WO2019113880A1

WO2019113880A1 - Protective agent for ancient bone resources

Info

Publication number: WO2019113880A1
Application number: PCT/CN2017/116123
Authority: WO
Inventors: 吕绍武; 张全超; 朱泓; 葛丹阳
Original assignee: 吉林大学
Priority date: 2017-12-14
Filing date: 2017-12-14
Publication date: 2019-06-20
Also published as: ZA201804005B; AU2018100753A4

Abstract

Disclosed is a protective agent for ancient bone resources, which is prepared by mixing a binder, propylene glycol, an antioxidant enzyme mimic, a plant extract antioxidant, an antibacterial agent, a preservative, a lysozyme and water. The binder therein comprises either of a water soluble protein and a water soluble starch. The synergistic effect of the components of the protective agent is enhanced through the coordination of different substance ingredients and contents thereof. The protective agent has excellent reversibility, protection, oxidation resistance and antibacterial ability after being sprayed on ancient bones. The protective agent does no harm to the human body and guarantees the safety of operators and visitors.

Description

An ancient bone resource protection agent

Technical field

The invention relates to the field of ancient bone resource protection, in particular to an ancient bone resource protection agent.

Background technique

China's history has a long history and has a long history. It has a history of more than 5,000 years. Ancient ruins are one of the most important Chinese cultural resources reserved for future generations. They are also precious national treasures. The cultural values they imply and the call for national consciousness and national consciousness are much higher than the value of material wealth. The remains unearthed from the remains of the site (ancient bone resources) are important cultural heritages reflecting the origin and development of the Chinese nation, a valuable material evidence of the history of Chinese civilization and culture, an important carrier of the history of civilization development in China for thousands of years, and a history of Chinese history. The “treasures” in the cultural heritage, these ancient bone resources are unique, irreplaceable, non-renewable, and it is urgent to properly preserve it.

At present, there are many kinds of protective agents for ancient bone resources, mainly resin-based protective agents, including: natural resin and nitro varnish, acrylic colloid dispersion system, acrylic emulsion product, polyvinyl acetate, polyvinyl alcohol Butyraldehyde, acrylic resin, trimethyl resin (methyl methacrylate-butyl methacrylate-methacrylic acid copolymer), in addition to polyethylene glycol (PEG) protective agent, but with people Their use, their shortcomings are gradually exposed, and their common shortcomings are poor reversibility and toxicity.

Natural resin and nitro varnish have poor reinforcement, and they have a certain color, which is not conducive to the protection and ornamental effect of the remains. It has not been put into use at present; the dispersion of acrylic colloid has not been produced in China, and the utilization rate is very small; The emulsion product has poor reversibility and is not used frequently. Polyvinyl acetate is not only poorly reversible, but its anti-aging effect can not meet people's needs. The reversibility of polyvinyl butyral is better than the above two materials, but the aging resistance effect Poor, irreversible after aging, damage to the bones; acrylic resin will affect the values of δ ¹⁵ N and δ ¹³ C, which is not conducive to the identification of the bones, and is often protected by acrylic resin after sampling; A protective agent used, which does not affect the identification of the sample, but has poor reversibility, and is dissolved by toxic organic reagents such as toluene and chloroform, posing a certain threat to the health of operators and visitors, and also has a certain environmental impact. Hazard. In addition to resin-based materials, polyethylene glycol (PEG) is also used for the protection of ancient bone resources, but it is easy to adhere to dust in high-humidity environments and is not currently in use.

Poor reversibility means that after the resin-based protective agent is applied to ancient bones by spraying or dripping, the curing action of the resin-based protective agent can reinforce the ancient bones, but at the same time, between the ancient bones and between the ancient bones and the soil. The blockage makes it difficult to remove the cured resin-based protective agent and does not return the ancient bones to the original bone texture state. The disadvantage of poor reversibility of the resin-based protective agent limits the re-acquisition and subsequent research of ancient bone samples using the resin as a protective measure.

Too much toxicity means that the resin-based protective agent often uses toluene and chloroform as solvents. For the operator's body: mild exposure to chloroform can cause conjunctival congestion and skin edema, and long-term exposure can lead to many diseases such as embryo toxicity, teratogenicity, liver necrosis or liver cancer, so the resin protective agent is operated. The body is very toxic. For archaeological sites such as Qinghai Minhe Lajia Site, Qinghai Ledu Liuwan Cemetery, Inner Mongolia Hamin Bus Station, etc., which have high attention and need to be displayed for a long time, the resin protection agent is also harmful to the visitors. Larger: Resin solvents such as chloroform and toluene can enter the visitor by inhalation or absorption through the skin, irritating the mucous membrane and anesthetizing the central nervous system, causing dizziness, headache, vomiting, weakness of the limbs, and confusion.

Summary of the invention

It is an object of the present invention to provide an ancient bone resource protecting agent to solve the above problems.

Specifically, the present invention relates to the following:

An ancient bone resource protecting agent, which comprises the following components: 10-25 parts of a binder, 10-25 parts of propylene glycol, 0.01-0.3 parts of an antioxidant enzyme mimetic according to 100 parts by weight of a protective agent, Plant extract antioxidant 0.01-0.05 parts, preservative 0.001-0.003 parts, lysozyme 0.1-0.3 parts, the balance is water;

The binder includes any one of a water-soluble protein and a water-soluble starch.

2. The ancient bone resource protecting agent according to Item 1, which comprises the following components: 12-22 parts by weight of the protective agent, 12-23 parts of propylene glycol, and 0.02 of antioxidant enzyme mimetic. - 0.25 parts, plant extract antioxidant 0.02-0.05 parts, preservative 0.0015-0.0025 parts, lysozyme 0.15-0.28 parts, the balance is water.

3. The ancient bone resource protecting agent according to Item 1 or 2, characterized in that it comprises the following components: According to 100 parts by weight of the protective agent, 13-20 parts of binder, 13-31 parts of propylene glycol, 0.04-0.22 parts of antioxidant enzyme mimetic, 0.03-0.045 parts of plant extract antioxidant, 0.0017-0.0023 parts of preservative, lysing The enzyme is 0.18-0.25 parts, and the balance is water.

4. The ancient skeletal resource protecting agent according to any one of items 1 to 3, wherein the water-soluble protein is any one or more of bovine serum albumin and soybean water-soluble protein.

5. The ancient bone resource protecting agent according to any one of items 1 to 4, wherein the binder is a water-soluble protein, and the water-soluble protein is 10-part by weight of the protective agent. 25 parts, preferably 12-22 parts of water-soluble protein, further preferably 13-20 parts of water-soluble protein.

The ancient bone resource protecting agent according to any one of items 1 to 5, wherein the binder is a water-soluble starch, and the water-soluble starch is 10-part by weight of the protective agent. 25 parts, preferably water soluble starch is 16-18 parts.

The ancient bone resource protecting agent according to any one of items 1 to 6, wherein the preservative is sorbic acid and a salt thereof, sodium hydroxymethylglycine, polyaminopropyl biguanide, double ( Any one or more of hydroxymethyl)imidazolidinyl urea, imidazolidinyl urea.

The ancient bone resource protecting agent according to any one of items 1 to 7, wherein the preservative is sorbic acid and a salt thereof, and the sorbic acid and the sorbic acid are 100 parts by weight of the protective agent. The salt is from 0.002 to 0.006 parts.

The ancient bone resource protecting agent according to any one of items 1 to 8, wherein the preservative is sodium hydroxymethylglycine, and the sodium hydroxymethylglycine is 100 parts by weight of the protective agent. It is 0.002-0.005 parts.

The ancient bone resource protecting agent according to any one of items 1 to 9, wherein the preservative is polyaminopropyl biguanide, and the polyaminopropyl biguanide is 100 parts by weight of the protective agent. It is 0.002 parts.

The ancient bone resource protecting agent according to any one of items 1 to 10, wherein the preservative is bis(hydroxymethyl)imidazolidinyl urea, and the weight of the protective agent is 100 parts. The bis(hydroxymethyl)imidazolidine urea is from 0.002 to 0.005 parts.

The ancient bone resource protecting agent according to any one of items 1 to 11, wherein the preservative is imidazolidinyl urea, and the imidazolidinyl urea is 0.002 by weight of the protective agent. -0.006 parts.

The ancient bone resource protecting agent according to any one of the items 1 to 12, wherein the plant extract antioxidant is any one or more of a tea polyphenol and a rosemary extract.

The ancient bone resource protecting agent according to any one of items 1 to 13, wherein the plant extract antioxidant is tea polyphenol, and the tea polyphenol is 100 parts by weight of the protective agent. 0.01-0.05 parts.

The ancient bone resource protecting agent according to any one of items 1 to 14, wherein the plant extract antioxidant is a rosemary extract, and the rose is 100 parts by weight of the protective agent. The fragrant extract is 0.01-0.05 parts.

The ancient bone resource protecting agent according to any one of items 1 to 15, wherein the antioxidant enzyme mimetic is a selenium-containing cyclodextrin having glutathione peroxidase activity, Any one or more of selenopeptides and selenoproteins.

The ancient skeletal resource protecting agent according to any one of items 1 to 16, wherein the antioxidant enzyme mimetic is a selenium-containing cyclodextrin, a selenopeptide, a selenoprotein, and a weight of a protective agent. The antioxidant enzyme mimetic is 0.01-0.3 parts in 100 parts.

The ancient bone resource protecting agent provided by the invention comprises the following components: 10-25 parts by weight of the protective agent, 10-25 parts of propylene glycol, 0.01-0.3 parts of antioxidant enzyme mimetic, and plant extracting antioxidant 0.01 according to the weight of the protective agent. -0.05 parts, preservative 0.001-0.003 parts, lysozyme 0.1-0.3 parts, the balance is water;

The ancient bone resource protecting agent provided by the invention comprises any one of a water-soluble protein and a water-soluble starch. One of water-soluble protein and water-soluble starch and propylene glycol can be used as a raw material of the substrate, and the base component of the ancient bone resource protecting agent can be formed by mixing. The two raw materials of the substrate are not only low in toxicity but also have good water solubility. Sex, and has a certain bonding effect, after spraying onto the surface of ancient bones, a film is formed, which realizes the reversibility and protection of ancient bone resource protection agents; by adding non-toxic or low-toxic antioxidant components - Antioxidant enzyme mimics, plant extract antioxidants, and the ancient skeletal resource protectant's antioxidant capacity, reducing the oxidative damage of ancient oxygen resources to the ancient bone resources during excavation, transportation and display; by adding specific content The antiseptic component (preservative and lysozyme) imparts anti-corrosion ability to ancient bone resource protection agents and reduces the erosion of ancient bone resources by environmental microorganisms in excavation, transportation and display environments. The obtained ancient bone resource protection agent has a dynamic viscosity value η of 5-300 mPa·s (measured by a NDJ-1 rotary viscometer), and has good reversibility, protection, anti-oxidation and antibacterial ability after spraying ancient bones. .

Preferably, the ancient bone resource protecting agent provided by the invention comprises the following components: 12-22 parts by weight of the protective agent, 12-23 parts of propylene glycol, 0.02-0.25 parts of antioxidant enzyme mimetic, plant extracting 0.02-0.05 parts of antioxidant, 0.0015-0.0025 parts of preservative, 0.15-0.28 parts of lysozyme, The amount is water.

Through repeated tests, one of the water-soluble protein and water-soluble starch and propylene glycol can be used as a raw material of the substrate, and the base component of the ancient bone resource protecting agent can be formed by mixing, and the raw materials of the two substrates are not only very toxic. It is low and has good water solubility; after a certain proportion of the ancient bone resource protection agent is sprayed onto the ancient bone resources, it will form a protective film on the surface to protect the ancient bone resources. Because the two substrates have good water solubility, the protective film formed on the surface of ancient bone resources can be easily washed away with water, and the ancient bone resources return to the original bone texture state, which realizes the protection of ancient bone resources. The reversibility of the agent.

In the process of excavation, transportation and display of ancient bone resources, oxidation will cause greater damage. In order to avoid the damage caused by oxidation to ancient bone resources. It has been verified by many experiments that the non-toxic or low-toxic antioxidant components-antioxidant enzyme mimics and plant extracting antioxidants can be added to the formulation of ancient bone resource protectant, which can confer the ability of ancient bone resource protection agents to resist oxidation. It greatly reduces the oxidative damage of ancient bone resources during excavation, transportation and display. The antioxidant enzyme mimetic is selected from any one or more of selenium-containing cyclodextrin and selenopeptide-containing. Selenium is an essential trace element in the human body and has long been regarded as an important antioxidant. Selenium is also a component of the important antioxidant enzyme, glutathione peroxidase, which guarantees glutathione peroxidase. It removes active oxygen and exerts anti-oxidation effect, which can effectively prevent oxidation reaction of biomolecules. Selenium-containing cyclodextrin is a polysaccharide containing selenium. The oral administration of LD50 is 3.6g/kg (low toxicity) in mice. The selenopeptide is a peptide molecule containing selenium. The oral LD50 of mice is 2.8-4.1g/kg (low toxicity). ). The selenium-containing cyclodextrin, selenopeptide and other molecules have glutathione peroxidase activity (called antioxidant enzyme mimic), which not only has antioxidant activity, but also has stronger stability than natural enzymes, and is more suitable. Add to the ancient bone resource protection agent. The plant extracting antioxidant is selected from any one or more of tea polyphenols and rosemary extracts. Tea polyphenols are the main active substances in tea. They are non-toxic natural antioxidants with strong anti-oxidation properties. As early as 1995, China Light Industry Association applied them as antioxidants in the food industry. Approved food additives are widely used in food preservation. Rosemary extract is a natural antioxidant that protects biomolecules against oxidation. The antioxidants in this extract are mainly rosmarin, rosmarinic acid, ursolic acid, carnosol, etc. Rosemary extract has been widely used in air cleaners, perfumes, soaps, lotions, and in beverages, skin oils, and hair tonics. The above-mentioned antioxidant component is applied to the ancient bone resource protection agent not only to prevent oxidative damage of ancient bone resources, but also to protect the safety of operators.

Further, the selenopeptide-containing one of Arg-Gly-Sec-Arg-Asn and Sec-Arg-Gly-Asp is selected One or more, in the selenopeptide-containing Sec is selenocysteine. Preferably, the selenopeptide-containing peptide is Arg-Gly-Sec-Arg-Asn, and the selenopeptide-containing peptide is 0.025-0.045 parts by weight of 100 parts by weight of the protective agent. Further, the selenopeptide-containing peptide is 0.03-0.04 parts. It has been verified that the ancient skeletal resource protectant formulation contains the parts by weight of the selenopeptide, and the anti-oxidation effect is good.

Preferably, the selenopeptide-containing peptide is Sec-Arg-Gly-Asp, and the selenopeptide-containing peptide is 0.03-0.05 parts by weight of 100 parts by weight of the protective agent. Further, the selenopeptide-containing peptide is from 0.035 to 0.045 parts. It has been verified that the ancient skeletal resource protectant formulation contains the parts by weight of the selenopeptide, and the anti-oxidation effect is good.

Due to the limitations of the excavation, transportation and display of ancient bone resources, it is impossible to truly achieve the sterility of the relevant environment. Therefore, various environmental microbes will erode ancient bone resources, resulting in changes or loss of ancient bone resource traits. The ancient bone resources of regeneration are a major loss. After repeated tests, the non-toxic or low-toxic antiseptic components-preservatives and lysozyme were added to the formulation of ancient bone resource protection agents, which gave the ancient bone resource protection agent anti-corrosion ability and reduced the ancient bone resources in excavation and transportation. Showcase environmental bacteria erosion in the environment. The compound preservative has the activity of inhibiting mold, yeast and aerobic bacteria, and has been widely used as a preservative in the fields of food, beverage, pickles, tobacco, medicine and cosmetics. Lysozyme is a non-toxic, non-side-effect protein with natural antibacterial activity, decomposing Bacillus subtilis and radiation-resistant micrococcal bacteria in Gram-positive bacteria, against Escherichia coli, common proteobacteria and parahemolytic arc Gram-negative bacteria such as bacteria also have a certain dissolution effect, and have been widely used in the preservation of aquatic products, meat products, cakes, milk powders and beverages. The above antiseptic component does not need to be heated during the sterilization and antiseptic process, so it can be applied to the protection of ancient bone resources without damaging the ancient bone resources.

The three components of the substrate component, the antioxidant component and the antiseptic component are subjected to a large number of tests, and the components of the ancient bone resource protecting agent are synergistically enhanced, and the ancient bones are sprayed very much. Good reversibility, protection, antioxidant and antibacterial ability. Among them, the binder is selected from the nutrients of the daily diet of human beings, and the human is non-toxic.

After further optimization, the ancient bone resource protecting agent provided by the embodiment of the invention comprises the following components: 13-20 parts by weight of the protective agent, 13-21 parts of propylene glycol, and 0.04-0.22 of the antioxidant enzyme mimetic. Ingredients, plant extract antioxidant 0.03-0.045 parts, preservative 0.0017-0.0023 parts, lysozyme 0.18-0.25 parts, the balance is water.

Further, the water-soluble protein selects bovine serum albumin, soybean water-soluble protein, has a good adhesion effect, and is easy to wash off. Preferably, the water-soluble protein is any one or more of bovine serum albumin and soybean water-soluble protein, and the water-soluble protein is 14-19 parts by weight of 100 parts by weight of the protective agent. By It is verified that the ancient bone resource protectant formulation contains the water-soluble protein in the parts by weight, and the reversibility effect is good.

Further, the binder is a water-soluble starch, and the water-soluble starch is 15-18 parts by weight of 100 parts by weight of the protective agent. It has been verified that the ancient bone resource protectant formulation contains the parts by weight of water-soluble starch, and the reversibility effect is good.

Further, the preservative is selected from any one or more of sorbic acid and its salts, sodium hydroxymethylglycine, polyaminopropyl biguanide, and imidazolidinyl urea. In the “Technical Specifications for Cosmetics Safety” approved by the State Food and Drug Administration in 2015, the maximum allowable concentration of sorbic acid and its salt preservatives is 0.6%, and the maximum allowable concentration of sodium hydroxymethylglycinate is 0.5%. The maximum allowable concentration of propyl biguanide is 0.3%, and the maximum allowable concentration of imidazolidinyl urea is 0.6%. The preservatives selected in the present invention are all lower than the above technical specifications, indicating that the safety is high.

Preferably, the preservative is sodium sorbate, and the sodium sorbate is from 0.0013 to 0.0027 parts by weight of the protective agent. Further, the sodium sorbate is from 0.0015 to 0.002 parts. It has been verified that the ancient bone resource protectant formulation contains the parts by weight of sodium sorbate, and has good antiseptic and antibacterial effects.

Preferably, the preservative is sodium hydroxymethylglycine, the sodium hydroxymethylglycine is 0.0012-0.0025 parts by weight of 100 parts by weight of the protective agent; further, the sodium hydroxymethylglycine is 0.002-0.0023 parts. . It has been verified that the ancient skeletal resource protectant formulation contains the parts by weight of sodium hydroxymethylglycine, and has good antiseptic and antibacterial effects.

Preferably, the preservative is polyaminopropyl biguanide, the polyaminopropyl biguanide is 0.001-0.002 parts by weight of 100 parts by weight of the protective agent; further, the polyaminopropyl biguanide is 0.0013-0.0017. It has been verified that the ancient bone resource protectant formulation contains the parts by weight of polyaminopropyl biguanide, and has good antiseptic and antibacterial effect.

Preferably, the preservative is imidazolidinyl urea, the imidazolidinyl urea is 0.0016-0.0028 parts by weight of the protective agent, and further, the imidazolidinyl urea is 0.0018-0.0026. It has been verified that the ancient bone resource protectant formulation contains the parts by weight of imidazolidinyl urea, and has good antiseptic and antibacterial effects.

The ancient bone resource protecting agent provided by the embodiment of the invention uses a binder and propylene glycol as a substrate, and selects a specific kind of antioxidant (antioxidant enzyme mimetic, plant extract antioxidant), lysozyme, and is mixed with water. Through the combination of different material components and their contents, each component synergizes with each other, and it has very good reversibility, protection, anti-oxidation and antibacterial ability after spraying ancient bones. Moreover, the components of the ancient bone resource protecting agent provided by the invention are non-toxic or low-toxic substances, and the added amount thereof refers to the national food or cosmetic standard, and the obtained bone resource protecting agent has no damage to the human body, and the operator is guaranteed. And The safety of the viewer.

Detailed ways

The present invention will be further described in detail below by way of specific examples.

Example 1

An ancient bone resource protecting agent comprising the following components: 10 parts by weight of protective agent, 10 parts of bovine serum albumin, 10 parts of propylene glycol, 0.01 part of selenium cyclodextrin, 0.01 part of tea polyphenol, 0.001 part of sodium sorbate , 0.1 part of lysozyme, the balance is water; the content of each component is mixed to obtain the spraying agent of ancient bone resource protection agent.

Example 2

An ancient bone resource protecting agent, comprising the following components: 15 parts of soybean water-soluble protein, 15 parts of propylene glycol, 0.03 parts of selenopeptide (Arg-Gly-Sec-Arg-Asn), and 10 parts by weight of protective agent 0.04 parts of fragrant extract, 0.002 parts of sodium hydroxymethylglycine, 0.2 parts of lysozyme, the balance is water; the content of each component is mixed to obtain the spraying agent of ancient bone resource protection agent.

Example 3

An ancient bone resource protection agent comprising the following components: 25 parts by weight of protective agent, 25 parts of bovine serum albumin, 25 parts of propylene glycol, 0.3 parts of selenium cyclodextrin, 0.05 parts of tea polyphenol, 0.003 parts of sodium sorbate , lysozyme 0.3 parts, the balance is water; the content of each component is mixed to obtain the spraying agent of ancient bone resource protection agent.

Example 4

An ancient bone resource protection agent comprising the following components: 10 parts of bovine serum albumin, 25 parts of propylene glycol, 0.01 parts of selenium cyclodextrin, 0.03 parts of tea polyphenol, polyaminopropyl biguanide according to 100 parts by weight of protective agent 0.0045 parts, 0.2 parts of lysozyme, the balance is water; the content of each component is mixed to obtain the spraying agent of ancient bone resource protection agent.

Example 5

An ancient bone resource protecting agent comprising the following components: 17 parts of soybean water-soluble protein, 18 parts of propylene glycol, and 0.035 parts of selenopeptide (Arg-Gly-Sec-Arg-Asn) according to 100 parts by weight of protective agent, 0.036 parts of fragrant extract, 0.0021 parts of sodium hydroxymethylglycine, 0.21 parts of lysozyme, the balance is water; the content of each component is mixed to obtain the spraying agent of ancient bone resource protection agent.

Example 6

An ancient bone resource protecting agent comprising the following components: 10 parts of water-soluble starch, 10 parts of propylene glycol, 0.01 parts of Arg-Gly-Sec-Arg-Asn, rosemary according to 100 parts by weight of protective agent 0.01 parts of extract, 0.001 parts of imidazolidinyl urea, 0.1 part of lysozyme, the balance is water; the content of each component is mixed to obtain the spraying agent of ancient bone resource protection agent.

Example 7

An ancient bone resource protecting agent comprising the following components: 25 parts of water-soluble starch, 25 parts of propylene glycol, 0.3 parts of selenium-containing cyclodextrin, 0.05 parts of tea polyphenol, 0.003 parts of sodium sorbate, according to 100 parts by weight of the protective agent. 0.3 parts of lysozyme, the balance is water; the content of each component is mixed to obtain the spraying agent of ancient bone resource protection agent.

Example 8

An ancient bone resource protecting agent comprising the following components: 16 parts of water-soluble starch, 18 parts of propylene glycol, 0.17 parts of selenium cyclodextrin, 0.039 parts of tea polyphenol, and 0.0018 parts of sodium sorbate according to 100 parts by weight of protective agent. 0.23 parts of lysozyme, the balance is water; the content of each component is mixed to obtain the spraying agent of ancient bone resource protection agent.

Example 9

An ancient bone resource protecting agent comprising the following components: 11 parts of water-soluble starch, 20 parts of propylene glycol, 0.03 parts of sele-containing peptide (Sec-Arg-Gly-Asp), rosemary extract according to 100 parts by weight of protective agent 0.033 parts, 0.0036 parts of sodium hydroxymethylglycine, 0.2 parts of lysozyme, the balance is water; the content of each component is mixed to obtain the spraying agent of ancient bone resource protection agent.

Example 10

An ancient bone resource protecting agent comprising the following components: 20 parts of water-soluble protein, 22 parts of propylene glycol, 0.016 parts of sele-containing peptide (Sec-Arg-Gly-Asp), rosemary extract according to 100 parts by weight of protective agent 0.034 parts, 0.0015 parts of polyaminopropyl biguanide, 0.26 parts of lysozyme, the balance is water; the content of each component is mixed to obtain the spraying agent of ancient bone resource protection agent.

The ancient bone resource protecting agents prepared in Examples 1-10 were tested for reversibility, protection, oxidation resistance and antibacterial properties, respectively.

Table 1 Example 1-10 Ancient bone resource protectant composition table (the number of parts is 100 parts by weight of protective agent)

First, the reversibility determination

1. The ancient bone resource protecting agents prepared in Examples 1-3 and 10 were determined by fluorescence labeling for reversibility.

(1) using a protein-fluorescent labeling kit to fluorescently label the binder;

(2) Proportionally arranging the ancient bone resource protection agent provided by the invention and spraying it on ancient bones, and the thickness of the spraying is 100±10 μm;

(3), after drying, check the fluorescent coverage on the bone on a box-type UV-visible transflectometer, perform fluorescence photography and use Image-Pro Plus software for fluorescence quantification, the data is defined as m;

(4), after the same bone is thoroughly washed with running water for 5 minutes, after drying, fixed at the same position and repeat the operation in (3), the obtained data is defined as n;

(5) The fluorescence reduction rate X = (m - n) / m × 100%.

2. The ancient bone resource protection agent prepared in Example 4-6 was tested for reversibility by means of iodine water.

(1) Proportionally arranging the ancient bone resource protection agent provided by the invention and spraying it on ancient bones, and the thickness of the spraying is 100±10 μm;

(2), adding iodine water, taking pictures, and quantifying its color as m;

(3), after the same bone is thoroughly washed with flowing water for 10 minutes, after drying, fixed at the same position and repeated (2) operation, the obtained data is defined as n;

(4) Blue reduction rate X = (m - n) / m × 100%.

The results obtained are shown in Table 2.

Table 2 Results of reversibility determination of ancient bone resource protection agents

It can be seen from Table 2 that when the ancient bone resource protecting agent prepared by the embodiment of the present invention takes soluble protein or starch as one of the raw materials, the X value range is: 95.2% ≦X≦1.0, indicating that the protective agent can be conveniently watered. Washed off; and when the washing operation was repeated again and the measurement was performed, it was found that all experimental groups X= 1.0, indicating that all protective agents are washed away, showing superior reversibility.

Second, the protection and oxidation resistance determination

(1) Draw a line on the surface of the ancient bone as a boundary mark, and measure the bone hardness by a portable hardness tester after drawing the line;

(2) uniformly spraying the ancient bone resource protection agent prepared by the embodiment of the present invention on one side surface of the ancient bone by the drawing line, and the side of the ancient bone resource protecting agent is called the protective end, and the other end is called the protective end. Non-protective end, after the dry, the bone hardness of the protective end is determined as b, and 8 points are randomly selected to measure the thickness of the protective film formed by the protective agent, and the improvement rate of the protective agent on the bone hardness is calculated as Φ=(ba)/ a × 100%; wherein, spraying three times, spraying in sequence, the first spraying protective film thickness is 45-55μm, the second spraying protective film thickness is 75-95μm, the third spraying protection The film thickness is 115-135 μm;

(3) After placing the ancient bones sprayed 3 times at room temperature and avoiding direct sunlight for 6 months and 12 months, determine the bone hardness c of the protective end and the bone hardness d of the unprotected end, respectively, and calculate the bone hardness of the protective end. The rate Y = (bc) / b × 100%, and the bone hardness reduction rate of the unprotected end Z = (ad) / a × 100%. The results are shown in Table 3.

Table 3 Results of determination of antioxidant properties of ancient bone resource protectants

It can be seen from Table 3 that the spraying of the ancient bone resource protection agent is carried out: the thickness of the protective film is 45-55 μm, the value of Φ is 60% ≦ Φ ≦ 73%; the spraying of the ancient bone resource protection agent is carried out twice: protection The film thickness is 75-95μm, the Φ value range is 95% ≦Φ≦143%; 3 times of ancient bone resource protection agent spraying: the protective film thickness is 115-135μm, the Φ value range is 139% ≦Φ≦201%; It can be seen from the above data that the ancient bone resource protection agent provided by the embodiment of the present invention can effectively form a protective film on the bone surface and enhance the bone hardness by spraying one or more times on the ancient bone.

The bone hardness reduction rate at 6 months and 12 months after spraying was measured. 6 months: The Y value range is 2.8% ≦Y ≦ 6.5%; the Z value range is 18.0% ≦Z ≦ 24.5%. 12 months: The Y value range is 6.1% ≦Y ≦ 8.9%; the Z value range is 37.2% ≦Z ≦ 42.9%.

It can be seen from the above data that the ancient bones that have not been sprayed with ancient bone resource protection agents have a significant decrease in hardness after being exposed to direct sunlight for 6 months and 12 months, which is caused by the damage of ancient bones by oxidation. . The ancient bones sprayed with the protective agent described in this patent are exposed to light at room temperature for 6 months and 12 months.

The decline is not obvious, indicating that the antioxidant substances (antioxidant enzymes and antioxidants) contained in ancient bone resource protection agents can effectively reduce the damage of ancient bones by oxidation, thus effectively protecting precious ancient bone resources.

In addition, the archaeological excavation process is a sudden change of the environment of ancient bone resources. As the balance system between ancient bones and buried environment is broken, the above ground environment (including temperature, humidity, light, bacteria, etc.) will give ancient bone resources. Bring serious damage. According to the requirements of ancient bone in situ display, displacement display, scientific research, etc., the protection of ancient bone resources can be divided into two types: "in situ protection" and "extraction protection".

“In-situ protection” refers to the site protection that does not change the excavation location of the ancient bones; “extraction protection” refers to the protection of ancient bones during the process of peeling ancient bones from the buried soil. The first movement after the cultural relics were unearthed, the quality of protection will directly affect the future display and research work.

The in-situ protection work is relatively simple, and the ancient bone resource protection agent provided by the invention is sprayed on the ancient bone exposed on the surface of the soil to a thickness of 40-140 μm, and the ancient bone resource protection agent is infiltrated into the soil, and the area is reached. The surface of the ancient bones exposed to the surface of the earth is more than 1.5 times and the depth is more than 0.3m, thus achieving the role of protecting ancient bones below the surface of the earth. The extraction and protection work must first evaluate the degree of fragmentation (completeness, rupture, porosity, decay, chalking, etc.) and hardness of the extracted ancient bone resources. Price, for the more complete and harder ancient bones can be peeled off from the soil, and then sprayed on the surface of 40-140μm of the ancient bone resource protection agent provided by the present invention, and then used for subsequent display and scientific research For the ancient bones with high degree of fracture or poor hardness, it is necessary to first bond and reinforce. The ancient bone resource protection agent provided by the invention is injected into the ancient bone by multiple in-situ drip infiltration method, so that the purpose of ancient bone extraction can be satisfied. Ancient bones were bonded by the adhesion of ancient bone resource protectants, and the hardness of ancient bones was also increased after the ancient bone resource protectants dried, and then used for subsequent display and scientific research. The ancient bone preservation conditions are different, and the protection effect of ancient bone resource protection agents is also different. It can be used to track the evaluation of the ancient bones and the work of the spray protection agent in 3 months or 6 months.

Third, the antibacterial determination

Because there is no antibacterial testing standard for archaeological protective agents in China, only the daily chemical product standards are referred to. The ancient bone resource protection agents prepared in Examples 1-10 of the present invention were respectively entrusted to "China Daily Chemical Industry Research Institute Analysis and Testing Center" and "Guangdong Province Microbial Analysis and Testing Center" to "QBT 2738-2012 daily chemical products antibacterial and antibacterial "Evaluation method of effect" is a test standard, and the ancient skeletal resource protecting agent against bacteria (Escherichia coli) is separately detected by referring to the bacteriostatic effect test method (antibacterial ring method) of the antibacterial type daily chemical product described in 7.5 of the standard. The antibacterial effect of the fungus) and the fungus (Candida albicans), the evaluation of the antibacterial effect of the standard 7.5.5 indicates that "the inhibition zone has a diameter of more than 7 mm, the product has a bacteriostatic effect", and the present invention provides 1-10 The diameter of the antibacterial ring of the ancient bone resource protection agent is more than 12mm, which proves that the antibacterial effect is obvious.

Further, from the formulation of the ancient bone resource protecting agent provided by the present invention, it can be presumed that it can be used for inhibiting mold.

The ancient bone resource protecting agent provided by the embodiment of the invention uses one or more of water-soluble protein and water-soluble starch and propylene glycol as a substrate for an ancient bone resource protecting agent, and the two substrates are not only low in toxicity but also have Very good water solubility. After a certain proportion of the ancient bone resource protection agent is sprayed onto the ancient bone resources, a protective film is formed on the surface to protect the ancient bone resources. Since the two substrates have good water solubility, the protective film formed on the surface of the ancient bone resources can be conveniently washed away with water, and the ancient bone resources are returned to the original state, thereby realizing the reversibility of the ancient bone resource protecting agent; Non-toxic or low-toxic natural antioxidant enzymes (glutathione peroxidase), natural antioxidants (plant extract antioxidants), which confers the ability of ancient bone resource protectants to fight oxidation, reducing ancient bone resources Oxidative damage during excavation, transportation, and display.

The above description is only the preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes can be made to the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims

An ancient bone resource protecting agent characterized by comprising the following components: 10-25 parts by weight of the protective agent, 10-25 parts of propylene glycol, 0.01-0.3 parts of antioxidant enzyme mimetic, plant extract Antioxidant 0.01-0.05 parts, preservative 0.001-0.003 parts, lysozyme 0.1-0.3 parts, the balance is water;

The binder includes any one of a water-soluble protein and a water-soluble starch.
The ancient bone resource protecting agent according to claim 1, which comprises the following components: 12-22 parts by weight of the protective agent, 12-23 parts of propylene glycol, and 0.02- antioxidant enzyme mimetic. 0.25 parts, plant extract antioxidant 0.02-0.05 parts, preservative 0.0015-0.0025 parts, lysozyme 0.15-0.28 parts, the balance is water.
The ancient bone resource protecting agent according to claim 1, which comprises the following components: 13-20 parts by weight of the protective agent, 13-31 parts of propylene glycol, and 0.04-31 of antioxidant enzymes. 0.22 parts, plant extract antioxidant 0.03-0.045 parts, preservative 0.0017-0.0023 parts, lysozyme 0.18-0.25 parts, the balance is water.
The ancient bone resource protecting agent according to claim 1, wherein the water-soluble protein is any one or more of bovine serum albumin and soybean water-soluble protein.
The ancient bone resource protecting agent according to claim 1, wherein the binder is a water-soluble protein, and the water-soluble protein is 10-25 parts by weight, preferably water-soluble protein, based on 100 parts by weight of the protective agent. It is further preferably from 12 to 22 parts, and further preferably, the water-soluble protein is from 13 to 20 parts.
The ancient bone resource protecting agent according to claim 1, wherein the binder is water-soluble starch, and the water-soluble starch is 10-25 parts by weight, preferably water-soluble starch, based on 100 parts by weight of the protective agent. It is 16-18 parts.
The ancient bone resource protecting agent according to claim 1, wherein the preservative is sorbic acid and a salt thereof, sodium hydroxymethylglycine, polyaminopropyl biguanide, bis(hydroxymethyl)imidazolidinyl group Any one or more of urea, imidazolidinyl urea.
The ancient bone resource protecting agent according to claim 7, wherein the preservative is sorbic acid and a salt thereof, and the sorbic acid and salts thereof are 0.002-0.006 parts by weight of 100 parts by weight of the protective agent. .
The ancient bone resource protecting agent according to claim 7, wherein the preservative The sodium hydroxymethylglycine is 0.002-0.005 parts by weight of 100 parts by weight of the protective agent.
The ancient bone resource protecting agent according to claim 7, wherein the preservative is polyaminopropyl biguanide, and the polyaminopropyl biguanide is 0.002 part by weight based on 100 parts by weight of the protective agent.
The ancient bone resource protecting agent according to claim 7, wherein the preservative is bis(hydroxymethyl)imidazolidinyl urea, and the bis(hydroxymethyl)imidazole is 100 parts by weight of the protective agent. The alkyl urea is from 0.002 to 0.005 parts.
The ancient bone resource protecting agent according to claim 7, wherein the preservative is imidazolidinyl urea, and the imidazolidinyl urea is 0.002-0.006 parts by weight of 100 parts by weight of the protective agent.
The ancient bone resource protecting agent according to claim 1, wherein the plant extract antioxidant is any one or more of a tea polyphenol and a rosemary extract.
The ancient bone resource protecting agent according to claim 13, wherein the plant extract antioxidant is tea polyphenol, and the tea polyphenol is 0.01-0.05 parts by weight of 100 parts by weight of the protective agent.
The ancient bone resource protecting agent according to claim 13, wherein the plant extract antioxidant is rosemary extract, and the rosemary extract is 0.01-0.05 based on 100 parts by weight of the protective agent. Share.
The ancient bone resource protecting agent according to claim 1, wherein the antioxidant enzyme mimetic is a selenium-containing cyclodextrin, a selenopeptide, or a selenoprotein containing glutathione peroxidase activity. Any one or more of them.
The ancient bone resource protecting agent according to claim 16, wherein the antioxidant enzyme mimetic is a selenium-containing cyclodextrin, a selenopeptide, a selenoprotein, and an antioxidant enzyme according to 100 parts by weight of the protective agent. The mimetic is 0.01-0.3 parts.