CN115716924A - High-molecular hydrogel and preparation method and application thereof - Google Patents
High-molecular hydrogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of agricultural planting, and particularly relates to a high-molecular hydrogel and a preparation method and application thereof. The preparation method of the polymer hydrogel comprises the following steps: carboxymethyl cellulose and chitosan are used as raw materials, and spherical hydrogel is prepared under the action of a cross-linking agent, wherein the cross-linking agent is fumaric acid. The high-molecular hydrogel prepared by the method disclosed by the invention is strong in biocompatibility, free of pollution to the environment, mild in reaction condition, strong in operation feasibility, low in material cost and the like, and the obtained hydrogel product is green and free of pollution, good in water absorption effect and wide in application prospect in the aspect of agriculture.
Description
Technical Field
The invention belongs to the technical field of agricultural species planting, and particularly relates to a high-molecular hydrogel as well as a preparation method and application thereof.
Background
In recent years, with rapid changes in climate, the incidence of drought worldwide has increased year by year. In addition, the impact of drought on crop production is further exacerbated as the world population continues to grow, agricultural water usage increases year-to-year, and available fresh water decreases. Drought has become one of the barriers limiting agricultural production and social development in arid regions of china. As the major food crop in this area, the growth and development and yield quality of corn are suffering serious damage from drought. Therefore, it has become one of the important researches to study how to alleviate the adverse effects of drought on the growth of corn.
Hydrogel (SAH) is an emerging polymeric material in recent years, and its use is considered to be an effective water-saving irrigation strategy, widely used in arid and semi-arid regions. Hydrogels are cross-linked three-dimensional (3D) polymer networks that can absorb and retain large amounts of water and solute molecules in a swollen state due to the attachment of various hydrophilic groups, such as carboxyl, amino, hydroxyl groups, to their polymer backbone. The hydrophilic polymer can increase the water holding capacity of soil and reduce water stress conditions. During rainfall/irrigation, SAH absorbs and retains large amounts of water and acts as an additional pore reservoir. As the soil dries during the drought period, the water absorbed by SAH is released into the soil and can be absorbed by the roots of the plants. SAH retains drainage, thus reducing irrigation frequency, thereby saving water during drought.
However, the hydrogels currently available are based on monomers or polymers of acrylic acid or polyacrylamide, which are extracted from petroleum and are difficult to degrade in the soil. In addition, in some cases, their degradation products may have biotoxicity, and thus, the research of an environmentally friendly hydrogel has become one of the focuses of increasing interest to researchers. Carboxymethyl cellulose (CMC) is a cellulose derivative, has the characteristics of good water solubility, strong hygroscopicity, no toxicity and strong salt resistance, and hydrogel synthesized by taking CMC as a raw material has the characteristics of high water content, good biodegradability, no toxicity and the like, and is widely applied to the fields of agriculture and biomedicine. The Chitosan (CSN) has rich resources, simple preparation method and low price, and can be used in many fields due to good chemical and physical properties and combination with various substances. Therefore, how to prepare the green degradable hydrogel by taking the two polysaccharides as raw materials has important significance in relieving drought in the sandy soil.
Disclosure of Invention
In order to solve the problems, the invention provides the polymer hydrogel and the preparation method and the application thereof, the prepared polymer hydrogel has the characteristics of strong biocompatibility, no pollution to the environment, mild reaction conditions, strong operation feasibility, low material cost and the like, and the obtained hydrogel product is green and pollution-free, has a good water absorption effect and has a wide application prospect in the aspect of agriculture.
The invention solves the technical problems through the following technical scheme.
The first purpose of the present application is to provide a method for preparing a polymer hydrogel, comprising the following steps: the preparation method comprises the steps of taking carboxymethyl cellulose and chitosan as raw materials, and preparing spherical hydrogel under the action of a cross-linking agent, wherein the cross-linking agent is fumaric acid.
Preferably, the method comprises the following steps:
s1, dissolving fumaric acid in water, heating and stirring until the fumaric acid is completely dissolved to obtain a fumaric acid solution;
and S2, mixing the methyl cellulose solution with the fumaric acid solution obtained in the step S1 to obtain a mixed solution, dripping the mixed solution into a chitosan acetic acid solution under the condition of heating and stirring, and filtering, cleaning and drying to obtain the high-molecular spherical hydrogel after dripping.
Preferably, in S1, the concentration of the fumaric acid solution is 0.6%, the heating temperature is 35-55 ℃, and the stirring speed is 200-400 rpm.
Preferably, in S2, the methylcellulose solution is a methylcellulose aqueous solution, and the concentration of the methylcellulose aqueous solution is 1%.
Preferably, in S2, the chitosan solution is a chitosan acetic acid solution, and the concentration of the chitosan acetic acid solution is 1 to 3%.
Preferably, in S2, the volume ratio of the methylcellulose solution to the fumaric acid to the chitosan acetic acid solution is 1.
Preferably, in S2, the heating temperature is 40-60 ℃, the stirring speed is 400-650 rpm, the drying mode is room temperature air drying or vacuum freeze drying, the vacuum freeze drying temperature is-80 ℃, and the time is 40h.
The second objective of the present invention is to provide a polymer hydrogel prepared by the above preparation method.
The third purpose of the invention is to provide the application of the polymer hydrogel in relieving corn drought stress in sand blown soil.
Preferably, the mass ratio of the polymer hydrogel to the sand-blown soil is 1-2.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention takes natural polymer chitosan and cellulose derivatives as raw materials to prepare the polymer hydrogel, has the characteristics of mild reaction conditions, strong operation feasibility, low material cost and the like, and the obtained hydrogel has strong biocompatibility, no environmental pollution, high water absorption rate which can reach 30-80 g/g and can adsorb a large amount of water.
(2) Compared with the hydrogel prepared from the existing polyacrylamide, polyacrylate or derivatives thereof, the polymer hydrogel prepared by the invention is not only nontoxic and harmless to seeds, but also easily degradable in natural environment, environment-friendly and capable of consolidating sand blown by the wind in agriculture. After the hydrogel is mixed with sandy soil, the sandy soil can be kept stable and is not easy to collapse; but also can improve the physical structure of the soil by improving the porosity and permeability of the soil, and effectively relieve the drought effect of the corn.
Drawings
FIG. 1 is a schematic process scheme for the preparation of CMC/FU/CSN hydrogels according to the present invention;
FIG. 2 is a schematic process scheme for the preparation of CMC/FU/CSN hydrogels according to the present invention;
FIG. 3 is a graph showing the change in water absorption swelling ratio of CMC/FU/CSN hydrogels prepared according to the present invention;
FIG. 4 is a graph showing the change of water retention of CMC/FU/CSN hydrogel prepared by the present invention;
FIG. 5 is a scanning electron micrograph of a CMC/FU/CSN hydrogel prepared in example 2 of the present invention;
FIG. 6 is a Fourier infrared spectrum of the CMC/FU/CSN hydrogel prepared in example 2 of the present invention;
FIG. 7 is a diffractogram of the spectrum of CMC/FU/CSN hydrogel prepared in example 2 of the present invention;
FIG. 8 is a thermogravimetric analysis of a CMC/FU/CSN hydrogel prepared in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention, which will be limited only by the appended claims, wherein the various materials, reagents, instruments and equipment used in the following examples are commercially available or may be prepared by conventional methods.
Example 1
A preparation method of polymer hydrogel comprises the following steps:
s1, dissolving fumaric acid FU in water, and stirring at 40 ℃ and 300rpm until the fumaric acid FU is completely dissolved to obtain a FU aqueous solution with the concentration of 0.6 wt%;
s2, dissolving the methyl cellulose CMC in water, and stirring the solution at 45 ℃ and 500rpm until the CMC is completely dissolved to obtain a CMC aqueous solution with the concentration of 1 wt%;
placing the chitosan CSN in acetic acid aqueous solution with the concentration of 1 percent, stirring and completely dissolving the chitosan CSN in the acetic acid aqueous solution with the concentration of 1 weight percent at the temperature of 65 ℃ and the rpm of 750 to obtain CSN acetic acid solution;
mixing a CMC aqueous solution and the FU aqueous solution obtained from S1 in equal volume, uniformly stirring to form a CMC/FU mixed solution, heating a CSN acetic acid solution to 40 ℃, stirring at 500rpm, then dripping the CMC/FU mixed solution into the CSN acetic acid solution, after all dripping is finished, enabling the solution to pass through a 60-mesh screen, repeatedly washing with deionized water, and then naturally drying at room temperature to obtain a high-molecular spherical hydrogel named as CMC/FU/CSN hydrogel, wherein the preparation process is shown in figure 1, and the reaction mechanism is shown in figure 2.
Example 2
A preparation method of polymer hydrogel comprises the following steps:
s1, dissolving fumaric acid FU in water, and stirring at 40 ℃ and 300rpm until the fumaric acid FU is completely dissolved to obtain a FU aqueous solution with the concentration of 0.6 wt%;
s2, dissolving methyl cellulose CMC in water, and stirring at 45 ℃ and 500rpm until the CMC is completely dissolved to obtain a CMC aqueous solution with the concentration of 1 wt%;
placing the chitosan CSN in acetic acid water solution with the concentration of 1%, and stirring and completely dissolving the chitosan CSN in the acetic acid water solution with the concentration of 2wt% at the temperature of 65 ℃ and the speed of 750rpm to obtain CSN acetic acid solution;
and (2) mixing the CMC aqueous solution and the FU aqueous solution obtained in the S1 in equal volume, uniformly stirring to form a CMC/FU mixed solution, heating the CSN acetic acid solution to 40 ℃, stirring at 500rpm, then dripping the CMC/FU mixed solution into the CSN acetic acid solution, after all dripping is finished, enabling the solution to pass through a 60-mesh screen, repeatedly washing with deionized water, and then naturally drying at room temperature to obtain the macromolecular spherical hydrogel named as CMC/FU/CSN hydrogel.
Example 3
A preparation method of polymer hydrogel comprises the following steps:
s1, dissolving fumaric acid FU in water, and stirring at 40 ℃ and 300rpm until the fumaric acid FU is completely dissolved to obtain a FU aqueous solution with the concentration of 0.6 wt%;
s2, dissolving methyl cellulose CMC in water, and stirring at 45 ℃ and 500rpm until the CMC is completely dissolved to obtain a CMC aqueous solution with the concentration of 1 wt%;
placing the chitosan CSN in acetic acid water solution with the concentration of 1%, and stirring and completely dissolving the chitosan CSN in the acetic acid water solution with the concentration of 3wt% at the temperature of 65 ℃ and the speed of 750rpm to obtain CSN acetic acid solution;
mixing a CMC aqueous solution with the FU aqueous solution obtained in the step S1 in an equal volume, uniformly stirring to form a CMC/FU mixed solution, heating a CSN acetic acid solution to 40 ℃, stirring at 500rpm, then dripping the CMC/FU mixed solution into the CSN acetic acid solution, after all dripping is finished, enabling the solution to pass through a 60-mesh screen, repeatedly washing with deionized water, and then naturally air-drying at room temperature to obtain the macromolecular spherical hydrogel which is named as CMC/FU/CSN hydrogel.
In order to search for the properties of the hydrogel obtained, the CMC/FU/CSN hydrogels obtained in examples 1, 2 and 3 were analyzed for water absorption and water retention to determine the optimum ratio of CMC/FU/CSN.
Example 4
The preparation method of the polymer hydrogel is general to example 2, and the difference is that in S2, the polymer spherical hydrogel obtained by vacuum freeze drying at-80 ℃ for 40h is named as CMC/FU/CSN hydrogel.
FIG. 3 is a graph showing the change of water absorption swelling ratio of CMC/FU/CSN hydrogels provided in examples 1, 2 and 3 of the present invention in indoor environment with time. As can be seen in FIG. 3, the swelling rate of the hydrogel increased with time. And equilibrates at 84 h. The influence of the CSN component on the swelling ratio is determined by changing the amount of CSN in the composite hydrogel, so that the optimal amount of CSN is determined. As can be seen from the figure, the swelling ratio of the composite hydrogel tends to increase first and then decrease when the amount of CMC and the amount of FU used as a crosslinking agent are constant. When the concentration of CSN was 2wt%, the swelling ratio reached a peak. Thus, the optimum concentration of CSN was determined to be 2wt%.
FIG. 4 is a graph showing the change of the water retention rate of CMC/FU/CSN hydrogel in the indoor environment with time, which is provided in example 1 of the present invention. As can be seen from fig. 4, the water retention of the hydrogel gradually decreased with time. The influence of the component CSN on the water holding rate is determined by changing the dosage of CSN in the composite hydrogel, thereby determining the optimal dosage of CSN. As can be seen from FIG. 4, in order to satisfy the effect of sustained release of hydrogel, the optimum concentration of CSN was 2wt%. The swelling rate and the water retention rate are comprehensively considered, and under the condition that the use amount of the CMC and the cross-linking agent FU is certain, when the concentration of the CSN is 2wt%, the hydrogel achieves the optimal performance.
In order to illustrate the performance of the prepared hydrogel, the CMC/FU/CSN hydrogel obtained in example 2 is analyzed for relevant performance, and the surface appearance and microstructure of the hydrogel in example 2 are observed by a Scanning Electron Microscope (SEM); observing the crystal structure of the hydrogel by energy dispersive diffraction (EDS); the composition of the hydrogel was analyzed by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA).
FIG. 5 is a Scanning Electron Microscope (SEM) image of the CMC/FU/CSN hydrogel provided in example 2 of the present invention. Wherein, a in FIG. 5 is SEM picture of hydrogel sample after air drying for 0 d; in fig. 5 b is an SEM picture of the hydrogel sample after soil exposure experiment 15 d. As can be seen from fig. 5, a in fig. 5 a is clearly observed a gel network comprising micropores and macropores, so that it allows the liquid to penetrate directly into the polymer network by fluid diffusion, thus obtaining a greater swelling index. In fig. 5 b the eroded and hollow surface morphology of the hydrogel can be seen, indicating that the hydrogel is being degraded.
FIG. 6 is a Fourier infrared spectrum (FT-IR) of the CMC/FU/CSN hydrogel provided in example 2 of the present invention. As can be seen from fig. 6, FTIR spectra show the chemical characteristics of CMC, CSN, FU and crosslinked hydrogel. CMC is 3600-3200cm -1 、2915cm -1 、1598cm -1 And 1060cm -1 Shows characteristic absorption peaks corresponding to-OH, -CH, -COOH and-CO groups, while CSN is 3600-3250cm -1 、2929cm -1 、1655cm -1 Shows absorption peaks for-OH and-NH, -CH 2 A group; FU is 3084cm -1 、1699cm -1 、1276cm -1 、896cm -1 And 645cm -1 Shows absorption peaks corresponding to the stretching vibrations of C = C-H, C = O, -CO, -OH and O = C-O. CMC/FU/CSN hydrogel 1075cm -1 The appearance of the peaks is highlighted probably by the-COO-groups of CMC and NH of CSN 3 + Ionic interactions between groups. Also, the crosslinked hydrogel was at 1415cm -1 The intensity and clarity of the band at-COOH was almost eliminated, probably due to the interaction during chemical crosslinking. These all indicate the success of the hydrogel synthesis.
FIG. 7 is an energy spectrum diffraction pattern (EDS) of the CMC/FU/CSN hydrogel of example 2 of the present invention. As can be seen from FIG. 7, by analyzing the elemental composition of the sample by EDS, the peaks of C and O can be seen, which indicates that the hydrogel material has oxygen-containing functional groups on the surface, and in addition, the Na peak in the raw material is also appeared to further prove the success of the synthesis of the composite material.
FIG. 8 is a thermogravimetric analysis (TGA) of the CMC/FU/CSN hydrogel of example 2 of the present invention. As can be seen from fig. 8, for CMC, the weight loss phase occurs mainly in the 270 ℃ to 310 ℃ in the TGA curve due to thermal degradation of the functional groups (-COOH and-OH groups) in CMC. For CMC/FU/CSN hydrogels, the peak was weakened and shifted to 260 ℃. Probably due to the fact that more functional groups participate in the chemical crosslinking reaction of CMC/FU/CSN.
The CMC/FU/CSN hydrogels obtained in examples 2 and 4 were subjected to a water absorption property test, and the swelling ratio of the synthesized hydrogels was tested using the teabag method. The specific operation steps are as follows: respectively putting 0.100g of dried hydrogel of the CMC/FU/CSN hydrogel obtained in the embodiment 2 and the embodiment 4 into a nylon filter bag with a diameter of 6.5 multiplied by 6.5cm and a diameter of 100 meshes which can be closed; immersion in deionized water, taking care not to submerge the bag mouth completely into the water, the filter bag cannot touch the container wall. The filter bag was taken out at regular intervals, hung in air to a position where no water droplets seeped, and weighed. And subtracting the dry weight from the wet weight of the sample to obtain the water absorption capacity of the sample, wherein the ratio of the water absorption capacity of the sample to the dry weight of the sample is the water absorption rate of the hydrogel. The water absorption of the hydrogel obtained in example 2 was 80g/g and the water absorption of the hydrogel obtained in example 4 was 30g/g, in three replicates.
Application example 1
In order to further illustrate that the CMC/FU/CSN hydrogel obtained by the invention can be used for improving aeolian sandy soil and relieving corn drought stress, a corn potting experiment is carried out on the hydrogel obtained in example 1, and the specific experiment comprises the following steps:
test soil: ningxia sandy soil. The basic physicochemical properties of the matrix are: the pH value is 9.02, the organic matter is 1.34g/kg, the quick-acting phosphorus is 1.37mg/kg, the quick-acting nitrogen is 9.11mg/kg, and the quick-acting potassium is 24.75mg/kg.
The test plant is a test corn material, namely Nongkogao No. 8, has compact plant type, thick and strong stem and developed root system, and is suitable for planting the spring and summer corns in Ningxia province.
The experiment was set up with 3 treatments: 1) Normal water supply (CK); 2) Moderate Drought (MD); 3) Moderate drought + hydrogel (MDH) (example 1 hydrogel addition 0.3wt% in air dried form) was repeated 6 times per treatment. The test is carried out in a greenhouse of northwest agriculture and forestry science and technology university, the time is from 6 months and 28 days in 2022 to 8 months and 2 days in 2022, the temperature and the light source are natural, and the moisture is manually controlled.
The experimental steps are as follows: selecting full and consistent corn seeds, sterilizing the corn seeds with 1% NaClO solution before sowing the corn seeds, and repeatedly washing the corn seeds with distilled water until the corn seeds are clean. Corn seeds were then planted in pots of the same size (height x calibre =18cm x 15 cm) with 5 random sprinkles per pot. 2kg of sieved aeolian sandy soil is filled in each basin, and phosphorus, potassium and nitrogen fertilizers with the same amount are added into each plastic bucket according to the field fertilization standard, wherein the dosage is respectively N0.22g/kg and P 2 O 5 0.49g/kg and K 2 O0.18 g/kg, N46% urea, and P46% heavy calcium carbonate as N, P and K fertilizers 2 O 5 46%) and potassium chloride (K) 2 O60%). And then mixed with each treatment. The water content of the soil is adjusted by adding tap water to reach the target water content (normal water supply: 60% of the field water capacity; moderate drought: the field water capacity)40% of). And (4) final singling in a two-leaf period and reserving a plant. And (4) every day at 18:00 weigh to replenish lost moisture to maintain the set soil moisture content for each treatment. Each treatment was 6 replicates. After 35d, the aerial parts and the underground parts of the corn plants were collected and subjected to the measurement of the relevant indexes, and the results are shown in table 1.
TABLE 1 Effect on maize seedling growth under different treatments
Note: the data in the table are the mean ± standard error of 3 replicates with different lower case letters indicating significant differences at the 5% level.
As can be seen from Table 1, with the aggravation of drought, the fresh weight average of the height, the stem thickness, the overground part and the underground part of the corn plant shows a descending trend, and the addition of the hydrogel alleviates the situation. Compared with the corn seedlings without hydrogel materials under moderate drought conditions, the plant height of the corn seedlings applied with the hydrogel of example 1 is increased by 10.28%, the stem thickness is increased by 108.95%, the fresh weight of the overground part is increased by 89.30%, and the fresh weight of the underground part is increased by 102.86%. Different measurement indexes show different change trends along with the increase of the drought degree, but it can be determined that the addition of the hydrogel improves the plant height, the stem thickness, the fresh weight of the overground and underground parts of the corn plants and promotes the growth of seedlings. The synthetic hydrogel material can effectively relieve the drought stress of the corn.
In conclusion, the invention provides a preparation method of CMC/FU/CSN hydrogel material, which takes carboxymethyl cellulose and chitosan as raw materials and prepares the CMC/FU/CSN hydrogel material by a chemical crosslinking method, and the preparation method is simple and convenient and has strong operability. The obtained hydrogel product is not only nontoxic and harmless to plants, but also easily degradable in natural environment and friendly to environment.
The CMC/FU/CSN hydrogel obtained by the invention can be used as a water retention agent to be applied to agricultural production. The hydrogel prepared by the invention is not only used for improving sandy soil, but also can be used for relieving the growth of plants in arid and semi-arid regions.
It should be noted that, when the present invention relates to numerical ranges, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those in the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred embodiment and all changes and modifications that fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The preparation method of the polymer hydrogel is characterized by comprising the following steps: carboxymethyl cellulose and chitosan are used as raw materials, and spherical hydrogel is prepared under the action of a cross-linking agent, wherein the cross-linking agent is fumaric acid.
2. The method for preparing polymer hydrogel according to claim 1, comprising the steps of:
s1, dissolving fumaric acid in water, heating and stirring until the fumaric acid is completely dissolved to obtain a fumaric acid solution;
and S2, mixing the methyl cellulose solution with the fumaric acid solution obtained in the step S1 to obtain a mixed solution, dripping the mixed solution into a chitosan acetic acid solution under the condition of heating and stirring, and filtering, cleaning and drying to obtain the high-molecular hydrogel after dripping.
3. The method for preparing a polymer hydrogel according to claim 2, wherein the fumaric acid solution in S1 has a mass concentration of 0.6%, a heating temperature of 35 to 55 ℃, and a stirring rotation speed of 200 to 400rpm.
4. The method for producing a polymer hydrogel according to claim 2, wherein the methylcellulose solution in S2 is a methylcellulose aqueous solution, and the mass concentration of the methylcellulose aqueous solution is 1%.
5. The method for preparing polymer hydrogel according to claim 2, wherein in S2, the chitosan solution is chitosan acetic acid solution, and the mass concentration of the chitosan acetic acid solution is 1-3%.
6. The method for preparing polymer hydrogel according to claim 2, wherein in S2, the volume ratio of the methylcellulose solution to the fumaric acid to the chitosan acetic acid solution is 1.
7. The method for preparing polymer hydrogel according to claim 2, wherein the heating temperature in S2 is 40-60 ℃, the stirring speed is 400-650 rpm, the drying mode is room temperature air drying or vacuum freeze drying, the vacuum freeze drying temperature is-80 ℃, and the time is 40h.
8. A polymeric hydrogel prepared by the method of any one of claims 1 to 7.
9. The use of the polymeric hydrogel of claim 8 in sandstorm soil to alleviate corn drought stress.
10. The application of the polymer hydrogel in relieving corn drought stress in sand blown by wind as claimed in claim 9, wherein the mass ratio of the polymer hydrogel to the sand blown by wind is 1-2.
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