CN116332356A - Chlorophyll-based method for degrading PPCPs in water body - Google Patents
Chlorophyll-based method for degrading PPCPs in water body Download PDFInfo
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- CN116332356A CN116332356A CN202111601159.5A CN202111601159A CN116332356A CN 116332356 A CN116332356 A CN 116332356A CN 202111601159 A CN202111601159 A CN 202111601159A CN 116332356 A CN116332356 A CN 116332356A
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- DGNIJJSSARBJSH-NLJAFYFLSA-L magnesium (E)-3-[(3R)-16-ethenyl-11-ethyl-3-methoxycarbonyl-12,17,21,26-tetramethyl-4-oxo-7,24-diaza-23,25-diazanidahexacyclo[18.2.1.15,8.110,13.115,18.02,6]hexacosa-1(22),2(6),5(26),7,9,11,13,15(24),16,18,20-undecaen-22-yl]prop-2-enoic acid Chemical compound [Mg++].CCc1c(C)c2cc3nc(cc4[n-]c(c(\C=C\C(O)=O)c4C)c4[C@@H](C(=O)OC)C(=O)c5c(C)c(cc1[n-]2)nc45)c(C)c3C=C DGNIJJSSARBJSH-NLJAFYFLSA-L 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
- C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N5/00—Undifferentiated human, animal or plant cells, e.g. cell lines; Tissues; Cultivation or maintenance thereof; Culture media therefor
- C12N5/04—Plant cells or tissues
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N2509/00—Methods for the dissociation of cells, e.g. specific use of enzymes
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Abstract
The application provides a method for degrading PPCPs based on chlorophyll. Chlorophyll widely existing in natural water is used as a photosensitizer, PPCPs such as cimetidine can be obviously degraded, and the degradation rate of the PPCPs to the cimetidine after 24 hours can reach more than 80%. The method does not need to use a special light source or a special catalyst for catalytic degradation, and the treatment method is simple and easy to realize; no chemical reagent is needed to be added, no secondary pollution is generated, and the method is environment-friendly and low in cost.
Description
Technical Field
The application belongs to the field of water treatment, and particularly relates to a method for degrading PPCPs in a water body based on chlorophyll.
Background
The pharmaceutical and personal care products (Pharmaceuticals and Personal Care Products, PPCPs) include a range of chemicals including various drugs (e.g., antibiotics, antineoplastic agents, anxiolytic, hormonal, retarder and sympathoid, anti-inflammatory, slimming, analgesic, antihypertensive, contraceptive, antidepressant, etc.) and personal care products (e.g., soaps, shampoos, toothpastes, perfumes, skin care products, hair sprays, hair dyes, hair conditioners, etc.), which are closely related to human life. With the improvement of living and medical standards of people, PPCPs are widely used. Most of the medicines applied to human or animal bodies cannot be completely absorbed by the bodies, and are discharged out of the bodies along with excrement, urine and the like in the form of bodies or metabolites and enter the environment. In addition, most personal care products are also directed into the environment during use. A large number of PPCPs continuously enter the environment, so that a false persistence phenomenon is caused, and potential risks are brought to human health and ecological environment safety.
The traditional PPCPs treatment process comprises the following steps: physical adsorption, advanced oxidation, ozone oxidation, photocatalysis, activated sludge, and the like. Although the physical adsorption method is efficient and simple, PPCPs cannot be removed fundamentally; the advanced oxidation method has the advantage of high reaction speed, but the Fenton oxidation technology is not easy to generate hydroxyl free radicals under neutral conditions, and products or byproducts generated by the ozone oxidation method have toxicity; photocatalytic methods, such as ultraviolet radiation, require excitation of the catalyst under ultraviolet light to generate photoelectrons and holes to effect oxidation or reduction of the contaminants.
In the traditional PPCPs treatment method, physical or chemical reagents are required to be added into a sample to be treated, and secondary pollution is at risk.
The cimetidine is mainly used for inhibiting gastric acid secretion and reducing acidity, and is a medicine for relieving or curing digestive tract ulcer diseases to a certain extent. The way of entering the environment comprises the discharge of metabolites, medical wastewater, pharmaceutical wastewater and the like. In water environments, the detection concentration of cimetidine is very wide ranging from 32ng/L (river water) to 17651ng/L (sewage treatment plant water intake).
Disclosure of Invention
In one aspect, the present application provides the use of chlorophyll or chlorophyll-containing cells for degrading cimetidine or ranitidine.
In one aspect, the present application provides a method of degrading cimetidine or ranitidine comprising the steps of:
s1, adding chlorophyll or cells containing chlorophyll into a sample to obtain a mixture, wherein the concentration of the chlorophyll in the mixture is 0.25-1mg/L;
s2, placing the mixture prepared in the step S2 under a white fluorescent lamp for reaction for 12-48h.
In some embodiments, the step S1 further comprises a step of adjusting pH to 5-11 in the sample; in some embodiments, the pH in the sample is adjusted to 7.
In some embodiments, the white fluorescent lamp in step S2 has an illumination intensity of 5000-50000lux; in some embodiments, the illumination intensity is from 5000 to 45000lux; in some embodiments, the illumination intensity is 8000-35000lux; in some embodiments, the illumination intensity is 8000-30000lux.
In some embodiments, the chlorophyll or chlorophyll-containing cells are, or are derived from, green algae or vegetables; in some embodiments, the green algae is selected from the group consisting of: at least one of Sphaerotheca nodosa, chlorella, scenedesmus; in some embodiments, the green alga is selected from the group consisting of a gracilis parapsilosis; in some embodiments, the vegetable is selected from spinach; in some embodiments, the chlorophyll is selected from: at least one of chlorophyll a, chlorophyll b, chlorophyll c, chlorophyll d, chlorophyll f; in some embodiments, the chlorophyll is chlorophyll a; in some embodiments, the chlorophyll is synthetic chlorophyll.
In some embodiments, the sample is selected from a water sample; in some embodiments, the water body sample is selected from at least one of seawater, sewage, wastewater.
In one aspect, the present application provides a method of preparing the chlorophyll or chlorophyll-containing cells, comprising the steps of:
1) Inoculating green algae into the culture medium, and culturing for 8-10 days under aeration;
2) Centrifuging the green algae suspension prepared in the step 1) at 5000-9000rpm for 8-15min, removing supernatant, and retaining green algae cells;
3) To the green algae cells obtained in step 2) according to 1: (10-30) (v/v) adding 90% ethanol, and centrifuging at room temperature for 20-30 hr in dark place to obtain supernatant, wherein the supernatant is chlorophyll solution.
In some embodiments, 90% ethanol is added to the green algae cells produced in step 2) in a ratio of 1:20 (v/v) in step 3). In some embodiments, centrifugation is performed at 5000-9000rpm in step 3); in some embodiments, centrifugation is performed for 8-15min.
In one aspect, the application also provides application of chlorophyll or chlorophyll-containing cells prepared by the preparation method in degrading cimetidine or ranitidine.
Drawings
FIG. 1 shows the degradation rate of cimetidine at different pH conditions (chlorophyll concentration of 0.5mg/L, light intensity of 30000 lux) in example 2;
fig. 2 is the effect of different chlorophyll concentrations on cimetidine degradation in example 3 (ph=7, light intensity 30000 lux);
fig. 3 is the effect of light intensity on cimetidine degradation in example 4 (ph=7, chlorophyll concentration 0.5 mg/L).
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, which do not represent limitations on the scope of the present invention. Some insubstantial modifications and adaptations of the invention based on the inventive concept by others remain within the scope of the invention.
Example 1
Step 1: chlorophyll is extracted from cells of the species Cephalosporium nodosum (Raphidocelis subcapitata), and is specifically as follows:
step 1.1: inoculating Cephalosporium nodosum into Bristol culture medium, and initial density of cells of Cephalosporium nodosum after inoculation is about 10 4 Introducing air filtered by a 0.45 mu m filter membrane into the cell/mL, and culturing for 8-10d to logarithmic phase;
step 1.2: centrifuging the Cephalosporium proxeticum solution obtained in the step 1.1 at 7000rpm for 10min, removing supernatant, and collecting Cephalosporium proxeticum cells;
step 1.3: in the obtained Cephalosporium moelle cells of 1.2 according to 1:20 Adding 90% ethanol in the ratio of (v/v), and centrifuging at 7000rpm for 10min at room temperature for 24h without light to obtain chlorophyll ethanol solution;
step 1.4: and (3) measuring the chlorophyll concentration of the obtained chlorophyll ethanol solution. Taking a proper amount of chlorophyll ethanol solution according to the following formula 1:100 was diluted with deionized water, absorbance was measured using an ultraviolet spectrophotometer at 630, 647, 664, 750nm wavelength, and substituted into the formula:
12.12(A 664 -A 750 )-1.58(A 647 -A 750 )-0.08(A 630 -A 750 ) Calculating to obtain a value of chlorophyll a concentration;
step 2: 50ml deionized water adjusted to pH 7 by NaOH and HCl is added into a 100ml triangular flask, and 100mg/L of cimetidine Ding Muye (more than or equal to 99 percent) is added into a reaction vessel to make the initial concentration of the mixture be 500 mug/L;
step 3: adding the chlorophyll solution prepared in the step 1.3 into the reaction vessel in the step 2 to ensure that the chlorophyll concentration is 0.5mg/L;
step 4: placing the reaction vessel under a white fluorescent lamp, adjusting the illumination intensity to 30000lux, placing the reaction vessel on a rotary oscillator for oscillation at room temperature, sampling and analyzing the residual concentration of the cimetidine at different times, wherein the rotating speed is 150 rpm;
step 5: the analytical detection method of the cimetidine comprises the following steps: the sample was filtered through a 0.22 μm organic filter and analyzed by high performance liquid chromatography (HPLC Waters Alliance e 2695) equipped with an ultraviolet-visible light detector. The detection method comprises the following steps: the mobile phase was methanol and 0.1% phosphoric acid water (24:76), the detection was carried out at a wavelength of 220nm, the flow rate was 1.0mL/min, and the sample injection amount was 100. Mu.L using a Kromasil-C18 column (4.6X105 mm,5 μm). The recovery of cimetidine was 101% and LOD was 6.95. Mu.g/L.
When the degradation time is 24 hours, the removal rate of the cimetidine is 97%.
Example 2 pH Effect on the Rate of Semipide Ding Quchu
The aqueous solution of cimetidine in step 2 of example 1 was adjusted to pH 3, 5, 7, 9, 11, respectively, with the other steps and parameters being the same as in example 1.
After 24h of degradation, the removal rate of cimetidine is shown in figure 1. The removal rate of the cimetidine under the acidic condition is 10-57%, and the removal rate under the neutral and alkaline conditions is more than 90%.
In natural water environments, the pH of the water is near neutral, so that subsequent experiments were performed at ph=7.
Example 3 Effect of chlorophyll concentration on the Rate of Semiphene Ding Quchu
The aqueous solution of cimetidine in step 2 of example 1 was adjusted to pH 7 and chlorophyll a concentration in step 3 was adjusted to 0, 0.25, 0.5, 1mg/L, with the other steps and parameters being the same as in example 1.
After 24h of degradation, the removal rate of cimetidine is shown in figure 2.
As can be seen from fig. 2, when the concentration of chlorophyll a is 0, the degradation rate of cimetidine is 0, and in a certain concentration range, as the concentration of chlorophyll a increases, the degradation rate of cimetidine also increases. When the concentration of chlorophyll a is 1mg/L, the degradation rate of the cimetidine can reach 93 percent after 9 hours of reaction, which is slightly higher than the degradation rate (88 percent) when the concentration of chlorophyll a is 0.5mg/L, and when the illumination time reaches 24 hours, the degradation rates of the cimetidine reach the same (97 percent).
Considering that the concentration range of chlorophyll in the actual water environment is far below 1mg/L, the subsequent control experiments were all carried out based on example 2 (chlorophyll a concentration 0.5 mg/L).
Example 4 Effect of illumination intensity on Seimit Ding Quchu Rate
The aqueous solution of cimetidine in step 2 of example 1 was adjusted to pH 7 and the light intensity in step 4 was adjusted to 0, 8000, 22000, 30000lux, the other steps and parameters being the same as in example 1.
After 24h of degradation, the removal rate of cimetidine is shown in figure 3.
As can be seen from fig. 3, the degradation rate of cimetidine increases with the increase in the light intensity. The degradation rate of the cimetidine under the illumination condition of 30000lux is higher than that of 8000lux, the degradation rate of the cimetidine can reach 76% after 9 hours of reaction, and the degradation rate of the cimetidine is 50% when the light intensity is 8000 lux.
Example 5 Effect of degradation time on Seimit Ding Quchu Rate
Based on the single-factor experimental conditions, the degradation experiment is carried out on the cimetidine by adopting the conditions of chlorophyll concentration of 0.5mg/L, pH value of 7 and illumination intensity of 30000lux, and the influence of different degradation times on the degradation rate of the cimetidine is researched. The results of the study showed that the degradation rates of cimetidine were 26%, 60%, 76% and 97% when the degradation times were 3, 6, 9 and 24 hours, respectively. With the increase of the degradation time, the degradation efficiency is increased, and the time of the degradation reaction is selected to be 24 hours, so that the degradation rate of the cimetidine reaches the maximum value.
Example 6
6.1 removal effect of artificially synthesized chlorophyll
Based on the above single factor experimental conditions (illumination intensity 30000lux, ph 7, chlorophyll a concentration 0.5 mg/L), the degradation experiments of cimetidine were performed using artificially synthesized chlorophyll a (purity > 96%, purchased from Wako Pure Chemical Industries, ltd.) instead of chlorophyll extracted from the aforementioned cells of p. Experiments show that the degradation rate of the cimetidine is 17% after 24 hours of reaction.
6.2 chlorophyll removal Effect from spinach
The extraction steps of chlorophyll extracted from spinach are as follows:
step 1: chlorophyll is extracted from spinach leaves, and the chlorophyll is specifically as follows:
step 1.1: cleaning vegetable leaves, airing, removing midrib, weighing 10g of the leaves, shearing, and putting into a mortar;
step 1.2: adding appropriate amount of 90% ethanol, 0.1g calcium carbonate and silicon dioxide into a mortar, grinding into homogenate until the tissue turns white, standing in dark for 5-10min, filtering with filter paper, transferring into brown standard sample bottle, and preserving;
step 1.4: and (3) measuring the chlorophyll concentration of the obtained chlorophyll ethanol solution. Taking a proper amount of chlorophyll ethanol solution according to the following formula 1:100 was diluted with deionized water, absorbance was measured using an ultraviolet spectrophotometer at 630, 647, 664, 750nm wavelength, and substituted into the formula:
12.12(A 664 -A 750 )-1.58(A 647 -A 750 )-0.08(A 630 -A 750 ) Calculating to obtain a value of chlorophyll a concentration;
based on the above single factor experiment conditions (illumination intensity 30000lux, pH 7, chlorophyll concentration 0.5 mg/L), the degradation experiment of cimetidine was performed using chlorophyll extracted from spinach leaves, and after 24 hours of reaction, the degradation rate of cimetidine was 89%.
EXAMPLE 7 removal Effect of the methods of the present application on other PPCPs
Under the single factor experiment condition (illumination intensity is 30000lux, pH is 7, chlorophyll concentration is 0.5 mg/L), a degradation experiment is carried out on ranitidine through chlorophyll solution extracted from the cell of the Cephalosporium hupezium, and when the degradation time is 24 hours, the removal rate of ranitidine is 80%, which indicates that the method has the removal effect on other PPCPs.
Comparative example removal of cimetidine by other methods known in the art
(1) The UV254 lamp is used for irradiating the cimetidine solution, and after 24 hours of reaction, the degradation rate of the cimetidine is 30 percent, which is far lower than the degradation rate (97 percent) of the chlorophyll system to the cimetidine under the condition of a white fluorescent lamp.
(2) The method for degrading the cimetidine by using the ozone oxidation method is characterized in that the cimetidine is completely degraded after 5 minutes of reaction, but the toxicity of the product is higher than that of the parent compound [1] 。
③UV/TiO 2 Photocatalytic degradation of cimetidine was carried out for 30min with a degradation rate of 56% but using TiO 2 Is easy to cause agglomeration, thereby reducing the surface area available for photocatalytic reaction and having larger energy consumption compared with the research system [1-2] 。
Reference to the literature
1.Quaresma A V,Sousa B A,Rubio K,et al.Degradation of cimetidine by oxidative processes,mass spectrometry products elucidation and toxicity evaluation[J].Journal of Environmental Chemical Engineering,2020,8(6):104522.
2.Kanakaraju D,Motti C A,Glass B D,et al.Photolysis and TiO2-catalysed degradation of diclofenac in surface and drinking water using circulating batch photoreactors[J].Environmental Chemistry,2014,11(1):51-62.
Claims (9)
1. Use of chlorophyll or chlorophyll-containing cells for degrading cimetidine or ranitidine.
2. A method of degrading cimetidine or ranitidine comprising the steps of:
s1, adding chlorophyll or cells containing chlorophyll into a sample to obtain a mixture, wherein the concentration of the chlorophyll in the mixture is 0.25-1mg/L;
s2, placing the mixture prepared in the step S2 under a white fluorescent lamp for reaction for 12-48h.
3. The method according to claim 2, wherein the step S1 further comprises a step of adjusting pH to 5-11 in the sample;
preferably, the pH in the sample is adjusted to 7.
4. The method according to claim 2, wherein the white fluorescent lamp in step S2 has an illumination intensity of 5000-50000lux;
preferably, the illumination intensity is 5000-45000lux;
preferably, the illumination intensity is 8000-35000lux;
preferably, the illumination intensity is 8000-30000lux.
5. The use/method according to any one of claims 1 to 4, wherein the chlorophyll or chlorophyll-containing cells are or originate from green algae or vegetables;
preferably, the green algae is selected from: at least one of Sphaerotheca nodosa, chlorella, scenedesmus;
preferably, the green alga is selected from the group consisting of a Graptosphaeria nodorum;
preferably, the vegetable is selected from spinach.
6. The use/method according to any one of claims 1-4, wherein the chlorophyll is selected from the group consisting of: at least one of chlorophyll a, chlorophyll b, chlorophyll c, chlorophyll d, chlorophyll f;
preferably, the chlorophyll is chlorophyll a;
preferably, the chlorophyll is synthetic chlorophyll.
7. The use/method according to any one of claims 1-4, wherein the sample is selected from the group consisting of a water sample;
preferably, the water body sample is selected from at least one of seawater, sewage and wastewater.
8. A method for preparing chlorophyll or chlorophyll-containing cells according to any one of the applications/methods of claims 1-4, characterized in that it comprises the following steps:
1) Inoculating green algae into the culture medium, and culturing for 8-10 days under aeration;
2) Centrifuging the green algae suspension prepared in the step 1) at 5000-9000rpm for 8-15min, removing supernatant, and retaining green algae cells;
3) To the green algae cells obtained in step 2) according to 1: (10-30) (v/v) adding 90% ethanol, and centrifuging at room temperature for 20-30 hr in the dark to obtain supernatant which is chlorophyll solution;
preferably, 90% ethanol is added to the green algae cells prepared in step 2) in a ratio of 1:20 (v/v) in step 3);
preferably, in step 3) centrifugation is carried out at 5000-9000 rpm; preferably, centrifugation is carried out for 8-15min.
9. Use of chlorophyll or chlorophyll-containing cells prepared by the preparation method according to claim 8 for degrading cimetidine or ranitidine.
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