CN109650350B - Method for large-scale preparation of polysaccharide modified nano-selenium and application - Google Patents
Method for large-scale preparation of polysaccharide modified nano-selenium and application Download PDFInfo
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Abstract
The invention belongs to the field of selenium resource utilization, and particularly relates to a method for preparing polysaccharide modified nano-selenium in a large scale and application thereof. The method comprises the steps of mixing a polysaccharide aqueous solution and a reducing agent aqueous solution, adding deionized water to obtain a mixed solution, then adding a sodium selenite aqueous solution, uniformly stirring, and purifying to obtain a polysaccharide modified nano-selenium aqueous solution. The invention provides a simple preparation method for large-scale industrial production of nano-selenium, and better solves the problems of corrosion and pollution caused by acetic acid in the industrial production process. The increase of the reaction system to industrial scale is a huge breakthrough compared to other small scale laboratory reaction systems. The prepared polysaccharide modified nano-selenium is 80-120 nm in size and is relatively stable. Therefore, the selenium-enriched food can be widely applied to selenium-enriched products, selenium-enriched foods and various medical products.
Description
Technical Field
The invention belongs to the field of selenium resource utilization, and particularly relates to a method for preparing polysaccharide modified nano-selenium in a large scale and application thereof.
Background
Selenium is a necessary trace element for animals and plants, and plays a certain role in antioxidant defense, immune regulation and anti-aging. Selenium deficiency is one of the common diseases of livestock and poultry. Selenium cannot be synthesized by a human body per se and must be taken in from the outside, the selenium belongs to an ultra-trace element in the geological chemistry, and the natural selenium only has one stable isotope with the atomic weight of 79. From the prior art it is known that the grey element selenium and the black element selenium are almost biologically inactive and toxic, while the knowledge of the biological properties of the red element selenium is vague. Selenium is a metalloid element in the fourth period, and the research on selenium by scientists in China mainly focuses on the properties and the application of selenium, for example, gray selenium is widely applied to the technical fields of photocells, copy and the like because of good light spot characteristics and unidirectional conductivity. The crystal form selenium has lower melting point, photoconductivity and high activity, and has wide market application in the field of chemical industry. For example, CN 105707659 a discloses an antidote prepared by compounding nano-selenium, chitosan and mycotoxin in a ratio and a preparation method thereof, but the synthesis conditions are harsh and the requirements on equipment are high. CN 1264521C discloses a nano-selenium prepared by reacting chitin (including chitosan, water-soluble chitosan and chitosan oligosaccharide) with selenium compound, which is only suitable for small-scale production. CN 104825484B discloses a preparation method of chitosan or carboxymethyl chitosan functionalized nano selenium compound, but potassium iodide is additionally added in the reaction process, thereby causing waste of chemical reagents. CN 104496954B discloses a method for preparing functionalized nano-selenium, but it also uses acetic acid in the preparation process of the reaction, which is not favorable for industrial production. CN 103420344B discloses a method for synthesizing nano-selenium at normal temperature and normal pressure, wherein the synthesized nano-selenium has smaller size. CN 108208349A discloses the application of nano-selenium in agricultural production and processing, and expands the application of selenium in the aspects of food, health care products and the like. CN 105154474B provides a biological preparation method of red nano-selenium, which not only can reduce the production cost of nano-selenium, but also opens up new medicinal value and health care application for chlorella pyrenoidosa. In the existing nano-selenium synthesis process, surface modification is basically carried out by adding polysaccharide, surfactant, protein and the like, so that the stability of nano-selenium is improved. These methods can achieve better modification results in laboratory scale experiments. However, when the volume is increased to 10 liters or even higher, the problems of insolubility of the modifier, serious aggregation and precipitation, complicated subsequent separation, great toxic and side effects and the like exist. Taking chitosan as an example, the most widely used nano selenium synthesis modifier is prepared by using 10 liters or 30 liters of reaction system according to the empirical formula ratio of small-scale synthesis, even a large amount of acetic acid can not be well dissolved, and the nano selenium synthesis modifier causes damage to reaction equipment and environmental pollution. Similar problems exist with other modifying agents that are currently used in large quantities. In general, the existing nano-selenium technology has the following disadvantages: 1. at present, all patents for synthesizing nano selenium are small-scale synthesis, and industrial large-scale production cannot be carried out; 2. in the prior art, when nano-selenium is synthesized, the added modifier needs to be pretreated, so that the problems of complex process, expensive nano-selenium cost, environmental pollution, equipment corrosion and the like are caused. Therefore, the development of a simple, environment-friendly, and large-scale nano-selenium synthesis technology is urgently needed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a method for preparing polysaccharide modified nano selenium in a large scale.
The invention also aims to provide application of the method for preparing the polysaccharide modified nano-selenium on a large scale.
The purpose of the invention is realized by the following scheme:
a method for preparing polysaccharide modified nano selenium in a large scale comprises the following steps:
(1) mixing and stirring a polysaccharide aqueous solution and a reducing agent aqueous solution to obtain a mixed solution 1;
(2) adding water into the mixed solution 1 obtained in the step (1), and continuously stirring to obtain a mixed solution 2;
(3) adding a sodium selenite aqueous solution into the mixed solution 2 obtained in the step (2), uniformly stirring to form a reaction system, and reacting to obtain a polysaccharide modified nano selenium aqueous solution;
(4) and (4) purifying the polysaccharide modified nano-selenium aqueous solution obtained in the step (3) to obtain a purified polysaccharide modified nano-selenium aqueous solution.
The polysaccharide in the step (1) is at least one of lentinan, chitosan, water-soluble chitosan derivatives, chitosan oligosaccharide, corious versicolor polysaccharide, agrocybe aegerita polysaccharide and auricularia auricula polysaccharide.
The lentinan is derived from lentinus edodes fruiting bodies.
The concentration of the polysaccharide in the polysaccharide aqueous solution in the step (1) is 5-10 g/L.
The reducing agent in the step (1) is preferably vitamin C (Vc).
The concentration of the reducing agent in the reducing agent water solution in the step (1) is 50-80 mM.
The stirring conditions in the step (1) are as follows: stirring for 15-60 minutes at 50-120 rpm; preferably at 90 rpm, for 30 minutes.
The amount of the water used in the step (2) is calculated according to the proportion of 50-100L of water to 100-200 g of polysaccharide.
The stirring conditions in the step (2) are as follows: stirring for 5-20 minutes at 40-80 rpm.
And (4) the concentration of sodium selenite in the sodium selenite aqueous solution in the step (3) is 2-4 g/L.
And (3) in the reaction system in the step (3), the mass ratio of the polysaccharide to the reducing agent to the sodium selenite is (0.1-5): 1: (0.1-1); preferably (0.5-2): 1: (0.17-1); more preferably (0.6 to 0.8): (0.9-1.1): (0.4-0.6); most preferably 0.7: 1: 0.5.
the volume of the reaction system in the step (3) is 50L or more, preferably 50 to 1000L, more preferably 100 to 1000L, more preferably 200 to 500L, and most preferably 500L.
The stirring conditions in the step (3) are as follows: stirring for 2-5 minutes at 50-100 rpm.
The reaction conditions in the step (3) are as follows: the pressure is 0.1-1 MPa, the reaction temperature is 15-70 ℃, and the reaction time is 4-12 h;
preferably, the reaction conditions in step (3) are: the pressure is 0.1MPa, the reaction temperature is 50 ℃, and the reaction time is 8 h.
And (4) performing ultrafiltration on the polysaccharide modified nano-selenium aqueous solution obtained in the step (3) by using a filter membrane.
The specification of the filter membrane is a filter membrane with the cut-off molecular weight of 1-200 KD; preferably, the filter membrane with the molecular weight cut-off of 5-100 KD; more preferably, the filter has a molecular weight cut-off of 5kD, 10kD or 100 kD.
The method for preparing the polysaccharide modified nano-selenium on a large scale is applied to the preparation of the polysaccharide modified nano-selenium on a large scale.
The large scale is the scale with the reaction system of more than 50L, preferably the scale with the reaction system of 50-1000L; further preferably 100-1000L of reaction scale; further preferably 200-1000L; the most preferable reaction scale is 200-500L.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention provides a simple preparation method for industrially producing nano-selenium on a large scale, which increases a reaction system to an industrial scale, and is a huge breakthrough compared with other reaction systems in small-scale laboratories.
2. The traditional modifier polysaccharide needs pretreatment, so that the cost of the synthesized nano selenium is expensive, or stable nano selenium cannot be obtained, and the production process is complex.
Drawings
FIG. 1 is an infrared spectrum of 500L lentinan-nano-selenium, elemental nano-selenium and lentinan in example 1.
FIG. 2 is the UV spectrum of 500L lentinan-nano selenium of example 1.
FIG. 3 is a graph showing the three yields of 500L lentinan-nano-selenium in example 1.
FIG. 4 is a graph of experimental results of different polysaccharide-modified nano-selenium prepared in examples 4-7; wherein, the picture (A) is chitosan oligosaccharide, the picture (B) is coriolus versicolor polysaccharide, the picture (C) is agrocybe aegerita polysaccharide, and the picture (D) is auricularia auricula polysaccharide.
FIG. 5 is a graph showing the particle size and potential of the selenium nanoparticles prepared in examples 8 to 11; wherein, the graph (A) is a particle size graph and the graph (B) is a potential graph.
FIG. 6 is a graph showing the pre-and post-dialysis solubility of lentinan-nano-selenium prepared in example 11; wherein, the picture (A) is a 25mL lentinan picture-solubility picture before nano-selenium dialysis, and the picture (B) is a potential picture of 25mL lentinan picture-solubility picture after nano-selenium dialysis.
FIG. 7 is a graph comparing particle size and potential of lentinan-nanoselenium prepared in example 1, example 11 and example 12 on different scales; wherein, the graph (A) is a particle size graph, and the graph (B) is a potential graph.
FIG. 8 is a transmission electron microscope result chart of lentinan-nano-selenium prepared in example 1, example 11 and example 12; wherein, the picture (a) is a transmission electron microscope picture of nano-selenium of a 25mL reaction system, and is multiplied by 37000; FIG. (b) is a transmission electron micrograph of nano-selenium, x 97000, in a 10L reaction system; FIG. (c) is a transmission electron micrograph of nano-selenium, X97000, of a 500L reaction system.
Fig. 9 is a graph comparing the stability of lentinan-nanoselenium prepared in example 1, example 11 and example 12 on different scales.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
In a 500 liter reactor, 100L of 10g/L lentinan (Shaanxi Fuke natural products Co., Ltd., 1 kg/bag 50%, CAS No. 37339-90-5) aqueous solution and 100L of 80mM Vc aqueous solution were mixed uniformly. Pumping the mixed solution into a 500L fermentation tank, adding water to 450L, starting the fermentation tank, stirring at the stirring speed of 90 r/min for 5min, and continuously mixing the lentinan aqueous solution and the Vc aqueous solution uniformly. Then, 30L of an aqueous solution containing 700g of sodium selenite was slowly added thereto using a low pressure water pump. Sealing the fermentation tank, setting the revolution number to be 70 r/min, and reacting for 8h under the conditions that the pressure is 0.1MPa and the reaction temperature is 50 ℃. After the reaction is finished, the prepared lentinan modified nano water selenium solution is led out through a discharge hole of the fermentation tank and is placed in a clean barrel. Then filtering the nanometer selenium water solution modified by lentinan by a filter membrane (the cut-off molecular weight is 10KD) to obtain the purified nanometer selenium water solution modified by lentinan (called lentinan-nanometer selenium for short), and storing at the temperature of 4 ℃.
FIG. 1 is an infrared spectrum of lentinan-nano-selenium, elemental nano-selenium and lentinan prepared in example 1. As shown in the figure, the nano-selenium and the hydroxyl on the lentinan act to ensure that the stretching vibration peak of-OH is 3400cm -1 Blue shifting to 3434cm -1 ，-H 2 The deformation vibration peak of O + is from 1600cm -1 The blue is shifted to 1650cm -1 Which shows the successful combination of the nano-selenium and the lentinan.
FIG. 2 is the UV spectrum of lentinan-nano-selenium prepared in example 1. It can be known from the figure that the nano-selenium produced in the embodiment has a strong absorption peak at a wavelength of about 280nm, and because the lentinan alone has no absorption peak, the ultraviolet spectrum obtained by the experiment has one more absorption peak, which is caused by the appearance of the nano-particles, and thus the successful synthesis of the lentinan modified nano-selenium is illustrated.
The experiment of example 1 was repeated 3 times, and fig. 3 is a graph showing the yield of lentinan-nano-selenium prepared by three experiments. As can be seen from the figure, the yield of the nano-selenium obtained by 3 times of industrial production is about 50 percent, which shows that the repeatability of the test is good, namely the reaction condition for preparing the nano-selenium on a large scale is mature, and the yield is stable.
Example 2
In a 25ml reactor, chitosan (national medicine group chemical reagent limited, biochemical reagent, batch number 20160525, 100 g/bottle) is used as a modifier to prepare nano-selenium. First, 0.05g of chitosan was mixed with 5mL of 80mM Vc aqueous solution, 0.2mL of 1% (v/v) acetic acid was added to dissolve the mixture, 5mL of water was added thereto, and the mixture was stirred at 90 rpm for 5 min. Then, 5mL of 23.3g/L aqueous sodium selenite solution was added thereto, and the mixture was reacted at 50 ℃ under 0.1MPa for 8 hours with an rpm of 70, whereby the resulting solution was a transparent orange solution. And finally, filtering the chitosan-modified nano-selenium aqueous solution by a filter membrane (the cut-off molecular weight is 10KD) to obtain a purified chitosan-modified nano-selenium aqueous solution, wherein the appearance of the purified chitosan-modified nano-selenium aqueous solution is orange, and the purified chitosan-modified nano-selenium aqueous solution is stored at the temperature of 4 ℃.
After the obtained orange solution is placed for 120 hours, a large amount of lime-red flocculent precipitates appear, the precipitates cannot be evenly shaken and dispersed, and the chitosan nano selenium precipitates in a large amount and has poor stability.
Example 3
Nano-selenium was prepared in a 25ml reactor by replacing the acid soluble chitosan of example 2 with carboxymethyl chitosan (degree of substitution greater than 80%, mclin Mackin). First, 0.05g of carboxymethyl chitosan is uniformly mixed with 5mL of Vc aqueous solution with the concentration of 80mM, then 5mL of water is added, and the mixture is stirred for 5min at 90 r/min. Then 5mL of sodium selenite aqueous solution with the concentration of 23.3g/L is added, the rotation speed is set to be 70 r/min, and the reaction is carried out for 8h at 50 ℃ under 0.1 MPa. Finally, filtering the carboxymethyl chitosan modified nano selenium aqueous solution through a filter membrane (the cut-off molecular weight is 10KD) to obtain a purified carboxymethyl chitosan modified nano selenium aqueous solution, and storing at 4 ℃.
The experimental result shows that although carboxymethyl chitosan is easily dissolved in water, when the Vc aqueous solution is dripped into the mixed solution of carboxymethyl chitosan and sodium selenite, nano selenium rapidly coagulates, and the nano selenium with stable property can not be prepared.
Example 4
The difference between this example and example 3 is that chitosan (molecular weight: 3600, CAS number 148411-57-8, qingdao boshi-shiji biotechnology limited) is used instead of chitosan as a modifier to prepare nano-selenium, and the specific steps are as follows: in a 25mL reactor, 0.05g of chitosan oligosaccharide is uniformly mixed with 5mL of Vc aqueous solution with the concentration of 80mM, and the mixture is stirred for 5min at 90 r/min; then, 5mL of an aqueous solution of sodium selenite at a concentration of 23.3g/L was added thereto, the reaction was carried out at a rotation speed of 70 rpm at 50 ℃ under 0.1MPa for 8 hours, and the reaction mixture was filtered through a filter (molecular weight cut-off: 10KD) at the end of the reaction. The prepared chitosan oligosaccharide nano selenium has improved stability, but is still easy to aggregate and precipitate in the dialysis process.
Example 5
The difference between the embodiment and the embodiment 3 is that the nano-selenium is prepared by using coriolus versicolor polysaccharide (molecular weight is more than 1.3 × 106, 1 kg/bag, purity of 10% -50%, Shanxi Yuning Biotech Co., Ltd.) as a modifier, and the specific steps are as follows: in a 25mL reactor, 0.05g coriolus versicolor polysaccharide and 5mL Vc aqueous solution with the concentration of 80mM are mixed uniformly and stirred for 5min at 90 r/min. Finally adding 5mL of sodium selenite aqueous solution with the concentration of 23.3g/L, setting the revolution number to be 70 r/min, reacting for 8h at the temperature of 50 ℃ under 0.1MPa, and filtering through a filter membrane (the molecular weight cut-off: 10KD) after the reaction is finished. The obtained coriolus versicolor polysaccharide nano selenium aqueous solution is still easy to coagulate.
Example 6
The difference between the embodiment and the embodiment 3 is that the tea mushroom polysaccharide (1 kg/bag, 98% of radix angelicae dahuricae biotechnology limited) is used as a modifier to prepare the nano-selenium, and the specific steps are as follows: in a 25mL reactor, 0.05g of agrocybe aegerita polysaccharide and 5mL of 80mM Vc aqueous solution are uniformly mixed, stirred for 5min at 90 r/min, then 5mL of 23.3g/L sodium selenite aqueous solution is added, the rotation number is set to be 70 r/min, the reaction is carried out for 8h at the temperature of 50 ℃ under 0.1MPa, and the mixture is filtered by a filter membrane (the molecular weight cut-off: 10KD) after the reaction is finished. The obtained agrocybe aegerita polysaccharide nano-selenium aqueous solution is still easy to coagulate.
Example 7
The difference between the embodiment and the embodiment 3 is that black fungus polysaccharide (30%, more than 80 mesh, 1 kg/bag, shanxi Ci Yuan biotechnology, Ltd.) is used as a modifier to prepare nano selenium, and the specific steps are as follows: in a 25mL reactor, 0.05g of auricularia auricula polysaccharide and 5mL of Vc aqueous solution with the concentration of 80mM are mixed uniformly, stirred for 5min at 90 r/min, then 5mL of sodium selenite aqueous solution with the concentration of 23.3g/L is added, the rotation number is set to be 70 r/min, the reaction is carried out for 8h at the temperature of 50 ℃ under 0.1MPa, and the filtration is carried out by a filter membrane (molecular weight cut-off: 10KD) after the reaction is finished. The obtained black fungus polysaccharide nano selenium aqueous solution is still easy to be coagulated.
FIG. 4 is an experimental image of the nano-selenium modified by different polysaccharides prepared in examples 4-7, wherein the chitosan oligosaccharide is shown in the drawing (A), the coriolus versicolor polysaccharide is shown in the drawing (B), the agrocybe cylindracea polysaccharide is shown in the drawing (C), and the auricularia auricular polysaccharide is shown in the drawing (D). The comparison shows that the chitosan oligosaccharide and the coriolus versicolor polysaccharide modified nano selenium can generate precipitation in the reaction process, and the agrocybe cylindracea polysaccharide and the black fungus polysaccharide can generate coagulation in the process of dialysis and purification of the nano selenium, which indicates that the four polysaccharides are not suitable for industrial production of the nano selenium.
Example 8
The difference between this example and example 3 is that tween 40 (molecular weight 1285) is used as a modifier to prepare nano-selenium, and the specific steps are as follows: in a 25mL reactor, 0.05g tween 40 was first mixed with 5mL of 80mM aqueous Vc solution and stirred at 90 rpm for 5 min. And finally, adding 5mL of sodium selenite aqueous solution with the concentration of 23.3g/L, setting the revolution number to be 70 r/min, reacting for 8h at 50 ℃ under 0.1MPa, and filtering through a filter membrane (the molecular weight cut-off: 10KD) after the reaction is finished to obtain the Tween 40 modified nano-selenium aqueous solution.
Example 9
The difference between this example and example 3 is that tween 60 (molecular weight 607) is used as a modifier to prepare nano-selenium, and the specific steps are as follows: in a 25mL reactor, 0.05g tween 60 was first mixed with 5mL of 80mM aqueous Vc solution and stirred at 90 rpm for 5 min. And finally, adding 5mL of sodium selenite aqueous solution with the concentration of 23.3g/L, setting the revolution number to be 70 r/min, reacting for 8h at 50 ℃ under 0.1MPa, and filtering through a filter membrane (the molecular weight cut-off: 10KD) after the reaction is finished to obtain the Tween 60 modified nano-selenium aqueous solution.
Example 10
The difference between this example and example 3 is that tween 80 (molecular weight 1312) is used as a modifier to prepare nano-selenium, and the specific steps are as follows: in a 25mL reactor, 0.05g tween 80 was first mixed with 5mL of 80mM aqueous Vc solution and stirred at 90 rpm for 5 min. And finally, adding 5mL of sodium selenite aqueous solution with the concentration of 23.3g/L, setting the revolution number to be 70 r/min, reacting for 8h at 50 ℃ under 0.1MPa, and filtering through a filter membrane (the molecular weight cut-off: 10KD) after the reaction is finished to obtain the Tween 80 modified nano-selenium aqueous solution.
Example 11
In a 25ml reactor, lentinan (Shaanxi Furan natural products Co., Ltd., 1 kg/bag 50%, CAS No. 37339-90-5) is used as a modifier to prepare nano-selenium. First, 0.05g of lentinan is mixed with 5mL of Vc aqueous solution with the concentration of 80mM uniformly, then 5mL of water is added, and the mixture is stirred for 5min at 90 r/min. Adding 5mL of sodium selenite aqueous solution with the concentration of 23.3g/L, setting the revolution number to be 70 r/min, reacting for 8h at 50 ℃ under 0.1MPa, filtering the obtained lentinan modified nano-selenium solution through a filter membrane (the molecular weight cut-off is 10KD) to obtain a purified lentinan modified nano-selenium aqueous solution, and storing at 4 ℃.
FIG. 5 is a graph showing the particle size and potential of the nano-selenium particles obtained by preparing Tween 40, Tween 60, Tween 80 and lentinan in examples 8 to 11. As can be seen from the figure, the particle size of the nano-selenium modified by lentinan is the smallest, and the potential is kept at 34.37ev, which shows that the modification of lentinan is more stable than that of tween, and is more beneficial to industrial production. FIG. 6 is a graph of the pre-and post-dialysis solubility of 25mL lentinan-modified nano-selenium of example 11. As can be seen from the figure, the solubility of the nano-selenium modified by the small-scale lentinan is not influenced in the dialysis process, and a good state is still kept, so that the lentinan can be used as a good modifier, and the feasibility of the method is preliminarily proved.
Example 12
In a 10-liter reactor, lentinan (Shaanxi forest Freund natural products Co., Ltd., 1 kg/bag 50%, CAS No. 37339-90-5) is used as a modifier to prepare the nano-selenium. First, 20g of lentinan and 2L of Vc aqueous solution with the concentration of 80mM are mixed uniformly, then 2L of water is added, and the mixture is stirred for 5min at 90 r/min. Adding 0.5L sodium selenite aqueous solution with concentration of 23.3g/L, setting rotation number at 70 r/min, reacting at 50 deg.C under 0.1MPa for 8 hr, filtering with filter membrane (molecular weight cut-off: 10KD) to obtain purified nanometer selenium solution modified by lentinan, and storing at 4 deg.C.
The particle size of the polysaccharide-modified nano-selenium prepared in example 1, example 11 and example 12 was characterized, and fig. 7 is a graph comparing the particle size (a) and potential (b) of the lentinan-modified nano-selenium prepared in example 1, example 11 and example 12 on different scales. As can be seen from the figure, the hydrated particle size of the nano-selenium obtained by three different reaction scales is kept about 120nm, and the potential value is kept near-15 mv, which illustrates that the reaction system of the invention for expanding the nano-selenium can not cause interference to the synthesis process. FIG. 8 is a transmission electron micrograph of lentinan-modified nanoselenium prepared according to example 1(500L lentinan), example 11(25mL lentinan) and example 12(10L lentinan), wherein Panel (a) is a transmission electron micrograph of nanoselenium at 37000 for a 25mL reaction system; FIG. (b) is a transmission electron micrograph of nano-selenium, x 97000, in a 10L reaction system; FIG. (c) is a transmission electron micrograph of nano-selenium, X97000, of a 500L reaction system. As can be seen from the figure, the actual particle size of the nano-selenium obtained by the three systems is 80-120 nm, and the stability and the dispersibility are good. Further, the stability of the polysaccharide-modified nano-selenium prepared in example 1, example 11 and example 12 was characterized. Fig. 9 is a graph comparing the stability of lentinan-nanoselenium prepared in example 1, example 11 and example 12 on different scales. As can be seen from the figure, the nano-selenium obtained by the three systems is placed for 21 days, the particle size change is not large, and the feasibility of the 500L lentinan nano-selenium synthesis scheme is proved.
Example 13
In a 10 liter reactor, chitosan is used as a modifier to prepare nano selenium. First, 20g of chitosan (national drug group chemical reagent Co., Ltd., biochemical reagent, batch 20160525, 100 g/bottle) was mixed with 2L of 80mM Vc aqueous solution, then 1% (v/v) acetic acid aqueous solution was used to dissolve the chitosan, 2L of water was added, and stirring was carried out at 90 rpm for 5 min. Then adding 2L of 23.3g/L sodium selenite aqueous solution, setting the revolution at 70 r/min, and reacting at 50 ℃ under 0.1MPa for 8 h. Then filtering the chitosan modified nano-selenium aqueous solution through a filter membrane (the cut-off molecular weight is 10KD) to obtain a purified chitosan modified nano-selenium aqueous solution, and storing at 4 ℃.
In the process of dissolving chitosan, it was found that chitosan was aggregated in a large amount and could not be dissolved. Even if the concentration of the acetic acid aqueous solution is increased to 5% (v/v) and 10% (v/v), the solubility of the chitosan is slightly increased but the chitosan cannot be completely dissolved, so that the subsequent preparation of the nano selenium cannot be carried out. And the use of high-concentration acetic acid not only causes the corrosion of the reactor, but also brings about the problem of environmental pollution. After the sodium selenite aqueous solution is added, the prepared nano-selenium is found to be precipitated in a large amount and has poor stability.
From the above results, it can be seen that the nano-selenium modified by chitosan oligosaccharide, coriolus versicolor polysaccharide, agrocybe cylindracea polysaccharide and auricularia auricula polysaccharide is very unstable and is not suitable for industrial production. The chitosan modified nano-selenium needs to be dissolved by additionally adding acetic acid, so that equipment is corroded, and pollution is brought; the water-soluble chitosan can be coagulated in pilot plant production, and the stable nano-selenium cannot be obtained. The particle size and stability of the nano-selenium modified by tween series are not as good as those of the nano-selenium modified by lentinan, and further, the nano-selenium modified by lentinan has good stability through the synthesis of systems with different scales by comparison, and is suitable for industrial production.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A method for preparing polysaccharide modified nano selenium in large scale is characterized by comprising the following steps:
(1) mixing and stirring polysaccharide or polysaccharide water solution and reducing agent water solution to obtain mixed solution 1;
(2) adding water into the mixed solution 1 obtained in the step (1), and continuously stirring to obtain a mixed solution 2;
(3) adding a sodium selenite aqueous solution into the mixed solution 2 obtained in the step (2), uniformly stirring to form a reaction system, and reacting to obtain a polysaccharide modified nano selenium aqueous solution;
(4) purifying the polysaccharide modified nano selenium solution obtained in the step (3) to obtain a purified polysaccharide modified nano selenium aqueous solution;
the polysaccharide in the step (1) is lentinan which is not subjected to any treatment;
the mass ratio of the polysaccharide to the reducing agent to the sodium selenite in the reaction system in the step (3) is (0.1-5): 1: (0.1 to 1);
the volume of the reaction system in the step (3) is more than 50L.
2. The method for large scale production of polysaccharide modified nano-selenium according to claim 1, wherein:
the reducing agent in the step (1) is vitamin C.
3. The method for large scale production of polysaccharide modified nano-selenium according to claim 1, wherein: the mass ratio of the polysaccharide to the reducing agent to the sodium selenite in the reaction system in the step (3) is (0.5-2): 1: (0.17-1).
4. The method for large scale production of polysaccharide modified nano-selenium according to claim 1, wherein:
the concentration of the polysaccharide in the polysaccharide aqueous solution in the step (1) is 5-10 g/L;
the concentration of the reducing agent in the reducing agent water solution in the step (1) is 50-80 mM;
the concentration of sodium selenite in the sodium selenite aqueous solution in the step (3) is 2-4 g/L.
5. The method for large scale production of polysaccharide modified nano-selenium according to claim 1, wherein: the amount of water used in the step (2) is calculated according to the proportion of 50-100L of water to 100-200 g of polysaccharide.
6. The method for large scale production of polysaccharide modified nano-selenium according to claim 1, wherein:
the reaction conditions in the step (3) are as follows: the pressure is 0.1-1 MPa, the reaction temperature is 15-70 ℃, and the reaction time is 4-12 h;
and (4) performing purification in a mode of performing ultrafiltration on the polysaccharide modified nano selenium solution obtained in the step (3) through a filter membrane with the molecular weight cutoff of 1-200 KD.
7. The method for large scale production of polysaccharide modified nano-selenium according to claim 1, wherein:
the stirring conditions in the step (1) are as follows: stirring for 15-60 minutes at 50-120 rpm;
the stirring conditions in the step (2) are as follows: stirring for 5-20 minutes at 40-80 rpm;
the stirring conditions in the step (3) are as follows: stirring for 2-5 minutes at 50-100 rpm.
8. The method of any one of claims 1 to 7, wherein the method is applied to large-scale preparation of the polysaccharide-modified nano-selenium.
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| CN111329876A (en) * | 2020-03-25 | 2020-06-26 | 广东暨创硒源纳米研究院有限公司 | Application of nano-selenium and modification thereof in preparation of anti-allergic drugs or anti-allergic preparations |
| CN112544982B (en) * | 2020-10-10 | 2022-09-27 | 暨南大学 | Nano-selenium pickering emulsion and preparation method and application thereof |
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| CN112970945B (en) * | 2021-03-03 | 2024-01-19 | 珠海暨创硒源纳米科技有限公司 | Method for preparing nano-selenium in liquid phase and mixing equipment |
| CN113768146B (en) * | 2021-07-29 | 2023-11-03 | 暨南大学 | Functional nano selenium hydrogen-rich water and preparation method and application thereof |
| CN113875989B (en) * | 2021-09-23 | 2023-09-29 | 山东安为先生物科技有限公司 | Functionalized water-soluble nano-selenium, preparation method and application |
| CN114031048B (en) * | 2021-11-09 | 2024-03-15 | 广州天科生物科技有限公司 | Preparation method of nano selenium |
| WO2023082213A1 (en) * | 2021-11-13 | 2023-05-19 | 暨南大学 | Novel coronavirus protein antigen nanovaccine, preparation method therefor and application thereof. |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357317A (en) * | 2000-12-15 | 2002-07-10 | 上海四通纳米技术港有限公司 | Prepn of superfine Se particle |
| CN1415310A (en) * | 2002-11-18 | 2003-05-07 | 安徽大学 | Nano selenium of chitin and its preparation method |
| CN103420344A (en) * | 2012-05-14 | 2013-12-04 | 武汉理工大学 | Preparation method for nano-selenium |
| CN106692181A (en) * | 2017-01-23 | 2017-05-24 | 暨南大学 | Application of nano-selenium serving as CIK (cytokine-induced killer) cell sensitizer |
| CN107412280A (en) * | 2016-02-16 | 2017-12-01 | 香港理工大学深圳研究院 | There are the nanometer selenium hydrosol and preparation, the store method and application of antitumor activity |
-
2019
- 2019-01-23 CN CN201910064563.XA patent/CN109650350B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357317A (en) * | 2000-12-15 | 2002-07-10 | 上海四通纳米技术港有限公司 | Prepn of superfine Se particle |
| CN1415310A (en) * | 2002-11-18 | 2003-05-07 | 安徽大学 | Nano selenium of chitin and its preparation method |
| CN103420344A (en) * | 2012-05-14 | 2013-12-04 | 武汉理工大学 | Preparation method for nano-selenium |
| CN107412280A (en) * | 2016-02-16 | 2017-12-01 | 香港理工大学深圳研究院 | There are the nanometer selenium hydrosol and preparation, the store method and application of antitumor activity |
| CN106692181A (en) * | 2017-01-23 | 2017-05-24 | 暨南大学 | Application of nano-selenium serving as CIK (cytokine-induced killer) cell sensitizer |
Non-Patent Citations (2)
| Title |
|---|
| "Construction of selenium nanoparticles / β-glucan composites for enhancement of the antitumor activity";Xuewei Jia et al.;《Carbohydrate Polymers》;20141012;第117卷;第2.3部分，图4 * |
| Xuewei Jia et al.."Construction of selenium nanoparticles / β-glucan composites for enhancement of the antitumor activity".《Carbohydrate Polymers》.2014,第117卷第434-442页. * |
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Denomination of invention: A method for large-scale preparation of polysaccharide modified selenium nanoparticles and its application Effective date of registration: 20230313 Granted publication date: 20220802 Pledgee: Bank of China Limited Guangzhou Development Zone Branch Pledgor: GUANGDONG JICHENG SELENIUM SOURCE NANO RESEARCH INSTITUTE Co.,Ltd. Registration number: Y2023980034693 |