 80 ℃ of stirring 30min, (A1) drops to wherein with solution, behind above-mentioned mixed solution stirring 4h, leaves standstill 24h under the room temperature.Filter, washing, 60 ℃ of vacuum-dryings obtain hydrogen bond type rare-earth metal complexes Y (pydc)
3(pydaH)
35H
2O.With other rare earth ion RE
3+Substitute Y
3+, can prepare and meet above-mentioned general formula R E
xM '
yM "
zNH
2The hydrogen bond type rare-earth metal complexes of O.
Embodiment 2
(1) part (pydc)
2-(pydaH
2)
2+Synthetic
With 2,6-diamino-pyridine (pyda) (2.0mmol) and the tetrahydrofuran (THF) (THF) of triethylamine (4.0mmol) (50mL) solution dropwise join pyridine-2,6-dioctyl phthalate (pydcH
2) (2.0mmol) tetrahydrofuran (THF) (THF) is (50mL) in the solution, stirs 15min.Heating reflux reaction 8h then.At room temperature stir 12h after the reaction mixture cooling, obtain yellow turbid liquid, leave standstill, filter, washing obtains yellow solid powder (pydc) after the drying
2-(pydaH
2)
2+
(2) preparation of rare earth compounding
Take by weighing Yttrium trinitrate 0.1655g and be dissolved in and make solution (A2) in the 10mL water, take by weighing above-mentioned part (pydc)
2-(pydaH
2)
2+0.4980g in 30mL water, be mixed with solution (D2) 60 ℃ of stirring and dissolving.Then solution A 2 is dropped in the solution D 2,60 ℃ of stirring reaction 4h leave standstill 24h under the room temperature.Filter, washing, 60 ℃ of vacuum-dryings obtain hydrogen bond type rare-earth metal complexes Y (pydc)
3(pydaH)
35H
2O.With other rare earth ion RE
3+Substitute Y
3+, can prepare and meet above-mentioned general formula R E
xM '
yM "
zNH
2The hydrogen bond type rare-earth metal complexes of O.
Embodiment 3
Take by weighing Yttrium trinitrate 0.1655g and be dissolved in and make solution (A3) in the 10mL water, take by weighing the part (pydc) among the embodiment 2
2-(pydaH
2)
2+0.3324g in 30mL water, be mixed with solution (D3) 60 ℃ of stirring and dissolving.Then solution A 3 is dropped in the solution D 3,60 ℃ of stirring reaction 4h leave standstill 24h under the room temperature.Filter, washing, 60 ℃ of vacuum-dryings obtain hydrogen bond type rare-earth metal complexes Y
2(pydc)
4(pydaH)
210H
2O.With other rare earth ion RE
3+Substitute Y
3+, can prepare and meet above-mentioned general formula R E
xM '
yM "
zNH
2The hydrogen bond type rare-earth metal complexes of O.
Embodiment 4
Various hydrogen bond type rare-earth metal complexes prepared in embodiment 1 and 3 are done minimal inhibitory concentration (MIC) test respectively, data are as follows: title complex to colibacillary MIC between 50～100mg/L, to the MIC (the more little expression antibacterial effect of MIC is good more) between 100～200mg/L of streptococcus aureus.The result shows that the MIC of gained title complex is far smaller than the regulation of the antiseptic-germicide MIC＜800mg/L of chemical industry standard code, and antibacterial effect is obvious.
The main range of application of the said goods is packaging material, building coating, sports goods, wood for furniture The aspects such as material, rubber plastic, adhesive, toy, biological medicine, agricultural, have the antimicrobial efficiency height, The advantages such as has a broad antifungal spectrum, antibiotic timeliness length have better Escherichia coli, staphylococcus aureus etc. Antibacterial action.
Claims (7)
1, hydrogen bond type rare-earth metal complexes is characterized in that, general structure is:
RE
xM’
yM”
z·nH
2O
In the formula:
RE is a rare earth ion;
M ' is a pyridine-2,3-dioctyl phthalate, pyridine-2,4-dioctyl phthalate, pyridine-2,5-dioctyl phthalate, pyridine-2,6-dioctyl phthalate, pyridine-3,4-dioctyl phthalate or pyridine-3,5-dioctyl phthalate;
M " be 2,6-diamino-pyridine, 1,10-phenanthroline or other organic ligand;
X is 1～3, and y is 1～3, and z is 1～3, and n is 1～15 integer.
2. hydrogen bond type rare-earth metal complexes according to claim 1 is characterized in that, is scandium, yttrium or lanthanide rare.
3. hydrogen bond type rare-earth metal complexes according to claim 1 is characterized in that, described hydrogen bond type rare-earth metal complexes is Y
2(pydc)
4(pydaH)
2NH
2O;
Wherein: pyda is 2, and 6-diamino-pyridine, pydc are pyridine 2, the dianion in the 6-dioctyl phthalate after two proton ionization, n=10.
4. prepare the method for each described hydrogen bond type rare-earth metal complexes of claim 1～3, it is characterized in that, comprise the steps:
(1) the rare-earth salts dissolving is prepared the rare earth ion solution A;
(2) with part M ' and part M " be dissolved in respectively in the solvent, obtain solution B and C;
(3) solution B is mixed with solution C, be heated to 50～80 ℃, stir 10～30min, add solution A, 50～80 ℃ of reaction precipitation 4～6h collect rare earth metal complex then from reaction product.
5. method according to claim 4 is characterized in that, described rare-earth salts is Yttrium trichloride, Yttrium trinitrate, yttrium oxalate, Lanthanum trichloride or lanthanum nitrate; Solution A middle-weight rare earths ionic concn is 0.01～0.20molL
-1, in the solution B, the concentration of part M ' is 0.02～0.20molL
-1, part M in the solution C " concentration be 0.02～0.40molL
-1The solute in the solution B and the mol ratio of the solute in the solution C are 1:1～1:3, and the solute in the solution A and the mol ratio of the solute in the solution B are 1:1～1:3.
6. prepare the method for each described hydrogen bond type rare-earth metal complexes of claim 1～3, it is characterized in that, comprise the steps:
(1) the rare-earth salts dissolving is prepared the rare earth ion solution A;
Described rare-earth salts is selected from muriate, oxalate or the nitrate of rare earth;
(2) with part M ' and part M " in solvent, 50～80 ℃ of reaction 12～24h, synthetic compound M '
aM "
b, then with compound M '
aM "
bHeating for dissolving obtains solution D in solvent;
(3) solution A is mixed with solution D, be heated to 50～80 ℃, precipitin reaction 4～6h collects rare earth metal complex then from reaction product.
7. method according to claim 6 is characterized in that, described rare-earth salts is Yttrium trichloride, Yttrium trinitrate, yttrium oxalate, Lanthanum trichloride or lanthanum nitrate; Solution A middle-weight rare earths ionic concn is 0.01～0.20molL
-1Part M ' and part M " mol ratio be 1:1～1:3, in the solution D, M '
aM "
bConcentration be 0.02～0.20molL
-1The solute in the solution A and the mol ratio of the solute in the solution D are 1:1～1:3.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891679A (en) * | 2009-05-19 | 2010-11-24 | 上海华明高技术（集团）有限公司 | Preparation method of pyridinedicarboxylic acid and diaminopyridine proton transfer compound |
| CN102060866A (en) * | 2010-12-10 | 2011-05-18 | 上海师范大学 | Rare earth ternary complex as well as preparation method and application thereof |
| CN103694266A (en) * | 2014-01-02 | 2014-04-02 | 华东理工大学 | Hydrogen-bonded rare-earth metal europium complex fluorescent material and preparation method thereof |
| CN107129728A (en) * | 2017-05-19 | 2017-09-05 | 浙江伟星新型建材股份有限公司 | A kind of antibiotic fungus-resisting paint and preparation method thereof |
| CN111747974A (en) * | 2020-07-02 | 2020-10-09 | 湖南工学院 | Binuclear cage-shaped yttrium complex and preparation method and application thereof |
| CN114736222A (en) * | 2022-03-30 | 2022-07-12 | 厦门稀土材料研究所 | Rare earth-based complex antibacterial agent and preparation method thereof |
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2008
- 2008-10-31 CN CNA2008102021011A patent/CN101456875A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891679A (en) * | 2009-05-19 | 2010-11-24 | 上海华明高技术（集团）有限公司 | Preparation method of pyridinedicarboxylic acid and diaminopyridine proton transfer compound |
| CN101891679B (en) * | 2009-05-19 | 2014-04-16 | 上海华明高技术（集团）有限公司 | Preparation method of pyridinedicarboxylic acid and diaminopyridine proton transfer compound |
| CN102060866A (en) * | 2010-12-10 | 2011-05-18 | 上海师范大学 | Rare earth ternary complex as well as preparation method and application thereof |
| CN102060866B (en) * | 2010-12-10 | 2013-01-16 | 上海师范大学 | Rare earth ternary complex as well as preparation method and application thereof |
| CN103694266A (en) * | 2014-01-02 | 2014-04-02 | 华东理工大学 | Hydrogen-bonded rare-earth metal europium complex fluorescent material and preparation method thereof |
| CN107129728A (en) * | 2017-05-19 | 2017-09-05 | 浙江伟星新型建材股份有限公司 | A kind of antibiotic fungus-resisting paint and preparation method thereof |
| CN111747974A (en) * | 2020-07-02 | 2020-10-09 | 湖南工学院 | Binuclear cage-shaped yttrium complex and preparation method and application thereof |
| CN111747974B (en) * | 2020-07-02 | 2023-05-05 | 湖南工学院 | Binuclear caged yttrium complex and preparation method and application thereof |
| CN114736222A (en) * | 2022-03-30 | 2022-07-12 | 厦门稀土材料研究所 | Rare earth-based complex antibacterial agent and preparation method thereof |
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