CN101554181A - Chitin thimerosal - Google Patents

Chitin thimerosal Download PDF

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Publication number
CN101554181A
CN101554181A CNA2008101034620A CN200810103462A CN101554181A CN 101554181 A CN101554181 A CN 101554181A CN A2008101034620 A CNA2008101034620 A CN A2008101034620A CN 200810103462 A CN200810103462 A CN 200810103462A CN 101554181 A CN101554181 A CN 101554181A
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chitin
thimerosal
water
derivativ
malic acid
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魏亚中
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CHITOSAN BIOTECH (BEIJING) Co Ltd
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CHITOSAN BIOTECH (BEIJING) Co Ltd
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Abstract

The invention relates to a chitin thimerosal comprising the following components according to the weight percentage: 0.1-50 of chitin derivative, 0.03-3 of malic acid, 0.01-17 of cypress essential oil and the balance of deionized water. The chitin thimerosal is applied to sterilization, has a spectrum antibiosis function and has the advantages of no poison, no side effect, no secondary pollution, available materials, simple preparation method, low cost and good effect.

Description

Chitin thimerosal
Technical field
The present invention relates to a kind of preparation method and application of chitin thimerosal.
Background technology
Mention disinfectant, people at first expect may be pasteurization liquid, bleaching powder with pungent taste.These traditional disinfectants are most can to cause secondary pollution to environment; Along with bacterium and virus drug resistance improve constantly, new virus constantly occurs, and its effectiveness reduces; In addition, its toxicity or corrosivity also can damage when being directly used in skin.
Chemosterilant has been experienced in the development of sterilization product (technology), as the application of clorox, the tincture of iodine, peroxide, the application of hibitane, improved chemosterilant, as make compound for the bromogeramine that improves bactericidal effect, for improving glutaraldehyde+hardening agent, the preservative of sterilization speed, and the change of formulation etc.
The expert points out that the bactericide and the disinfectants that are regardless of occasion, a large amount of use in time ground chemical analysis will cause serious consequence to environment.Using the most direct purpose of disinfectant is the kill harmful microorganism, allows virus have no place to hide.But these disinfectants kill is not limited to harmful microorganism, and useful microorganism is also together killed.In addition, long-term a large amount of chemical analysis disinfectant, bactericidal agents of using have made the microorganisms pesticide resistance, and sterilization effect reduces greatly; And the medicament residue that remains in the environment such as our life, production is more and more, becomes new pollution source, grows new harmful microorganism, we healthy of serious threat.Such as the peroxide disinfectant, because they have strong oxidability, can be with all microorganism killings.And the peroxide disinfectant of high concentration also stimulates, damages mucocutaneous, corrosives.The high concentration chlorine-containing disinfectant has the obvious stimulation effect to people's respiratory mucosa and skin, and article are had corrosion and discoloration, still is carcinogen simultaneously.Because the disinfectant of chemical analysis can not natural degradation, also can cause secondary pollution to environment.
Paying attention to 21st century natural, healthy, environmental protection, biotechnology has just like become the topic of very hot door.In past 50 years, people use chemical antibacterial agent to do disinfection, and the problems such as toxicity, pesticide resistance, safety and the feature of environmental protection that face can't effectively solve always, thereby influence its range of application, and then limit its development.Biological product itself is nontoxic, and organic matter is changed into after simple, harmless inorganic matter such as carbonic acid gas, the water, and these microorganisms are reduced to extinction thereupon, do not have residue or secondary pollution.
" sterilization method " of biodegradation technique is, extract, tame the beneficial microbe of occurring in nature, to surpass the speed decomposing organic pollutant of hundreds and thousands of times of other natural bacterias, make harmful virus and bacterium not have host, parasitic media or source of nutrition, until its death.European at present and the U.S. is generally using biological degradation and disposal of refuse technology, i.e. bio-enzyme degradation technology.
Because a kind of enzyme is only effective to a bacterioid, broad-spectrum antiseptic, just must act on simultaneously by several enzymes.But in enzyme composite, various enzymes are the use activity of can cancelling each other together, and very easily loses activity, and is difficult for preserving.
In recent years, chitin (Chitin) is because possess excellent physiological function, and safety non-toxic, and its pharmaceutical value is generally acknowledged by clinical medicine.Its biologically active comprises and suppresses growth of microorganism, physiological adaptation, Biodegradable, anti-inflammatory, stops blooding, preserves moisture, promotes regeneration, adsorbs heavy metal and eliminates toxin etc.Chitin (Chitin) and multiple derivative (Chitosan) thereof all have effect such as antibiotic, anti-infective, antiviral, antitumor in various degree.A large amount of free amine group positive charges that distributing on the chitin molecule chain form cationic polyelectrolyte in water, effects such as the link of bridge formation, electric field neutralization, ionic adsorption, coordination chelating, radical reaction are arranged.Physio-chemical study shows that chitin can be removed suspension in the water, organic matter, peculiar smell, pigment in water treatment, and can remove heavy metal harmful in the water and bacterium.Yet natural chitin itself is insoluble in water, extremely be difficult for being utilized, so its range of application and effect is limited.Chitin has another name called shitosan, chitosamine, chitin, chitosan, chitin, chitosan, removing protein for natural shrimp and crab shells gets with calcareous purifying afterwards, structure and fiber-like seemingly belong to animal fiber, avirulence, have no side effect and have positively charged distinct advantages.
And the chitin product can be divided into for four generations according to the improvement and the quality of technology: crab shrimp shell meal, polymeric acidic dissolubility chitin, low macromolecule water-solubility chitin, macromolecular water-soluble chitin.
The macromolecular water-soluble chitin, quality far surpasses all existing chitin products, have the advantage that " polymer acid dissolubility spherical chitosan " reaches " low macromolecule water-solubility spherical chitosan " concurrently, but the shortcoming of having got rid of both, be global scientist's dream high-grade chitin for a long time, really can bring into play the superfine product of all good characteristics of natural chitin.The macromolecular water-soluble chitin has powerful biologically active, the adsorptivity to harmful substance, safety, stability and natural environmental-protective concurrently, and its natural resources that will pass into silence of making reclaim utilization once again, and can not bring secondary pollution.
Although people have had certain cognition to the antibacterial mechanisms of chitin,, the antibacterial efficacy that how to improve it makes it to reach the purpose of sterilization, is the problem of scientists study always.Therefore, in the sterile products worldwide, chitin is also as just a kind of auxiliary adding ingredient.At present, still not having the document record is the natural disinfectant bactericidal agent product of active ingredient with the chitin.
The present invention is directed to the shortcoming and the plurality of advantages of utilizing chitin of chemosterilant, carried out meticulous research, finished chitin thimerosal of the present invention.
Summary of the invention
The object of the present invention is to provide a kind of nontoxic, have no side effect, non-secondary pollution, raw material is easy to get, the preparation method is simple, cost is low, effective chitin thimerosal.
Another object of the present invention is to provide a kind of preparation method of chitin thimerosal.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of chitin thimerosal, it comprises: chitosamine Chitosan (chitin derivativ, be efficient high-purity crust, purity>99.99%), malic acid, Chinese juniper another name for oil, water, its prescription is: chitin derivativ 0.1~50%, malic acid is 0.03~3%, and Chinese juniper another name for oil is 0.01~17%, and all the other are water.
A kind of preparation method of chitin thimerosal is characterized in that, to a certain amount of chitosamine Chitosan (efficient high-purity crust of chitin derivativ, purity>99.99%) add the malic acid of ormal weight in, add Chinese juniper another name for oil again, deionized water mixes, stir, make finished product.
A kind of optimized technical scheme is characterized in that, described chitin derivativ is to modify through hydrolysis (to control the pH value, readjust the arrangement and the molecular weight distribution of strand.) after the efficient high-purity crust of macromolecular water-soluble, described efficient high-purity crust is that deacetylation is greater than 90%; Purity is greater than 99.00%; Viscosity is less than 499ml '.
Described chitin derivativ is for being dissolved in fully in cold water or the hot water.
A kind of optimized technical scheme is characterized in that, the hydrolysis of described chitin derivativ, its pH value 3.5-7.5, the macromolecular water-soluble chitin molecule amount Mw=0.5-5.0x10 that obtains 5
Described macromolecular water-soluble chitin derivativ is to obtain according to common method for hydrolysis, and promptly chitin is through the derivative of the chitin of deacetylation acquisition, and it is high deacetylized, high-purity, and middle low-viscosity and molecular structure are macromolecule and arrange.
A further object of the present invention is, the application of described chitin thimerosal aspect sterilization, and it has the antibiotic purposes of spectrum.
Use the effective ingredient of chitosamine Chitosan (chitin derivativ) as sterilization, this is because its molecular structure of antimicrobial factors and the cellulose of chitin are very approaching.Unique difference is in the functional group on C-2, and cellulose is a hydroxy, and chitin is an amido, produces antibacterial ability by this amido, our it is colloquially called hexa polyose.
Chitosamine is polysaccharose (polysaccharide) natural polymer that is extracted through biochemical program by the aquatic products shrimp and crab shells, through hydrolysis, again through the adjusting of antimicrobial factors, obtain chitosamine le6 (ChitoSanle6) and can effectively go out, have the degerming usefulness of wide spectrum for the various kinds different strain except that bacterium, mould, saccharomycete.
Antimicrobial factors is regulated auxiliary agent and is comprised malic acid and Chinese juniper another name for oil, and described malic acid is a food grade additives.Can effectively excite and keep the biologically active of chitin antibacterial ability, further promote the purpose that antibacterial efficacy reaches sterilization.
General bacterium is to be Main Ingredients and Appearance with protein, and filterable virus, its main composition is a lipid, does not have protein, Chinese juniper another name for oil has the effect of solubilizing lipids, makes the sterilization scope of thimerosal effective more comprehensively.
The disinfective action principle
The effective ingredient of this product: chitosamine is the polysaccharose natural goods, solve homogeneously in the water with the molecular conformation of dissociating, through smearing, immersion way or sprayer unit, chitosamine is along with water smoke is dispersed in the space, after air contacts, drop to ground and be dispersed in metope and article surface, chitosamine presents degerming usefulness, can go out and remove bacterium and the mould that above-mentioned environment (comprising air, ground, metope, article surface) exists, eliminate pathogeny and smelly source by microorganisms.
The wide spectrum degerming usefulness of chitosamine comes from two Biochemical Mechanism:
1. chitosamine is the natural polymer of positively charged, combines the vital movement of restriction micro-organisms with the sialic acid of microorganism phosphide body.
2. the chitosamine oligosaccharides penetrates cells of microorganisms, suppresses DNA and is transcribed into RNA and stops cell division until destruction.
The deodorizing apparatus of chitosamine is shaped on two:
1. antibioticly can eliminate the stink that bacterium and mould cause.
3. chitosamine is the cationic macromolecule, can adsorb N, the P that causes smelly source, the acid radical anion of three kinds of elements of S.
Chitin thimerosal stops bacterium, mould, saccharomycetic multiplying by above-mentioned effect, and does not influence the balance of natural ecological.
Advantage of the present invention: the processing procedure of the thimerosal of the present invention's research, modify the molecular structure of chitin with hydrolysis, excite the usefulness of hexa polyose in the chitin, make the antibiotic property of chitin improve 1000 times, effective dose is 1/1000 of a general chitin, thereby makes this natural biological macromolecule of chitin material change the leading role into by the supporting role in the sterile products field.
Chitin is with its particular structure, and is inhibited to bacterium and mould.Especially staphylococcus aureus, Escherichia coli, small intestine are tied scorching Yersinia, Salmonella typhimurtum and these five kinds of common toadstools of Liszt's monokaryon hyperplasia bacterium and have stronger inhibitory action.And effectively suppress the Candida albicans of pneumobacillus, mould coccus, trichophyton mentagrophytes etc. human body and common pathogeny bacterium and the smelly source bacterium of living environment.
As a kind of novel nontoxic macromolecular material, the chitin raw material source is abundant, and have good water-solubility, adsorptivity and flocculation function, chitin reclaims easily, itself is nontoxic, chitin and derivative thereof can be avoided the secondary pollution of using chemical reagent to bring at short notice by biological degradation.
The present invention is a raw material with the snow crab, through the natural polymer material of biochemical program extraction.Be positively charged active animal fiber molecule, and be faintly acid, have sterilization, sterilization, cleaning, deodorizing concurrently, purify air, multiple function such as antistatic.
The present invention can be gone out except that common pathogeny bacterium and smelly source bacterium in human body and living environment such as pathogenic entero becteria, pyococcus, pathogenic saccharomycete and bacterial spore, air pernicious gas (NH4/CH2O) is eradicated toxin and bacterium and pernicious gas in stench and musty, the absorbed air, cause pure and fresh breath, possess natural, pure and fresh, clean, health, comfortable healthy function.
Crust have the unexistent characteristic of cellulose, is the edibility animal fiber of cation.The present technique product is a kind of by the boiomacromolecule polysaccharose natural goods (polysaccharide) that is extracted in the shellfish, and its excellent physiological function, pharmaceutical value are generally acknowledged by clinical medicine.Product of the present invention is at room temperature placed, and does not decompose, not impact effect.In a word, be a kind of nontoxic, have no side effect, non-secondary pollution, raw material is easy to get, the preparation method is simple, cost is low, effective chitin thimerosal.
Below by embodiment the present invention is further elaborated, but and does not mean that limiting the scope of the invention.
Embodiment
Embodiment
Add the ormal weight malic acid in a certain amount of chitin derivativ of the present invention, add Chinese juniper another name for oil again, mix, stir, thin up is made solvent shape finished product again.
Embodiment 1~4
Its formula ratio is as shown in table 1:
Table 1 formulation content (mg/l)
Composition Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Chitin derivativ 20000 10000 5000 450000
Malic acid 2000 2000 1000 25000
Chinese juniper another name for oil 1000 1000 1000 10000
Testing result
Table 2 is each embodiment testing results after to various bacterial classification effect 30min
Table 2
Figure A20081010346200071
"+" represents that long bacterium "-" expression is aseptic in the table 2, and the thimerosal in concentration range of the present invention all can suppress the growth of above bacterium as can be seen from the table.
Table 3 is the bactericidal assay examining report of chitin thimerosal of the present invention
Test site: U.S. Celsis Laboratory
Table 3
Figure A20081010346200082
MIC=1,000,000/ thinner ratio (example: thinner ratio=100, MIC=1,000,000/100=10,000ppm) "+" the long bacterium of expression "-" expression is aseptic in the table 3,
Conclusion: the above-mentioned bactericidal assay examining report of doing in greater than 0.001% scope when the concentration of thimerosal of the present invention.Result of the test shows: when chitin thimerosal concentration of the present invention 0.00195% the time, begin to bring into play the effect of sterilization, with the lifting of thimerosal concentration, the sterilization kind constantly increases.When thimerosal reached 0.5% above concentration, the bacterial classification of surveying all went out and removes.
The air sterilization effect approval test
The experiment at microorganism detection center, Guangzhou is the evaluation of doing at air sterilization effect specially, according to the detection of U.S. U.S. Celsis, with the concentration of thimerosal minimum 0.02% air is carried out the Disinfection Effect detection of different action times, shown in table 4 and table 5.
Table 4 testing result
As can be seen from Table 4, the Escherichia coli that the present invention exists in to air in same concentration, staphylococcus glucose bacterium, black-koji mould etc. all have effect, and action time is long more, and bactericidal effect is good more.
Table 5 is removed the testing result of gas
Figure A20081010346200092
As can be seen from Table 5, under the present invention acts on, nitrogen, ammonia, formaldehyde gas etc. are all had removal effect, especially PARA FORMALDEHYDE PRILLS(91,95) gas under least concentration, removal effect is the fastest best.
Acute oral toxicity test
Sense environmental conditions: 21 ℃ of temperature, humidity 63%
Laboratory animal: the NIH mouse, body weight 18~22 grams are provided by Guangdong Medical Lab Animal Center, and are as shown in table 6.
Table 6
Figure A20081010346200101
Conclusion: after giving the thimerosal of variable concentrations of the present invention, all animal subjects are the no abnormality seen reaction in the observation period, does not have dead.Female, male its mouse oral acute toxicity maximum tolerated dose is greater than the 5000mg/kg body weight.According to acute toxicity grading criteria in " disinfection technology standard ", tried the true border of thing nontoxic level material.
An intact skin irritant test
Test item: an intact skin irritant test
Sense environmental conditions: 20 ℃ of temperature, humidity 62%
Laboratory animal: new zealand rabbit, regular grade is provided by Guangdong Medical Lab Animal Center, and experimental result is listed in table 7.
Table 7
Conclusion: in the whole observation period, the highest skin irritation index of rabbit skin is 0, and according to the skin irritatin test evaluation standard determination in " disinfection technology standard ", the thimerosal of different proportionings of the present invention is a nonirritant to stimulus intensity of rabbit skin.
Acute eye irritation test
Sense environmental conditions: 20 ℃ of temperature, humidity 62%
Laboratory animal: new zealand rabbit, provide by Guangdong Medical Lab Animal Center, experimental result is listed in table 8.
Table 8
Figure A20081010346200111
Table 8 has been listed animal subject and has once been contacted behind the thimerosal of the present invention eyes corneal injury, iris infringement, conjunctival congestion and chemosis four aspects, judges by grade scale and is tried stimulation and the degree of injury of thing to eyes
Conclusion: in the whole observation period, it is 0 that the thimerosal of various concentration of the present invention stimulates average score cornea or iris infringement to 3 tame lagophthalmos, conjunctival congestion or oedema are 0, judge according to the acute eye irritation test evaluation criterion in " disinfection technology standard ", tried thing man lagophthalmos stimulus intensity is belonged to nonirritant.

Claims (5)

1. chitin thimerosal, it comprises: chitin derivativ, malic acid, Chinese juniper another name for oil, water, its prescription is: chitin derivativ 0.1~50%, malic acid are 0.03~3%, and Chinese juniper another name for oil is 0.01~17%, and all the other are deionized water.
2. chitin thimerosal according to claim 1, its preparation method are the malic acid that adds ormal weight in a certain amount of chitin derivativ, add Chinese juniper another name for oil again, and deionized water mixes, and stirs, and makes finished product.
3. chitin thimerosal according to claim 2 is characterized in that, described chitin derivativ is the efficient high-purity crust of macromolecular water-soluble after hydrolysis is modified, and described efficient high-purity crust is that deacetylation is greater than 90%; Purity is greater than 99.00%; Viscosity is less than 499ml '.
4. chitin thimerosal according to claim 3 is characterized in that, the hydrolysis of described chitin derivativ, its pH value 3.5-7.5, the macromolecular water-soluble chitin molecule amount Mw=0.5-5.0x10 that obtains 5
5. chitin thimerosal, its application aspect sterilization.
CNA2008101034620A 2008-04-07 2008-04-07 Chitin thimerosal Pending CN101554181A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103691307A (en) * 2013-12-27 2014-04-02 浙江农林大学天目学院 Environment deodorant containing microorganism strains and application of environment deodorant
CN104321063A (en) * 2012-05-18 2015-01-28 积克隆斯基大学 The use of chitosan polymer in the treatment and prevention of infections caused by coronaviruses
CN104663658A (en) * 2015-02-04 2015-06-03 苏州康华净化系统工程有限公司 Sterilizing agent and preparation method thereof
CN105013304A (en) * 2014-04-28 2015-11-04 重庆市洁霖源环保科技有限公司 Automotive interior scavenger
CN106962271A (en) * 2017-03-25 2017-07-21 上海宇元生物科技有限公司 The cultural method of chitin poultry
CN109329312A (en) * 2018-10-30 2019-02-15 重庆市海洁消毒卫生用品有限责任公司 A kind of antibacterial agent and preparation method thereof
CN112773729A (en) * 2021-03-17 2021-05-11 陈耕 Alcohol disinfectant safe to skin and preparation method thereof
CN114053295A (en) * 2020-07-29 2022-02-18 以勒企业股份有限公司 Use of chitosan and its derivatives in antimicrobial and antiviral

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104321063A (en) * 2012-05-18 2015-01-28 积克隆斯基大学 The use of chitosan polymer in the treatment and prevention of infections caused by coronaviruses
CN103691307A (en) * 2013-12-27 2014-04-02 浙江农林大学天目学院 Environment deodorant containing microorganism strains and application of environment deodorant
CN103691307B (en) * 2013-12-27 2016-03-02 浙江农林大学天目学院 A kind of environment deodorant containing microbial strains and uses thereof
CN105013304A (en) * 2014-04-28 2015-11-04 重庆市洁霖源环保科技有限公司 Automotive interior scavenger
CN104663658A (en) * 2015-02-04 2015-06-03 苏州康华净化系统工程有限公司 Sterilizing agent and preparation method thereof
CN106962271A (en) * 2017-03-25 2017-07-21 上海宇元生物科技有限公司 The cultural method of chitin poultry
CN109329312A (en) * 2018-10-30 2019-02-15 重庆市海洁消毒卫生用品有限责任公司 A kind of antibacterial agent and preparation method thereof
CN114053295A (en) * 2020-07-29 2022-02-18 以勒企业股份有限公司 Use of chitosan and its derivatives in antimicrobial and antiviral
CN112773729A (en) * 2021-03-17 2021-05-11 陈耕 Alcohol disinfectant safe to skin and preparation method thereof

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Application publication date: 20091014