CN114014947B - Eutectic solvent for degrading algal polysaccharide and preparation method and application thereof - Google Patents
Eutectic solvent for degrading algal polysaccharide and preparation method and application thereof Download PDFInfo
- Publication number
- CN114014947B CN114014947B CN202210019325.9A CN202210019325A CN114014947B CN 114014947 B CN114014947 B CN 114014947B CN 202210019325 A CN202210019325 A CN 202210019325A CN 114014947 B CN114014947 B CN 114014947B
- Authority
- CN
- China
- Prior art keywords
- eutectic solvent
- algal polysaccharide
- hydrogen bond
- algal
- polysaccharide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The embodiment of the invention discloses a eutectic solvent for degrading algal polysaccharide and a preparation method and application thereof, belonging to the technical field of algal polysaccharide deep processing. The eutectic solvent is formed by mixing a hydrogen bond acceptor and a hydrogen bond donor, wherein the amount of the hydrogen bond acceptor is 30-40% of the mass of the eutectic solvent; wherein the hydrogen bond receptor is choline chloride, and the hydrogen bond donor is prepared from the following components in a mass ratio of (24-30): (25-35): (5-11) glucose, urea and citric acid. The eutectic solvent disclosed by the invention has the advantages of natural sources, safety, no toxicity, biodegradability and the like, meets the requirements of industrial development direction and environmental protection, and meanwhile, when the algal polysaccharide is degraded by adopting the eutectic solvent disclosed by the invention, the molecular weight of the algal polysaccharide degradation product is controllable by controlling degradation conditions, so that a novel method is provided for preparing the algal polysaccharide degradation product with specific molecular weight.
Description
Technical Field
The embodiment of the invention relates to the technical field of algal polysaccharide deep processing, and particularly relates to a eutectic solvent for degrading algal polysaccharide, and a preparation method and application thereof.
Background
The seaweed is rich in polysaccharide, including alginic acid, agar, carrageenan, fucoidin (also called fucoidan), Laminan (containing beta-1.3-glucan structure), Ulkans (ulva polysaccharide, rich in sulfated rhamnose), Porphyran (Porphyran polysaccharide) and the like, the seaweed polysaccharide which is industrially produced in large scale at present comprises sodium alginate (the structure is polyuronic acid sodium salt), agar (the structure is galactose-anhydrogalactose polymer), carrageenan (the structure is polygalactosulfate), fucoidin (the structure is sulfated fucosan), and other seaweed polysaccharides are sold as research samples but are not industrially produced. Algal polysaccharides are currently used in food, household, textile and other industrial fields as thickeners, rheology/texture modifiers.
The seaweed polysaccharide is degraded to prepare oligosaccharide or oligosaccharide, and the biological activity of the seaweed polysaccharide can be obviously improved. The alginate oligosaccharide has biological activities of protecting nerve cells, relieving the effect of neurotoxic protein, promoting the proliferation of human skin keratinocytes, improving the immunoreaction activity or reducing the bidirectional immunoregulation of inflammatory factor expression in different models and the like. The agar oligosaccharide has prebiotic activity, and has effects of resisting oxidation, improving blood lipid, improving liver function, protecting enzyme activity, inhibiting melanin synthesis, resisting inflammation, and resisting dental caries. The carrageenan oligosaccharide has the effects of anticoagulation, antiangiogenesis/antitumor, blood pressure reduction, antivirus, anti-aging, nerve protection, water absorption and moisture retention, freeze-thawing resistance, cytoprotection, inflammation inhibition, photoprotection, antioxidation, antibiosis and fresh keeping, radiation damage reduction and the like (Cosmetics 2018, 5, 68; Mar, Drugs 2018, 16, 459; Mar, Drugs 2020, 18, 144; Bioresource Technology Reports 13 (2021) 100623; Fuguang, and the like: the research progress of the biological activity of alginate oligosaccharide).
Among the methods for preparing oligosaccharide/oligosaccharide derived from seaweed, reported methods include an acid hydrolysis method (Liuxue, et al: research on the preparation of marine rhamnosulfate oligosaccharide; CN 03138969.4), a microwave method (baiting, et al: research on the preparation of mannuronic acid oligosaccharide by the microwave method and its in vitro antioxidant activity), an oxidation method (a method for degrading algal polysaccharide, CN 112920289A), an enzymatic hydrolysis method (Int J Biol Macromol. 2020 Oct 1;160: 288-. The acidolysis method requires the use of an acidic reagent such as hydrochloric acid or sulfuric acid, and is limited in safety, waste liquid treatment, and the like, and is rarely used. The microwave in the microwave method is used as an energy source, and needs to be combined with other degradation modes, and industrial example application is not seen. Oxidation methods various specific oxidation systems have been reported, such as the Fenton method, etc., in which UV-H2O2Or UV-O3The system has the advantages of greenness, no pollution, no residue, high efficiency and the like. The enzymolysis method is a main research direction in recent years, and has the advantages of high hydrolysis degree, high product specificity, high enzymolysis mode diversity and the like. However, the above methods all require dissolving the polysaccharide in water (water phase) and then degrading, for example, the concentration of the algal polysaccharide in the water phase in CN112920289A is 2.5-10 mg/mL, which is only 0.25% -1% by mass; when Junjun Yan et al (Int J Biol Macromol. 2020 Oct 1;160: 288-; for industrial production, such substrate concentrations are not ideal. The reason why the concentration of the polysaccharide in the aqueous solution is low is that the high-concentration aqueous solution of the polysaccharide has high viscosity, and the process operations such as stirring and pumping of the high-viscosity solution are difficult to perform, so that the polysaccharide can only be prepared into the low-concentration aqueous solution of the polysaccharide, resulting in low system efficiency. In addition, after the polysaccharide is degraded in the water phase, a large amount of water needs to be removed by separating the degradation product from the water phase, and the water removal generally adopts evaporation or membrane treatment, so that the energy consumption is high, and the time consumption is highLong, flux attenuation of the membrane element, and the like.
In conclusion, the concentration of polysaccharide in the degradation system is difficult to increase, the separation and recovery cost of degradation products is one of the limiting factors of the production of the algal oligosaccharide, and the solution of the problems is beneficial to the large-scale preparation and the practicability of the algal oligosaccharide.
Disclosure of Invention
Therefore, the embodiment of the invention provides a eutectic solvent for degrading algal polysaccharide and a preparation method and application thereof.
In order to achieve the above object, the embodiments of the present invention provide the following technical solutions:
according to the first aspect of the embodiment of the invention, the eutectic solvent for degrading the algal polysaccharide is provided, the eutectic solvent is formed by mixing a hydrogen bond acceptor and a hydrogen bond donor, and the amount of the hydrogen bond acceptor is 30-40% of the mass of the eutectic solvent; wherein the hydrogen bond receptor is choline chloride, and the hydrogen bond donor is prepared from the following components in a mass ratio of (24-30): (25-35): (5-11) glucose, urea and citric acid.
Preferably, in the eutectic solvent of the present invention, the hydrogen bond acceptor is used in an amount of 35% by mass of the eutectic solvent.
Preferably, in the eutectic solvent of the present invention, the hydrogen bond donor is formed by mixing, in a mass ratio of (24-30): 30: (5-11) glucose, urea and citric acid.
According to a second aspect of the embodiments of the present invention, there is provided the above method for preparing the eutectic solvent for degrading algal polysaccharide, heating the hydrogen bond acceptor and the hydrogen bond donor at a temperature of 90-110 ℃ under stirring conditions to melt them into a liquid.
According to a third aspect of the embodiments of the present invention, there is provided a method for degrading algal polysaccharides, comprising adding algal polysaccharides into the above-mentioned eutectic solvent, stirring at 50-70 ℃ for 1-8h, and performing solid-liquid separation to obtain a solid phase, i.e. algal polysaccharide degradation product.
The algal polysaccharide is suspended/dispersed in a eutectic solvent in a solid state to form a heterogeneous system with two simultaneous solid/liquid phases. In the heterogeneous system, the algal polysaccharide is dispersed in the eutectic solvent in the form of solid particles, the system is in a solid/liquid two-phase state in the whole degradation process, and the influence of the improvement of the algal polysaccharide concentration on the viscosity of the system is small because polysaccharide sugar chains are not extended, so that the algal polysaccharide concentration can be improved as much as possible within the stirring capacity range of equipment to improve the production efficiency; after degradation, the algal polysaccharide degradation product can be obtained through simple solid-liquid separation operation without removing water, so that the process can be simplified, and the energy consumption can be reduced.
Preferably, in the method for degrading algal polysaccharide according to the present invention, the mass volume ratio (g/ml) of algal polysaccharide to the eutectic solvent is 1: (3-4).
Preferably, the method for degrading algal polysaccharides of the present invention further comprises: the solid phase was washed with an ethanol solution and then dried.
Preferably, in the method for degrading algal polysaccharides, the mass fraction of the ethanol solution is 30-95%; the drying temperature is 50-70 ℃.
According to a fourth aspect of the embodiments of the present invention, there is provided a method for preparing a algal polysaccharide degradation product with controllable molecular weight, mixing algal polysaccharide with the eutectic solvent, and stirring the mixture at a predetermined temperature (B, ° C) for a predetermined time (a, h), wherein the number average molecular weight Mn (x, kDa) of the algal polysaccharide degradation product, the predetermined time (a), the predetermined temperature (B), and the amount (C) of citric acid satisfy the following formula: 0.0012x2 + 0.0475x + 1.1591=101.95060-5.17165*A-2.34950*B-2.61460*C+0.066023*A*B+
0.019391*A*C+0.022803*B*C+0.074275*A2+0.014379*B2+0.046666*C2A is more than or equal to 1 and less than or equal to 8, B is more than or equal to 50 and less than or equal to 70, and C is the weight part of citric acid in each 100 parts of the eutectic solvent; and (3) obtaining the seaweed polysaccharide degradation product with the target molecular weight by controlling the preset temperature (B), the preset time (A) and the dosage (C) of the citric acid.
Preferably, in the method for preparing algal polysaccharide degradation products of a target molecular weight according to the present invention, the mass-to-volume ratio (g/ml) of the algal polysaccharide to the eutectic solvent is 1: (3-4).
The embodiment of the invention has the following advantages:
1. the inventor carries out a great deal of research work on the types and the dosage proportions of the raw materials of the liquid-phase medium eutectic solvent for degrading the algal polysaccharide, and finds that the choline chloride is adopted as a hydrogen bond receptor, and the glucose, the urea and the citric acid with specific proportions are adopted as hydrogen bond donors, so that the obtained eutectic solvent not only has the advantages of natural sources, safety, no toxicity, biodegradability and the like, but also meets the industrial development direction and the environmental protection requirements, and more importantly, compared with other hydrogen bond receptors, such as choline, choline bitartrate and the like; or other sugars such as sucrose, lactose, etc.; or other organic acids such as malic acid, tartaric acid and the like, when the deep eutectic solvent is adopted to degrade the algal polysaccharide, the molecular weight of the algal polysaccharide degradation product is controllable by controlling degradation conditions including degradation temperature, degradation time and the percentage content of the organic acid citric acid in the deep eutectic solvent, and a novel method is provided for preparing the algal polysaccharide degradation product with specific molecular weight.
2. The degradation method of the invention has the following advantages: the concentration of the seaweed polysaccharide in the system is high, the degradation efficiency is high: the seaweed polysaccharide particles are dispersed in the eutectic solvent, so that the seaweed polysaccharide particles are insoluble, the viscosity of the system is low, the concentration of polysaccharide in the system is high and can reach 20-25% (W/W), and the seaweed polysaccharide particle content can be further improved; low water consumption and low energy consumption: in the whole process, no or only a small amount of water is needed, and the degradation product can be obtained only by solid-liquid separation in the separation process after degradation, so that the energy consumption is low, the efficiency is high, and the method has a good industrialization prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
FIG. 1 is a GPC-RI-MALLS graph of agar before and after degradation provided by the present invention, (a) is a GPC-RI-MALLS graph before degradation, and (b) is a GPC-RI-MALLS graph after degradation;
FIG. 2 is GPC-RI-MALLS graphs of carrageenan before and after degradation provided by the invention, (a) is GPC-RI-MALLS graph before degradation, and (b) is GPC-RI-MALLS graph after degradation;
FIG. 3 is GPC-RI-MALLS graphs before and after degradation of sodium alginate provided by the present invention, (a) is GPC-RI-MALLS graph before degradation, and (b) is GPC-RI-MALLS graph after degradation;
FIG. 4 is a GPC-RI-MALLS graph of fucoidan before and after degradation, wherein (a) is a GPC-RI-MALLS graph before degradation, and (b) is a GPC-RI-MALLS graph after degradation;
FIG. 5 is GPC-RI-MALLS graphs of ulvan before and after degradation provided by the present invention, (a) is GPC-RI-MALLS graph before degradation, and (b) is GPC-RI-MALLS graph after degradation;
FIG. 6 is a mass spectrum of agar degradation products provided by the present invention;
FIG. 7 is a mass spectrum of a carrageenan degradation product provided by the present invention;
FIG. 8 is a mass spectrum of a sodium alginate degradation product provided by the present invention;
FIG. 9 is a mass spectrum of a fucosan degradation product provided by the present invention;
fig. 10 is a mass spectrum of an ulva polysaccharide degradation product provided by the present invention;
FIG. 11 is a scan of the IR spectra of sodium alginate provided by the present invention before and after degradation;
FIG. 12 is a scanning electron microscope image of the surface of sodium alginate before and after degradation provided by the present invention, (a) untreated sodium alginate, number average molecular weight 198.6 kDa; (b) sodium alginate degradation products with the number average molecular weight of 112.4 kDa; (c) sodium alginate degradation products with the number average molecular weight of 15.4 kDa; (d) untreated sodium alginate, number average molecular weight 198.6 kDa; (e) sodium alginate degradation products with the number average molecular weight of 112.4 kDa; (f) sodium alginate degradation product with 15.4 kDa of number average molecular weight, wherein scales (a) - (c) are 50 μm, and scales (d) - (f) are 2 μm.
Detailed Description
The present invention is described in terms of specific embodiments, and other advantages and benefits of the present invention will become apparent to those skilled in the art from the following disclosure. 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.
Example 1
The embodiment provides a eutectic solvent for degrading algal polysaccharide, and raw materials of the eutectic solvent comprise 35g of choline chloride, 30g of glucose, 30g of urea and 5g of citric acid.
The preparation method of the eutectic solvent comprises the following steps: the method comprises the steps of uniformly mixing 35g of choline chloride, 30g of glucose, 30g of urea and 5g of citric acid, transferring the mixture into a flask, placing the flask into an electric heating constant-temperature jacket set to be 100 ℃ for heating and stirring simultaneously, gradually melting the mixture in the flask into liquid, stopping heating after all solid materials are melted into transparent and uniform liquid, wherein the liquid is a eutectic solvent for degrading the algal polysaccharide, and the eutectic solvent still keeps good flowing liquid appearance at 25 ℃.
Example 2
The raw materials of the eutectic solvent for degrading the algal polysaccharide provided by the embodiment comprise 35g of choline chloride, 27g of glucose, 30g of urea and 8g of citric acid.
The preparation method of the eutectic solvent is the same as that of example 1.
Example 3
The raw materials of the eutectic solvent for degrading the algal polysaccharide provided by the embodiment comprise 35g of choline chloride, 24g of glucose, 30g of urea and 11g of citric acid.
The preparation method of the eutectic solvent is the same as that of example 1.
Example 4
The raw materials of the eutectic solvent for degrading the algal polysaccharide provided by the embodiment comprise 30g of choline chloride, 24g of glucose, 35g of urea and 11g of citric acid.
The preparation method of the eutectic solvent is the same as that of example 1.
Example 5
The raw materials of the eutectic solvent for degrading the algal polysaccharide provided by the embodiment comprise 40g of choline chloride, 30g of glucose, 25g of urea and 5g of citric acid.
The preparation method of the eutectic solvent is the same as that of example 1.
Example 6
The present embodiment provides a method for degrading algal polysaccharides, comprising:
25g of algal polysaccharide was added to 75ml of the eutectic solvent of example 1, stirred and placed in an electric heating thermostat at 60 ℃ with stirring and heat preservation for 2 h. And (3) carrying out suction filtration on the obtained mixture by using a Buchner funnel padded with 300-mesh filter cloth, retaining the powdery solid on the filter cloth, and obtaining a liquid phase which is a eutectic solvent and can be repeatedly used. Mixing the powdery solid with 100ml of ethanol solution with the mass fraction of 75%, stirring at room temperature for 20 minutes, performing suction filtration by using a Buchner funnel padded with 300-mesh filter cloth, drying the obtained powdery solid in a hot air drying box at 60 ℃ to obtain the algal polysaccharide degradation product, wherein the obtained liquid phase is the ethanol solution dissolved with the eutectic solvent, and separating the ethanol and the eutectic solvent by distillation, wherein the ethanol and the eutectic solvent can be repeatedly used.
Example 7
The method for degrading algal polysaccharide provided by this example is different from example 6 in that the mixture of algal polysaccharide and eutectic solvent is stirred and kept for 6 hours in an electric heating constant temperature jacket at 60 ℃.
Test example 1
Degradation of different algal polysaccharides
The following algal polysaccharides were treated using the method of example 6: agar (commercially available, Hainan Dafu), carrageenan (commercially available, Jiaji), sodium alginate (commercially available, Qingdao Mingyue), fucoidin (commercially available, Qingdao Jiejing), ulva polysaccharide (extracted from ulva powder by the method described in Algal Research 39 (2019) 101422) for degradation, and the above seaweed polysaccharides are all in powder appearance.
Using gel chromatography-differential-multi-angle laser light scattering: (GPC-RI-MALS) and the molecular weight of the seaweed polysaccharide and its degradation product, with a mobile phase of 0.1M NaNO3The detectors were Optilab T-rEX and DAWN HELEOS II (Wyatt technology, CA, USA) used in series at a flow rate of 0.4 ml/min at a column temperature of 45 ℃ and the analytical columns were Ohpak SB-805 HQ (300X 8 mm), SB-804 HQ (300X 8 mm), SB-803 HQ (300X 8 mm) used in series. 5 mg of sample is added with 1 ml of mobile phase, after shaking and dissolving at 45 ℃, the sample is centrifuged for 10 min at 14000 r/min, 100 mul of supernatant is taken for sample loading detection, and the obtained molecular weight determination results are shown in table 1.
TABLE 1 molecular weight determination results
Wherein, Mn: a number average molecular weight; mw: weight average molecular weight.
The GPC-RI-MALLS measurement results of agar, carrageenan, sodium alginate, fucoidin and ulvan before and after degradation are respectively shown in figures 1-5, wherein: (a) shows a GPC-RI-MALLS chart before degradation; (b) shows a GPC-RI-MALLS chart after degradation. The result shows that the method has obvious degradation effect on different algal polysaccharides.
Test example 2
Molecular weight determination of degradation products (liquid mass method)
The method of example 7 was used to degrade different algal polysaccharides and the molecular weight of the algal polysaccharide degradation products was determined by liquid chromatography-mass spectrometry. The mass spectrum data of the degradation products of agar, carrageenan, sodium alginate, fucoidan and ulvan are respectively shown in fig. 6-fig. 10. The results show that the five algal polysaccharides selected in the invention, including agar, carrageenan, sodium alginate, fucoidan and ulvan polysaccharide, all contain disaccharide, trisaccharide (the segment with the theoretical molecular weight of 300-750) and oligosaccharide with larger molecular weight (the mass-to-charge ratio m/z is less than or equal to 2000) segments, and the mass spectrum data verifies the existence of degradation products and the effectiveness of the degradation method.
Test example 3
The degradation degree of algal polysaccharide is controlled by time, temperature and organic acid dosage
The test design is carried out according to the Box-Behnken method by taking sodium alginate as a raw material and the eutectic solvent of the embodiments 1-3 as a liquid phase medium, setting the temperature at 50 ℃, 60 and 70 ℃ respectively and setting the treatment time at 3, 4 and 5h respectively, and the other operations are the same as the embodiment 6. The degradation parameters for each test, as well as the viscosity and number average molecular weight Mn of the sodium alginate degradation products obtained, are shown in Table 2. And (3) performing regression analysis on the kinematic viscosity (eta) and the number average molecular weight Mn of the sodium alginate degradation product by taking time, temperature and the weight part of citric acid in each 100 weight parts of eutectic solvent as parameters, and establishing a quadratic ternary equation. Wherein the viscosity measurement is to measure the viscosity of a 3% aqueous solution of the degradation product by using an NDJ-5S type rotational viscometer, and the viscosity is in positive correlation with the molecular weight, so that the molecular weight can be approximately represented by the viscosity. The viscosity of untreated sodium alginate at the same concentration is 7520 mPa.s, the Mn is 198.6 kDa, the viscosity of degradation products at different treatment parameters is 3.58-74.8 mPa.s, and the Mn is 15.4-60.8 kDa, which shows that the treated sodium alginate is obviously degraded.
TABLE 2 results of degradation parameters, viscosity of degradation products and number average molecular weight Mn
Wherein the equation of the square root of the kinematic viscosity of the sodium alginate degradation product "Sqrt (eta)" with the time (A), the temperature (B) and the weight part (C) of citric acid in each 100 weight parts of eutectic solvent is as follows:
Sqrt(η)=101.95060-5.17165*A-2.34950*B-2.61460*C+0.066023*A*B+
0.019391*A*C+0.022803*B*C+0.074275*A2+0.014379*B2+0.046666*C2
the fit equation F-value is 28.34 and P-value is 0.0001, indicating that the fit is extremely significant.
The equation of the square root of the kinematic viscosity of sodium alginate degradation products "Sqrt (η)" and the number average molecular weight Mn (x) is: sqrt (η) = 0.0012x2 + 0.0475x + 1.1591，R² = 0.9672。
According to the model and the equation, the influence factors on the degradation degree of the sodium alginate are temperature, the weight part of citric acid in each 100 weight parts of eutectic solvent and time in sequence, and the temperature and the weight part of the citric acid in each 100 weight parts of eutectic solvent, the temperature and the time have obvious interaction.
The target number average molecular weight of the sodium alginate degradation product is set to be 30, 50, 80 and 100kDa, the numerical values of the parameters of temperature, time and percentage content of citric acid are deduced reversely according to an equation, and the number average molecular weight of each degradation sample is determined after tests are carried out according to the numerical values of the parameters, the result is shown in Table 3, the difference between the actual measurement value and the theoretical value is only 2kDa within the theoretical value range of the number average molecular weight of 30 and 50kDa, and the difference between the actual measurement value and the theoretical value is about 6kDa within the theoretical value range of the number average molecular weight of 80 and 100kDa, and the accuracy of the model is more effective for the heterogeneous substance of algal polysaccharide, which is the specific molecular weight, which indicates that the algal polysaccharide degradation product can be obtained by controlling the degradation conditions of algal polysaccharide.
TABLE 3 comparison of theoretical and measured results
Test example 4
Infrared spectra scans of untreated sodium alginate and samples of degradation products from example 6 were performed at different degrees of degradation. The scanning results are shown in fig. 11, in which: (a) untreated sodium alginate, number average molecular weight 198.6 kDa; (b) sodium alginate degradation products with the number average molecular weight of 71.3 kDa; (c) sodium alginate degradation products with the number average molecular weight of 38.3 kDa; (d) sodium alginate degradation products with the number average molecular weight of 15.4 kDa. The results showed that there was no significant change in the overall peak shape and the position of each characteristic absorption peak, indicating that the degradation treatment of the present invention had no effect on the sugar chain structural characteristics of algal polysaccharides.
And carrying out surface scanning electron microscope imaging analysis on the sodium alginate and the degradation products thereof. The results of the analysis are shown in FIG. 12, (a) untreated sodium alginate, number average molecular weight 198.6 kDa; (b) sodium alginate degradation products with the number average molecular weight of 112.4 kDa; (c) sodium alginate degradation products with the number average molecular weight of 15.4 kDa; (d) untreated sodium alginate, number average molecular weight 198.6 kDa; (e) sodium alginate degradation products with the number average molecular weight of 112.4 kDa; (f) sodium alginate degradation products with the number average molecular weight of 15.4 kDa, wherein scales (a) - (c) are 50 mu m, and scales (d) - (f) are 2 mu m. The result shows that the seaweed polysaccharide particles after degradation treatment still keep the original particle shape, but the surface appearance is changed, the surface roughness is increased, corrosion-like appearances such as holes, gullies and the like appear, and the corrosion-like appearances are more obvious along with the increase of the degradation degree, which indicates that the degradation occurs on the surfaces of the seaweed polysaccharide particles and gradually deepens.
It should be noted that there are differences between different molecular weight determination methods, and different molecular weight determination results can be obtained by using different methods for the same sample.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The eutectic solvent for degrading algal polysaccharide is characterized in that the eutectic solvent is formed by mixing a hydrogen bond acceptor and a hydrogen bond donor, wherein the amount of the hydrogen bond acceptor is 30-40% of the mass of the eutectic solvent; wherein the hydrogen bond receptor is choline chloride, and the hydrogen bond donor is prepared from the following components in a mass ratio of (24-30): (25-35): (5-11) glucose, urea and citric acid.
2. The eutectic solvent for degrading algal polysaccharide according to claim 1, wherein the amount of the hydrogen bond acceptor is 35% of the mass of the eutectic solvent.
3. The eutectic solvent for degrading algal polysaccharide according to claim 1 or 2, wherein the hydrogen bond donor is prepared from (24-30): 30: (5-11) glucose, urea and citric acid.
4. The method for preparing the eutectic solvent for degrading algal polysaccharide according to any one of claims 1 to 3, wherein the hydrogen bond acceptor and the hydrogen bond donor are heated at a temperature of 90-110 ℃ under stirring to be melted into liquid.
5. A method for degrading algal polysaccharide, characterized in that algal polysaccharide is added into the eutectic solvent of any one of claims 1 to 3, stirred for 1 to 8 hours at 50 to 70 ℃, and solid-liquid separation is carried out, and the obtained solid phase is the algal polysaccharide degradation product.
6. The method for degrading algal polysaccharide according to claim 5, wherein the mass volume ratio of algal polysaccharide to the eutectic solvent is 1: (3-4).
7. The method for degrading algal polysaccharides of claim 5, wherein said method for degrading algal polysaccharides further comprises: the solid phase was washed with an ethanol solution and then dried.
8. The method for degrading algal polysaccharides of claim 7, wherein the ethanol solution is 30% -95% by mass; the drying temperature is 50-70 ℃.
9. A method for preparing algal polysaccharide degradation product with controllable molecular weight, which is characterized in that algal polysaccharide is mixed with the eutectic solvent of any one of claims 1 to 3 and then stirred at a preset temperature B for a preset time A, wherein the algal polysaccharide degradation product has a number average molecular weight Mn which is equal to the number average molecular weight Mn of the algal polysaccharide degradation product and is stirred at the preset temperature B for the preset time A, the preset temperature B, the preset time B, the preset temperature B, the preset time A, the preset time B, the temperature B, the preset time A, the preset time B, the seaweed polysaccharide degradation product, the time B, the seaweed polysaccharide degradation product, the time B,the amount of citric acid C satisfies the following formula: 0.0012x2 + 0.0475x + 1.1591=101.95060-5.17165*A-2.34950*B-2.61460*C+0.066023*A*B+
0.019391*A*C+0.022803*B*C+0.074275*A2+0.014379*B2+0.046666*C2X is the number average molecular weight Mn of algal polysaccharide degradation products, A is more than or equal to 1 and less than or equal to 8, B is more than or equal to 50 and less than or equal to 70, and C is the weight part of citric acid in each 100 weight parts of the eutectic solvent; and obtaining the seaweed polysaccharide degradation product with the target molecular weight by controlling the preset temperature B, the preset time A and the dosage C of the citric acid.
10. The method as claimed in claim 9, wherein the ratio of the algal polysaccharide to the eutectic solvent is 1: (3-4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210019325.9A CN114014947B (en) | 2022-01-10 | 2022-01-10 | Eutectic solvent for degrading algal polysaccharide and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210019325.9A CN114014947B (en) | 2022-01-10 | 2022-01-10 | Eutectic solvent for degrading algal polysaccharide and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114014947A CN114014947A (en) | 2022-02-08 |
| CN114014947B true CN114014947B (en) | 2022-07-08 |
Family
ID=80069695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210019325.9A Active CN114014947B (en) | 2022-01-10 | 2022-01-10 | Eutectic solvent for degrading algal polysaccharide and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114014947B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114990172A (en) * | 2022-06-10 | 2022-09-02 | 合肥工业大学 | Xylaria extracellular polysaccharide and eutectic solution extraction method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110251462B (en) * | 2019-07-31 | 2021-08-10 | 浙江海洋大学 | Oral liquid with blood pressure lowering and antithrombotic effects |
| CN110684129A (en) * | 2019-09-10 | 2020-01-14 | 北京理工大学 | Sodium alginate green preparation method based on choline eutectic solvent |
| CN112695029B (en) * | 2020-12-25 | 2022-05-31 | 北京雷力海洋生物新产业股份有限公司 | Genetic engineering strain for high yield of fucoidin degrading enzyme and preparation method thereof |
| CN112794930B (en) * | 2021-02-02 | 2023-03-21 | 菏泽高新区优科生物科技有限公司 | Liquid medium for degrading beta-glucan and method for degrading beta-glucan |
-
2022
- 2022-01-10 CN CN202210019325.9A patent/CN114014947B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114014947A (en) | 2022-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ale et al. | Designed optimization of a single-step extraction of fucose-containing sulfated polysaccharides from Sargassum sp. | |
| Wang et al. | Sulfated modification, characterization and structure–antioxidant relationships of Artemisia sphaerocephala polysaccharides | |
| Shingel | Current knowledge on biosynthesis, biological activity, and chemical modification of the exopolysaccharide, pullulan | |
| Moreno et al. | Chemical and rheological properties of an extracellular polysaccharide produced by the cyanobacterium Anabaena sp. ATCC 33047 | |
| Murano | Chemical structure and quality of agars from Gracilaria | |
| Martínez-Sanz et al. | Advanced structural characterisation of agar-based hydrogels: Rheological and small angle scattering studies | |
| Guidara et al. | Effect of extraction procedures on the chemical structure, antitumor and anticoagulant properties of ulvan from Ulva lactuca of Tunisia coast | |
| Wang et al. | Nanostructures assembly and the property of polysaccharide extracted from Tremella Fuciformis fruiting body | |
| Wang et al. | Synthesis and characterization of phosphorylated galactomannan: the effect of DS on solution conformation and antioxidant activities | |
| CN114014947B (en) | Eutectic solvent for degrading algal polysaccharide and preparation method and application thereof | |
| Osada et al. | Effect of sub-and supercritical water treatments on the physicochemical properties of crab shell chitin and its enzymatic degradation | |
| CN111234047B (en) | Exopolysaccharide rich in fucose and preparation method and application thereof | |
| CN108727509B (en) | Moso bamboo shoot shell arabinogalactan and preparation and application thereof | |
| Li et al. | Structure of a fucose-rich polysaccharide derived from EPS produced by Kosakonia sp. CCTCC M2018092 and its application in antibacterial film | |
| Zhu et al. | Purification, in-depth structure analysis and antioxidant stress activity of a novel pectin-type polysaccharide from Ziziphus Jujuba cv. Muzaoresidue | |
| Mendonça et al. | Characterization of levan produced by a Paenibacillus sp. isolated from Brazilian crude oil | |
| US11952436B2 (en) | Ultrasound and pressure assisted method for extracting pectin rich in RG-I | |
| Guezennec et al. | Sulfation and depolymerization of a bacterial exopolysaccharide of hydrothermal origin | |
| Shi et al. | Primary structure, physicochemical properties, and digestive properties of four sequentially extracted polysaccharides from Tremella fuciformis | |
| Jouanneau et al. | Hybridity of carrageenans water-and alkali-extracted from Chondracanthus chamissoi, Mazzaella laminarioides, Sarcothalia crispata, and Sarcothalia radula | |
| Abad et al. | NMR analysis of fractionated irradiated κ-carrageenan oligomers as plant growth promoter | |
| Jakhu et al. | Production and characterization of microalgal exopolysaccharide as a reducing and stabilizing agent for green synthesis of gold-nanoparticle: a case study with a Chlorella sp. from Himalayan high-altitude psychrophilic habitat | |
| CN105237644B (en) | A kind of cellulose with low degree and preparation method thereof | |
| Volk et al. | Structural investigation of a polysaccharide released by the cyanobacterium Nostoc insulare | |
| Raguénes et al. | A novel exopolymer-producing bacterium, Paracoccus zeaxanthinifaciens subsp. payriae, isolated from a “kopara” mat located in Rangiroa, an atoll of French Polynesia |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |