TWI769639B - Multifunctional adsorption complex, manufacturing method an use thereof - Google Patents

Abstract

This invention relates to a multifunctional adsorption complex, a manufacturing method and a use thereof. The multifunctional adsorption complex comprises a tannin trivalent iron complex which is manufactured by reaction of a tannic acid material and an iron salt material. The multifunctional adsorption complex can adsorb multiple biological and chemical substances.

Description

Multifunctional adsorption complex and its preparation method and use

The present invention relates to a multifunctional adsorption complex and its preparation method and application, which can effectively adsorb and remove various biological substances and chemical substances.

At present, water resources are often polluted by a variety of substances. These pollutants include various chemical substances or biological substances, and these substances are harmful to living organisms. Properly dispose of to remove harmful substances. The current methods for removing harmful substances in water include reverse osmosis, aeration, disinfection, etc., but these methods are still relatively inconvenient in implementation. In recent years, adsorbent materials have also been developed to adsorb and remove harmful substances in water. For example, the Republic of China Patent Publication No. TW 202042884(A) provides an adsorbent material that can remove heavy metals, which is a microparticle containing aluminosilicate compounds. Compound and activated carbon particles, which have the effect of adsorbing lead ions and preventing aluminum from leaching out. The ROC Patent Publication No. TW 201934215(A) also provides an adsorbent for the treatment of polluted water. The adsorbent is made of particulate clay minerals, and the clay minerals can be set to allophane or filamentous aluminum. Stone, polluted water treatment body.

However, most of the existing adsorption materials are designed for a single characteristic substance. Therefore, if you want to remove different substances in the polluted water, you need to use a variety of adsorption materials, which is time-consuming.

Today, in view of the fact that the existing adsorbent materials still have room for improvement in practical use, the inventor has worked tirelessly to improve them with the help of their rich professional knowledge and years of practical experience. Research and create the present invention.

The invention relates to a multifunctional adsorption complex, which comprises a tannin trivalent iron complex, and the preparation method is obtained by the action of a tannic acid material and an iron salt material, and has the functions of adsorbing biological substances and chemical substances. the ability of sexual substances.

The present invention also relates to a preparation method of a multifunctional adsorption complex, which comprises mixing a material and an iron salt material uniformly, and reacting at an action temperature for an action time to obtain the multifunctional adsorption complex.

The present invention also relates to a method for removing biological or chemical substances, which is to act on a multifunctional adsorption complex with a solution to adsorb and remove the biological or chemical substances contained in the solution, wherein The multifunctional adsorption complex system comprises tannin trivalent iron complex

In one embodiment of the present invention, the iron salt material is ferric chloride.

In one embodiment of the present invention, the adsorbed biological substances include lipopolysaccharide (Lipopolysaccharide) and microbial toxins.

In one embodiment of the present invention, the chemical substances include antibiotics, pigments and plastic particles.

In one embodiment of the present invention, the antibiotics are Amikacin, Ceftriaxone, Colistin, Doxycycline, Tigecycline and Promethazine. Special (Trimethoprim) at least one of them.

In one embodiment of the present invention, the action temperature of the tannic acid material and the iron salt material is 23-28° C., and the action time is 1-10 minutes.

In one embodiment of the present invention, 0.002 M ferric chloride and 0.001 M tannic acid are uniformly mixed and acted to obtain the multifunctional adsorption complex.

Therefore, the preparation method of the multifunctional adsorption complex of the present invention is simple, and has the ability to adsorb various substances, including endotoxins, microbial toxins, antibiotics, pigments and plastic particles, etc., and has a wide range of applications.

In order to enable a more complete and clear disclosure of the effects that the technical means of the present invention can achieve, the detailed description is as follows, please refer to the disclosed drawings together.

The invention relates to a multifunctional adsorption complex and a manufacturing method thereof. The multifunctional adsorption complex comprises a tannin trivalent iron complex, and the preparation method is to mix the tannic acid material and the iron salt material uniformly, and place the It is obtained after one action temperature and one action time; in the preferred embodiment of this case, the iron salt material is ferric chloride, and the prepared tannin trivalent iron complex can adsorb various biological and chemical substances, Contains pigments, plastic particles, antibiotics, endotoxins and microbial toxins, etc.

In addition, the following specific examples can further prove the scope of practical application of the present invention, but are not intended to limit the scope of the present invention in any form.

1. Preparation of tannin trivalent iron complex

Prepare 0.002 M ferric chloride solution and 0.001 M tannic acid solution, respectively, and mix the two solutions in a volume ratio of 1:1 to obtain a mixed solution. Act for 1-10 minutes, then centrifuge the mixed solution at 2000 rpm for 5 minutes, first collect the supernatant to remove large particles; then centrifuge the supernatant at 13,000 rpm for 10 minutes, and collect the precipitate, and The volume of the precipitate was concentrated to 1 mL to obtain a tannin ferric complex concentrate; in this example, the ferric chloride and tannic acid solution were reacted at 25° C. for about 5 minutes.

The prepared tannin trivalent iron complex was analyzed by Fourier-transform infrared spectroscopy (FTIR), see the first figure (A), and tannic acid and tannin trivalent iron complex The spectra of the compounds are very similar. Since tannic acid is a water-soluble substance, if it does not interact with ferric chloride, it will be present in the supernatant and removed during preparation. However, the precipitate obtained after centrifugation in this case is analyzed. The results of the FTIR spectrum are very similar, so it can be confirmed that tannic acid does interact with ferric chloride and form a complex.

Please refer to the first figure (B) again, in order to measure the absorption spectrum of the tannin ferric complex using a spectrophotometer (UV-Vis spectra), it can be observed that it has a single absorption at the wavelength of 575 nm peak.

Then use Dynamic Light Scattering/Zeta Potential Analyzer to measure the particle size and Zeta potential of tannin trivalent iron complex, where the absolute value of Zeta potential represents the surface charge of the measured object The higher the absolute value of Zeta potential, the higher the amount of charge on the surface of the measurement object, the repulsive force between the charges will prevent the measurement object from gathering, and the structure of the measurement object is more stable; refer to the second figure (A), this implementation The particle size of the tannin trivalent iron complex prepared by example is 207 nm, which belongs to the size of nanomaterials; and according to the second figure (B), the Zeta potential of the tannin trivalent iron complex is about -32 mV , belongs to the material with high absolute value of Zate potential, indicating that its structure is stable.

Please refer to the third figure again, which is a transmission electron microscope (Transmission electron microscope) photograph of the tannin trivalent iron complex in this case, and it can be known that it presents a network structure.

2. Tannin ferric complex adsorption test

(1) Pigment adsorption test

First prepare a crystal violet solution and react it with different concentrations of tannin ferric complexes at room temperature for 15 minutes; centrifuge the crystal violet solution, remove the supernatant, and then use 1 X PBS Buffer (Phosphate-Buffered Saline) washes the precipitate for three times to wash off the unadsorbed crystal violet; finally, the precipitate is reacted with methanol for 5 minutes to elute the crystal violet from the precipitate and obtain a The eluate, and then measure the absorbance of the eluate at a wavelength of 595 nm (OD595 for short), the crystal violet absorption of the tannin ferric complex can be obtained. Please refer to the fourth figure (A), which is the OD595 of the eluate obtained after adsorption with different concentrations of tannin ferric complex. As the concentration of tannin ferric complex used increases, the final The OD595 of the eluate also increased, indicating that the adsorption amount of tannin ferric iron complex to crystal violet was dose-dependent; the fourth figure (B) is the observation photo of the eluate after adsorption , it can be seen that the higher the dosage of tannin ferric complex is used for adsorption, the darker the color of the eluate obtained at the end, indicating that the content of crystal violet in the eluate is higher.

(2), plastic particle adsorption test

In this test, commercially available tea bags were used for testing. First, the tea bags were put into pure water, heated and boiled for 10 minutes, and then the tea bags were removed. Because it has a high amount of plastic particles, it is called the plastic particle group; in addition, take the tannin trivalent iron complex prepared in this case, and evenly mix it with the boiling liquid of the tea bag at a volume ratio of 1:9 to obtain a mixed The mixed solution was treated at room temperature for 1 hour, and then the mixed solution was centrifuged. The supernatant after centrifugation was called sample 1, and the sediment part after centrifugation was called sample 2. The plastic particle group, sample 1 and sample 2 were vacuum filtered with filter paper respectively, and then the filter paper was stained with nylon red dye in the dark for 30 minutes, and finally filtered with a TRITC filter or FITC filter in a fluorescence microscope. microscopic observation to detect the fluorescence of plastic particles; please refer to the fifth figure, no matter using a TRITC filter or a FITC filter to observe, a considerable number of plastic particle light spots can be observed in the plastic particle group. In sample 1 obtained after the treatment of ferric iron complex, the number of light spots was significantly reduced, indicating that the amount of plastic particles contained in it was significantly reduced; in the second sample, a considerable amount of light spots could be observed, indicating that tannin ferric iron A large number of plastic particles were indeed adsorbed on the complex.

(3) Antibiotic adsorption test

First, the tannin trivalent iron complex (hereinafter referred to as Fe-TA) of this case was mixed with six kinds of antibiotic solutions in a volume ratio of 1:9 to obtain a mixed solution, and the mixed solution was kept at room temperature. Act for 1 hour; centrifuge the mixed solution after the action, collect the supernatant after centrifugation, mix it with 10 ⁵ CFU of Escherichia coli, and co-cultivate at 37 ° C for 24 hours, and finally add alamarBlue reagent to the bacterial solution. The color change of the reagent is used as an indicator of the growth of E. coli to evaluate the effect of the antibiotics acting on Fe-TA on the growth of E. coli. If the growth of E. coli is in good condition, the alamarBlue reagent will appear pink, and if the E. coli does not survive , the reagent will appear blue. The antibiotics used in this study were Amikacin, Ceftriaxone, Colistin, Doxycycline, Tigecycline and Trimethoprim ), and the ATCC number of E. coli used in the test is ATCC 25922. Please refer to Figure 6 and Figure 7, the control group in the figure is the antibiotic without the action of Fe-TA, while the Fe-TA group is the antibiotic solution after the action with Fe-TA; according to the sixth figure, Amica Star, ceftriaxone and colistin can effectively inhibit the growth of Escherichia coli at higher concentrations, so they appear blue; however, the group that was co-cultured with Escherichia coli after the action of antibiotics and Fe-TA , the growth of E. coli will be restored, so it will appear pink after reacting with the reagent; see also Figure 7, deoxytetracycline, tiger tetracycline, and promethazine also have the ability to inhibit the growth of E. coli, but After acting with Fe-TA, its ability to inhibit bacterial growth is obviously reduced; therefore, the tannin ferric complex prepared by the present invention does have the ability to adsorb antibiotics.

(4), Endotoxin adsorption test

In this example, the adsorption capacity of tannin trivalent iron complex (hereinafter referred to as Fe-TA) to endotoxin lipopolysaccharide (LPS) was tested, and the blood extract of horseshoe crab, which would produce agglutination reaction with LPS, was used (Limulus Amebocyte Lysate) for detection. The Fe-TA prepared by the present invention is mixed with LPS solutions of different concentrations, and after acting at room temperature for 1 hour, the supernatant is centrifuged and collected to obtain the LPS solution after treatment; then the untreated LPS solution ( The control group) and the LPS solution (Fe-TA group) treated with Fe-TA were reacted with the Limulus limulus blood extract respectively, and the agglutination of the Limulus limulus blood extract was observed. Please refer to Figure 8. In the control group, in the group added with 0.1 μg/mL LPS or 1 μg/mL LPS, the Limulus limulus blood extract had obvious agglutination. Thick material (the red circle in the figure); on the contrary, in the Fe-TA group, after the LPS treated with Fe-TA, after the action of the Limulus limulus blood extract, the coagulation situation is less obvious, and the fluidity in the test tube is less obvious. It can flow freely in the test tube (the red circle in the figure); this result shows that the tannin trivalent iron complex prepared by the present invention also has the effect of adsorbing LPS, and can reduce the agglutination reaction induced by LPS .

(5) Microbial toxin adsorption test

The purpose of this experiment is to test the adsorption capacity of tannin trivalent iron complex (hereinafter referred to as Fe-TA) for toxin B produced by Clostridium difficile VPI10463.

First, Clostridium difficile VPI10463 was cultured for 4 days to produce toxin B (Toxin B) and release toxin B in the culture medium; the bacterial cells were filtered and the culture medium was concentrated to Toxin B was concentrated 10 times; the concentrated toxin B was reacted with different amounts of Fe-TA for 1 hour at room temperature, then Fe-TA was removed by centrifugation, and the supernatant after the action was collected; Western blot analysis to obtain the content of toxin B, which has a molecular weight of 270 kDa. Please refer to the ninth figure, "NC" is the negative control group without toxin B, "PC" is the positive control group with toxin B, "Treated sup." is the supernatant collected after interacting with Fe-TA and centrifuging According to the ninth figure, the content of toxin B in the supernatant will decrease with the increase of the weight of Fe-TA acting on it, and when the weight of Fe-TA used is more than 0.175 mg, almost No toxin B can be detected, and this result shows that the tannin trivalent iron complex prepared by the present invention can also effectively adsorb toxin B.

To sum up, the multifunctional adsorption complex disclosed by the present invention comprises a tannin ferric complex, which has the ability to adsorb various biological substances and chemical substances, including adsorption of pigments, plastic particles, antibiotics, endotoxins and Microbial toxins, etc.; in addition, the multifunctional adsorption complex prepared by the present invention can also be easily removed from the acting solution after the adsorption is completed, which is quite convenient to use.

To sum up, the multifunctional adsorption complex of the present invention and its preparation method and use can indeed achieve the expected use effect through the above disclosed embodiments, and the present invention has not been disclosed before the application. Fully comply with the provisions and requirements of the Patent Law. It is indeed a virtue to file an application for an invention patent in accordance with the law.

However, the above-mentioned descriptions are only preferred embodiments of the present invention, and are not intended to limit the scope of protection of the present invention; those who are familiar with the art, rely on the characteristic scope of the present invention, do other things, etc. Effective changes or modifications should be regarded as not departing from the design scope of the present invention.

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The first figure: the FTIR and absorbance analysis diagram of the tannin trivalent iron complex of the present invention.

The second figure: the particle size and Zeta potential analysis diagram of the tannin trivalent iron complex of the present invention.

The third figure: the electron microscope observation photograph of the tannin trivalent iron complex of the present invention.

The fourth figure: the analysis diagram of the adsorption pigment of the tannin ferric complex compound of the present invention.

The fifth figure: the analysis diagram of the adsorption of plastic particles by the tannin trivalent iron complex of the present invention.

Figure 6: Analytical diagram (1) of the adsorption of antibiotics by the tannin trivalent iron complex of the present invention.

Figure 7: Analytical diagram (2) of the adsorption of antibiotics by the tannin trivalent iron complex of the present invention.

The eighth figure: the analysis diagram of the adsorption of endotoxin by the tannin ferric complex of the present invention.

The ninth figure: the analysis diagram of the adsorption of microbial toxins by the tannin trivalent iron complex of the present invention.

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Claims (10)

A method for removing biological or chemical substances with tannin ferric complex, which is to act on a tannin ferric complex with a solution to adsorb biological or chemical substances in the solution , and then remove the tannin ferric complex in the solution to remove biological substances or chemical substances in the solution, wherein the preparation method of the tannin ferric complex is a The tannic acid material is obtained by acting on an iron salt material, and the chemical substance includes antibiotics and plastic particles. The method of claim 1, wherein the iron salt material is ferric chloride. The method of claim 1, wherein the biological substance comprises lipopolysaccharide. The method according to claim 1, wherein in the preparation method of the tannin ferric complex, the concentration of the tannic acid material is 0.001M, and the concentration of the ferric chloride is 0.002M. The method of claim 1, wherein the antibiotic is Amikacin, Ceftriaxone, Colistin, Doxycycline, Tigecycline and Trimethoprim. The method according to claim 1, wherein the preparation method of the tannin trivalent iron complex is to mix the tannic acid material and the iron salt material uniformly, and act at 23-28° C. for 1-10 minutes to obtain a The tannin trivalent iron complex was obtained. The method of claim 6, wherein the tannic acid material and the iron salt material are reacted at 25°C for 5 minutes. The method of claim 1, wherein the biological substance comprises microbial toxins. The method of claim 8, wherein the microbial toxin is Toxin B produced by Clostridium difficile VpI10463. The method of claim 1, wherein the chemical substance further comprises crystal violet.

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