CN108782606B - Rosin-based terpene-titanium dioxide hybrid nano material, preparation method and antibacterial application thereof - Google Patents
Rosin-based terpene-titanium dioxide hybrid nano material, preparation method and antibacterial application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a rosin-based terpene-titanium dioxide hybrid nano material, which takes rosin-based terpene or derivatives thereof and a titanium source as raw materials to carry out hydrothermal reaction. The raw material rosin-based terpene or the derivative thereof adopted by the invention is a product synthesized by taking rosin which is an important renewable resource in China as a raw material, and has the characteristics of easily available raw materials, environmental protection and the like; the hybrid nanomaterial prepared by the method of the invention contains rosin skeleton functional groups and has special material structure and appearance. Compared with the titanium dioxide hybrid nano material prepared by the traditional method, the titanium dioxide hybrid nano material provided by the invention has better antibacterial performance, is basically nontoxic, and has special application potential in the fields of food packaging and the like.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a rosin-based terpene-titanium dioxide hybrid nano material, a preparation method and an antibacterial application thereof.
Background
Nano TiO 22The product has the advantages of large specific surface area, strong dispersibility, strong ultraviolet absorption, heat conduction, magnetism and other excellent performances, and is widely used in the fields of industry, colloid, food, materials, environmental protection and the like. In recent years, TiO is obtained by various methods such as sol-gel, hydrothermal method, template method, coprecipitation method and the like2Functional materials with various shapes such as nano particles, nano hollow spheres and the like. Mixing nanometer TiO2The material can be hybridized with other substances such as quantum dots, other inorganic substances, organic substances and the like to obtain the material containing TiO2And other substances.
At present, the development of a hybrid nanomaterial with low toxicity and strong antibacterial activity is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and relates to a preparation method of a rosin-based terpene-titanium dioxide hybrid nano material. The preparation method provided by the invention has the advantages of easily obtained raw materials, simple operation, basically non-toxic product and excellent antibacterial application potential.
Specifically, the method provided by the invention is to carry out hydrothermal reaction by taking rosin-based terpene or derivatives thereof and a titanium source as raw materials.
The rosin-based terpene or the derivative thereof is a product synthesized by taking rosin which is an important renewable resource in China as a raw material, and has the characteristics of easily available raw materials, environmental protection and the like. The hybrid nanomaterial prepared by the method contains rosin skeleton functional groups, and has special material structure and appearance, and the obtained product is basically non-toxic and has excellent antibacterial application potential.
The rosin-based terpene or the derivative thereof can be selected from one or more of abietic acid (shown as a formula I) or abietic acid-based derivatives (shown as formulas II to VI):
wherein R is1～R6Each independently selected from substituted or unsubstituted alkyl, alkylamine or alkanol. The alkyl groups referred to in the above groups are all preferably C1～C10More preferably C1～C5Linear alkyl group of (1). In the above-mentioned alkyl, alkylamine or alkanol, one or more hydrogen atoms may further be each independently replaced by C1～C10Is preferably C1～C5Substituted with a linear alkyl group.
Preferably, said R is1May be an alkylamine; the alkyl group on the alkylamine is C1～C5The linear alkyl group of (1); 1, 2 or 3 hydrogen atoms of the amino group on the alkylamine are substituted with a methyl group.
Preferably, said R is2～R6May each be independently selected from unsubstituted alkyl or alkyl alcohols; the alkyl groups in the above groups are all preferably C1～C10More preferably C1～C5Linear alkyl group of (1).
As a particularly preferred embodiment of the present invention, the rosin-based terpene derivative is selected from one or more of the following compounds:
the titanium source is an inorganic titanium source and can be selected from titanium chloride, titanium sulfate, tetrabutyl titanate or titanium dioxide.
The invention further discovers that the shape of the hybrid nano material can be accurately regulated and controlled to be a nano tube or a micro-nano microsphere by regulating the dosage ratio of the raw materials and the pH value of the reaction system. Specifically, the method comprises the following steps:
according to the invention, the molar ratio of the titanium source to the rosin-based terpene or the derivative thereof is preferably 0.01-50: 1, and preferably 0.1-10: 1. The invention further discovers through a great deal of practice that when the molar ratio of the two is 0.1-1: 1 (preferably, the ratio of the two is not 1:1), the nano microspherical shape of the final product is favorably formed; when the molar ratio of the two is in the range of 1-10: 1 (preferably, the ratio of the two is not 1:1), the final product is favorably formed into a nanotube shape.
The pH value of the reaction system can be in the range of 2-14. According to the invention, a great deal of practice further discovers that when the pH value of the system is neutral, preferably 6.5-7.5, the nano microspherical nano-composite material is beneficial to the formation of a final product; when the pH value of the system is strong alkali, preferably 12-14, the final product is favorably formed into a nanotube shape. The pH value can be adjusted by using a common regulator, such as sodium hydroxide, urea or hydrochloric acid.
The solvent adopted in the reaction system of the invention is ethanol, deionized water or the mixed solution of the above solvents. In the specific operation, the ratio of the mass of the raw material (i.e. the total mass of the rosin-based terpene derivative and the titanium source) to the mass of the solvent can be controlled to be 1: 10-50, preferably 1: 1-15.
The hydrothermal reaction temperature is 110-180 ℃. The reaction time is preferably 1 to 72 hours, under the above temperature conditions, to ensure sufficient reaction.
As a preferred aspect of the present invention, the method comprises the steps of: adding rosin-based terpene or derivatives thereof and a titanium source into ethanol and/or deionized water according to the molar ratio of 0.1-1: 1; and adding a pH value regulator to regulate the pH value to 6.5-7.5, uniformly stirring, and carrying out hydrothermal reaction at 110-180 ℃.
As a preferred aspect of the present invention, the method comprises the steps of: adding rosin-based terpene or derivatives thereof and a titanium source into ethanol and/or deionized water according to the molar ratio of 1-10: 1; and adding a pH value regulator to regulate the pH value to 12-14, uniformly stirring, and carrying out hydrothermal reaction at 110-180 ℃.
The hydrothermal reaction according to the invention can be carried out in conventional reaction vessels, such as high-pressure reaction vessels or reaction vessels known to the person skilled in the art, without particular requirements of the invention.
The method of the invention also comprises the following steps: and cooling a product obtained by the hydrothermal reaction, washing and drying. The cooling, washing and drying steps may be performed by various methods well known to those skilled in the art. For example: the cooling can be natural cooling or forced cooling; the washing can be performed by using absolute ethyl alcohol; the drying may include, but is not limited to, drying directly in an oven, drying in an oven after suction filtration, infrared drying, and the like. The drying is preferably carried out at 75 to 95 ℃.
The invention also protects the rosin-based terpene-titanium dioxide hybrid nano material prepared by the method.
The nano material prepared by the method is a titanium dioxide hybrid nano material containing rosin functional groups. Through analysis of a scanning electron microscope, the nano material provided by the invention is a relatively uniform nano tube or nano microsphere structure with a hollow structure; through infrared and XRD analysis, the titanium dioxide hybrid nanomaterial contains rosin functional groups, and cytotoxicity tests show that the material is non-toxic to Coca2 cells.
The invention further protects the application of the rosin-based terpene-titanium dioxide hybrid nano material prepared by the method in the antibacterial aspect; preferably, the nanomaterial can be used to prepare food packaging materials.
Compared with the titanium dioxide hybrid nano material prepared by the traditional method, the titanium dioxide hybrid nano material provided by the invention has better antibacterial performance, is basically nontoxic, and has special application potential in the fields of food packaging and the like.
Drawings
FIG. 1 SEM photograph of the material obtained in example 1;
FIG. 2 is an IR spectrum of the material obtained in example 1;
FIG. 3 photo of cytotoxicity of example 1 material;
FIG. 4 photograph showing the bacteriostatic properties of the material obtained in example 1
FIG. 5 is a transmission electron micrograph of a material obtained in example 2;
FIG. 6 an IR spectrum of the material obtained in example 2;
FIG. 7 XRD pattern of the material obtained in example 2;
FIG. 8 is a transmission electron micrograph of a material obtained in example 3;
FIG. 9 an IR spectrum of the material obtained in example 3;
FIG. 10 SEM photograph of the material obtained in example 4;
FIG. 11 SEM photograph of the material obtained in comparative example 1;
FIG. 12 is an IR spectrum of the material obtained in comparative example 1;
FIG. 13 is a transmission electron micrograph of the material obtained in comparative example 2;
FIG. 14 is a transmission electron micrograph of the material obtained in comparative example 3.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
The following examples employ the following test methods:
the microstructure and morphology of the prepared sample were observed by a field emission scanning electron microscope (SEM, JSM-7001F, Japan).
The samples were subjected to structural analysis using a transmission electron microscope, model Hitachi (HIACHI) H-7500, at a voltage of 80000.0V.
An X-ray diffractometer (XRD) was used for the crystalline phase analysis of the sample. Diffraction spectra analysed at XRD (Bruker D8ADVANCE, germany) were recorded from 15 to 70; the rate was 0.05 °/s using CuKa (wavelength 0.154056nm, 40 milliamp, 40 kV).
The prepared sample is recorded in an infrared spectrum through Fourier transform infrared (Thermo Nicolet 380FTIR) spectrum, and the wave number range is 500-4000 cm-1。
The leaching solution (solvent is ethanol) of the prepared sample is subjected to a Coca2 cytotoxicity test by the MTS method.
The antibacterial performance test method comprises the following steps: uniformly pouring the sterilized agar culture medium into a sterilized culture dish with a diameter of 90mm, and adjusting the agar culture medium to 10 degrees after the agar is solidified8～109cfu/mL of bacterial liquid to be detected and a solid culture medium cooled to about 50-60 ℃ are mixed according to the volume ratio of 1: 10. And (3) pouring 20mL of the mixed solution onto the prepared agar surface uniformly, and punching after the culture medium is solidified. Adding a certain amount of evenly dispersed TiO2Hybrid nanomaterials. The plates were then transferred to a thermostat and incubated at 37 ℃ for 12h, and the zone of inhibition diameter was measured.
Example 1
The embodiment provides a preparation method of a rosin-based terpene-titanium dioxide hybrid nano material, which specifically comprises the following steps:
taking 10mL of 0.10mol/L titanium sulfate aqueous solution and 10mL of 0.3mol/L rosin derivative ethanol solution with the structural formula shown as (I), wherein the molar ratio of a system titanium source to the rosin derivative is 1: and 3, adjusting the pH value of the system to be 7, adding the system into a reaction kettle, putting the reaction kettle into an oven at the temperature of 130 ℃ for reaction for 12 hours, cooling to room temperature, washing with absolute ethyl alcohol, removing a supernatant through centrifugal separation, retaining a precipitate, and repeating the steps for three times. And finally, placing the obtained product in a constant-temperature oven at 85 ℃ until the product is completely dried to obtain a powder sample with uniform particle size of the rosin olefin functionalized titanium dioxide hybrid with the appearance as shown in the figure 1.
The infrared of the sample is shown in FIG. 2 at 2936 and 2853cm-1And 1650cm-1The vibration bands at the left and right are attributed to C-H stretching vibration in the rosin-based compound, 618cm-1The peak is the absorption peak of Ti-O bond, which indicates that the titanium dioxide hybrid material containing rosin terpene functional group is formed.
The titanium dioxide hybrid material sample containing rosin terpene functional groups prepared in this example was used to prepare a leaching solution with absolute ethanol. The leach liquor was subjected to the Coca2 cytotoxicity test using the MTS method, and the cell photograph is shown in fig. 3. As a result, it was found that: coca2 cells were cultured in the culture solution containing the above leaching solution (the concentration of the hybrid material in the culture solution is 250-1000. mu.g/mL), and when the concentration of the titanium dioxide hybrid material in the culture solution is 500. mu.g/mL, the survival rate of Coca2 cells reaches 98.5%, and the microscopic photograph is shown in FIG. 3, which shows that the titanium dioxide containing rosin terpene prepared in this example is low-toxic or substantially non-toxic to Coca2 cells.
The antibacterial zone of the material used for antibacterial performance research is shown in figure 4, and the antibacterial zone can reach 12.80mm, so that the material has good antibacterial performance.
Example 2
The embodiment provides a preparation method of a rosin-based terpene-titanium dioxide hybrid nano material, which specifically comprises the following steps:
0.005mol of TiO2Putting the particles and 10mL of 10mol/L NaOH aqueous solution into an autoclave, adding 2mL of 0.25mol/L ethanol solution of modified rosin derivatives with the structural formula shown as (III), wherein the molar ratio of a system titanium source to the rosin derivatives is 10:1, pH 14, at 160 ℃ for 6 h. Cooling to room temperature, washing with absolute ethanol, removing supernatant by centrifugation, retaining precipitate, and repeating the above three times. And finally, placing the obtained product in a constant-temperature oven at 85 ℃ until the product is completely dried to obtain a white powder sample of the rosin terpene-containing titanium dioxide nanotube, wherein the appearance of the white powder sample is as shown in the figure 5.
The infrared ray of the material obtained in this example is shown in FIG. 6, at 3000cm-1Left and right and 1650cm-1The vibration bands at the left and right are attributed to C-H stretching vibration in the rosin-based compound, 617cm-1Is absorbed by a Ti-O bondPeaks, indicating the formation of a titanium dioxide hybrid material containing rosin terpene functionality. The XRD spectrum of the material is shown in figure 7, and compared with the standard spectrum, the material is in an anatase crystal form. When the concentration of the titanium dioxide hybrid material is 1000 mug/mL, the survival rate of Coca2 cells reaches 99.2%, which shows that the rosin terpene-containing titanium dioxide prepared in the embodiment has low toxicity or basically no toxicity to Coca2 cells. The antibacterial zone of the material used for antibacterial performance research is shown in the specification, and the antibacterial zone can reach 10.40mm, so that the material has good antibacterial performance.
Example 3
The embodiment provides a preparation method of a rosin-based terpene-titanium dioxide hybrid nano material, which specifically comprises the following steps:
mixing 0.016mol of TiO2Putting the particles and 20mL of 10mol/L NaOH aqueous solution into an autoclave, adding 20mL of 0.5mol/L modified abietic acid ethanol solution with the structural formula shown as (VI-1), wherein the molar ratio of a system titanium source to the rosin derivative is 1.6: 1, pH 13.5, at 170 ℃ for 8 h. Cooling to room temperature, washing with absolute ethanol, removing supernatant by centrifugation, retaining precipitate, and repeating the above three times. And finally, placing the obtained product in a constant-temperature oven at 85 ℃ until the product is completely dried to obtain a white powder sample of the rosin terpene-containing titanium dioxide nanotube, wherein the appearance of the white powder sample is as shown in the figure 8.
The resulting infrared is shown in FIG. 9 at 3000cm-1And 1650cm-1The vibration bands at the left and right are attributed to C-H stretching vibration in the rosin-based compound, 618cm-1The peak is the absorption peak of Ti-O bond, which indicates that the titanium dioxide hybrid material containing rosin terpene functional group is formed.
Through detection, the diameter of the inhibition zone of the titanium dioxide hybrid material prepared by the embodiment can reach 13.2mm, and the titanium dioxide hybrid material has excellent inhibition performance.
Example 4
The embodiment provides a preparation method of a rosin-based terpene-titanium dioxide hybrid nano material, which specifically comprises the following steps:
adding 0.00125mol of TiO2The pellets and 20mL of a 10mol/L aqueous NaOH solution were placed in an autoclave, and 5mL of a 0.2mol/L ethanol solution of a modified rosin derivative of the formula (IV-1) was added thereto, and the reaction was carried out at 110 ℃ for 2 hours while keeping the system pH at 13.8. Cooling to room temperature, washing with absolute ethanol, removing supernatant by centrifugation, retaining precipitate, and repeating the above three times. And finally, placing the obtained product in a constant-temperature oven at 85 ℃ until the product is completely dried to obtain a white powder sample of the rosin terpene-containing titanium dioxide nanotube, wherein the appearance of the white powder sample is as shown in the figure 10.
Through detection, the diameter of the inhibition zone of the titanium dioxide hybrid material prepared by the embodiment is 9.0mm, and the titanium dioxide hybrid material has better antibacterial performance.
Comparative example 1
The comparative example provides a preparation method of a titanium dioxide nano material, which comprises the following specific steps:
taking 10mL of 0.10mol/L titanium sulfate aqueous solution, adjusting the pH value of the system to be 7, adding the titanium sulfate aqueous solution into a reaction kettle, putting the reaction kettle into an oven at 130 ℃ for reaction for 12 hours, cooling to room temperature, washing with absolute ethyl alcohol, removing a supernatant through centrifugal separation, retaining a precipitate, and repeating the steps for three times. Finally, the obtained product is placed in a constant-temperature oven at 85 ℃ until the product is completely dried, and a titanium dioxide powder sample with uneven particles and the appearance as shown in the figure 11 is obtained.
The infrared of this sample is shown in FIG. 12 and is only 618cm-1And a Ti-O bond absorption peak appears at the position, which indicates that the material is a titanium dioxide material but does not contain organic functional groups.
The material is used for antibacterial performance research, and the diameter of a bacteriostasis zone is 5.2 mm.
Comparative example 2
The comparative example provides a preparation method of a titanium dioxide nano material, which comprises the following specific steps:
adding 0.010mmol TiO2The pellets were reacted with 20mL of a 10mol/L aqueous NaOH solution in an autoclave at 170 ℃ for 8 hours. Cooling to room temperature, washing with anhydrous ethanol, centrifuging to remove supernatantThe precipitate was retained and this was repeated three times. Finally, the obtained product is placed in a constant-temperature oven at 85 ℃ until the product is completely dried, and a white powder sample of the mixture of the titanium dioxide nanotubes and the large particles with the appearance as shown in the figure 13 is obtained.
Through detection, the diameter of the inhibition zone of the titanium dioxide hybrid material prepared by the embodiment is 6.7mm, and the titanium dioxide hybrid material has certain inhibition performance.
Comparative example 3
The comparative example provides a preparation method of a titanium dioxide nano material, which comprises the following specific steps:
adding 0.012g/ml TiO2The pellets were reacted with 20mL of a 10mol/L aqueous NaOH solution in an autoclave at 110 ℃ for 2 hours. Cooling to room temperature, washing with absolute ethanol, removing supernatant by centrifugation, retaining precipitate, and repeating the above three times. And finally, placing the obtained product in a constant-temperature oven at 85 ℃ until the product is completely dried to obtain the titanium dioxide particles with the appearance as shown in the figure 14, wherein a few white powder samples with nanotube structures appear.
Through detection, the diameter of the inhibition zone of the titanium dioxide hybrid material prepared by the embodiment is 3.5 mm.
While the above examples illustrate specific embodiments of the invention, it should be understood that these examples are intended only to illustrate embodiments of the invention and are not intended to limit the scope of the invention in any way. The appended claims and any variations thereof are intended to be included within the scope of the invention as claimed.
Claims (9)
1. The preparation method of the rosin-based terpene-titanium dioxide hybrid nanomaterial is characterized by comprising the following steps of: adding rosin-based terpene or derivatives thereof and a titanium source into ethanol and/or deionized water according to the molar ratio of 0.1-1: 1; adding a pH value regulator to regulate the pH value to 6.5-7.5, uniformly stirring, and carrying out hydrothermal reaction at 110-180 ℃;
or adding the rosin-based terpene or the derivative thereof and a titanium source into ethanol and/or deionized water according to the molar ratio of 1-10: 1; adding a pH value regulator to regulate the pH value to 12-14, uniformly stirring, and carrying out hydrothermal reaction at 110-180 ℃;
the rosin-based terpene or derivative thereof is selected from one or more of the following compounds:
2. the method of claim 1, wherein the titanium source is an inorganic titanium source.
3. The method of claim 1, wherein the titanium source is titanium chloride, titanium sulfate, tetrabutyl titanate, or titanium dioxide.
4. The method according to any one of claims 1 to 3, wherein the mass ratio of the raw material to the solvent is 1:10 to 50.
5. The method according to claim 4, wherein the mass ratio of the raw material to the solvent is 1: 1-15.
6. The rosin-based terpene-titanium dioxide hybrid nanomaterial prepared by the method of any one of claims 1 to 5.
7. The rosin-based terpene-titanium dioxide hybrid nanomaterial of claim 6, wherein the hybrid nanomaterial is a hollow nanotube or nanosphere structure.
8. Use of the rosin-based terpene-titanium dioxide hybrid nanomaterial of claim 6 or 7 in the preparation of an antibacterial material.
9. Use of the rosin-based terpene-titanium dioxide hybrid nanomaterial of claim 6 or 7 in the preparation of food packaging materials.
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