CN116514692B - Quaternary ammonium salt, preparation method and application of curable long-acting disinfection - Google Patents
Quaternary ammonium salt, preparation method and application of curable long-acting disinfection Download PDFInfo
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- CN116514692B CN116514692B CN202310096078.7A CN202310096078A CN116514692B CN 116514692 B CN116514692 B CN 116514692B CN 202310096078 A CN202310096078 A CN 202310096078A CN 116514692 B CN116514692 B CN 116514692B
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- quaternary ammonium
- ammonium salt
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
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- A—HUMAN NECESSITIES
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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Abstract
The invention discloses a quaternary ammonium salt, a preparation method and application thereof, comprising a compound shown in a formula (I),
Description
Technical Field
The invention relates to the technical field of novel quaternary ammonium salt compounds, in particular to a novel quaternary ammonium salt and a preparation method and application thereof.
Background
In general, microorganisms are commonly present on textile products (such as masks) that are commonly used by people and can rapidly proliferate under suitable conditions, causing infection and malodor the textile products stained with sweat and/or secretions. Functional textiles with antibacterial and bacteriostatic effects are produced. The international organization for standardization promulgates ISO18184:2019 "antiviral textile testing Standard", so that the textile industry is urgent to develop new disinfection, antibiosis and bacteriostasis technologies to meet the requirements of the number of microorganisms carried on textiles.
The amount of viruses and bacteria retained by different textiles varies according to the type: synthetic fiber fabrics are more suitable for bacterial reproduction than natural fiber fabrics; the polyester-cotton blended synthetic fiber fabric has more odor-producing bacteria (staphylococcus epidermidis and corynebacteria) and dermatophytes fungi than pure cotton, polyester cotton, terylene and polypropylene fiber fabrics; the residual quantity of staphylococcus aureus and typhoid bacillus is the smallest on pure cotton durable press fabric, and the residual quantity of staphylococcus aureus and typhoid bacillus is the largest on wool fiber fabric and leather (such as wool woven blanket).
Cotton fabrics belong to the class of polysaccharide fabrics which contain a large number of hydroxyl groups, and antibacterial agents used for binding hydroxyl groups (-OH) on cotton fabrics are natural antibacterial agents, inorganic antibacterial agents (metals such as Ag, cu, agCl, cuI, znO), organic antibacterial agents (such as novel quaternary silicone salts, diphenyl ethers, nitrofurans, organic nitrogen, etc.), etc., for example, hydroxyl groups on cotton fabrics can be bound with oxymethyl groups (-OCH 3) on novel quaternary silicone salts by high temperature; the hydroxyl group may also be attached to an unsaturated O or N group on the diphenyl ether, nitrofurans, or organic nitrogen to reduce the level of germ reproduction.
However, the antimicrobial agent for cotton fabrics requires high temperature conditions (100-120 ℃) to bind to the hydroxyl groups on the cotton fabric. The high temperature is not easy to realize the antibiosis of wool fiber fabrics, leather products, vegetable protein fiber fabrics, animal protein fiber fabrics, human hair, hand, foot skin and the like, and the combination of the common antibiosis agent of cotton fabrics with the hair, the skin and the like is less at low temperature or normal temperature, so that the antibiosis performance is lower. In addition, in recent years, fabrics made of vegetable proteins, such as soybean protein fiber quilts, are also put into daily life, and soybean protein fiber quilts are soft to the touch and have excellent affinity with the skin, moisture permeability and permeability far superior to cotton fabrics, luxurious and silky appearance, but often give off odor, and also require elimination of the odor generated by attachment of environmental microorganisms and metabolism of vegetable proteins, so there is an urgent need in the art for an antibacterial agent and/or an antibacterial method for wool fabrics, vegetable and animal protein fiber fabrics, skin products, hair, skin, etc. at low or normal temperature.
Disclosure of Invention
The invention aims at providing a quaternary ammonium salt for resisting and inhibiting bacteria, such as wool fiber fabrics, protein fiber fabrics (such as soybean protein fabrics, silk fabrics and the like) derived from plant animals, leather products, hair, skin and the like, wherein the quaternary ammonium salt contains sulfhydryl groups, and can be covalently combined and solidified with sulfhydryl groups of cysteine in proteins contained in the wool fiber fabrics, the leather products, the hair, the skin, the protein fiber fabrics and the like at low temperature or normal temperature (less than or equal to 50 ℃), so that the quaternary ammonium groups play a long-acting role in resisting bacteria. The quaternary ammonium salts, including compounds of formula (I),
Wherein R is selected from one of alkyl groups, and X is selected from halogen.
R is selected from straight-chain alkyl.
R is selected from C10-C22 linear alkyl.
X is chlorine or bromine.
It comprises the following compounds:
In a second aspect, the present invention provides an antimicrobial composition comprising a reducing agent, an oxidizing agent and at least one quaternary ammonium salt as described above, applied separately, the reducing agent being selected from tris (2-carboxyethyl) phosphine hydrochloride, tris (3-hydroxypropyl) phosphine, dithiothreitol or β -mercaptoethanol; the oxidant is selected from at least one of hydrogen peroxide, hypochlorite, permanganate and the like.
Wherein the quaternary ammonium salt, the reducing agent and the oxidizing agent are all aqueous solutions, and the mass percentage concentration of the aqueous solutions is 0.2% -3%, 1.5% -15% and 0.1% -5% respectively.
In a third aspect, the present invention provides a method for preparing the quaternary ammonium salt, comprising mixing isopropanol, 2-chloroacetylcysteine and glutathione, adding R-group (R is alkyl) dimethyl tertiary amine and potassium iodide at 45-70 ℃, and reacting at the temperature for 30-50 hours, stopping the reaction; and (3) cooling the reaction solution to room temperature, regulating the pH value to 6.0, and filtering to obtain a product mainly containing the quaternary ammonium salt.
In a fourth aspect, the present invention provides the use of a quaternary ammonium salt as described above in the formulation of an antibacterial agent.
In a fifth aspect, the present invention provides an antimicrobial method using the above antimicrobial composition, in particular for the antimicrobial of hair, skin, animal skin products, wool fabrics, animal and vegetable protein products, in particular: sequentially applying a reducing agent solution with the mass percentage concentration of 1.5-15%, a quaternary ammonium salt solution with the mass percentage concentration of 0.2-3% and an oxidant solution with the mass percentage concentration of 0.1-5% at normal temperature; preferably, the application amounts of the reducing agent, the quaternary ammonium salt and the oxidizing agent are respectively more than or equal to 0.2mg/m 2、≥0.1mg/m2、≥0.15mg/m2.
The quaternary ammonium salt provided by the invention contains sulfhydryl groups, and can be covalently combined with sulfhydryl groups of cysteine in proteins contained in wool fiber fabrics, protein fiber fabrics, leather products, hair, skin and the like at low temperature or normal temperature, so that the quaternary ammonium salt is solidified on the surfaces of the wool fiber fabrics, the protein fiber fabrics, the leather products, the hair, the skin and the like, and further the quaternary ammonium group is utilized to play an antibacterial and bacteriostatic role on the wool fiber fabrics, the leather products, the hair, the skin and the like. Because the quaternary ammonium salt is firmly combined with the sulfhydryl of the cysteine, the curing effect of the quaternary ammonium salt on the surfaces of wool fabrics, protein fabrics, leather products, hair, skin and the like is good, so that the long-acting antibacterial effect can be achieved, and experiments prove that the antibacterial effect can be up to 30 days. The quaternary ammonium salt has no irritation and toxicity, and good stability, and can be used as antibacterial agent for hand and foot skin surface and hair, animal skin product, hair fiber and plant animal protein fiber fabrics.
Drawings
FIG. 1 shows human keratin sequences and cysteines (letter c) and their proportions in a genome database;
FIG. 2 is a schematic diagram showing the principle of binding of thiol-containing amino acids in keratin with a quaternary ammonium salt of the present invention;
FIG. 3 shows the synthetic reaction scheme of the quaternary ammonium salt of the present invention;
FIG. 4 shows a mass spectrum of a synthetic substance according to the present invention (the main peak in the figure is the quaternary ammonium salt according to the present invention);
FIG. 5 shows the chemical structure of the quaternary ammonium salt molecule of example 1.
Detailed Description
Plant, animal and human cells contain a large amount of proteins, which are composed of more than 20 amino acids, wherein cysteine has sulfhydryl SH, disulfide bonds can be formed between sulfhydryl groups, so that the formed proteins have a higher structure and are physically expressed as having a certain hardness, such as keratin.
Keratin is a protective protein derived from cells differentiated from ectoderm, one of the structural proteins of these cells, found in hair, scales, nails, feathers, nails, hooves, horns, paws, beak, silk, cuticles and other epidermal structures. Keratin is insoluble or slightly soluble in water because it contains more cysteines (see fig. 1, 34 cysteines C among 505 amino acids), and intra-or inter-peptide cysteines cross-link to form abundant disulfide bonds (S-S bonds), making keratin particularly chemically stable and mechanically strong.
The invention provides a novel quaternary ammonium salt N, N-dimethyl N-R group (R group is preferably C 10-22 linear alkyl) amino acetyl cysteine chloride which is prepared by synthesizing chloroacetyl cysteine and R group (R group is preferably C 10-22 linear alkyl) amino dimethyl tertiary amine.
The novel quaternary ammonium salt compound reducer and the oxidant form an antibacterial composition which is used for antibacterial and bacteriostatic effects of keratin-containing substances (such as hair, skin, animal skin products, wool fabrics and plant animal protein fabrics), and the antibacterial and bacteriostatic mechanisms of the antibacterial composition are as follows: the keratin contains high content of cysteine (for example, human genome Xu Liu database shows that the keratin contains 7% of cysteine in the sequence), the disulfide bond structure of the original peptide chain or inter-chain cysteine of the keratin can be changed into two free sulfhydryl groups after the keratin is treated by a reducing agent, at this time, the quaternary ammonium salt containing sulfhydryl is applied to the position after the treatment by the reducing agent, then an oxidizing agent is applied, the reduced free sulfhydryl groups can be subjected to crosslinking reaction with the sulfhydryl groups of the quaternary ammonium salt to form new S-S disulfide bonds, so that the novel quaternary ammonium salt is combined with the keratin to solidify the quaternary ammonium salt on the keratin (see figure 2), and the aim of solidifying and combining the quaternary ammonium salt with the surfaces of hair, skin, animal skin products, wool fabrics and plant animal protein fabrics is achieved. After solidification, the quaternary ammonium group in the quaternary ammonium salt can be inserted into cell membranes of bacteria on hair, skin, animal skin products, wool fiber fabrics and animal and plant protein fiber fabrics so as to play an antibacterial and bacteriostatic role. The disulfide bond of keratin is reduced and then combined with the novel quaternary ammonium salt of the invention for oxidation recombination for solidification, and the combination and solidification are very firm, so that the quaternary ammonium salt with the antibacterial function can play a long-acting antibacterial and bacteriostatic role on hair, skin, animal skin products, wool fabrics and animal and plant protein fabrics. Furthermore, the reduction of disulfide bonds on keratin and the oxidation recombination of sulfhydryl groups on keratin and sulfhydryl groups on quaternary ammonium salt can all occur at low temperature or room temperature (less than or equal to 50 ℃), so that the novel quaternary ammonium salt can be used not only on various fabrics at normal temperature (including low temperature in winter and high temperature in summer in climatic sense), but also directly on the surface of materials such as hair, skin and animal skin products which are not suitable for high-temperature antibiosis, and the long-acting antibiosis and bacteriostasis effects of the novel quaternary ammonium salt used as an antimicrobial agent are not affected.
According to the operation of the sanitary department of the people's republic of China 2002, the antibacterial performance of the quaternary ammonium salt is detected, and experiments prove that the quaternary ammonium salt can continuously resist natural bacteria, so that the aim of cleaning sterile reproduction is fulfilled; the antibacterial agent provided by the invention is firmly combined with keratin, so that the antibacterial effect can be exerted for a long time, and experiments prove that the antibacterial effect can reach 30 days, and the antibacterial agent can be used in the fields of medical sanitation, public health safety, sanitary textiles, travel service industry, aquaculture and the like, such as disinfection, mildew prevention, epidemic prevention and the like, including hand and foot disinfection and bacteriostasis of people.
When in use, the solution of reducing agent (such as tri (2-carboxyethyl) phosphine hydrochloride) is used for reducing and treating hair, skin, animal skin products, wool fabrics and plant animal protein fabrics in a spraying, smearing or soaking mode, then the quaternary ammonium salt is used for spraying, smearing or soaking, and then the solution of oxidizing agent (such as hydrogen peroxide) is used for spraying, smearing or soaking, so that sulfhydryl groups on the quaternary ammonium salt and free sulfhydryl groups on the reduced protein reform disulfide bonds to be solidified, and the quaternary ammonium group in the quaternary ammonium salt can play a continuous and long-acting antibacterial effect on hair, skin, animal skin products, wool fabrics and plant animal protein fabrics, and can be used for sterilizing and inhibiting bacteria on hair, skin, animal skin products, wool fabrics and plant animal protein fabrics at normal temperature, especially on hands and feet of people, and has a good application prospect.
Among them, many reducing agents which can function are selected from at least one of tris (2-carboxyethyl) phosphine hydrochloride, tris (3-hydroxypropyl) phosphine, dithiothreitol and beta-mercaptoethanol; however, since most reducing agents commonly used for reducing keratin disulfide bonds contain mercapto groups, have unpleasant odor and are toxic, and are not suitable for use on skin and hair, tris (2-carboxyethyl) phosphine hydrochloride (Tris (2-carboxyethyl) phosphine hydrochloride, TCEP) is preferably used in the present invention, and does not contain mercapto groups, is non-irritating, non-toxic, has no odor, has high stability, has a wide pH working range, has strong reducibility, does not affect subsequent oxidation, is easy to operate, and has good reduction effect. The oxidizing agent capable of functioning is a plurality of oxidizing agents and can be selected from at least one of hydrogen peroxide, hypochlorite, permanganate and the like, and preferably a low-concentration hydrogen peroxide aqueous solution is used as the stable oxidizing agent, which is harmless to human, non-corrosive to articles, non-residual to the environment and convenient for application.
The term "alkyl" refers to an aliphatic hydrocarbon group, which may be branched or straight chain. Depending on the structure, the alkyl group may be a monovalent group or a divalent group (i.e., alkylene). In the present invention, the alkyl group is preferably an alkyl group having 10 to 22 carbon atoms, more preferably an alkyl group having 12 to 20 carbon atoms, even more preferably an alkyl group having 14 to 18 carbon atoms. Typical alkyl groups include, but are not limited to, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and the like. It is to be understood that references herein to "alkyl" include such alkyl groups in all configurations and conformations that may be present.
The term "halogen" or "halo" refers to fluorine, chlorine, bromine and iodine.
The present invention will be described more specifically with reference to the following examples, which are not intended to limit the present invention in any way.
The experimental methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are all commercially available.
Example 1: preparation of novel quaternary ammonium salts of the present invention
1.1, Synthesizing novel quaternary ammonium salt, wherein the synthetic reaction equation is shown in figure 3.
The specific reaction process is as follows: adding 10 mole parts of isopropanol (raw material I) into a reaction kettle, adding 1.05 mole parts of 2-chloroacetylcysteine (raw material II) under the protection of nitrogen, then adding 0.1 mole part of glutathione (raw material III) as a protective agent of the raw material II, slowly adding (about half an hour) 1 mole part of R-base (linear alkyl with R being C 10-22 in the embodiment) dimethyl tertiary amine (raw material IV) at 50-70 ℃, finally adding 0.5 mole part of potassium iodide (raw material V) as a catalyst, carrying out reflux reaction at 45-70 ℃ for 30-50 hours, and stopping the reaction when the mass percentage of chloride ions in the reaction liquid is 50-60% by using a potentiometric titration method. The reaction solution is cooled to room temperature, then the pH value is regulated to 6.0, stirred for 10min, filtered, and the filtrate is the novel quaternary ammonium salt-N, N-dimethyl N-R group (R is C 10-22 linear alkyl) aminoacetylcysteine chloride solution.
1.2, Preparation examples of novel quaternary ammonium salts: preparation of N, N-dimethyl N-R group (R is C16 straight chain alkyl) aminoacetylcysteine chloride
10 Mole parts of isopropanol (raw material one, commercially available) is added into a reaction kettle, 1.05 mole parts of 2-chloroacetylcysteine (raw material two, commercially available) is added under the protection of nitrogen, then 0.1 mole part of glutathione (raw material three, commercially available) is added, 1 mole part of hexadecyldimethyl tertiary amine (raw material four, commercially available) is slowly added (about half an hour) at 50-70 ℃, finally 0.5 mole part of potassium iodide (raw material five, commercially available) is added as a catalyst, reflux reaction is carried out for 30-50 hours at 45-70 ℃, and the reaction is stopped when the mass percentage of chloride ions in the reaction liquid is 50-60% by a potentiometric titration method. The reaction solution is cooled to room temperature, then the pH is regulated to 6.0, the reaction solution is stirred for 10min, the filtrate is the solution of the quaternary ammonium salt-N, N-dimethyl-N-hexadecylaminoacetylcysteine chloride, the appearance is yellowish and can be water solution, the quaternary ammonium salt (see figure 4) of the invention with the product content of about 70 percent is synthesized according to the conditions, the tail end of the quaternary ammonium salt is provided with free mercapto and positively charged alkyl long-chain novel quaternary ammonium salt chloride, the molecular formula is C 23H47N2O3 SCl, the molecular weight is 467.138, and the mass spectrum shows a cation main peak of 431.6, which accords with theoretical values.
Other novel quaternary ammonium salts are also prepared by the method, and only the hexadecyl dimethyl tertiary amine is replaced by the dimethyl tertiary amine corresponding to the alkyl, such as decyl dimethyl tertiary amine, dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, eicosyl dimethyl tertiary amine and docosyl dimethyl tertiary amine, which are all commercially available.
Example 2: novel quaternary ammonium salt antibacterial application
The embodiment provides an antibacterial method for hair, skin, animal skin products, wool fiber fabrics and protein fiber fabrics, which uses the novel quaternary ammonium salt disclosed by the invention, and specifically comprises the following steps: the preparation method comprises the steps of sequentially applying (such as smearing, spraying and soaking) on hair, skin, animal skin products, wool fibers and protein fiber fabrics, wherein the using process is summarized as three steps of reduction, combination and oxidization solidification, and the adopted reducing agent is named as component A, namely tris (2-carboxyethyl) phosphine hydrochloride solution with the concentration of 1.5% -15%; the adopted binding agent is named as a component B, namely a novel quaternary ammonium salt solution with the concentration of 0.2% -3%; the oxidant adopted is named as component C, namely hydrogen peroxide solution with the concentration of 0.1% -1%, wherein the solution refers to aqueous solution, and the concentration refers to mass percentage concentration. Wherein the application amount of the component A is more than or equal to 0.2mg/m 2, the application amount of the spray component B is more than or equal to 0.1mg/m 2 after 10 minutes, and the application amount of the spray component C is more than or equal to 0.15mg/m 2 after 10 minutes.
Experiment one, novel sterilizing experiment of quaternary ammonium salt
The experiment is carried out according to the disinfection technical Specification in the Ministry of health of the people's republic of China 2002, and the novel quaternary ammonium salt of the invention is prepared into liquid for the experiment according to a bacterial cloning method calculated by a bacterial culture and a coating plate for evaluating sterilization.
The preparation and process of the reagent are as follows:
3.1, test strain: coli (ATCC 25922) passage 5; staphylococcus aureus (ATCC 6538), passage 6; candida albicans (ATCC 10231), passage 6. Disinfectant neutralizer: 2-fold D/E neutralized broth. Dilution liquid: tryptone physiological saline solution (TPS), phosphate buffer (PBS, 0.03M,pH7.2). Organic interfering substances: 3% Bovine Serum Albumin (BSA). Candida albicans was cultured on Sage agar medium, and others on tryptone soy agar medium (TSA).
3.2, Novel quaternary ammonium salt solution: the quaternary ammonium salt of example 1 was dissolved in water to give an aqueous solution of N, N-dimethyl-N-hexadecylaminocysteine chloride having a weight concentration of 0.5 to 3%.
3.3, Neutralization experiment: the test solution of the test group is prepared by diluting a novel quaternary ammonium salt solution (namely 3.2) and standard hard water according to a volume ratio of 1:22, the neutralization time is 0.5min, and the test is repeated for 3 times. The neutralizing agent group used D/E neutralization broth (formula g/L: tryptone 5.0, yeast powder 2.5, glucose 10.0, sodium thioglycolate 1.0, sodium thiosulfate 6.0, sodium bisulphite 2.5, bromocresol purple 0.02, lecithin 7.0, pH 7.6.+ -. 0.2) as neutralizing agent was diluted with PBS in the same proportion for 1.0min, and the test was repeated 3 times.
3.4, Sterilization test method: according to the disinfection technical Specification (2002 edition) items 2.1.1.5.5 and 2.1.1.7.4. The novel quaternary ammonium salt solution (i.e. 3.2 preparation) of the test group is fixedly applied for 2.0min, 5.0min, 10.0min and 20.0min under the single mass concentration as four test groups (test group 1-test group 4), and the test temperature is room temperature. The average was calculated using 3 replicates.
3.5 Sterilizing the test bacterial suspension
The results of analysis by adopting three types of bacteria with antibacterial evaluation show that the novel quaternary ammonium salt solution (namely 3.2 preparation) has the disinfection effect and antibacterial activity meeting the national standard disinfection standards at the concentration of 0.5 percent. The following experiments all employed this concentration.
3.5.1 Quantitative killing effect on staphylococcus aureus
① Test strain: staphylococcus aureus (ATCC 6538), passage 6;
② 0.5% of novel quaternary ammonium salt solution (namely 3.2);
③ Neutralizing agent: 2-fold D/E neutralization broth;
④ Dilution liquid: tryptone physiological saline solution (TPS), phosphate buffer (PBS, 0.03M,pH7.2);
⑤ Organic interfering substances: 3% Bovine Serum Albumin (BSA);
⑥ Culture medium: tryptone soy agar medium (TSA);
⑦ Biological safety cabinet, constant temperature incubator, thermostat, vortex oscillator, aseptic equipment, electronic timer, etc.;
⑧ The detection basis is as follows: the sterilization technical Specification (2002 edition) 2.1.1.5.5, 2.1.1.7.4;
⑨ Neutralization agent identification test: the test uses 0.5% novel quaternary ammonium salt solution (i.e. 3.2 preparation), the action time is 0.5min, and the test temperature is constant at 20 ℃. The test was repeated 3 times. The novel quaternary ammonium salt solution (namely 3.2) with the concentration of 0.5 percent is diluted by standard hard water according to the ratio of 1:22 (antibacterial solution: standard hard water) to prepare test solution, meanwhile, the neutralizing agent solution is diluted by PBS according to the same proportion, the action time is 1.0min, and the test temperature is constant at 20 ℃. The test was repeated 3 times.
⑩ Sterilization test: the test time of the novel quaternary ammonium salt solution (namely 3.2) with the concentration of 0.5 percent is 2.0min, 5.0min, 10.0min and 20.0min, and the test temperature is constant at 20 ℃. The test was repeated 3 times, respectively sterilization group 1-sterilization group 3. Ambient temperature: 20.3-21.7 ℃; relative humidity: 45% -48%.
Results:
(1) The neutralizing agent identification test results are subjected to 3 repeated tests, and under the constant temperature test condition of 20 ℃,0.5% of novel quaternary ammonium salt solution (namely 3.2 preparation) is diluted according to the ratio of 1:22 (antibacterial solution: standard hard water), and the test solution is: the average colony number of the 1 st group growth is 0CFU/mL, the average colony number of the 2 nd group growth is 0CFU/mL, and the results of the 3 rd to 5 th group identification of the neutralizer group are respectively as follows: the average colony number is 1.40X10 7CFU/mL,1.50×107 CFU/mL and 1.60deg.X10 7 CFU/mL, the error rate between the three groups is 4.78%, the 6 th group is a negative control (the neutralizer test is shown in Table 1), and the killing effect on staphylococcus aureus is shown in Table 1.
Table 1 neutralizer identification of quantitative test results for killing Staphylococcus aureus
(2) After 3 repeated tests, the sterilization group 1-3 uses 0.5% novel quaternary ammonium salt solution (i.e. 3.2 preparation) under the constant temperature test condition of 20 ℃, the effect is 2.0min, 5.0min, 10.0min and 20.0min, and the killing logarithmic value of staphylococcus aureus in suspension is more than 5.00 (see table 2).
TABLE 2 killing effect on Staphylococcus aureus
3.5.2 Quantitative E.coli killing effect
① Test strain: coli (ATCC 25922), passage 5.
② 0.5% Novel quaternary ammonium salt solution (i.e., 3.2 formulation).
③ Neutralizing agent: 2-fold D/E neutralized broth.
④ Dilution liquid: tryptone physiological saline solution (TPS).
⑤ Organic interfering substances: 3% Bovine Serum Albumin (BSA).
⑥ Culture medium: tryptone soy agar medium (TSA).
⑦ Biological safety cabinet, constant temperature incubator, thermostat, vortex oscillator, aseptic equipment and electronic timer, etc.
⑧ The detection basis is as follows: the sterilizing technical Specification (2002 edition) 2.1.1.7.4.
⑨ Neutralization agent identification test: the test uses 0.5% novel quaternary ammonium salt solution (i.e. 3.2 preparation), the action time is 0.5min, and the test temperature is constant at 20 ℃. The test was repeated 3 times. The novel quaternary ammonium salt solution (namely 3.2) with the concentration of 0.5 percent is diluted by standard hard water according to the ratio of 1:22 (antibacterial solution: standard hard water) to prepare test solution, meanwhile, the neutralizing agent solution is diluted by PBS according to the same proportion, the action time is 1.0min, and the test temperature is constant at 20 ℃. The test was repeated 3 times.
⑩ Sterilization test: the test time of the novel quaternary ammonium salt solution (namely 3.2) with the concentration of 0.5 percent is 2.0min, 5.0min, 10.0min and 20.0min, and the test temperature is constant at 20 ℃. The test was repeated 3 times, respectively sterilization group 1-sterilization group 3. Ambient temperature: 20.3-21.7 ℃; relative humidity: 45% -48%.
Results:
(1) After 3 repeated tests, the test solution prepared by diluting 0.5% novel quaternary ammonium salt solution (namely 3.2) according to the ratio of 1:22 (antibacterial solution: standard hard water) is: the average colony number for group 1 was 0CFU/mL, and the average colony number for group 2 was 2.46X 10 3 CFU/mL. The neutralizing agent identification result is as follows: the average colony numbers for growth in group 3, group 4 and group 5 were 1.93X 10 7CFU/mL,2.05×107 CFU/mL and 2.17X 10 7 CFU/mL, respectively, the error rate between the three groups was 4.06%, and group 6 was a negative control (see Table 3).
Table 3 identification of E.coli Sterilization results by the neutralizer
(2) After 3 repeated tests, the novel quaternary ammonium salt solution (namely 3.2) with the concentration of 0.5 percent is applied for 2.0min, 5.0min, 10.0min and 20.0min under the constant temperature test condition of 20 ℃, and the killing logarithmic value of coliform in suspension is more than 5.00 (see table 4).
TABLE 4 killing effect on E.coli
3.5.3 Quantitative killing effect on candida albicans
① Test strain: candida albicans (ATCC 10231), passage 6.
② 0.5% Novel quaternary ammonium salt solution (i.e., 3.2 formulation).
③ Neutralizing agent: 2-fold D/E neutralized broth.
④ Dilution liquid: tryptone physiological saline solution (TPS), phosphate buffer (PBS, 0.03M,pH7.2).
⑤ Organic interfering substances: 3% Bovine Serum Albumin (BSA).
⑥ Culture medium: sand agar medium.
⑦ Biological safety cabinet, constant temperature incubator, thermostat, vortex oscillator, aseptic equipment and electronic timer, etc.
⑧ The method comprises the following steps: disinfection technical Specification (2002 edition, items 2.1.1.5.5, 2.1.1.7.4 and 2.1.1.9.3.1).
⑨ Neutralization agent identification test:
The test was repeated 3 times with a 0.5% novel quaternary ammonium salt solution (i.e., 3.2 formulation) for a period of 0.5min at a constant temperature of 20 ℃. The novel quaternary ammonium salt solution (namely 3.2) with the concentration of 0.5 percent is diluted by standard hard water according to the ratio of 1:20 (antibacterial solution: standard hard water) to prepare test solution, meanwhile, the neutralizing agent solution is diluted by PBS according to the same proportion, the action time is 0.5min, and the test temperature is constant at 20 ℃. The test was repeated 3 times.
⑩ Sterilization test: the test time of the novel quaternary ammonium salt solution (namely 3.2) with the concentration of 0.5 percent is 2.0min, 5.0min, 10.0min and 20.0min, and the test temperature is constant at 20 ℃. The test was repeated 3 times, respectively sterilization group 1-sterilization group 3. Ambient temperature: 20.3-21.7 ℃; relative humidity: 45% -48%. Neutralization agent identification test results: after 3 repeated tests, 0.5% novel quaternary ammonium salt solution (i.e. 3.2 formulation) was prepared under the constant temperature test condition of 20 ℃.
Results:
(1) The test solutions were diluted 1:20 (antiseptic solution: standard hard water) as follows: the average colony number of the growth of the 1 st group and the 2 nd group is 0CFU/mL, and the identification result of the neutralizer is as follows: the average colony numbers for growth in groups 3, 4 and 5 were 1.42X10 6CFU/mL,1.52×106 CFU/mL and 1.59X10 6 CFU/mL, respectively, the error rate between the three groups was 3.96%, and the group 6 was a negative control (see Table 5).
Table 5 results of the neutralizer identification test
(2) The killing effect on candida albicans: after 3 repeated tests, under the constant temperature test condition of 20 ℃, the novel quaternary ammonium salt solution (namely 3.2) with the concentration of 0.5 percent is applied for 2.0min, 5.0min, 10.0min and 20.0min, and the killing logarithmic values of candida albicans in suspension are all more than 4.00, as shown in table 6.
TABLE 6 killing effect on Candida albicans
The experimental result of 3.5 shows that the prepared novel quaternary ammonium salt solution with the concentration of 0.5 percent (namely 3.2) has the killing effect on escherichia coli, staphylococcus aureus and candida albicans with the logarithmic values of more than 5.0, 5.0 and 4.0 after the action time on bacterial suspension is 2.0 min.
All the sterilization results of the experiment I show that the antibacterial liquid prepared from the quaternary ammonium salt has sterilization and disinfection effects meeting the requirements of the sterilization technical Specification (2002 edition).
Other quaternary ammonium salts of the present invention have similar effects and are not described in detail herein.
Experiment two, novel quaternary ammonium salt skin irritation test (multiple complete skin irritation test)
4.1, Preparing quaternary ammonium salt solution and applying: the skin of the experimental animal was treated by applying the reducing agent component A, the binding agent component B and the oxidizing agent component C in this order according to the method of example 2, with 3wt% (i.e., 3.2 in experiment one) of the quaternary ammonium salt solution of N, N-dimethyl N-16 alkylaminoacetyl cysteine chloride.
4.2, 3 White rabbits in Japanese, female, weight 2.0kg-2.5kg, supplied by Changyang western mountain farm in Beijing city, common animals, production license number SCXK (Beijing) 2021-0008, quality qualification number 110329211100133123. Feed was supplied by the company si Bei Fu (beijing) biotechnology limited, production license number SCXK (beijing) 2019-0010, quality certification number 1103242100051559. The temperature of the animal house is 19-26 ℃, the relative humidity is 40-70%, the animal house is illuminated for 12 hours, and the animal house is dark for 12 hours. The animals can eat and drink water freely.
4.3, A contamination method: the dorsal spinal column of the Japanese white rabbits were dehaired at about 3cm by 3cm in area 24 hours before the test. The next day 0.5mL of 3% novel quaternary ammonium salt solution (i.e., 3.2 in experiment) of the stock solution of the sample to be tested is coated on the skin at the left side of 2.5cm x 2.5cm, the right side is used as a blank control (natural growth and synchronous shaving with the left side), and after 4 hours of coating, the sample to be tested is washed with warm water to remove the residual sample to be tested. The application was carried out once a day, and the procedure was as described above, with 14d consecutive applications. In order to facilitate the application of the test sample and the observation of the result, shaving is performed again if necessary.
4.4, Observation and evaluation: skin reactions were observed and scored 24h after each application, and scoring criteria and stimulation intensity ratings were referenced in "disinfection technical Specification (2002 edition) 2.3.3" skin irritation test "tables 2-11 and 2-12.
4.5, Test results: multiple skin irritation tests were performed using 3 animals and the local skin response was observed 24h after each application. No stimulus response was seen on both the left (sample) and right (control) sides of 3 animals 14d (see table 7).
TABLE 7 evaluation results of multiple complete skin irritation response of Japanese white rabbits
Through detection, the prepared novel quaternary ammonium salt antibacterial solution is 3% novel quaternary ammonium salt solution (namely 3.2 is prepared in experiment one) for carrying out a plurality of complete skin irritation tests on Japanese big ear white rabbits, and the total integral average value is 0.00 (< 0.5) of irritation index, and the irritation intensity belongs to nonirritant. The novel quaternary ammonium salt is proved to still belong to the safety range for skin application under the condition of high concentration. Meets the specification of qualification of skin disinfection application in the technical specification of disinfection (2002 edition).
Other quaternary ammonium salts of the present invention have similar effects and are not described in detail herein.
Experiment three, novel quaternary ammonium salt long-acting antibacterial test on leather
5.1, Equipment: the prepared novel quaternary ammonium salt antibacterial solution is a quaternary ammonium salt solution of 0.5 percent of N, N-dimethyl N-16 alkyl amino acetyl cysteine chloride (namely, the novel quaternary ammonium salt antibacterial solution is prepared in experiment one 3.2); nutrient agar medium (NA), nutrient Broth (NB); bacterial culture plates (5.0 cm. Times.5.0 cm).
And 5.2, detecting natural bacteria on the surface of the organic hard leather. A long-acting disinfection effect test for simulating human skin test is adopted, 30 leather surfaces are selected, 4 adjacent areas which are not easy to pollute each other are taken on each leather surface, and each area is a square area with stroke lines of 5cm multiplied by 5cm and used as a test area and a sampling area.
5.3 Methods
And after all the test areas are disinfected once, natural bacteria culture of the disinfection areas are collected at different time points, cloning units are counted, and the continuous disinfection effect is analyzed.
5.3.1, Adopting leather to simulate human skin, 30 leather surfaces, wherein each surface is provided with 4 adjacent areas which are not easy to pollute each other, each area is 5cm multiplied by 5cm by using a stroke line, and ① area 1 is designed: not processing; ② Region 2 and region 3: sterilizing with 75% alcohol; ③ region 4: the quaternary ammonium salt solution (the concentration is 0.5 percent, namely 3.2 percent) is used for disinfection treatment.
5.3.2, Disinfection mode: firstly dipping and rubbing the region 2 and the region 3 with absorbent cotton balls with 75% alcohol, and then spraying and sterilizing with 75% alcohol; spraying and sterilizing the area 4 by using the prepared novel quaternary ammonium salt antibacterial solution, sequentially applying a reducing agent component A, a binding agent component B and an oxidizing agent component C according to the three steps of reduction, combination and oxidization curing of the method in example 2, and spraying until the area is wet in each time; and (5) drying the areas 2, 3 and 4.
5.3.3, Sampling mode: 1mL of nutrient broth (commercially available) was dipped with a sampling cotton swab to fill the streaked area, i.e., the 5 cm. Times.5 cm area. Sampling for the first time: after 5min of sterilization, sampling bacteria in the area 1 and the area 2 by using a sampling cotton swab, and sampling the area 3 and the area 4; second sampling: after 15d, sampling bacteria in the areas 1,2 and 3 by using a sampling cotton swab; third sampling: after 30d, the bacteria of the above-mentioned region 1 to region 4 were collected with a sampling cotton swab. The same number of times was scraped with a cotton swab at the time of sampling, the whole nutrient broth was collected, 1mL of the broth was supplemented with the nutrient broth, shaking culture was performed at 37℃for 2 hours, and 0.3mL was then transferred to a bacterial culture plate for cultivation for about 18 hours.
The natural bacteria killing effect of the novel quaternary ammonium salt prepared by the detection on 30 leather surface samples after 5.0min,15d and 30d is as follows (see table 9).
Table 9 novel quaternary ammonium salt antibacterial liquor long-acting bactericidal leather surface field test
Through detection, compared with the surface area of untreated leather, the novel quaternary ammonium salt antibacterial solution is applied to spray the surface of an object, after the continuous action is carried out for 30 days, the antibacterial rate of the novel quaternary ammonium salt antibacterial solution on natural bacteria is 95.83%, and the novel quaternary ammonium salt antibacterial solution has continuous and long-acting antibacterial action, and the long-acting antibacterial time of one-time application reaches 30 days.
Other quaternary ammonium salts of the present invention have similar effects and are not described in detail herein.
Experiment four, novel long-acting antibacterial test for treating human hair with quaternary ammonium salt
6.1, Test strain: coli (ATCC 25922) passage 5; staphylococcus aureus (ATCC 6538), passage 6; candida albicans (ATCC 10231), passage 6.
Nutrient agar medium (NA), sand agar medium, nutrient Broth (NB); bacterial culture plates (5.0 cm. Times.5.0 cm).
6.2, Detecting the sample. The effect of 0.2% (i.e., 3.2 formulation in experiment one) of the quaternary ammonium salt solution of N, N-dimethyl N-16-alkylaminoacetyl cysteine chloride of the present invention was tested using human hair; selecting 50 g of hair, leaving half of the hair as an untreated control sample, and selecting 10g of the hair as an antibacterial hair sample after the hair is dried, wherein the reducing agent component A, the binding agent component B and the oxidizing agent component C are sequentially applied according to the three steps of reduction, combination and oxidization curing in example 2; 10g of hair is selected, stirred and washed by clear water for 30 minutes, dried and dried, 10g of hair is taken, and the reducing agent component A, the binding agent component B and the oxidizing agent component C are sequentially applied according to the three steps of reduction, combination and oxidization curing of the example 2, and the hair is treated after being dried, and is taken as a water washing sample after the hair is subjected to antibacterial treatment.
6.3 Methods
6.3.1, Antibacterial property test, according to the part 3 oscillation method of the evaluation of the antibacterial property of the GB/T20944.3-2008 textile.
6.3.2 And 6.2 samples were analyzed after three months and 90 days in the same manner as 6.3.1, and the analysis was performed in 6.3.3.
6.3.3, Taking test hair samples. 0.8 g each was weighed as a sample. 12 Erlenmeyer flasks of 250 ml were prepared, 0.8 g of untreated control sample was added to each of three beakers of 1-3, 0.8 g of antimicrobial treated hair sample was added to each of flasks of 4-6, 0.8 g of antimicrobial treated hair and then washed with water in each of flasks of 7-9, and three other beakers of 10-12 were not added with hair sample as a blank control, and then 70ml of 0.03M PBS buffer of pH7.5 was added to each of the beakers.
5Ml of three bacterial strain suspensions are respectively added into each flask by a suction pipe, 1 ml of liquid is sucked from each sesame seed cake, the mixture is transferred into 9 ml of PBS buffer solution for fully and uniformly mixing, then 1 ml of diluted liquid is sucked by the suction pipe and transferred into a culture dish, the culture dish is placed on a constant temperature oscillator, and the culture dish is vibrated for 18 hours at the temperature of 25 ℃ at 250-300 rpm.
6.3.4 After 18 hours of culture, calculating the bacteriostasis rate according to a bacteriostasis rate formula, wherein the bacteriostasis rate is = (the average value of the live bacteria control sample for 18 hours-the average value of the antibacterial sample)/the live bacteria average value of the control sample is multiplied by 100%.
6.4 Results
According to the requirement of the national standard 20944, the antibacterial result of 18 hours is detected, and the antibacterial result of the water washing sample 7-9 after the antibacterial treatment of the quaternary ammonium salt solution (namely the antibacterial treatment of the quaternary ammonium salt solution is prepared by experiment one 3.2) is basically the same as that of the antibacterial treatment hair sample 4-6. The quaternary ammonium salt 0.2% solution (namely 3.2 for experiment) is used for treating hair, the average of the control group for 0 hour of live bacteria of the escherichia coli is 2.2 multiplied by 10 7, the average of 18 hours is 3.1 multiplied by 10 4, and the antibacterial rate of a sample is more than 99%; the average value of the control group of staphylococcus aureus living bacteria is 2.1 multiplied by 10 7 in 0 hour, the average value of 18 hours is 2.6 multiplied by 10 4, and the antibacterial rate of the sample is more than 99%; the average of the control group of candida albicans living bacteria for 0 hour is 1.9 multiplied by 10 7, the average of the control group of candida albicans living bacteria for 18 hours is 7.1 multiplied by 10 5, and the antibacterial rate of the sample is more than 99 percent.
After detection, after 90 days (90 days of experimental design are long-acting), the results of the treated water hair washing samples 7-9 and the treated non-water hair washing samples 4-6 of the quaternary ammonium salt solution (namely, the quaternary ammonium salt solution is prepared by experiment one 3.2) are basically the same. After the hair is treated by the 0.2% solution (namely 3.2 for experiment) for 90 days, the average control group of the live escherichia coli for 0 hour is 2.1 multiplied by 10 7, the average control group of the live escherichia coli for 18 hours is 3.1 multiplied by 10 4, and the antibacterial rate of the sample is more than 99%; the average value of the control group of staphylococcus aureus living bacteria is 2.2 multiplied by 10 7 in 0 hour, the average value of 18 hours is 2.4 multiplied by 10 4, and the antibacterial rate of the sample is more than 99%; the average of the control group of candida albicans living bacteria for 0 hour is 1.9 multiplied by 10 7, the average of the control group of candida albicans living bacteria for 18 hours is 7.2 multiplied by 10 5, and the antibacterial rate of the sample is more than 99 percent.
Conclusion: the novel quaternary ammonium salt long-acting antibacterial effect is tested by adopting human hair, compared with untreated hair, the antibacterial rate of the hair treated by the 0.2% quaternary ammonium salt solution (namely 3.2 for experiment) is more than 99%, the antibacterial rate of the hair treated by the novel quaternary ammonium salt antibacterial solution is maintained to be 99% after the hair is placed for three months, the antibacterial solution has continuous and long-acting antibacterial effect, and the novel cured novel quaternary ammonium salt is firmly combined and is not influenced by washing.
Other quaternary ammonium salts of the present invention have similar effects and are not described in detail herein.
Experiment five, novel quaternary ammonium salt long-acting antibacterial test on wool knitting fabric
7.1, Experiment four.
The long-acting antibacterial disinfection effect is evaluated by designing 30 days according to GB/T20944.3-2008 standard detection for 18 hours.
The sample is a wool knitting piece. Cutting out cloth pieces with the same size, wherein one cloth piece is used as a control group, the other cloth piece is used as a test group, and the three steps of reduction, combination and oxidization curing of the example 2 are sequentially applied with a reducing agent component A, a binding agent component B and an oxidizing agent component C for treatment, and the treatment is completed after the cloth pieces are dried; the test group was bound using a solution of 0.5% (i.e., 3.2 in experiment one) of the quaternary ammonium salt of N, N-dimethyl N-16-alkylaminoacetyl cysteine chloride. 10 g of the treated cloth is taken, stirred and washed with purified water for 30 minutes, and is dried by spin-drying and airing (18 hours from the start of sample shearing, and the control sample is synchronously placed for 18 hours) for testing.
And (3) performing antibacterial detection after 10g of the treated cloth is placed for 90 days, and selecting untreated wool knitting cloth to be placed synchronously for 90 days as a control group for 90 days.
7.2 Results
Through detection, the novel quaternary ammonium salt is used for treating bacterial detection results in wool knitting cloth which is dried and placed in the cloth for 90 days after drying:
The average viable count of the escherichia coli in the control group is 2.5 multiplied by 10 7, and the viable count in the test group is 3.7 multiplied by 10 4, so that the antibacterial rate of the treated wool knitted fabric sample is calculated to be more than 99%; the average number of viable bacteria of staphylococcus aureus in a control group is 2.2 multiplied by 10 7, the number of viable bacteria in a test group is 7.2 multiplied by 10 4, and the antibacterial rate of a sample is more than 99%; the average number of viable bacteria of candida albicans in the control group is 2.1 multiplied by 10 7, the number of viable bacteria in the test group is 3.7 multiplied by 10 5, and the antibacterial rate of the sample is more than 99%.
The wool yarn woven cloth is treated by adopting novel quaternary ammonium salt in a 90-day test, and is left for 90 days after being dried, the number of viable bacteria of the wool yarn woven cloth for 0 hour and 18 hours of escherichia coli is 2.5X10 7 and 3.7X10 4 respectively, and the antibacterial rate of a sample is more than 99%; the viable count of staphylococcus aureus for 0 hour and 18 hours is 7.0X10 7 and 2.6X10 4 respectively, and the antibacterial rate of the sample is more than 99%; the 0-hour control group and the 18-hour viable count of candida albicans are 9.1 multiplied by 10 6,3.7×105 respectively, and the antibacterial rate of the sample is more than 99 percent.
Conclusion:
According to the experiment, after the novel quaternary ammonium salt treated wool knitting cloth is dried in the air and the bacterial detection result in the cloth is basically the same after the wool knitting cloth is placed for 90 days. The long-acting antibacterial effect of the quaternary ammonium salt is tested by adopting the wool knitting cloth, compared with untreated wool knitting cloth, the antibacterial rate of the wool knitting cloth treated by the prepared quaternary ammonium salt solution is more than 99%, and the antibacterial rate of the wool knitting cloth treated by the quaternary ammonium salt solution after being placed for 90 days is still more than 99%, which indicates that the quaternary ammonium salt solution has continuous and long-acting antibacterial effect, and the novel quaternary ammonium salt is firmly combined with the wool knitting cloth and is not influenced by water washing.
Other quaternary ammonium salts of the present invention have similar effects and are not described in detail herein.
Experiment six, long-acting antibacterial test of the quaternary ammonium salt in hands
8.1, Equipment: a quaternary ammonium salt solution of N, N-dimethyl N-16 alkylaminoacetyl cysteine chloride at a concentration of 0.2% (i.e., 3.2 formulation in experiment one); nutrient agar medium (NA), nutrient Broth (NB); bacterial culture plates (5.0 cm. Times.5.0 cm).
8.2, Detecting natural bacteria on the organic hard surface. The long-acting disinfection effect is tested by adopting the hands and the palms of the human hands, and a region with the palm of 5cm multiplied by 5cm on the surface of the whole palms and a region with the palm plane of four fingers of 5cm multiplied by 5cm are selected as test and sampling regions. So that there are 4 areas per person left and right hand as test areas.
8.3 Methods
8.3.1, Selecting test volunteers by staff in the same office, wherein the test time is 6 hours, and no hand washing is performed during the test; 6 volunteers, 1,2 volunteers are randomly selected, water spray is used for simulating and disinfecting hands, 3,4 volunteers are used for disinfecting hands by alcohol, 5,6 volunteers are used for disinfecting hands by the quaternary ammonium salt solution of the invention, and the disinfection is carried out according to the method that the reducing agent component A, the binding agent component B and the oxidizing agent component C are sequentially applied in three steps of reduction, combination and oxidation curing in example 2, and the treatment is completed after the hands are dried. 100 old 100 primordial notes retrieved by the bank counter are checked by each person half an hour after the start of the test, each kept at natural office, and sample cultures of each palm 2 area are collected twice for 3 hours and 6 hours.
8.3.2, Sampling mode: 1mL of nutrient broth was dipped with a sampling cotton swab to fill the streaked area, i.e., the 5 cm. Times.5 cm area. Sampling for the first time: sterilizing for 3 hours; second sampling: after disinfection for 6 h. The same number of times was scraped with a cotton swab at the time of sampling, the whole nutrient broth was collected, 1mL of the broth was supplemented with the nutrient broth, shaking culture was performed at 37℃for 2 hours, and thereafter 0.3mL was transferred to a bacterial culture plate for culture, and the experimental result was observed for about 18 hours.
8.4 Results
The natural bacteria killing effect of the prepared 0.2% quaternary ammonium salt solution or alcohol of the invention on the palm surface sample after the hand skin is disinfected is detected as follows (see table 10).
Table 10 long-acting disinfection field test of novel quaternary ammonium salts on hand skin
Conclusion: after detection, the surface of the sprayed product of the quaternary ammonium salt solution is applied to the palm part to sterilize, and then the sprayed product is subjected to normal hand living and working environment, and compared with control alcohol sterilization in 6 hours, the natural bacteria antibacterial rate is over 90 percent, which shows that the alcohol sterilization cannot be maintained for 6 hours, and the quaternary ammonium salt solution of the invention has long-acting antibacterial effect for 6 hours when being applied to the hands.
Other quaternary ammonium salts of the present invention have similar effects and are not described in detail herein.
Experiment seven, elimination of fungal infection of beriberi by the quaternary ammonium salt of the invention in feet
9.1, Equipment: using quaternary ammonium salt solution with concentration of 0.2% (i.e. 3.2 in experiment one) N, N-dimethyl-N-16 alkyl amino acetyl cysteine chloride; nutrient agar medium (NA), nutrient Broth (NB); bacterial culture plates (5.0 cm. Times.5.0 cm).
9.2, Volunteers: under informed consent, eight people in the same working environment are selected; four people with healthy beriberi and fungal infection are numbered 1-4, and four people with beriberi and fungal infection at 2-4 positions are numbered 5-8; the patients with beriberi symptoms, without soaking, erosion and seepage, are selected from those with more keratinized scales, peeling and cracking and persistent itching or pain, and the severity is determined as follows: none-; slight+; light++; moderate++; and severe +. +/-of + (on) ++ + +five scale degrees.
9.3 Methods
9.3.1 The skin area of the toe seam of the volunteer was examined, and 4 areas of the four toe seams of a single foot were used as examination areas. Check area naming: the left small toe is 1 big toe 5, the right big toe is 6, and the small toe is 10; the 1-2,2-3,3-4,4-5 inter-toe regions are designated S, T, U, V, respectively; the region between the big toe and the small toe of the right foot, i.e., the region between 6-7,7-8,8-9,9-10 is designated W, X, Y, Z.
9.3.2, Control procedure for eliminating fungal infections, each procedure being as follows: at the toe seam test part of 8 areas of each of eight volunteers STUWWXYZ, a cotton swab is dipped in the reducing agent component A, the binding agent component B and the oxidizing agent component C in sequence for coating treatment.
9.3.3, Operating once a day according to 9.3.2 for 10 consecutive days, observing the skin integrity of the fungal infection part, inquiring whether the individual has itching and stinging feeling, recording the individual condition every day, and carrying out statistics and analysis.
9.4 Results
Through detection, the prepared novel quaternary ammonium salt can effectively eliminate infectious fungi (recorded results of 15 days shown in table 11) after being applied to disinfecting foot toe seam skin, has no adverse effect on healthy toe skin, and can eliminate moderate and severe dermatophytosis dermatomycosis after being continuously used for 10 days after being cured and disinfected.
Table 11 novel quaternary ammonium salt treatment of fungal infection at toe joints
The results show that the quaternary ammonium salt has an elimination effect on foot fungal infection and has definite and effective effects on preventing and treating beriberi fungal infection.
Experiment eight, the long-acting antibacterial property of the novel quaternary ammonium salt treated protein fiber fabric
10.1, Equipment: the same strain and corresponding culture medium and culture conditions, i.e., escherichia coli (ATCC 25922), staphylococcus aureus (ATCC 6538), candida albicans (ATCC 10231) and the like, are adopted in the same strain as 3.5. Bacterial samples were picked from culture plates and inoculated into a triangular flask of culture medium, and shake-cultured at 37℃to a corresponding concentration, and freshly prepared bacterial solutions were subjected to an antibacterial test within 4 hours.
10.1.1 Selecting protein fiber fabric material. The animal protein fiber fabric, i.e. silk fabric silk embroidery fabric and the vegetable protein fiber fabric, i.e. soybean protein fiber fabric, are selected and can be obtained by market purchase.
10.1.2 Preparation of the textile material. From each sample fabric that entered the test, 1 cm small pieces were made, 0.4.+ -. 0.05g was weighed as one sample, 6 samples were taken for antimicrobial performance, and 3 samples were taken for the control sample.
10.1.3 Pretreatment of textile materials. Each sample is placed in a triangular glass bottle, the triangular bottle and the bottle cap of the sample are wrapped, the high-pressure sterilization is carried out from the high-pressure sterilization pot, and the wrapping material is removed and operated on a clean bench.
10.1.4 Treatment of protein fiber-based textile materials. The test sample is treated by three steps of reducing agent component A, binding agent component B (namely 3.2 in experiment I) with concentration of 0.5 percent is added, N-dimethyl N-16 alkyl amino acetyl cysteine chloride quaternary ammonium salt solution and oxidizing agent component C, and after the fabric material is dried, the fabric material is washed and dried by 100 milliliters of purified water to be used as an antibacterial fabric material (antibacterial soybean protein fiber cloth and antibacterial silk cloth material) for standby.
10.1.5 Long-acting antibacterial property of antibacterial textile materials after washing. 10.1.4 samples were washed 20 times and tested for their long-term antimicrobial properties, three swatches were selected for each sample and washed according to the test conditions, the washing operation (washing mode with reference to national test standard 20944.3-2008) being: 150 ml of purified water at 40 ℃,10 steel balls and washing for 45 minutes; after washing, the sample was taken out and washed 4 times with 100 ml of purified water at 40 ℃. The sample is washed for 20 times by repeating the washing operation for four times, and the sample is fully washed by water after washing and dried for standby.
10.2 Antibacterial evaluation test procedure
Preparing a plurality of 250mL triangular flasks, and adding test samples (antibacterial fabric materials) according to the following numbers, wherein roman numerals for control samples are respectively added into 3 flasks for each bacterium, the test samples are numbered by capital English letters for 10.1.4, and the samples washed 20 times by water are numbered by lowercase English letters for 10.1.5; antibacterial soybean protein fiber cloth: e.coli control 1/2/3, test group A/B/C, water-washed antibacterial test group a/B/C; staphylococcus aureus control 4/5/6, experimental group D/E/F, water-washed antibacterial experimental group D/E/F; candida albicans control 7/8/9, test group G/H/I, water-washed antibacterial test group G/H/I. An antibacterial silk cloth material, an escherichia coli group is controlled to 11/12/13, an experimental group R/S/T and a washing antibacterial experimental group R/S/T; staphylococcus aureus control 14/15/16, test group U/V/W, water-washed antibacterial test group U/V/W; candida albicans group control 17/18/19, experimental group X/Y/Z, water-washed antibacterial experimental group X/Y/Z. Then, in each flask, there was added (70.+ -. 0.1) mL (0.03 mol/L) of PBS buffer.
10.2.1, 0H sample as control sample
Adding 5mL of inoculum solution into each Erlenmeyer flask of all test groups by using a suction pipe, covering a bottle stopper, putting on a constant temperature oscillator at 24 ℃ for shaking for 1min at 250r/min, sucking 1mL of solution into a flask for test sample preparation by using the suction pipe, transferring into a test tube filled with 9mL of PBS buffer solution, carrying out gradient dilution according to the solution, respectively preparing two plates for parallel samples by using the test tube with each dilution multiple, culturing according to the specified time and temperature, and counting.
10.2.2 And 18h sampling to test sample
5ML of inoculum solution is respectively added into each Erlenmeyer flask of all test groups by using a suction pipe, a bottle stopper is covered, the Erlenmeyer flasks are placed on a constant temperature oscillator at 24 ℃ and are vibrated for 18h at 250r/min, 1mL of solution is sucked into the flasks of all samples by using the suction pipe, the flasks are transferred into a test tube filled with 9mL of PBS buffer solution, gradient dilution is carried out according to the solution, two plates are respectively manufactured for parallel samples for each test tube with dilution multiple, and the culture is carried out according to the specified time and temperature, and the count is carried out.
10.3, Respectively calculating the viable bacteria concentration of the bacterial liquid in the triangular flask after shaking for 0h and shaking for 18h, and calculating the antibacterial rate of the test sample and the control sample so as to evaluate the antibacterial effect of the sample. The calculated value of the bacteriostasis rate is taken as a result.
10.4, Antibacterial effect evaluation: evaluation of the antibacterial properties of the textiles according to GB/T20944.3-2008 the antibacterial effect was evaluated by the part 3 shaking method, and the results of the antibacterial tests of each group of samples are shown in Table 12 below.
Table 12 antimicrobial properties of two protein fiber fabrics treated with quaternary ammonium salt antimicrobial agents
The results in Table 12 show that according to GB/T20944.3-2008, after the protein fiber fabric is treated by the quaternary ammonium salt, the antibacterial rate of the sample to staphylococcus aureus and escherichia coli is more than or equal to 70%, or the antibacterial rate to candida albicans is more than or equal to 60%, which shows that the quaternary ammonium salt has an antibacterial effect after the protein fiber fabric is treated by the quaternary ammonium salt. In addition, the antibacterial rate of the quaternary ammonium salt treated protein fiber fabric sample is not less than 70% to staphylococcus aureus and escherichia coli after 20 times of water washing, or not less than 60% to candida albicans, so that the quaternary ammonium salt treated protein fiber fabric sample can resist 20 times of water washing and has a long-acting antibacterial effect.
In view of the fact that all proteins contain cysteine, the result shows that products such as fabrics manufactured by animal or plant proteins can be fixed on fabric materials by adopting the form of S-S disulfide bonds formed by reduction and reoxidation of the quaternary ammonium salt of the invention, the quaternary ammonium salt of the invention treats the protein fiber fabrics to enable the protein fiber fabrics to have a disinfection and antibacterial effect, and the quaternary ammonium salt of the invention treats the protein fiber fabrics to resist 20 times of water washing, has a long-acting antibacterial effect after water washing, and has a definite and effective antibacterial and bacteriostatic effect on developing antibacterial protein fiber fabrics.
Other quaternary ammonium salts of the present invention have similar effects and are not described in detail herein.
The experiment proves that the novel curing quaternary ammonium salt has an instant disinfection effect on fur fabrics, wool fabrics (clothes carpets and the like) and human foot skin, has unique long-time sterilization and antibacterial epidemic prevention functions on protein fiber fabrics from plant animal sources, is suitable for self-sanitation epidemic prevention, living home environment, working environment and the like, and has application prospects in the fields of disinfection, mildew prevention and epidemic prevention and the like of medical and health, public health safety, sanitary textiles, travel service industry, aquaculture and the like.
The foregoing is merely a preferred embodiment of the invention, and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended by the present invention.
Claims (8)
1. A quaternary ammonium salt having a compound represented by the formula (I),
Wherein R is selected from C10-C22 linear alkyl, and X is selected from halogen.
2. The quaternary ammonium salt according to claim 1, wherein X is chlorine or bromine.
3. The quaternary ammonium salt according to claim 1 or 2, comprising the following compounds:
4. An antimicrobial composition comprising a reducing agent, an oxidizing agent and at least one quaternary ammonium salt according to any one of claims 1-3,
The reducing agent is selected from tris (2-carboxyethyl) phosphine hydrochloride, tris (3-hydroxypropyl) phosphine, dithiothreitol or beta-mercaptoethanol;
The oxidizing agent is selected from at least one of hydrogen peroxide, hypochlorite and permanganate.
5. The antibacterial composition according to claim 4, wherein the quaternary ammonium salt, the reducing agent and the oxidizing agent are all aqueous solutions, and the mass percentage concentration of the quaternary ammonium salt, the reducing agent and the oxidizing agent is respectively 0.2% -3%, 1.5% -15% and 0.1% -5%.
6. A preparation method of quaternary ammonium salt is characterized in that isopropanol, 2-chloroacetylcysteine and glutathione are mixed, R-group dimethyl tertiary amine and potassium iodide are added at the temperature of 45-70 ℃ and react for 30-50 hours at the temperature, and the reaction is stopped; the pH value of the reaction solution is regulated to 6.0 after the reaction solution is cooled to room temperature, and the product mainly comprising quaternary ammonium salt is obtained after filtration; the quaternary ammonium salt is a compound of formula (I),
Wherein R is selected from C10-C22 linear alkyl, and X is selected from chlorine.
7. Use of a quaternary ammonium salt according to any one of claims 1-3 or an antimicrobial composition according to any one of claims 4-5 for the preparation of an antimicrobial agent for hair, skin, animal skin products, wool fabrics, vegetable protein products, in particular: the reducer solution with the mass percentage concentration of 1.5-15%, the quaternary ammonium salt solution with the mass percentage concentration of 0.2-3% and the oxidant solution with the mass percentage concentration of 0.1-5% are sequentially applied at normal temperature.
8. The method according to claim 7, wherein the application amounts of the reducing agent, the quaternary ammonium salt and the oxidizing agent are respectively not less than 0.2mg/m 2、≥0.1mg/m2、≥0.15mg/m2.
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