CN110731351B - Environment-friendly easy-to-clean sterilization and preservation composition and preparation method thereof - Google Patents
Environment-friendly easy-to-clean sterilization and preservation composition and preparation method thereof Download PDFInfo
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- CN110731351B CN110731351B CN201911024034.3A CN201911024034A CN110731351B CN 110731351 B CN110731351 B CN 110731351B CN 201911024034 A CN201911024034 A CN 201911024034A CN 110731351 B CN110731351 B CN 110731351B
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- nano
- silver
- biosurfactant
- bacteriostatic
- nano silver
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- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 64
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000004321 preservation Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000003670 easy-to-clean Effects 0.000 title claims abstract description 8
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 77
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 53
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 42
- 239000011159 matrix material Substances 0.000 claims description 36
- 239000003876 biosurfactant Substances 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 30
- 230000003385 bacteriostatic effect Effects 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 230000000844 anti-bacterial effect Effects 0.000 claims description 17
- -1 silver-titanium dioxide compound Chemical class 0.000 claims description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
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- 238000002156 mixing Methods 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 12
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- 239000011259 mixed solution Substances 0.000 claims description 10
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920000136 polysorbate Polymers 0.000 claims description 8
- MFPVDOIQNSMNEW-UHFFFAOYSA-N silver oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Ag+] MFPVDOIQNSMNEW-UHFFFAOYSA-N 0.000 claims description 8
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- 239000003755 preservative agent Substances 0.000 claims description 6
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- 239000012752 auxiliary agent Substances 0.000 claims description 5
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- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
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- 239000003381 stabilizer Substances 0.000 claims description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- UJEADPSEBDCWPS-SGJODSJKSA-N (2R,3R)-1-[(3S,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]butane-1,2,3,4-tetrol Chemical group C1([C@@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)C([C@H](O)[C@H](O)CO)O UJEADPSEBDCWPS-SGJODSJKSA-N 0.000 claims 1
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- ZTOKUMPYMPKCFX-CZNUEWPDSA-N (E)-17-[(2R,3R,4S,5S,6R)-6-(acetyloxymethyl)-3-[(2S,3R,4S,5S,6R)-6-(acetyloxymethyl)-3,4,5-trihydroxyoxan-2-yl]oxy-4,5-dihydroxyoxan-2-yl]oxyoctadec-9-enoic acid Chemical compound OC(=O)CCCCCCC/C=C/CCCCCCC(C)O[C@@H]1O[C@H](COC(C)=O)[C@@H](O)[C@H](O)[C@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](COC(C)=O)O1 ZTOKUMPYMPKCFX-CZNUEWPDSA-N 0.000 description 4
- HVCOBJNICQPDBP-UHFFFAOYSA-N 3-[3-[3,5-dihydroxy-6-methyl-4-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyoxan-2-yl]oxydecanoyloxy]decanoic acid;hydrate Chemical compound O.OC1C(OC(CC(=O)OC(CCCCCCC)CC(O)=O)CCCCCCC)OC(C)C(O)C1OC1C(O)C(O)C(O)C(C)O1 HVCOBJNICQPDBP-UHFFFAOYSA-N 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
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- 231100000956 nontoxicity Toxicity 0.000 description 4
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- 238000003860 storage Methods 0.000 description 4
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- 229920001661 Chitosan Polymers 0.000 description 2
- 241001672694 Citrus reticulata Species 0.000 description 2
- 241000192125 Firmicutes Species 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
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- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
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- 235000010492 gellan gum Nutrition 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/154—Organic compounds; Microorganisms; Enzymes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/157—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/16—Coating with a protective layer; Compositions or apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Food Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Microbiology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to an environment-friendly and easy-to-clean type sterilization and preservation composition and a preparation method thereof. The components of the composition are green and environment-friendly, can be used for conventional sterilization and disinfection and fruit sterilization and preservation, and has simple preparation method and easy industrial amplification production.
Description
Technical Field
The invention belongs to the technical field of disinfectant preparation, and particularly relates to a composite disinfectant preparation loaded with nano-silver, and a preparation method and application thereof.
Background
In the current safe disinfection and sterilization preparation, the nano silver has strong antibacterial capability and broad-spectrum sterilization effect, can not be accumulated and generate toxicity on human bodies, is used as an antibacterial active material for a long time, is an ideal safe and environment-friendly antibacterial agent, and even can be used in the field of fruit preservation. The traditional silver antibacterial agent is mainly realized by a way of releasing silver ions, the silver ions are firmly adsorbed on a bacterial cell membrane by means of coulomb attraction and combined with membrane protein to cause structural change to generate damage, and the silver ions can further penetrate through a cell wall to enter bacteria to strongly attract sulfydryl in the bacteria body and be rapidly combined with the sulfydryl, so that the protein of the bacteria is solidified, the activity of cell synthase is damaged, and the cells lose division and proliferation capacity and die. The silver nanoparticles have excellent heat transfer property, conductivity and catalytic performance, and the silver nanoparticle material can be obtained by a nanotechnology preparation method. The silver nanoparticles are metal silver simple substances with the particle size of nanometer level. As a new generation of natural antibacterial agent, the silver nanoparticle antibacterial agent has the characteristics of broad-spectrum antibacterial property, safety and no toxicity. The nano silver has obvious antibacterial effect on several common bacteria, yeasts and molds, and has the strongest antibacterial effect on gram-positive bacteria, gram-negative bacteria and other bacteria; with the increase of the concentration and the time, the antibacterial rate of the nano silver is increased.
The prior art discloses a plurality of preparation methods of nano silver and application of nano silver in disinfection and sterilization of various objects, but reports of nano silver in food such as fruits are less.
The general fresh-keeping of fruits has physical and chemical fresh-keeping technologies, such as refrigeration, decompression or vacuum storage, and the chemical fresh-keeping technology uses a chemical fresh-keeping agent, but with more and more attention paid to the complete problem of foods, the chemical fresh-keeping agent is gradually abandoned, and the efficient and nontoxic safe and environment-friendly fresh-keeping agent is sought. The nano silver is a nano material with nano-sized silver particles, has unique properties of the nano material and has the characteristics of bacteriostasis, catalysis and the like of metal silver, so the nano silver can be used as an inorganic antibacterial agent and has wide application prospect in food preservation. However, although the nano-silver antibacterial agent has a good effect and is widely applied to the surface disinfection of objects such as ceramics, the application of the nano-silver directly used for fruit preservation is limited in consideration of adverse factors of heavy metals on human health and the influence of the color of the metal on the appearance of products.
Therefore, at present, a safe, non-toxic and easily-washed nano-silver composite preparation formulation is still lacked, and the nano-silver composite preparation formulation is used for disinfecting, sterilizing and preserving the surfaces of various objects so as to inhibit the breeding of various moulds and bacteria on the surfaces of various objects including fruits.
Another inorganic antimicrobial agent commonly used today is a metal oxide antimicrobial agent such as Ti02ZnO, etc. Wherein Ti02The photocatalytic antibacterial agent is typical of catalytic antibacterial agents, has the advantages of strong stability, no toxic or side effect, spectral antibacterial effect and the like, and can be used for photocatalytic sterilization and decomposition of toxins secreted by bacteria. Is suitable for being used as a component of the slow-release inorganic antibacterial agent.
In addition, in the prior art, the glycolipid biosurfactant has the advantages of no toxicity, biodegradability, environmental friendliness and the like, and has good application prospects in the aspects of environmental protection, foods, cosmetics, detergents, medicines and the like. Many documents report that some kinds of glycolipids have bacteriostatic effects. For example, sophorolipids have a strong inhibitory effect on bacteria, particularly gram-positive bacteria. In addition, the glycolipid surfactant also has good thermal stability, good acid-base tolerance and high salt tolerance. The microbial fertilizer is nontoxic, free of side effects, nontoxic, tasteless and free of stimulation to human bodies, can be rapidly degraded by other microorganisms in the nature, cannot be left, cannot damage and pollute the environment, and cannot pollute water sources. Can be used for sterilizing and refreshing fruits with skin such as apple, pear, orange, red fruit, cucumber, tomato, etc. The prior methods for synthesizing sophorolipid comprise a microbial fermentation method and a biological enzyme catalysis method.
The conventional silver-containing sterilizing and freshness-retaining agents are listed below.
CN2010102577566 discloses an environment-friendly sterilizing, disinfecting and antistaling agent, which is formed by mixing hydrogen peroxide solution and colloidal silver solution. The colloidal silver is mainly used as a hydrogen peroxide stabilizer, so that the problems of poor stability and poor sterilization effect of a pure hydrogen peroxide product are solved, and the main sterilization component is hydrogen peroxide.
The research on the preservation of Nanyin composite preservative on Nanfeng mandarin oranges (Nanchang university, Lepan) discloses a Nanfeng mandarin orange fruit preservative which is prepared by mixing 1 percent of carboxymethyl chitosan, 1 percent of chitosan and glycerol according to a certain proportion to prepare a pure clear solution, and then adding a certain amount of nano-silver zirconium oxide into the pure clear solution to prepare the nano-silver composite preservative. The invention mainly depends on nano silver to inhibit the invasion of postharvest pathogenic bacteria and reduce postharvest loss.
CN201410746810 discloses a multifunctional nano silver antibacterial agent, which is characterized in that: 0.5 to 2 percent of silver nitrate, 0.5 to 2 percent of reducing agent, 0.2 to 1.3 percent of gellan gum, 2.5 to 4 percent of surfactant, 1.5 to 3 percent of auxiliary agent and 79.7 to 93.8 percent of 75 percent alcohol.
However, the research on the sterilizing surfactant disinfectant preparation compounded with nano-silver is not reported.
Therefore, in order to expand the disinfection and preservation application of nano-silver, it is necessary to develop a novel nano-silver compound preparation which is safe, non-toxic and easy to clean, and is used for disinfecting or preserving objects including fruits.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the environment-friendly and easy-to-clean type sterilization and preservation composition and the preparation method thereof.
The specific technical scheme of the invention is as follows.
In a first aspect, the invention provides an environment-friendly and easy-to-clean type sterilization and preservation composition, which mainly comprises the following components:
1) and (2) component A: a nano silver-titanium dioxide compound loaded by mesoporous silica, and hydrogen peroxide.
2) And (B) component: bacteriostatic biosurfactant, organic solvent and emulsifier.
Wherein, the bacteriostatic biosurfactant is preferably degradable glycolipid biosurfactant;
the organic solvent at least comprises ethanol;
the emulsifier is selected from tween.
3) Auxiliary components, including deionized water and suitable auxiliaries, such as film formers, cosolvents, dispersants or stabilizers.
Wherein, preferably, the auxiliary agent is selected from polyvinylpyrrolidone.
In a second aspect, the invention provides a preparation method of the environment-friendly easy-cleaning type sterilization and preservation composition, which comprises the following steps 1) to 4):
step 1): preparing a silicon dioxide loaded nano silver particle compound suspension from the nano silver slurry and mesoporous silicon dioxide particles, adding a proper amount of nano titanium dioxide, vibrating and stirring to prepare a mesoporous silicon dioxide loaded nano silver-titanium dioxide compound suspension.
The specific process is as follows:
s1: adding nano-silver particles into distilled water to prepare nano-silver slurry with the mass fraction of 1-5%, adding mesoporous silica particles with the mass of 5-20 times that of the nano-silver, stirring the mixed solution on a magnetic stirrer for 15-30min, then ultrasonically oscillating the mixed solution in an ultrasonic oscillator for 5-15min, and then standing and adsorbing the mixed solution for 30min to obtain a nano-silver particle composite suspension loaded by the mesoporous silica;
s2: adding nano titanium dioxide into the prepared silica-loaded nano silver particle composite suspension, magnetically and rapidly stirring for 15-25min at 50-60 ℃, and then oscillating and adsorbing for 30-60min by a 100-plus-200 rpm shaking table to obtain the mesoporous silica-loaded nano silver-titanium dioxide composite suspension.
Wherein, the addition amount of the nano titanium dioxide particles is 5-10 times of the mass of the nano silver, and the particle size is 5-100 nm.
Wherein the particle size of the nano silver particles is in the range of 10-100nm, preferably 10-50 nm; the particle size of the mesoporous silica microsphere is 30-500nm (preferably 50-300nm), and the pore diameter is 10-50 nm.
Step 2): and mixing the prepared supported nano silver-titanium dioxide compound suspension and a hydrogen peroxide solution or a hydrogen peroxide colloidal silver ion solution, and uniformly stirring to obtain the disinfection matrix solution.
In the step, the mass ratio of the compound suspension to the hydrogen peroxide solution is controlled so that the mass ratio of the nano silver to the hydrogen peroxide is 1:50-200, preferably 1: 50-100.
Further, dilution can be performed to adjust the mass concentration of the nano-silver in the disinfection matrix solution to 0.01-0.1%, preferably 0.01-0.05%, by using deionized water.
Wherein, when the hydrogen peroxide colloidal silver ion solution is adopted, the colloidal silver ion is not more than 0.1 percent of the weight of the hydrogen peroxide. The colloidal silver ion hydrogen peroxide solution can be prepared by mixing according to a method common in the field or can be selected from commercial products, such as norfu disinfectant.
Alternatively, when the mixing is performed with a hydrogen peroxide solution, a proper amount of colloidal silver ions may also be added, the amount being 0.05 to 0.1 wt% by mass of hydrogen peroxide.
Wherein, the hydrogen peroxide solution is preferably of pharmaceutical grade, and the volume concentration can be 40-90%.
Step 3): preparing a bacteriostatic degradable surfactant solution:
dissolving a proper amount of biosurfactant in an ethanol mixed solvent added with a proper amount of cosolvent to obtain a biosurfactant solution with the weight percent of 5-10, and mixing and compounding the biosurfactant solution with Tween emulsifier and deionized water to obtain the bacteriostatic surfactant matrix liquid.
In this step, the biosurfactant is preferably a bacteriostatic degradable biosurfactant.
Wherein, the bacteriostatic degradable biosurfactant is selected from glycolipid biosurfactant, preferably mannosylerythritol lipid (such as MEL-A/MEL-B) or sophorolipid, and more preferably the composition of the two mixed in any proportion.
Wherein, the cosolvent is selected from dimethyl sulfoxide or ethyl acetate, and ethyl acetate is preferred when the cosolvent is used for sterilizing vegetables and fruits.
Wherein, the proportion of ethanol and cosolvent in the ethanol-cosolvent mixed solvent is 10: 1-5.
Preferably, the volume ratio is 10: 3-5.
Wherein the tween emulsifier is selected from tween 60 or tween 80, preferably tween 80; the mass ratio of the biosurfactant to the Tween is controlled to be 5-6: 1.
Further, the concentration of the matrix solution may be adjusted with deionized water so that the final mass fraction of biosurfactant in the matrix solution is 0.1-1 wt%, preferably 0.5-1 wt%.
Step 4): and adjusting the prepared disinfection matrix liquid and the bacteriostatic surfactant matrix liquid to proper concentrations, mixing, adding optional polyvinylpyrrolidone, and uniformly stirring to prepare the environment-friendly easily-cleaned bactericidal preservative composition.
Wherein the mass ratio of the diluted disinfection matrix liquid to the bacteriostatic surfactant matrix liquid is 1:0.5-1.5, preferably 1:0.5-1.
Wherein, the addition amount of the polyvinylpyrrolidone is preferably 0 to 0.05 percent by weight; when the polyvinyl pyrrolidone is used for film coating sterilization and fresh keeping, the addition amount of the polyvinyl pyrrolidone can be properly adjusted by those skilled in the art according to the required film forming time, for example, 0.05-0.5% by weight.
Wherein, polyvinylpyrrolidone iodine (PVP-I) can also be adopted to replace polyvinylpyrrolidone.
In a third aspect, the invention provides the use of the composition for sterilization and preservation.
The fresh-keeping comprises the sterilization and fresh-keeping of fruits and vegetables, in particular to the film coating sterilization and fresh-keeping treatment of fruits with skins.
The beneficial effects of the present invention include, but are not limited to, the following aspects.
1) The disinfection and sterilization composition of the supported nano silver-titanium dioxide and the antibacterial surfactant, provided by the invention, disperses silver nanoparticles among the mesoporous silicon dioxide and the titanium dioxide through adsorption, so that the silver nanoparticles are uniformly dispersed, direct contact with an object is avoided, and the problem that the effect of a common silver nano bactericide is not lasting enough is solved; the titanium dioxide is used as an inorganic bactericidal component with a strong effect and has a synergistic bactericidal effect.
2) The composite nano inorganic metal antibacterial agent is combined with the mesoporous carrier, and due to the ordered pore channel structure, the large and uniform pore diameter, the larger specific surface area and the pore volume of the carrier material, the nano silver has strong adhesive force, free nano silver is greatly reduced, and the dispersity is excellent; meanwhile, due to the addition of the nano titanium dioxide, the adhesiveness of the nano silver particles is further improved, the slow-release effect is good, and the nano silver particles are matched with a film-forming component, so that the nano silver particle has the advantages of stable antibacterial performance, long sterilization time, convenience in use and the like, and has no toxic or side effect on the environment.
3) The carrier material has huge surface area and abundant pore structures, so that the carrier material can well adsorb foreign bacteria, prevent the bacteria from directly contacting with objects, form a locally enhanced sterilization effect due to the enrichment of nano silver on the surface of the carrier, and simultaneously maintain the long-term effective metal ion concentration.
4) The nano silver and colloidal silver particles not only have the sterilization function, but also have the stabilizing effect on the hydrogen peroxide, effectively inhibit the decomposition of the hydrogen peroxide and improve the storage time of the hydrogen peroxide.
5) The active agent adopts bacteriostatic degradable biological surfactant, the raw materials have bacteriostatic property, have no toxicity in chemical property and no side effect, are safe even being used for preserving foods, have no toxicity or stimulation to human bodies, can be rapidly degraded by microorganisms in the nature, do not remain, and do not damage and pollute the environment; the polyvinylpyrrolidone used as the auxiliary agent is also a food additive with higher safety.
6) The sterilization, disinfection and preservation composition disclosed by the invention contains the surfactant with good film-forming property and the polyvinylpyrrolidone, so that the sterilization, disinfection and preservation composition is suitable for sterilization, coating and preservation of fruits; meanwhile, due to the existence of the surfactant, the effect of quick cleaning can be achieved without an external detergent.
7) The product of the invention has wide application, and can be used for disinfecting the surfaces of daily life appliances and can also be used for disinfecting hand sanitizer and cleaning solution by adjusting the concentration; the addition amount of the polyvinylpyrrolidone is adjusted, and the sterilization coating preservative can also be used for sterilization coating preservation of fruits and vegetables, particularly fruits with skins.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.
Example 1
A preparation method of an environment-friendly and easy-to-clean type sterilization and preservation composition comprises the following steps:
1) preparing a mesoporous silica-loaded nano silver-titanium dioxide compound suspension:
s1: adding 10-20nm nano silver particles into distilled water to prepare 1L of nano silver slurry with the mass fraction of 2%, adding 210g of mesoporous silica particles, stirring the mixed solution on a magnetic stirrer for 15min, then continuously performing ultrasonic oscillation on the mixed solution in an ultrasonic oscillator for 10min, and then standing and adsorbing the mixed solution for 30min to obtain a silica-loaded nano silver particle composite suspension;
s2: and adding 155g of nano titanium dioxide into the prepared nano silver particle composite suspension loaded by the silicon dioxide, heating to 60 ℃, rapidly stirring for 20min under magnetic stirring, and then placing on a shaking table at 100rpm for oscillation and adsorption for 60min to obtain the nano silver-titanium dioxide composite suspension loaded by the mesoporous silicon dioxide.
2) And mixing the prepared supported nano silver-titanium dioxide compound suspension and 4.05kg of 50% hydrogen peroxide solution by mass, and uniformly stirring to prepare the disinfection matrix solution.
Further, a part of the disinfection matrix liquid is diluted by deionized water until the mass concentration of the nano-silver is 0.02%, so as to obtain diluted disinfection matrix liquid, and 1kg of the diluted disinfection matrix liquid is removed for standby.
3) Preparing bacteriostatic surfactant matrix liquid
S1: dissolving a composite biosurfactant composed of mannose erythritol ester (MEL-A) and sophorolipid in an equal mass ratio in an ethanol-ethyl acetate mixed solvent with the volume ratio of 10:3 to obtain a biosurfactant solution with the weight percent of 5;
s2: adding Tween 80 accounting for 20% of the mass of the surfactant into the biosurfactant solution, adding a proper amount of deionized water, and fully stirring and emulsifying to obtain a disinfection matrix solution; and (3) taking part of the disinfection matrix liquid to be diluted by deionized water until the mass concentration of the biosurfactant is 0.8 wt% for standby.
4) Mixing 1kg of the diluted disinfection matrix liquid obtained in the step 2) and 0.8kg of the diluted bacteriostatic surfactant matrix liquid obtained in the step 3), adding 1g of polyvinylpyrrolidone, and uniformly stirring to prepare the environment-friendly and easily-cleaned sterilization and preservation combined liquid.
Example 2
1) Preparing a mesoporous silica-loaded nano silver-titanium dioxide compound suspension:
s1: adding 20nm nano-silver particles into distilled water to prepare 100mL of nano-silver slurry with the mass fraction of 3%, adding 30g of mesoporous silica particles, stirring the mixed solution on a magnetic stirrer for 12min, then continuously performing ultrasonic oscillation in an ultrasonic oscillator for 15min, and then standing and adsorbing for 30min to obtain a silica-loaded nano-silver particle composite suspension;
s2: adding 15g of nano titanium dioxide into the prepared nano silver particle composite suspension loaded by the silicon dioxide, heating to 50 ℃, rapidly stirring for 20min under magnetic stirring, and then placing on a shaking table at 200rpm for oscillation and adsorption for 60min to obtain the nano silver-titanium dioxide composite suspension loaded by the mesoporous silicon dioxide.
2) And mixing the prepared supported nano silver-titanium dioxide compound suspension and 1.2kg of 50% hydrogen peroxide solution by mass, and uniformly stirring to prepare the disinfection matrix solution.
Further, diluting the disinfection matrix liquid with deionized water until the mass concentration of the nano-silver is 0.01%, and obtaining the diluted disinfection matrix liquid for later use.
3) Preparing bacteriostatic surfactant matrix liquid
S1: dissolving sophorolipid biosurfactant in an ethanol-ethyl acetate mixed solvent with the volume ratio of 10:5 to obtain 5 wt% biosurfactant solution;
s2: adding Tween 60 accounting for 20% of the mass of the surfactant into the biosurfactant solution, adding a proper amount of deionized water, and fully stirring and emulsifying to obtain a disinfection matrix solution;
s3: and (3) taking part of the disinfection matrix liquid to be diluted by deionized water until the mass concentration of the biosurfactant is 0.6 wt% for standby.
4) Mixing 1kg of the diluted disinfection matrix liquid obtained in the step 2) and 0.5kg of the diluted bacteriostatic surfactant matrix liquid obtained in the step 3), adding 0.5g of polyvinylpyrrolidone, and uniformly stirring to prepare the environment-friendly and easily-cleaned sterilization and preservation combined liquid.
Comparative example 1
Comparative example 1 was obtained by following the same procedure as in example 2 except that the supported nano silver-titanium dioxide composite suspension was replaced with a suspension having the same nano silver concentration (without mesoporous silica and nano titanium dioxide), and the product was designated as D1.
Comparative example 2
Only the diluted disinfection matrix solution (nano-silver mass concentration of 0.01% and hydrogen peroxide concentration of 2%) obtained in step 2) of example 2 was contained, and the product was recorded as D2.
Comparative example 3
Comparative example 3 was obtained by adjusting the mass concentration of the surfactant to 0.5 wt% while only containing the bacteriostatic surfactant-based liquid prepared in the same manner as in step 3) of example 2, and the product was denoted as D3.
Effect example 1
Bactericidal test
The sterilization performance of each composition is compared through the diameter of the inhibition zone, and the specific method is as follows: making filter paper into a round piece with a diameter of about 5-6mm, placing the round piece into a culture dish, covering the round piece, performing high-pressure sterilization treatment at 121 ℃, drying the round piece, immersing the round piece into different bacteriostatic composition solutions for 2-3min, drying the round piece for later use, and soaking the round piece in distilled water to be used as a blank control; clamping each filter paper disc treated by the composition solution by using sterile tweezers, placing the filter paper disc in a check type culture medium coated with a saprophytic bacteria suspension (penicillium, aspergillus and yeast saprophytic bacteria separated from the surface of a rotten apple), placing 2-3 discs on each culture medium, covering a culture dish, placing the culture dish in a thermostat at 28-30 ℃, culturing for 36h, starting observation, selecting a uniform and completely sterile growth inhibition zone, measuring the average diameter of the inhibition zone by using a vernier caliper (at least taking the average value of three groups), and recording the result (taking more than 10mm as sensitivity); meanwhile, the antibacterial persistence is detected by continuously observing for 3-5 days. The results are shown in the following table.
TABLE 1 zone of inhibition diameter test
According to the test results, except for the distilled water control treatment group, each group has an obvious bacteriostatic circle, and the bacteriostatic action on various pythium pathogens is proved. The inhibition zone of the test group of example 1-2 was significantly increased compared to the control group, which demonstrated that there was a synergistic interaction between the components.
With the increase of the culture time to the 5 th day, the filter paper sheets of the blank control group gradually grow mildew spots, the inhibition zones of the groups of the comparative examples 1 to 3 are obviously reduced, the color of the culture medium is gradually deepened, while the inhibition zones of the examples 1 to 2 are only slightly reduced, the color change is light, and the results prove that the supported nano-silver composite preparation has an obvious antibacterial effect and a lasting slow-release effect.
Effect example 2
Testing of fruit and vegetable freshness retaining property
100 ripe fresh tomatoes with similar sizes and complete surfaces, namely eight to nine ripe fresh tomatoes with similar sizes, are selected for each group, the products of the embodiment 1 and the comparative examples 1-3 are respectively used for spray coating treatment (no treatment is carried out on a blank control group), then the groups are placed in a constant temperature box with relative humidity of 45% at 25 ℃ for 11 days, and the total weight loss rate of the tomatoes of each group along with the preservation time and the rotting rate (percentage of rotted fruits to the total fruits and retention percentage integral value) after the test are observed. The weight loss results are shown in the table below.
Table 2 tomato weight loss ratio test
After the test is finished, the decay rates of the groups of the examples 1, D1-D3 and the blank group are respectively as follows: 0%, 2%, 4%, 3%, and 14%.
The weight loss rate is an important index of the fruit and vegetable fresh-keeping effect, the moisture content of the tomatoes is high, and the moisture is reduced under the respiratory metabolism and transpiration action during storage, so that the saturation and the glossiness are reduced. Compared with the control, the weight loss rate of the tomatoes in the coating treatment group of the sterilizing and refreshing composition in the example 1 is obviously reduced, and the weight loss rate is slowly increased along with the prolonging of the storage period; the weight loss rate of the D2 treatment group is higher than that of other control groups, so that the water retention of the simple disinfection treatment is not as good as that of the coating preservation treatment containing the surfactant and the polyvinylpyrrolidone; the product of example 1 containing mesoporous silica and titania forms a layer of modified atmosphere film on the surface of the object after coating treatment, which weakens cellular respiration and water transpiration, and the durability of the slow release effect and the sterilization capability are significantly stronger than those of the control group.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should also be understood that various alterations, modifications and/or variations can be made to the present invention by those skilled in the art after reading the technical content of the present invention, and all such equivalents fall within the protective scope defined by the claims of the present application.
Claims (6)
1. An environment-friendly easy-cleaning type sterilization and preservation composition is characterized by at least comprising the following components:
1) the disinfection matrix liquid comprises the following components: a mesoporous silica-supported nano silver-titanium dioxide composite and hydrogen peroxide;
2) the bacteriostatic biosurfactant matrix liquid comprises the following components: bacteriostatic biosurfactant, organic solvent and emulsifier;
wherein the organic solvent comprises at least ethanol;
the emulsifier is selected from Tween emulsifiers;
3) auxiliary components including deionized water and suitable auxiliaries;
the auxiliary agent is selected from at least one of a film forming agent, a cosolvent, a dispersing agent or a stabilizing agent;
wherein the bacteriostatic biosurfactant is selected from mannosylerythritol lipids, sophorolipids or a mixture thereof; and the auxiliary agent at least comprises polyvinylpyrrolidone.
2. A method for preparing the environment-friendly easy-to-clean sterilizing and refreshing composition as claimed in claim 1, which is characterized by comprising the following steps:
1) preparing a silica-loaded nano silver particle composite suspension from nano silver slurry and mesoporous silica particles, adding a proper amount of nano titanium dioxide, vibrating and stirring to prepare a mesoporous silica-loaded nano silver-titanium dioxide composite suspension;
2) mixing the prepared supported nano silver-titanium dioxide compound suspension and a hydrogen peroxide solution or a hydrogen peroxide colloidal silver ion solution, and uniformly stirring to prepare a disinfection matrix solution; controlling the mass ratio of the supported nano silver-titanium dioxide compound suspension to the hydrogen peroxide solution to enable the mass ratio of nano silver to hydrogen peroxide in the supported nano silver-titanium dioxide compound suspension to be 1:50-200, and adjusting the concentration of the disinfection matrix solution to 0.01-0.1% by mass with deionized water;
3) dissolving a proper amount of bacteriostatic biosurfactant in an ethanol mixed solvent added with a cosolvent to obtain a bacteriostatic biosurfactant solution with the weight percent of 5-10, and mixing and compounding the bacteriostatic biosurfactant solution with a Tween emulsifier and deionized water to obtain bacteriostatic biosurfactant matrix liquid;
wherein, deionized water is used for adjusting the concentration of the matrix liquid so that the final mass fraction of the bacteriostatic biosurfactant in the matrix liquid is 0.1-1 wt%;
4) and adjusting the prepared disinfection matrix liquid and the bacteriostatic biosurfactant matrix liquid to proper concentrations, mixing, adding a proper amount of polyvinylpyrrolidone, and uniformly stirring, thereby preparing the environment-friendly easily-cleaned bactericidal preservative composition.
3. The method according to claim 2, wherein the specific process of step 1) is as follows:
s1: adding nano-silver particles into distilled water to prepare nano-silver slurry with the mass fraction of 1-5%, adding mesoporous silica particles with the mass of 5-20 times that of the nano-silver, stirring the mixed solution on a magnetic stirrer for 15-30min, then ultrasonically oscillating the mixed solution in an ultrasonic oscillator for 5-15min, and then standing and adsorbing the mixed solution for 30min to obtain a nano-silver particle composite suspension loaded by the mesoporous silica;
s2: adding nano titanium dioxide into the prepared silica-loaded nano silver particle composite suspension, magnetically and rapidly stirring for 15-25min at 50-60 ℃, and then oscillating and adsorbing for 30-60min by a 100-plus-200 rpm shaking table to obtain the mesoporous silica-loaded nano silver-titanium dioxide composite suspension.
4. The preparation method according to claim 3, wherein the nano titanium dioxide particles are added in an amount of 5 to 10 times the mass of the nano silver particles; the particle size of the nano silver particles is 10-100 nm.
5. The method of claim 2, wherein:
the proportion of the ethanol to the cosolvent is 10: 1-5;
the cosolvent is selected from dimethyl sulfoxide or ethyl acetate;
the Tween emulsifier is selected from Tween 60 or Tween 80;
the mass ratio of the bacteriostatic biosurfactant to the Tween emulsifier is 5-6: 1.
6. Use of a composition according to claim 1 or a composition obtainable by a process according to any one of claims 2 to 5 as a disinfectant for disinfecting or refreshing vegetables and fruits.
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