CN102132700A - Double-schiff-base functionalized mesoporous silica antibacterial material and preparation method thereof - Google Patents
Double-schiff-base functionalized mesoporous silica antibacterial material and preparation method thereof Download PDFInfo
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- CN102132700A CN102132700A CN2011100097573A CN201110009757A CN102132700A CN 102132700 A CN102132700 A CN 102132700A CN 2011100097573 A CN2011100097573 A CN 2011100097573A CN 201110009757 A CN201110009757 A CN 201110009757A CN 102132700 A CN102132700 A CN 102132700A
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Abstract
The invention discloses a double-schiff-base functionalized mesoporous silica antibacterial material and a preparation method thereof. The double-schiff-base functionalized mesoporous silica antibacterial material has the aperture of 2-7nm and the specific surface area of 230-395m<2>/g through the measurement of a nitrogen adsorption/desorption isothermal line. The preparation method comprises the following steps of: firstly preparing mesoporous silica containing an active chlorine-based group; and sufficiently dispersing the functionalized mesoporous silica in toluene, adding double-schiff-base organic molecules (FPMBA) obtained through the condensation of amine and aldehyde into the mixture under the backflow conditions, and obtaining the double-schiff base functionalized mesoporous silica antibacterial material through cooling, filtering, washing and drying. The double-schiff base functionalized mesoporous silica antibacterial material prepared by adopting the preparation method disclosed by the invention has the advantages of having a regular one-dimensional pore structure, larger specific surface area and larger aperture, and the in-pore self-assembly of the antibacterial material is realized. As silylated reagent and ethyl orthosilicate are utilized for synthesis through in-situ cocondensation in a sol/gel system, the quantity of chlorine bases on porous surfaces is controllable; and therefore the controllability of the solid capacity of organic schiff base is realized.
Description
Technical field
The present invention relates to a kind of not anti-biotic material of alkali of two west that contains, be specifically related to mesopore silicon oxide anti-biotic material of a kind of two western not alkali functionalization and preparation method thereof.
Background technology
Along with the fast development of industrial technology and the increase of population, various environmental contaminants and harmful germ, poisonous insecticide serious threat human health and have been destroyed existent environment of people, and many researchers begin actively to take measures to reduce effectively this harm.Exploitation has the material of antibacterial activity, is widely used in biomedical product, packaging material and can protects our ecotope as the filter of air cleaning, therefore the research of this class new material is more and more paid close attention to by people.
Up to now, the method for the most frequently used acquisition antibacterial activity material is that ion by matter that some are had microbe killing properties or molecule adopt the method for physically trapping to be fixed on to obtain anti-biotic material on the matrix material.But this method for preparing anti-biotic material needs the amount of antibiotic active molecular very high, therefore increased the cost of preparation material greatly, and in use because simple physics absorption connected mode, make antimicrobial molecule remove out from matrix material easily, thereby make anti-biotic material greatly reduce antibacterial activity, may be drained into simultaneously and cause new pollution in the environment.In order effectively to avoid the generation of above-mentioned situation, more and more researchers begins to improve this method, the surface of adopting chemical method securely antibiotic active molecular to be fixed on material by covalent bond forms integral body with both and has prepared novel stable anti-biotic material, shows the excellent antibiotic activity in antibacterial test.So, for the selection of the matrix material of anti-biotic material, common have high polymer, plastics, nano particle, a clothes fiber etc.But, be subjected to the interference of environment easily and destroy structure forfeiture antibacterial activity by adopting the general antimicrobial molecule of anti-biotic material that these materials obtain as matrix material outer surface at material.In order to avoid the generation of this problem as far as possible, employing is similar to the capsule structure inorganic material and is wrapped to form good protective layer around antimicrobial molecule, so porous material is a well selection as matrix material.
Mesopore silicon oxide is a kind of as porous material, because its preparation method is simple relatively, the pore passage structure feature of high-sequential has bigger space, duct, make organic molecule or other functional molecular freely to enter, so mesopore silicon oxide is the excellent carrier that obtains functional material; Be incorporated into the structural molecule that is expected to obtain having high antibacterial activity in the western not alkali structure and will have good antibacterial activity F element.The research that this compound mesoporous material is used for antibacterial activity yet there are no report.
Summary of the invention
Goal of the invention: at the deficiencies in the prior art, the purpose of this invention is to provide the not mesopore silicon oxide anti-biotic material of alkali functionalization of a kind of two west, it is become have the survival rate of inhibition height, the anti-biotic material of characteristics such as structural stability height.Another object of the present invention provides the preparation method of above-mentioned material.
Technical scheme: in order to realize the foregoing invention purpose, the technical solution used in the present invention is:
A kind of two west is the mesopore silicon oxide anti-biotic material of alkali functionalization not, and the aperture of measuring through nitrogen adsorption/desorption isotherm is 2-7nm, and specific surface area is 230-395 m
2/ g.
A kind of not method of the mesopore silicon oxide anti-biotic material of alkali functionalization of two west for preparing: at first surfactant, low amounts of water, small amount of hydrochloric acid are evenly mixed, add inorganic silicon source ethyl orthosilicate and organic-silylation reagent, stir under the water bath condition, obtain containing the mesopore silicon oxide of active chloro group then through overaging, cooling, filtration, washing, drying and surfactant extracting; Once more above-mentioned resulting functional mesoporous silica is well dispersed in the toluene, counterflow condition adds down through amine and resulting pair of west of aldehyde condensation not alkali organic molecule (FPMBA), through cooling, suction filtration, washing, drying, obtain the not mesopore silicon oxide anti-biotic material of alkali functionalization of two west then.Concrete operations comprise following each step:
(1) under the room temperature, non-ionic surface active agent P123 is dissolved in the aqueous solution of hydrochloric acid, stirs to clarify, get the stillness of night;
(2) water-bath is 40 ℃, adds inorganic silicon source ethyl orthosilicate in the clear liquid of step (1), after continuing to stir 1 ~ 3h, makes its partial hydrolysis, gets solution system;
(3) dropwise add organic-silylation reagent in step (2) solution system, 40 ℃ of water-baths are stirred 24h, with the abundant hydrolysis in inorganic silicon source and organosilicon source;
(4) the resulting solution of step (3) is transferred to has in the teflon-lined stainless steel autoclave, be placed in 100 ℃ of baking ovens, aging 24h, through cooling, filtration, washing, drying, remove the mesopore silicon oxide that surfactant obtains containing active chloro group through extracting more then;
(5) meso pore silicon oxide material that contains active chloro group that step (5) is obtained is dispersed in the toluene, and 110 ℃ of temperature controls fully mix it by adding hot reflux, gets mixed solution.
(6) FPMBA is joined in the mixed solution in the step (5), 110 ℃ of temperature controls, add hot reflux 24h after, through cooling, suction filtration, washing, drying obtains the not mesopore silicon oxide anti-biotic materials of alkali functionalization of two west; Wherein, FPMBA and organic-silylation reagent mol ratio are 1:0.2 ~ 20.
The general formula of described organic-silylation reagent is: ClC
nH
2n-Si (OC
mH
2m+1)
3, n is 1～4 in the formula, m is 1～4; The mol ratio of organic-silylation reagent and inorganic silicon source ethyl orthosilicate is 1:1 ~ 20.
In the step (4), it is hydrochloric acid, the acetum of ethanol that the reagent that surfactant adopted is removed in extracting.
In the step (6), preferred, FPMBA and organic-silylation reagent mol ratio are 1:1.
In the step (6), FPMBA prepares by the following method: under nitrogen protection, be that 1:1 is with 2 according to mol ratio; 3,5, the 6-tetrafluoro is put in the ethanolic solution with small amount of acetic acid benzene methanediamine and terephthalaldehyde; stir 24h under the room temperature, obtain through suction filtration, washing, drying.Ethanolic solution with small amount of acetic acid is to splash into 2-3 in the 25ml ethanol to drip acetate.
The described two west not structural formula of alkali organic molecule is:
Beneficial effect: two western not mesopore silicon oxides of alkali functionalization have regular one-dimensional tunnel structure in the hole of the present invention's preparation, and specific surface area is big, has bigger aperture, self assembly in the hole of realization anti-biotic material.Utilize silylating reagent and ethyl orthosilicate original position cocondensation to synthesize in the sol/gel system owing at first adopt, the chloro amount of hole surface is controlled, thereby has realized the not controllability of alkali supported quantity of organic west.The present invention is not only in antibiotic field, and at aspects such as nano fluorescent senser element, biomolecule carrier wide application prospect arranged.
Description of drawings
Fig. 1 is nitrogen adsorption/desorption isotherm and the graph of pore diameter distribution of the functional material FPMBA-10-SBA of embodiment 2.
Fig. 2 is nitrogen adsorption/desorption isotherm and the graph of pore diameter distribution of the functional material FPMBA-15-SBA of embodiment 3.
Fig. 3 is nitrogen adsorption/desorption isotherm and the graph of pore diameter distribution of the functional material FPMBA-20-SBA of embodiment 4.
Fig. 4 is nitrogen adsorption/desorption isotherm and the graph of pore diameter distribution of the functional material FPMBA-5-SBA of embodiment 5.
Embodiment
The present invention will be further explained below in conjunction with specific embodiment.
The antibacterial activity of sample is as the criterion with the killing rate of the bacterial classification of staphylococcus aureus and calculates.
Staphylococcus aureus is verified its antibiotic property: adopt colony counting method to obtain the bacterial classification killing rate, according to microorganism formed single bacterium colony on solid culture medium, promptly be to form this cultural characteristic and the technical method that relates to by a unicellular breeding, promptly bacterium colony represent one unicellular.
Nitrogen adsorption/desorption isotherm is measured, and for the mensuration employing BET method of specific surface area, pore-size distribution adopts the BJH model to calculate.
Operation that other do not elaborate or medicine are routine operation or the conventional medicine of selecting.
Embodiment 1
The preparation of FPMBA: under nitrogen protection, according to mol ratio be 1:1 with 2,3,5, the 6-tetrafluoro is put in the ethanolic solution with small amount of acetic acid benzene methanediamine and terephthalaldehyde, stirs 24h under the room temperature, obtains through suction filtration, washing, drying.Ethanolic solution with small amount of acetic acid is to splash into 2-3 in the 25ml ethanol to drip acetate.
The two west that make the not structural formula of alkali organic molecule are:
Embodiment 2
2g non-ionic surface active agent P123 is dissolved in 15g water and 60g concentration is in the hydrochloric acid solution of 2mol/L, under the room temperature, 2000r/min stirs 30min to clarification, it is positioned under 40 ℃ of water bath condition, add ethyl orthosilicate 3.83g, behind the prehydrolysis 2h, adding chloropropyl-triethoxysilicane alkanisation reagent 0.49g(itself and ethyl orthosilicate mol ratio is 1:9), be transferred to behind the stirring 24h under 40 ℃ and have in the teflon-lined stainless steel autoclave, put into 100 ℃ of baking ovens, aging 24h, through filtering, wash with water, natural seasoning in air, last in the hydrochloric acid solution of ethanol extracting 24h remove surfactant, at room temperature dry, obtain containing chloro ratio in total silicon and be 10% mesopore silicon oxide (SBA-Cl-10%).Get SBA-Cl-10% pressed powder 1g and be dispersed in the dry toluene of 50ml, stir into homogeneous phase solution under the nitrogen protection condition.Mol ratio according to chloropropyl-triethoxysilicane alkanisation reagent and organic functional molecular is under the 1:1 condition, add not alkali (by the embodiment preparation) of the two west of 1.03g, 110 ℃, 24h under the counterflow condition, wash three times with dry toluene, absolute ethyl alcohol, each 30ml of absolute ether after filtration and respectively, obtain the not mesopore silicon oxide FPMBA-10-SBA of alkali functionalization of two west under the room temperature after the drying.It is 4.2nm that gained functionalization material is measured the aperture through nitrogen adsorption/desorption isotherm, and specific surface area is 290m
2/ g, as shown in Figure 1.Through adopting staphylococcus aureus to verify its antibiotic property, antibacterial activity is 86.0%.
2g non-ionic surface active agent P123 is dissolved in 15g water and 60g concentration is in the hydrochloric acid solution of 2mol/L, 2000r/min stirs 30min to clarification under the room temperature, it is positioned under 40 ℃ of water bath condition, add ethyl orthosilicate 3.61g, behind the prehydrolysis 1h, adding chloropropyl-triethoxysilicane alkanisation reagent 0.74g(itself and ethyl orthosilicate mol ratio is 1:5.7), be transferred to behind the stirring 24h under 40 ℃ and have in the teflon-lined stainless steel autoclave, put into 100 ℃ of baking ovens, aging 24h, through filtering, wash with water, natural seasoning in air, extracting 24h removes surfactant in the hydrochloric acid solution of ethanol at last, at room temperature dry, obtain containing chloro ratio in total silicon and be 15% mesopore silicon oxide (SBA-Cl-15%).Get above-mentioned pressed powder 1g and be dispersed in the dry toluene of 50ml, the following 110 ℃ of stirring and refluxing of nitrogen protection condition become homogeneous phase solution.Mol ratio according to chloropropyl-triethoxysilicane alkanisation reagent and organic functional molecular is under the 1:1 condition, add not alkali of the two west of 1.54g, 24h under 110 ℃ of counterflow conditions, wash three times with dry toluene, absolute ethyl alcohol, each 30ml of absolute ether after filtration and respectively, obtain the not mesopore silicon oxide FPMBA-15-SBA of alkali functionalization of two west under the room temperature after the drying.It is 3.7nm that gained functionalization material is measured the aperture through nitrogen adsorption/desorption isotherm, and specific surface area is 257m
2/ g, as shown in Figure 2.Through adopting staphylococcus aureus to verify its antibiotic property, antibacterial activity is 92.5%.
2g non-ionic surface active agent P123 is dissolved in 15g water and 60g concentration is in the hydrochloric acid solution of 2mol/L, stir 30min under the room temperature to clarification, it is positioned under 40 ℃ of water bath condition, add ethyl orthosilicate 3.40g, behind the prehydrolysis 3h, adding chloropropyl-triethoxysilicane alkanisation reagent 0.98g(itself and ethyl orthosilicate mol ratio is 1:4), be transferred to behind the stirring 24h under 40 ℃ and have in the teflon-lined stainless steel autoclave, put into 100 ℃ of baking ovens, aging 24h, through filtering, washing, natural seasoning in air, extracting 24h removes surfactant in the hydrochloric acid solution of ethanol at last, at room temperature dry, obtain containing chloro ratio in total silicon and be 20% mesopore silicon oxide (SBA-Cl-20%).Get above-mentioned pressed powder 1g and be dispersed in the dry toluene of 50ml, stir into homogeneous phase solution under the nitrogen protection condition.Mol ratio according to chloropropyl-triethoxysilicane alkanisation reagent and organic functional molecular is under the 1:1 condition, add not alkali of the two west of 2.06g, 24h under 110 ℃ of counterflow conditions, wash three times with dry toluene, absolute ethyl alcohol, each 30ml of absolute ether after filtration and respectively, obtain the not mesopore silicon oxide FPMAB-20-SBA of alkali functionalization of two west under the room temperature after the drying.It is 2.1nm that gained functionalization material is measured the aperture through nitrogen adsorption/desorption isotherm, and specific surface area is 231m
2/ g, as shown in Figure 3.Through adopting staphylococcus aureus to verify its antibiotic property, antibacterial activity is 98.6%.
Embodiment 5
2g non-ionic surface active agent P123 is dissolved in 15g water and 60g concentration is in the hydrochloric acid solution of 2mol/L, stir 30min under the room temperature to clarification, it is positioned under 40 ℃ of water bath condition, add ethyl orthosilicate 4.04g, behind the prehydrolysis 2h, adding chloropropyl-triethoxysilicane alkanisation reagent 0.25g(itself and ethyl orthosilicate mol ratio is 1:19), be transferred to behind the stirring 24h under 40 ℃ and have in the teflon-lined stainless steel autoclave, put into 100 ℃ of baking ovens, aging 24h, through filtering, washing, natural seasoning in air, extracting 24h removes surfactant in the hydrochloric acid solution of ethanol at last, at room temperature dry, obtain containing chloro ratio in total silicon and be 5% mesopore silicon oxide (SBA-Cl-5%).Get above-mentioned pressed powder 1g and be dispersed in the dry toluene of 50ml, stir into homogeneous phase solution under the nitrogen protection condition.Mol ratio according to chloropropyl-triethoxysilicane alkanisation reagent and organic functional molecular is under the 1:1 condition, add not alkali of the two west of 0.51g, 24h under 110 ℃ of counterflow conditions, wash three times with dry toluene, absolute ethyl alcohol, each 30ml of absolute ether after filtration and respectively, obtain the not mesopore silicon oxide FPMBA-5-SBA of alkali functionalization of two west under the room temperature after the drying.It is 6.0nm that gained functionalization material is measured the aperture through nitrogen adsorption/desorption isotherm, and specific surface area is 390m
2/ g, as shown in Figure 4.Through adopting staphylococcus aureus to verify its antibiotic property, antibacterial activity is 17.3%.
Claims (6)
1. two west mesopore silicon oxide anti-biotic material of alkali functionalization not, it is characterized in that: the described two west not mesopore silicon oxide anti-biotic material of alkali functionalization are 2-7nm through the aperture that nitrogen adsorption/desorption isotherm is measured, and specific surface area is 230-395 m
2/ g.
2. one kind prepares the not method of the mesopore silicon oxide anti-biotic material of alkali functionalization of the described two west of claim 1, it is characterized in that, may further comprise the steps:
(1) under the room temperature non-ionic surface active agent P123 is dissolved in the aqueous solution of hydrochloric acid, stirs to clarify, get clear liquid;
(2) 40 ℃ of water-baths add inorganic silicon source ethyl orthosilicate in the clear liquid of step (1) gained, continue to stir 1 ~ 3h, make its partial hydrolysis, get solution system;
(3) dropwise add organic-silylation reagent in the solution system of step (2), water-bath keeps 40 ℃ of temperature down, stirs 24h, with the abundant hydrolysis in inorganic silicon source and organosilicon source, gets solution;
(4) the resulting solution of step (3) is transferred to has in the teflon-lined stainless steel autoclave, be placed in 100 ℃ of baking ovens, aging 24h, through cooling, filtration, washing, drying, remove the mesopore silicon oxide that surfactant obtains containing active chloro group through extracting more then;
(5) under the nitrogen protection, the meso pore silicon oxide material with active chloro group that step (4) is obtained is dispersed in the toluene, and 110 ℃ of temperature controls add hot reflux it is fully mixed, and gets mixed solution;
(6) with two west not the alkali organic molecule join in the mixed solution in the step (5), 110 ℃ of temperature controls, add hot reflux 24h after, through cooling, suction filtration, washing, drying obtains the not mesopore silicon oxide anti-biotic materials of alkali functionalization of two west; Wherein, not alkali organic molecule and organic-silylation reagent molar ratio range are 1:0.2 ~ 20 in two west;
The general formula of described organic-silylation reagent is: ClC
nH
2n-Si (OC
mH
2m+1)
3, n is 1～4 in the formula, m is 1～4; The mol ratio of organic-silylation reagent and inorganic silicon source ethyl orthosilicate is 1:1 ~ 20.
3. the two west of preparation according to claim 2 are the method for the mesopore silicon oxide anti-biotic material of alkali functionalization not, it is characterized in that: in the step (4), it is hydrochloric acid, the acetum of ethanol that the reagent that surfactant adopted is removed in extracting.
4. the two west of preparation according to claim 2 are the methods of the mesopore silicon oxide anti-biotic material of alkali functionalization not, it is characterized in that: in the step (6), the described pair of west not alkali organic molecule and organic-silylation reagent mol ratio is 1:1.
5. the two west of preparation according to claim 2 are the method for the mesopore silicon oxide anti-biotic material of alkali functionalization not, it is characterized in that: in the step (6), the described two west not structural formula of alkali organic molecule are:
6. the two west of preparation according to claim 2 are the methods of the mesopore silicon oxide anti-biotic material of alkali functionalization not, it is characterized in that: in the step (6), the described pair of west not alkali organic molecule is to make by the following method:
Under nitrogen protection, according to mol ratio be 1:1 with 2,3,5, the 6-tetrafluoro is put in the ethanolic solution with small amount of acetic acid benzene methanediamine and terephthalaldehyde, stirs 24h under the room temperature, through suction filtration, washing, dry getting final product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103156844A (en) * | 2011-12-15 | 2013-06-19 | 天津市国际生物医药联合研究院 | Application of Schiff base compound in inhibition of activity of NDM-1 |
| CN106866907A (en) * | 2017-03-07 | 2017-06-20 | 上海师范大学 | A kind of preparation method and application of Bis-Schiff Bases fluorescent polymer |
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| US6251280B1 (en) * | 1999-09-15 | 2001-06-26 | University Of Tennessee Research Corporation | Imprint-coating synthesis of selective functionalized ordered mesoporous sorbents for separation and sensors |
| JP2006131592A (en) * | 2004-11-09 | 2006-05-25 | Toyota Central Res & Dev Lab Inc | Organic compound-based porous composite material |
| CN101270188A (en) * | 2008-05-16 | 2008-09-24 | 太原理工大学 | Method for functionalization of periodic mesoporous organosilicon |
| CN101879459A (en) * | 2010-06-08 | 2010-11-10 | 上海师范大学 | Preparation method and application of Schiff base functionalized ordered mesoporous PMO material solid supported Cu(I) heterogeneous catalyst |
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2011
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Patent Citations (4)
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| US6251280B1 (en) * | 1999-09-15 | 2001-06-26 | University Of Tennessee Research Corporation | Imprint-coating synthesis of selective functionalized ordered mesoporous sorbents for separation and sensors |
| JP2006131592A (en) * | 2004-11-09 | 2006-05-25 | Toyota Central Res & Dev Lab Inc | Organic compound-based porous composite material |
| CN101270188A (en) * | 2008-05-16 | 2008-09-24 | 太原理工大学 | Method for functionalization of periodic mesoporous organosilicon |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103156844A (en) * | 2011-12-15 | 2013-06-19 | 天津市国际生物医药联合研究院 | Application of Schiff base compound in inhibition of activity of NDM-1 |
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| CN106866907A (en) * | 2017-03-07 | 2017-06-20 | 上海师范大学 | A kind of preparation method and application of Bis-Schiff Bases fluorescent polymer |
| CN106866907B (en) * | 2017-03-07 | 2018-12-04 | 上海师范大学 | A kind of preparation method and application of Bis-Schiff Bases fluorescent polymer |
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