阅读说明：本技术 一种硒纳米颗粒及其制备方法 (A kind of selenium nano particle and preparation method thereof ) 是由 高林 高玉聪 于 2019-08-06 设计创作，主要内容包括：本发明公开了一种硒纳米颗粒的制备方法,涉及有生物活性的单质硒相关技术领域,包括以下步骤：在0-100℃的反应温度下,使反应介质中的可溶性硒源和可溶性氧化还原试剂反应一段时间来制备的,所述反应介质中含有能亲和元素硒的大分子,选自可溶性蛋白或蛋白水解产物或它们的组合,所合成的颗粒的尺寸覆盖在20-100nm的范围内。本发明公开了一种尺寸范围为20-100nm的硒纳米颗粒。本发明通过将硒源与还原剂或氧化剂按照1：10-1：4比例,直接混合反应可以来制备稳定的超小尺寸硒颗粒,大分子通过硒和大分子的氮/氧之间的作用亲和吸附在超小硒颗粒的表面,这能保证超小硒颗粒在水溶液中能很好地分散,不聚集,具有更好的生物利用度。(The invention discloses a kind of preparation methods of selenium nano particle, include the elemental selenium correlative technology field of bioactivity, the following steps are included: under 0-100 DEG C of reaction temperature, soluble selenium source and dissolvable redox reagent in reaction medium is set to react a period of time to prepare, macromolecular containing the affine elemental selenium of energy in the reaction medium, selected from soluble protein or protein hydrolysate or their combination, the size of synthesized particle is covered in the range of 20-100nm.The invention discloses the selenium nano particles that a kind of size range is 20-100nm.The present invention by by selenium source and reducing agent or oxidant according to 1:10-1:4 ratio, direct hybrid reaction can prepare stable super-small granules of selenium, macromolecular passes through the affine surface for being adsorbed on extra small granules of selenium of effect between selenium and nitrogen/oxygen of macromolecular, this can guarantee that extra small granules of selenium can disperse well in aqueous solution, do not assemble, there is better bioavilability.)

1. a kind of preparation method of selenium nano particle, which comprises the following steps: under 0-100 DEG C of reaction temperature, Soluble selenium source and dissolvable redox reagent in reaction medium is set to react a period of time to prepare, the reaction medium In contain the combination macromolecular of affine elemental selenium, it is synthesized selected from soluble protein or protein hydrolysate or their combination The size of particle be covered in the range of 20-100nm.

2. a kind of preparation method of selenium nano particle according to claim 1, it is characterised in that:

The selenium atom on macromolecular and granules of selenium surface occurs affine.

3. a kind of preparation method of selenium nano particle according to claim 1, it is characterised in that:

The redox reagent can restore or aoxidize selenium source and form elemental selenium.

4. a kind of preparation method of selenium nano particle according to claim 1, it is characterised in that:

It is described with the affine macromolecular of selenium can the various biologies in source, including plant, animal, the thick digestion extraction of bacterium and fungi Object, selenium combination macromolecular should also include any type of mixing macromolecular and molecular modification, or the nucleic acid-protein digested Product and their modified molecules.

5. a kind of preparation method of selenium nano particle according to claim 1, it is characterised in that:

The selenium source can be selected from following selenic acid and selenium salt: H₂Se0₃, H₂Se0₄, Na₂Se0₃, Na₂Se, H₂Se, Na₂Se0₄, Na₂SSe0₃。

6. a kind of preparation method of selenium nano particle according to claim 1, it is characterised in that:

The selenium binding molecule with the concentration of at least 0.01% mass ratio exist in water reaction medium.

7. a kind of preparation method of selenium nano particle according to claim 1, it is characterised in that:

The reductant-oxidant is selected from l-Glutathione, L-cysteine, L-AA, citric acid, citrate, thio second Amide, the thio -6- azauridine of 2-, sulfide-oxidizing enzyme-gemma meat soup, 2- thiobarbituricacidα-, 2- thiocytosine, 1- thioglycerin, Thioglycolate salt culture solution, thioacetic acid, 6- thioguanine, thiolactic acid, thiomalic acid, 2- purinethol, thiocarbamide, 4- sulphur For uridine and H₂O₂。

8. a kind of selenium nano particle is that the size range being prepared according to the described in any item methods of claim 1-7 is The granules of selenium of 20-100nm.

9. a kind of selenium nano particle according to claim 8, it is characterised in that: including amorphous selenium in the granules of selenium Extra small granules of selenium.

10. a kind of selenium nano particle according to claim 8, it is characterised in that: the granules of selenium includes monoclinic crystal selenium Extra small granules of selenium.

Technical field

The present invention relates to the granules of selenium correlative technology fields for having bioactivity, and relate more specifically to a kind of with 20- The selenium nano particle of 100nm particle size and its preparation method of selenium nano particle.

Background technique

Selenium is microelement necessary to people, in principal mode is in the mammalian body existed in the form of selenoprotein, In The catalytic action played the role of in some enzyme reactions, selenium also have oxidation resistant.

Granules of selenium is made with certain fungies and bacterial reduction selenate and selenite, this is also microorganism removing toxic substances selenium Inorganic salts metabolic way (referring to Applied and Environmental Microbiology, 2004,70,52-60, Structural spectral features of selenium nanospheres produced by Se-respiring bacteria).It is present in microbial cell and extracellular (seeing above) by the granules of selenium that microorganism is detoxified, but these selenium Whether grain has the bioavilability that is utilized by plant or animal or absorption of human body, not studies have reported that.

Although the method for preparing granules of selenium is reported, pass through these report methods granules of selenium generated, due to Particle surface is not decorated stable molecule, granules of selenium be in aqueous solution it is unstable, they, which are readily collected in, is formed together more Big micron particles.Therefore, extra small granules of selenium that is stable, not being collected as micron order bulky grain is prepared, and then is kept this The bioavilability of granules of selenium is very important.

Summary of the invention

(1) the technical issues of solving

In view of the deficiencies of the prior art, the present invention provides a kind of selenium nano particle and preparation method thereof, background is solved The problem of being proposed in technology.

(2) technical solution

In order to achieve the above object, the present invention is achieved by the following technical programs:

A kind of preparation method of selenium nano particle, comprising the following steps: under 0-100 DEG C of reaction temperature, reaction is made to be situated between Soluble selenium source and dissolvable redox reagent reaction a period of time in matter contain parent come what is prepared in the reaction medium With the combination macromolecular of elemental selenium, it is selected from soluble protein or protein hydrolysate or their combination, synthesized particle Size is covered in the range of 20-100nm.

Optionally, the selenium atom on macromolecular and granules of selenium surface occurs affine.

Optionally, the redox reagent can restore or aoxidize selenium source and form elemental selenium.

Optionally, it is described with the affine macromolecular of selenium can the various biologies in source, including plant, animal, bacterium and fungi Thick digestion extract, selenium combination macromolecular should also include any type of mixing macromolecular and molecular modification, or the core of digestion Acid-protein product and their modified molecules.

Optionally, the selenium source can be selected from following selenic acid and selenium salt: H₂Se0₃, H₂Se0₄, Na₂Se0₃, Na₂Se, H₂Se, Na₂Se0₄, Na₂SSe0₃。

Optionally, the selenium binding molecule with the concentration of at least 0.01% mass ratio exist in water reaction medium.

Optionally, the reductant-oxidant is selected from l-Glutathione, L-cysteine, L-AA, citric acid, lemon Hydrochlorate, thioacetamide, the thio -6- azauridine of 2-, sulfide-oxidizing enzyme-gemma meat soup, 2- thiobarbituricacidα-, 2- α-sulphur born of the same parents are phonetic Pyridine, 1- thioglycerin, thioglycolate salt culture solution, thioacetic acid, 6- thioguanine, thiolactic acid, thiomalic acid, 2- sulfydryl are fast Purine, thiocarbamide, 4-thiourdine and H₂O₂。

It is the granules of selenium of 20-100nm that a kind of selenium nano particle, which is the size range being prepared according to the method described above,.

It optionally, include the extra small granules of selenium of amorphous selenium in the granules of selenium.

Optionally, the granules of selenium includes the extra small granules of selenium of monoclinic crystal selenium.

(3) beneficial effect

The present invention provides a kind of selenium nano particle and preparation method thereof, have it is following the utility model has the advantages that

(1), the present invention is by the way that by selenium source and reducing agent or oxidant, according to 1:10-1:4 ratio, direct hybrid reaction can be with Prepare stable super-small granules of selenium, macromolecular by effect between selenium and nitrogen/oxygen of macromolecular it is affine be adsorbed on it is super The surface of small granules of selenium, this can guarantee that extra small granules of selenium can disperse well in aqueous solution, does not assemble.

(2), extra small granules of selenium prepared by the present invention has better bioavilability, and better biological effectiveness can be made For a more efficiently nutrition addition.

Detailed description of the invention

Fig. 1 is the transmission electron microscopy of the granules of selenium between 22nm to the 70nm particle size range that the embodiment of the present invention one synthesizes Mirror photo figure.

Fig. 2 is the electron diffraction diagram for the amorphous selenium particle that the embodiment of the present invention one synthesizes.

Fig. 3 is that the transmission electron microscope of 30nm to size granules of selenium between 100nm that the embodiment of the present invention four synthesizes shines Piece figure.

Fig. 4 is the electron diffraction diagram for the monoclinic system granules of selenium that the embodiment of the present invention four synthesizes.

Specific embodiment

Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.

In the description of the present invention, it is to be understood that, term " center ", " longitudinal direction ", " transverse direction ", " length ", " width ", " thickness ", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom" "inner", "outside", " up time The orientation or positional relationship of the instructions such as needle ", " counterclockwise ", " axial direction ", " radial direction ", " circumferential direction " be orientation based on the figure or Positional relationship is merely for convenience of description of the present invention and simplification of the description, rather than the device or element of indication or suggestion meaning must There must be specific orientation, be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.

In the present invention, term "comprising", " comprising ", " having ", and any variant is intended to including for nonexcludability Object so that process, method, article, device or composition, the list it includes element be not necessarily limited to those elements, but It may include these other not expressly listed or intrinsic processes, method, article, equipment or component.Particle, ball, selenium Term in this application is interchangeably used, they all represent the extra small granules of selenium formed in reaction described here.It is right For those skilled in the art, the specific meanings of the above terms in the present invention can be understood according to specific conditions.

In addition, term " first ", " second " etc. are used for description purposes only, it is not understood to indicate or imply relatively important Property or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or Person implicitly includes one or more of the features.

Disclosed innovation provides one or more at least following advantages in various embodiments.However, not institute These advantages having all are derived from each disclosed innovation, these advantages are not limited to each claimed invention.

In general, selenium source compound, for example, the reducing agent of sodium selenite and about 4 times of molar ratio, such as lemon acid-mixed It closes.These materials are dissolved in the water reaction system containing selenium combination macromolecular first.In reaction medium, when granules of selenium When the 20-100nm range that size reaches, selenium combination macromolecular can be coated on the surface of granules of selenium, delay and stop granules of selenium The mutual aggregation further grown up between particle.Selenium combination macromolecular is often referred to polymer molecule, poly- or oligomeric including height Nucleotide, albumen, carbohydrate, peptides, soluble protein and nucleic acid molecules.These selenium combination high molecular materials can be incorporated into institute's shape At granules of selenium surface, enhance the electrostatic repulsion between different granules of selenium, prevent variable grain from further assembling.Lack selenium knot In the reaction medium for closing macromolecular, reaction polymerization can prepare unbodied or monoclinic system element granules of selenium, these selenium rapidly Grain will eventually become micron-sized granules of selenium, not have bioavilability.

In the invention of the disclosure, reproducibility reagent can be reducing agent or oxidant, can restore selenium salt into simple substance Selenium.

Such as a kind of reducing agent utilized that reacts is l-Glutathione

Na₂SeO₃+4GSH+H₂O→Se+2H₂O+2GSSG+2NaOH

What another reaction utilized is oxidant, such as H₂O₂

Na₂Se+H₂O₂→Se+2NaOH

Aggregation is formed simple substance granules of selenium by selenium atom generated, and the latter is to be made of selenium atom, and surface-assembled has surely Determine the macromolecular of granules of selenium.

In a preferred embodiment, reaction medium is water and at least contains a type of selenium combination macromolecular.Selenium combines big Molecule includes the nitrogen of amine or nucleic acid base, and the surface of particle is integrated to the selenium atom in granules of selenium generated, thus anti- Only particle is further grown.

In preferred embodiments, the amount of selenium combination macromolecular should be compatible with reactive component and reacts Jie aqueous Matter at least accounts for about 0.01% (mass ratio), preferably at least accounts for about 0.1%, it might even be possible to up to 80%.If it is desirable, can be same When using two or more selenium combination macromoleculars mixture.

In preferred embodiments, selenium binding molecule includes soluble protein, gathers/oligopeptides amino acid, microorganism ribose Nucleic acid or microorganism DNA, artificial synthesized ribonucleic acid or DNA, plant polyose, mushroom polysaccharide.

In a preferred embodiment, the selenium source, such as selenium salt or selenic acid are directly reacted with reducing agent, such as chemicals mercaptan or Hydroxyl alcohol or oxidant, such as 0₂, 0₃, H₂0₂Or free radical oxygen species.Other representative selenium sources include H₂Se0₃, H₂Se0₄, Na₂Se0₃, Na₂Se, H₂Se, Na₂Se0₄, Na₂SSe0₃Or analog well-known to those skilled in the art.It is other representative Reducing agent well-known to those skilled in the art includes cysteine, glutathione, ascorbic acid, mercaptan, citric acid, L- paddy Guang Sweet peptide, L-AA, citrate, thioacetamide, the thio -6- azauridine of 2-, sulfide-oxidizing enzyme-gemma meat soup, 2- are thio Barbiturates, 2- thiocytosine, 1- thioglycerin, thioglycolate salt culture solution, thioacetic acid, 6- thioguanine, thiolactic acid, Thiomalic acid, 2- purinethol, thiocarbamide, 4-thiourdine etc..Two or more selenium salt and two or more can be used The mixture of reducing agent is reacted.

In a preferred embodiment, at a temperature of between 0-100 DEG C, one or more above-mentioned two classes materials be blended in containing It is no more than 24 hours in the water-containing reacting medium of selenium combination macromolecular.Preferred reaction temperature is with different reactant and difference Selenium combination macromolecular and change.

For example, sodium selenite and L-cysteine are rubbed in the aqueous reaction system containing soluble legumin with about 1:4 You react than being reacted under conditions of preferred reaction temperature is about 40 DEG C.In the aqueous reaction body containing plant polyose In system, sodium selenide and H₂O₂With the molar ratio of about 1:1 preferred reaction temperature about at 80 DEG C under conditions of reacted. In the aqueous solution containing artificial synthesized ribonucleic acid, sodium selenite and sodium citrate are with the molar reactive ratio of about 1:6 excellent The reaction temperature of choosing is about to be reacted under conditions of 80 DEG C.In the aqueous reaction system containing plant polyose, selenic acid with L-AA with the reaction of about 1:4 molar ratio than preferred reaction temperature about at 70 DEG C under conditions of reacted.Most Whole product is granules of selenium of the particle size in 20-100nm of surface modification selenium combination macromolecular.

Selenium salt/acid can be reacted with mercaptan/hydroxyl alcohol in water-containing reacting medium with the molar ratio of 1:4.This ratio Example does not have king-sized influence to the quality of final products when being changed to 8:1 from 1:32.The concentration of preferred reactant selenium salt can To be changed to 0.5mol/L from 50umol/L, although higher and lower concentration can be used as.Reaction can if necessary To be stirred by blender.

The product of the reaction can obtain granules of selenium powder by simply removing water.Those skilled in the art can be passed through The method of known evaporation, filtering is realized.