CN101227884A - Corrosion protection system including cationic surfactant - Google Patents
Corrosion protection system including cationic surfactant Download PDFInfo
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- CN101227884A CN101227884A CNA2005800512598A CN200580051259A CN101227884A CN 101227884 A CN101227884 A CN 101227884A CN A2005800512598 A CNA2005800512598 A CN A2005800512598A CN 200580051259 A CN200580051259 A CN 200580051259A CN 101227884 A CN101227884 A CN 101227884A
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Abstract
The present invention is constituted by an instrument (1) for use in laparoscopic surgery, including a grip (2) which is provided with an actuator (3) , and which effects, through a linkage (3', 5, 6), the manipulation of an effector (9) . The effector (9) is positioned at a first end portion of a tubular element (7) , the tubular element (7) being attached to the grip (2) of the instrument (1) . The linkage (3', 5, 6) causes the relative movement of the actuator (3) to be non- linear relative to the relative movement of the effector (9) .
Description
The present invention relates to new protective system based on cationic surfactant.
Use in this area to comprise that the protective system of cationic surfactant is known, described cationic surfactant be derived from fatty acid and esterification binary amino acid condensation and have following formula (1) structure:
Wherein:
X
-Be Br
-, Cl
-Or HSO
4 -
R
1: be to have 8~14 carbon atoms and be connected to the straight chained alkyl of alpha-amino satisfied fatty acid or hydroxy acid through amido bond,
R
2: be the straight or branched alkyl or the aromatic group of 1~18 carbon atom, and
R
3: be
-NH
3
Wherein n is 0~4.
Cationic surfactant is used as antiseptic in grocery trade be known.Because it is formed, food is easy to the culture medium as microorganism, and this may jeopardize human health.Therefore, the food requirement excellent protection is to prevent microbial contamination.Because life-time service, the classification of cationic surfactant need be effective to preventing the microbial growth height, also is safe usually for human and mammiferous absorption simultaneously.
Because it is formed, many cosmetics are easy to the culture medium as microorganism, and this may cause that make-up preparation changes, and also can jeopardize human health simultaneously.Therefore, make-up composition necessarily requires excellent protection, to prevent microbial contamination.For this reason, use a large amount of antiseptic to suppress or reduce microbiologic population.
The most of protective systems that use show incompatibility to human skin at present, as stimulation and Sensitive disease, and also toxic to the mankind.On the other hand, confirmed to be derived from lauric acid and arginic cationic surfactant and be protection material, the particularly ethyl ester of the lauramide of arginine mono-hydrochloric salts, hereinafter be called LAE at microorganism.In actual applications, LAE presents good tolerability, and the mankind are shown extremely low toxicity.LAE has the chemical constitution of the formula shown in the back (2).If mention the not cationic moiety of the molecule of electronegative counter ion in this application, this part of molecule will be called cationic compound LAE so
+The sign that comprises the whole molecule of counter ion depends on the kind of counter ion, and LAE is a hydrochlorate, and corresponding bromate is expressed as LAE bromide or LAE Br.
Compound L AE is with to being present in the active and harmless and celebrated to the mankind of different microorganisms (as antibacterial, mycete and yeast) in foods and cosmetics and the preparation.
The preparation of cationic surfactant is documented among Spain patent ES 512643 and International Patent Application WO 96/21642, WO 01/94292 and the WO 03/064669.
Interaction between cationic surfactant and other molecules is known.The watery colloidal combination of cationic surfactant and anion is documented among the WO 03/094638, and this combination results contains the cationic surfactant of about stoichiometry and the solid chemical compound of the watery colloidal chemical compound of anion.The another kind combination of cationic surfactant is documented among the WO02/087328, and this combination relates to potassium sorbate, calcium sorbate or sorbic acid, and it is effective at the food antiseptic camber.
Be documented in the synergistic activity that these protective systems among WO 02/087328 and the WO 03/094638 are characterised in that them.The antibacterial activity that has been found that the combination of other chemical compounds of LAE and following formula (1) definition and ion commonly used that great majority are used to protect foods and cosmetics and preparation and nonionic antiseptic now is higher than the given activity of each composition when using separately with same dose.When the amount of formula (1) chemical compound and other antibacterial reduces, observed synergism.Therefore, antiseptic combination shows the disadvantageous toxic action that provides and/or stimulation and/or Sensitive disease and also reduces.
In practical study, observed cationic surfactant by partial hydrolysis, consequently its biological effect reduces.In with all fresh products of cationic surfactant antiseptical, all may observe this phenomenon.For example, observed the application of LAE in the fresh products that is selected from fish, meat and vegetable.In order to improve the effect of cationic surfactant in these products, need some means to prolong the biological agent of cationic surfactant.
Continue to need to realize more effective anti-corrosion method in different technical fields.Especially, research is requiring the new protective system of the antiseptic of less amount to cause extensive concern with zone that mammal directly contacts, as for the anticorrosion of food be added to the antiseptic of cosmetics.
Therefore, the purpose of this invention is to provide than the more effective protective system of present known protective system in this area.More specifically, the purpose of this invention is to provide protective system based on the further improvement of LAE.
To realize above-mentioned purpose as the cationic surfactant of antiseptic with mineral acid or organic acid salt form by providing.As implied above, the cationic surfactant that is used as antiseptic is hydrochloric acid as known in the art, hydrobromic acid and vitriolic salt, and these selections of mineral acid are not included in the scope of this embodiment of the present invention.In addition, can use any suitable inorganic or organic acid.
The combination of the salt by cationic surfactant and organic acid or mineral acid or any alkali are provided has further realized above-mentioned purpose.The combination of some salt and cationic surfactant is known, and as some salt of sorbic acid, these selections are not included in the scope of the present invention.
By cationic surfactant of the present invention and another kind of ester compounds being provided or also having realized purpose of the present invention with the combination of amide or enzyme inhibitor.
Also can realize purpose of the present invention by the combination that cationic surfactant and other cationic molecule are provided.
At last, by provide make molecule more difficult because of enzyme or other sources the influence hydrolysis and the cationic surfactant of the form of also more difficult and other matter interactions, can realize purpose of the present invention.According to this aspect of the invention, by being encapsulated in liposome or the micelle or by other similar manners, separates cationic surfactant with surrounding.
The application comprises the following drawings:
Fig. 1: the antisepsis of Different L AE salt in cooking Carnis Gallus domesticus, provide the meansigma methods that three log cfu/g of every day and every kind of processing mode measure,
Fig. 2: LAE and salt be combined in antisepsis in the bratwurst sausage, provide the meansigma methods that three log cfu/g of every day and every kind of processing mode measure,
Fig. 3: in concentration, provide the meansigma methods of three LAE concentration determinations of every day and every kind of processing mode with the combined administration of LAE and ester LAE after soaking chickpea,
Fig. 4: LAE and ester be combined in the antisepsis of soaking in the chickpea, provide the meansigma methods that three log cfu/g of every day and every kind of processing mode measure,
Fig. 5: LAE and cationic molecule be combined in the antisepsis of cooking in the Carnis Gallus domesticus, provide the meansigma methods that three log cfu/g of every day and every kind of processing mode measure,
Fig. 6: the antisepsis of the LAE of encapsulation in cooking Carnis Gallus domesticus provides the meansigma methods that three log cfu/g of every day and every kind of processing mode measure.
Fig. 7: the LAE of encapsulation provides the meansigma methods of three log cfu/g mensuration of every day and every kind of processing mode as the antisepsis of cooking in the Carnis Gallus domesticus that is combined in of acetate and other ester compounds and organic acid salt.
I. the salt of cationic surfactant
The following describes this one side that salt new, more effective cationic surfactant is provided.
The application has put down in writing some new product forms of the cationic surfactant of formula (1), particularly new salt.
In formula (1), n and radicals X, R1、R
2And R3Described as defined above.
Generic term " cationic surfactant " has also covered these new product forms of cationic surfactant, thereby if mention " cationic surfactant " among the application, so also comprises these new product forms, more especially these new salt.
The counter ion X of definition in the following formula (1)
-It is counter ion as known in the art.According to a first aspect of the invention, cationic surfactant has the counter ion that is different from chloride ion, bromide ion and sulfate ion accordingly.
Common organic acid can be as the source that obtains other counter ions.Described organic acid for example is citric acid, lactic acid, acetic acid, fumaric acid, maleic acid, gluconic acid, propanoic acid, sorbic acid, benzoic acid, carbonic acid, glutamic acid or other aminoacid, lauric acid and fatty acid such as oleic acid and linoleic acid.
Common mineral acid can be as the source that obtains other counter ions.Described common mineral acid for example is phosphoric acid, nitric acid and Hydrogen thiocyanate.Single phosphoric acid and its dehydrogenation form are suitable as anion.
The another kind of anion of selecting to be based on phenolic compound.Described phenolic compound for example is butylated hydroxyanisol (BHA) and relevant compound butyl hydroxy-methylbenzene (BHT), tert-butyl hydroquinone (TBHQ) and parabens, as methyl parahydroxybenzoate, 4-hydroxyphenylacetic acid ethyl ether, propyl p-hydroxybenzoate and butyl p-hydroxybenzoate.
As the source of the anion in the cationic surfactant, what be more suitable for is to use mineral acid listed above and organic acid salt.Can use the common salt of organic acid and mineral acid.
For anionic selection, therefrom deriving anionic precursor compound, particularly initial acid or initial salt itself, whether to show antisepsis unimportant.Unique standard is that it must be suitable as the anion with the cationic preservative combination.Yet, showing at precursor compound itself under the situation of antisepsis, its combination as anion and cationic preservative can show more favourable activity distribution, particularly can observe collaborative antisepsis.
For example, the salt of the cationic surfactant of Shi Heing is citrate, fumarate, malate, gluconate, laruate, lactate, tert-butyl hydroquinone salt, propyl p-hydroxybenzoate salt and phosphate.
Can use method common in this area to prepare the new salt of cationic surfactant.
Use anion or cation ion exchange resin can dispose the electric charge of the counter ion of initial existence, may further comprise the steps
1. use required final counter ion balance and configuration ion exchange resin,
2. carry out exchange process, wherein X by the cationic surfactant that adds following formula (1)
-Be any suitable group, as Cl,
3. finish exchange process,
4. Ren Xuan purification.
Also can use other conventional methods (i.e. displacement, direct Acid-Base reaction etc.) of the salt of preparation cationic surfactant.
II. the combination of cationic surfactant and salt
The following describes this one side of combination of the salt of cationic surfactant and organic acid or mineral acid.
Food and cosmetics comprise the molecule that has negative charge.Because cationic surfactant can easily provide the charged ion part of molecule, the cationic moiety of molecule can interact with negative charge, thereby is reduced and realizes any biological effect.
The purpose that adds the salt of organic acid or mineral acid or any other organic base that is fit to or inorganic base is; the negative charge and the cationic surfactant of salt are interacted; thereby around the molecule of cationic surfactant, produce protection, avoid the anion component in cationic surfactant and food or the cosmetics to interact like this.This will improve the biological activity of cationic surfactant.
Usually, the bacterial action in the foods and cosmetics makes these product acidifys.When using cationic surfactant and salt or suitable alkali to make up, can realize stablizing effect and can control pH value.The structure and the effect that therefore, can keep cationic surfactant.
For required compound action, can select any salt of organic acid or mineral acid.The organic acid that is fit to that is used to prepare salt is citric acid, lactic acid, acetic acid, fumaric acid, maleic acid, gluconic acid, propanoic acid, sorbic acid, benzoic acid, carbonic acid, glutamic acid or other aminoacid, lauric acid and fatty acid such as oleic acid and linoleic acid.The mineral acid that is fit to is phosphoric acid, sulphuric acid, nitric acid and hydrochloric acid.
Can prepare these acid and the cationic salt of any suitable bio-compatible.The salt that is fit to for example is sodium citrate, sodium acetate, sodium glutamate, fumaric acid sodium, natrium malicum, gluconic acid sodium salt, sodium laurate, sodium lactate and sodium hexameta phosphate.
The another kind of anion of selecting to be based on phenolic compound.Described phenolic compound for example is a butylated hydroxyanisol (BHA) and hydroxy-methylbenzene (BHT), tert-butyl hydroquinone (TBHQ) and the parabens of relevant compound butylization, as methyl parahydroxybenzoate, 4-hydroxyphenylacetic acid ethyl ether, propyl p-hydroxybenzoate and butyl p-hydroxybenzoate.The phenolic compound that is fit to is tert-butyl hydroquinone, propyl p-hydroxybenzoate, and its salt that is fit to for example is tert-butyl hydroquinone sodium and Sodium Propyl Hydroxybenzoate.
The another kind of selection is any suitable alkali and the combination of cationic surfactant.The alkali that is fit to is glucamine and ethanolamine, and its salt that is fit to for example is the hydrochlorate of glucamine and the hydrochlorate of ethanolamine.
Put down in writing the combination with some salt in this area, these known combinations are not included in the application's the scope.Described known combination for example is the combination of LAE and calcium sorbate and potassium sorbate.
The combination of the salt of cationic surfactant and organic acid or mineral acid can be solid form or liquid form.When described combination was solid form, it contained the salt of at least a cationic surfactant and at least a organic acid or mineral acid.Cationic surfactant can be any known cationic surfactant, preferably uses LAE.If use LAE, so according to embodiment preferred, can be by the such chloride of known formulations in this area, bromide or sulfate, maybe can be the different salt described in other parts of the application.The different salt of identical cationic surfactant can exist simultaneously.Different cationic surfactants can exist simultaneously, and wherein different cationic surfactants can be identical or different salt.
When the combination of the salt of cationic surfactant and organic acid or mineral acid is liquid, can use any suitable solvent.Salt by dissolving or dispersible cationic surfactant and organic acid or mineral acid in solvent can more prepare objective composition with imitating.The example of the solvent that is fit to comprises monohydric alcohol, as normal-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl group alcohol, n-pentyl alcohol, isoamyl alcohol, sec-amyl alcohol, n-hexyl alcohol, methyl amyl alcohol, ethyl-butyl alcohol, heptyl alcohol, n-octyl alcohol, secondary octyl alcohol, 2-ethylhexyl alcohol, iso-octyl alcohol, n-nonyl alcohol, 2,6-2,6-dimethyl-4-heptanol, the positive pure and mild Hexalin of decyl; Glycols and polyhydric alcohol are as ethylene glycol, diethylene glycol, triethylene glycol, TEG, propylene glycol, dipropylene glycol, 1,4-butanediol, 2,3-butanediol, hexanediol, ethohexadiol and glycerol; Cellosolve is as glycol monomethyl methyl ether, glycol ethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol butyl ether, ethylene glycol bisthioglycolate butyl ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, ethylene glycol ethyl hexyl ether, diethylene glycol ethylether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol dibutyl ethers, methyl proxitol, propylene glycol ethylether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethylether, tripropylene glycol methyl ether, TEG dimethyl ether and TEG dibutyl ethers; Crown ether is as phendioxin 5-hat-5, phendioxin 2-hat-4, phendioxin 8-hat-6 and dibenzo-18-hat-6; Ketone is as ethyl butyl ketone, dipropyl ketone, methyl amyl ketone, methyl hexyl ketone. and diisobutyl ketone; And fatty acid, as the above-mentioned fatty acid of 3~30 carbon atoms.
The concentration of the salt of dissolving or dispersive organic acid or mineral acid is not particularly limited in above-mentioned solvent, and can according to circumstances select aptly.
III. the combination of cationic surfactant and ester compounds, amide or enzyme inhibitor
The following describes this one side of combination of cationic surfactant and another kind of ester compounds or amide.
Can use various ester compounds and amide.Being used for this ester compounds that is fit on the one hand of the present invention is the ester of the ester of triethyl citrate, glyceryl triacetate, diacetine, glycerol, amino acid whose ester and fatty acid.When needed, can use the combination of these esters.The amide that is fit to is arginic acetamide.
Cationic surfactant such and other ester compounds combinations of bromide, chloride or sulfate routinely.What be more suitable for is to use cationic surfactant as the salt of acetic acid, lactic acid or glutamic acid.
Reason for the effect of above-mentioned cationic surfactant and other ester compounds or amide combination there is no scientific foundation, but imagination be since exist other esterification compound or the amide molecule that may delay cationic surfactant owing to be similar to the enzyme that phenomenon such as competition causes and decompose.For the antibacterial action of above-mentioned cationic surfactant, molecule must be complete.The hydrolysis meeting of ester or amido bond reduces the antibacterial action of chemical compound.
The more unsettled bonding that exists in the cationic surfactant is the ester functional group that produces respective acids.Amido link is highly stable, but also may be subjected to the influence of some enzyme.
Because intention uses the combination of cationic surfactant and other ester compounds to reduce the decomposition that the enzyme influence produces down, therefore clearly, make up the identical final effect that can pass and realize with other ester compounds combinations by chemical compound with direct inhibitory enzyme hydrolysing activity.Described enzyme inhibitor for example is the product genistein.
Cationic surfactant has the structure that is easy to by the identification of the natural metabolism ability of biology.This is to explain its hypotoxic one of the main reasons.A shortcoming of this specific character is that cationic surfactant may be by partly hydrolysis of the native enzyme in the numerous food.Any food (even these food are cooked at last) that contains the food (vegetable, meat, fish etc.) of crude ash and add thick product in preparation all may reduce the valid density of cationic surfactant.
The inventor has been found that in the product of these types, adds the effect that enzyme inhibitor has improved cationic surfactant.In addition, adding is not that the simple ester or the amide of specificity enzyme inhibitor delayed the hydrolysis of cationic surfactant, and has improved its effect.Even decompose not obvious (5-10% of cationic surfactant primary quantity), effect is also significantly improved, and may be because uniformity/efficient is better.
Many cosmetics contain might the also residual natural additive that enzymatic activity is arranged.In addition, according to definition, cosmetics are coated on the skin, inside, oral cavity etc.In all these are used, cosmetics will contact with organized enzyme.
With identical in the food, have been found that to add the effect that enzyme inhibitor has improved cosmetics.In addition, adding is not that the simple ester or the amide of specificity enzyme inhibitor delayed the hydrolysis of cationic surfactant, and has improved its effect.Even decompose not obvious (5-10% of cationic surfactant primary quantity), effect is also significantly improved, and may be because efficient is better.
The enzyme delayer and the inhibitor that are fit to for example are ester, amide and enzyme inhibitor, those as hereinafter listing.
Ester:
1. amino acid whose any alcohol ester, arginine ethyl ester for example,
2. the fatty acid ester of glycerol, list, two-and three-acyl glyceride,
3. glyceryl triacetate, diacetine,
4. the fatty acid ester of ascorbic acid,
5. acetic acid, lactic acid, citric acid, the tartaric ester of single and two glycerol,
6. the sucrose ester of fatty acid,
7. sucrose glyceride,
8. any other ester molecule that is fit to.
Amide:
1. native peptides, dipeptides, albumen etc.,
2. any suitable amide molecule, for example arginic acetamide.
Enzyme inhibitor:
1. genistein,
2. the sugar of lupin and peptide,
3. any other enzyme inhibitor that is fit to.
This preferred ester on the one hand of the present invention is arginine methyl esters, arginine ethyl ester and arginine propyl ester.
The combination of cationic surfactant and ester, amide or enzyme inhibitor can be solid or liquid form.If the combination of cationic surfactant and ester, amide or enzyme inhibitor is a liquid form, can use all kinds of solvents so.The example of solvent comprises monohydric alcohol, as normal-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl group alcohol, n-pentyl alcohol, isoamyl alcohol, sec-amyl alcohol, n-hexyl alcohol, methyl amyl alcohol, ethyl-butyl alcohol, heptyl alcohol, n-octyl alcohol, secondary octyl alcohol, 2-ethylhexyl alcohol, iso-octyl alcohol, n-nonyl alcohol, 2,6-2,6-dimethyl-4-heptanol, the positive pure and mild Hexalin of decyl; Glycols and polyhydric alcohol are as ethylene glycol, diethylene glycol, triethylene glycol, TEG, propylene glycol, dipropylene glycol, 1,4-butanediol, 2,3-butanediol, hexanediol, ethohexadiol and glycerol; Cellosolve is as glycol monomethyl methyl ether, glycol ethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol butyl ether, ethylene glycol bisthioglycolate butyl ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, ethylene glycol ethyl hexyl ether, diethylene glycol ethylether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol dibutyl ethers, methyl proxitol, propylene glycol ethylether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethylether, tripropylene glycol methyl ether, TEG dimethyl ether and TEG dibutyl ethers; Crown ether is as phendioxin 5-hat-5, phendioxin 2-hat-4, phendioxin 8-hat-6 and dibenzo-18-hat-6; Ketone is as ethyl butyl ketone, dipropyl ketone, methyl amyl ketone, methyl hexyl ketone. and diisobutyl ketone; And fatty acid, as the above-mentioned fatty acid of 3~30 carbon atoms.
IV. the combination of cationic surfactant and other cationic compounds
The following describes this one side of combination of cationic surfactant and another kind of cationic compound.
Because high cationic surfactant characteristic, cationic surfactant has the tendency of the anionic sites that is attached to its applied complex matrix.Described complex matrix has covered the foods and cosmetics preparation.These anionic sites in the complex matrix can comprise albumen, glycoprotein, surfactant, silicon oxide etc.
If cationic surfactant mixes with other cationic molecule, its activity has unexpected raising.This is that cationic surfactant is easier to be attached in the microorganism because compare with other anionic sites of the cationic molecule blocking-up that has been added into.In other words, having reduced will be by the effective anionic sites in the material that uses the cationic surfactant processing.
Itself needn't necessarily show any antisepsis with blended other cationic molecule of cationic surfactant.Certainly, if other cationic molecule have some known anticorrosion activity (even slight), can observe synergism so, and the combination under the sort of situation is effective unexpectedly.
Other cationic molecule can be selected from following chemical compound group:
1. glucamine and other monosaccharide amines,
2. the oligomer of chitosan, chitosan and other polyamines class such as polylysine, etc.,
3. cationic polysaccharide (being cationic starch),
4. cationic amino acid and peptide, glutamic acid for example,
5. amino acid whose ester,
Liposome and
7. any other cationic molecule that is fit to.
The example that is fit to of above-mentioned cation reagent is amino acid whose ester, more especially arginine ethyl ester.
The combination of cationic surfactant and other cationic compounds can be solid or liquid form.If the combination of cationic surfactant and ester, amide or enzyme inhibitor is a liquid form, can use all kinds of solvents so.The example of solvent comprises monohydric alcohol, as normal-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl group alcohol, n-pentyl alcohol, isoamyl alcohol, sec-amyl alcohol, n-hexyl alcohol, methyl amyl alcohol, ethyl-butyl alcohol, heptyl alcohol, n-octyl alcohol, secondary octyl alcohol, 2-ethylhexyl alcohol, iso-octyl alcohol, n-nonyl alcohol, 2,6-2,6-dimethyl-4-heptanol, the positive pure and mild Hexalin of decyl; Glycols and polyhydric alcohol are as ethylene glycol, diethylene glycol, triethylene glycol, TEG, propylene glycol, dipropylene glycol, 1,4-butanediol, 2,3-butanediol, hexanediol, ethohexadiol and glycerol; Cellosolve is as glycol monomethyl methyl ether, glycol ethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol butyl ether, ethylene glycol bisthioglycolate butyl ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, ethylene glycol ethyl hexyl ether, diethylene glycol ethylether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol dibutyl ethers, methyl proxitol, propylene glycol ethylether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethylether, tripropylene glycol methyl ether, TEG dimethyl ether and TEG dibutyl ethers; Crown ether is as phendioxin 5-hat-5, phendioxin 2-hat-4, phendioxin 8-hat-6 and dibenzo-18-hat-6; Ketone is as ethyl butyl ketone, dipropyl ketone, methyl amyl ketone, methyl hexyl ketone. and diisobutyl ketone; And fatty acid, as the above-mentioned fatty acid of 3~30 carbon atoms.
V. the cationic surfactant of packing forms
This one side of cationic surfactant that provides with encapsulation or other physical protection forms is provided.
The foods and cosmetics of processing comprises molecule or the additive that some have negative charge.Because cationic surfactant is cationic molecule, so it can interact with this negative charge, thereby cationic surfactant will descend as the activity of antiseptic.
In addition, these cationic preservative have the structure that is easy to by the identification of the natural metabolism ability of biology.This is to explain its hypotoxic one of the main reasons.A shortcoming of this specific character is that cationic surfactant may be by the partly hydrolysis of native enzyme that exists in numerous food and cosmetics and/or numerous food or the cosmetic applications.
Encapsulation/soverlay technique (because the surfactant properties of cationic surfactant, physics, chemical technology) is a protection additive and each composition avoids influenced by the invasive preservation condition or for the known way of the rate of release that improves these products.The surfactant properties of cationic surfactant makes may exist multiple different automatic agglutinate structure (micelle, mesomorphic phase etc.).
Theoretically, these technology are for avoiding cationic surfactant not have help with contacting of anionic sites and/or enzyme, because in case cationic surfactant is released, its will be immediately with anionic sites or and enzyme interacting, thereby its activity will descend, just look like be not capped the same.
Surprisingly, cover cationic surfactant by the physical chemistry means and can increase its efficient.Utilize different automatic coagulation (auto-aggregation) structures also can increase the efficient of cationic surfactant.Observe, different encapsulation technologies has been improved stability under situations such as different temperature, pH, humidity.Also improved cationic surfactant and enzyme has been decomposed the stability that influences.
Can be based on this beyond thought performance of following facts explain, cationic surfactant preferably produces with microorganism rather than anionic sites and/or enzyme and interacts, and in case contact microorganism, this contact will be permanent and irreversible.Therefore, all these encapsulation technologies finally all can improve the activity of cationic surfactant.
Encapsulation technology can be based on physical method (spray cooling, spray drying, rotation disc atomizing, fluid bed coating, fixed nozzle coextrusion, spinning head coextrusion, immersion nozzle coextrusion, disc type coating etc.).
Perhaps, based on chemical method (be separated, solvent evaporation, solvent extraction, interfacial polymerization, simple and complicated cohesion, in-situ polymerization, liposome technology, nanometer encapsulation etc.).
Because the surfactant properties of cationic surfactant can exist other possibility methods of encapsulation/covering cationic surfactant or physical/chemical ground to change the mode that adds cationic surfactant.For example, blended micelle, O/w emulsion, water-in-oil emulsion, microemulsion (o/w, w/o or co-continuous), multilayer emulsion, cationic surfactant in different solvents solubilising or dissolve different salt or product, with the automatic coagulation (micelle (size and amount), mesomorphic phase etc.) of change cationic surfactant, or the like.
Can use following coating agent:
1. plant, animal or mineral oil, for example Petiolus Trachycarpi oil (35-80 ℃ of fusing point);
2. plant, animal or mineral fat;
3. plant or animal organism polymer;
4. surfactant (nonionic, anionic, cationic);
5. lecithin;
Cyclodextrin and
7. can cover any other suitable product of cationic surfactant.
VI. the improved combination of different efficacies
Among superincumbent part I~V, different protective systems has been described, its purpose separately is to improve protective system as known in the art.Had been found that the bioactive different schemes of improving cationic surfactant such as LAE.These schemes all can be improved the effect of acquisition by only adding LAE separately.
Can make up the different schemes of putting down in writing in the upper part.In part I, the bioactive difference of different LAE salt has been described.Sulphuric acid, hydrochloric acid and hydrobromic salt are as known in the art, and detect the improvement that replaces described counter ion to realize with other counter ions, described other counter ions such as acetate, glutamate and lactate surprisingly.The combination that improved another kind of selection is the salt of cationic surfactant such as LAE and organic acid or mineral acid.Have been found that LAE and organic acid salt for example the combination of sodium citrate improved biological effect.The common LAE of chloride form can provide this evidence.Obviously another kind of selection the according to the present invention is combination different schemes of the present invention.Therefore, another embodiment of the invention is the different LAE salt of combination, for example makes up acetate, glutamate, Glu and lactate and mineral acid or organic acid salt.Press similar manner, can make up other embodiments of the present invention to obtain further improved embodiment.
Embodiment
Explain the present invention in more detail below by following examples.
For measuring the effect that protective system of the present invention is realized, use following experimental technique:
(1) antisepsis in the mensuration cosmetics
This method is based on Antimicrobial Effectiveness Testing USP 24
ThEdition, 1999 (pp.1809-1811).Its objective is undesirable growth of microorganism that the antibacterial activity that confirms protective system of the present invention is enough to avoid preservation and use to preparation that negative effect is arranged, and prevent adverse effect (the Real Farmacopea of pollutant
1
StEdici ó n, 1997).
This analysis comprises for each microorganism with 10
8The inoculated mixture of cfu/ml concentration pollutes protected preparation, and in time measures the survivaling cell number.This inoculated mixture is made of following microorganism:
Pseudomonas aeruginosa (bacillus pyocyaneus) ATCC 9027
Staphylococcus aureus (golden Portugal bacterium) ATCC 6538
Candida albicans (golden candidiasis) ATCC 10231
Aspergillus niger (Aspergillus niger) ATCC16404
Escherichia coli (escherichia coli) ATCC 8739
Make-up composition to be analyzed is assigned in the disinfecting container each flask 50g product.Each container 0.5ml inoculum (10
8Cfu/ml) inoculation.Aimed concn is about 10
6Cfu/ml.All container lucifuges remain under 20-25 ℃ the temperature.
Detect the level of microbial contamination 0 hour, 7 days, 14 days and 28 days.Dilute in the buffering protein peptone by nertralizer, estimate clump count with the antiseptic that is fit to.The culture medium that is used to count microorganism is: the Semen sojae atricolor tryptone (35-37 ℃, 48 hours) that is used to measure antibacterial; The sand that contains chloromycetin that fungus and yeast are used is protected Ruo Shi agar (25 ℃, 3-5 days).
According to Antimicrobial Effectiveness Testing USP 24th Edition, 1999 (pp.1809-1811), following meeting the following conditions, then antibiotic antiseptic is considered to be effectively in product and emulsion, to comprise those that are applied to mucosa at the topical products of being made by aqueous substrate or carrier, the nose of not sterilizing:
√ reached at 14 days and is not less than 2.0 logarithm apart from the bacterial population of initial calculation and reduces, and the counting with respect to 14 days does not increase when detecting in 28 days; And
√ does not observe increase apart from the counting of the initial calculation of yeast and mycete.
(2) antisepsis in the mensuration pigeon chest
Preparation method
1. fresh pigeon chest is cut into slices.
2. saline (8.70% sodium chloride and 4.35% tripolyphosphate in the water) is added in the new fresh chicken meat, its amount is 11.5g saline/88.5g meat in control formulation, is 11.5g saline and 88.4g meat in the preparation of handling with antiseptic.
3. saline and meat were mixed 15 minutes, in the preparation of handling with antiseptic, add antiseptic after 14 minutes, its amount is 0.2g/kg.
4. vacuum cooled was rotated 30 minutes.
5. sample is vacuum-packed in sterilization bag, and cooks under 85 ℃ 30 minutes.
6. will cook Carnis Gallus domesticus 4 ℃ of following cold preservations.
7. will cook Carnis Gallus domesticus is cut into irregularly shaped.
8. then, in the sterilization vacuum packaging bag, preserving chicken nugget under 10 ℃.
Analyze
After preserving 7,14,21,28,35,42,49 and 56 days, analyze three samples (total aerobic bacteria).Analyze total aerobic bacteria by each sample of digestion 25g in 225g peptone buffered water.In the peptone buffered water, dilute.Collect the tryptose soya agar of each dilution, and cultivated 48 hours down at 35 ℃.
Calculate each log cfu/g meansigma methods of handling and analyzing three samples of natural law.
(3) antisepsis in the mensuration bratwurst sausage
Bratwurst sausage
Preparation method
The composition of all samples is: the back pork of chopping, lower abdomen meat, flavoring agent, salt and additive (milk protein, diphosphonic acid, antioxidant (E-300) and flavor potentiator (E-621)).
1. on cutting machine, grind the back pork of chopping, add each composition in the following order: additive (except protective system), lower abdomen meat, flavoring agent and protective system (as independent cationic surfactant or with other product mixes).Also add ice, with the temperature (maximum 5 ℃) of control meat.Incorporation time is 12 minutes.
2. the material vacuum was mixed (92%) 1 minute.
3. mixture is filled in the natural casing.Be immersed in the saline solution 30 minutes before the casing.
4. bratwurst sausage is placed on the cooking table.On 80 ℃ of stoves, cooked 1 hour.
5. after cooking, use cold water injection bratwurst sausage 5 minutes, and place cooling preservation chamber (0-5 ℃, 24 hours).
6. second day, packing bratwurst sausage (each packing contains five sausages), and 80 ℃ of following pasteurizes 30 minutes.Then, in cold water, soaked 30 minutes.
7. last, the labelling bratwurst sausage, and under 5 ℃, preserved 90 days.
Analyze
Analytic sample (total aerobic bacteria) reaches 90 days.
Analyze total aerobic bacteria by digestion 25g sausage in 225g peptone buffered water.In the peptone buffered water, dilute.Collect the tryptose soya agar of each dilution, and cultivated 48 hours down at 35 ℃.
Calculate each log cfu/g meansigma methods of handling and analyzing three samples of natural law.
(4) be determined at the antisepsis of soaking in the chickpea
Soak chickpea
Chickpea is the main component in many instant foods.Before cooking, chickpea must at room temperature flood in water 24 hours.During this period, sweat may take place, therefore, chickpea will be not suitable for eating.Immersion process can not carry out under refrigerated storage temperature, because the structure of chickpea may suffer damage.
Preparation method
With chickpea in water in soaking 24 hours (in the sample of handling, adding antiseptic this moment) under 30 ℃ and the 50%HR; With
2. after 24 hours, filter chickpea.
Analyze
Analyze three samples (concentration of total aerobic bacteria and cationic surfactant) and reach 24 hours.
Analyze total aerobic bacteria by digestion 25 g chickpeas in 225g peptone buffered water.In the peptone buffered water, dilute.Collect the tryptose soya agar of each dilution, and cultivated 48 hours down at 35 ℃.
Calculate each log cfu/g meansigma methods of handling and analyzing three samples of natural law.
Use internal verification method (internally validated method), analyze LAE by HPLC.
In following examples, illustrate in greater detail the antibacterial effect that product of the present invention and they show.
Embodiment 1 (reference)
Preparation LAE chloride
Prepare LAE chloride (LAE) by International Patent Application WO 96/21642 and WO 01/94292 described mode.
Embodiment 2
Preparation LAE acetate
Wash Resin A mberlite IRA402 (chloride form) with water.Add sodium acetate (Fluka) solution, wash resin thereafter once more with water.In resin column, add LAE solution, collect fraction.The fraction that lyophilizing is collected.Obtain the LAE acetate, the solid white powder.
Embodiment 3
Preparation LAE lactate
Wash Resin A mberlite IRA402 (chloride form) with water.Add sodium lactate (Fluka) solution, wash resin thereafter once more with water.In resin column, add LAE solution, collect fraction.The fraction that lyophilizing is collected.Obtain the LAE lactate, the solid white powder.
Embodiment 4
Preparation LAE glutamate, Glu
Wash Resin A mberlite IRA402 (chloride form) with water.Add sodium glutamate (Fluka) solution, wash resin thereafter once more with water.In resin column, add LAE solution, collect fraction.The fraction that lyophilizing is collected.Obtain the LAE lactate, the solid white powder.
Embodiment 5
LAE (LAE+palm) with the Petiolus Trachycarpi oil encapsulation
In the high speed shear mixer, above 80g LAE, spraying 20g hot melt Petiolus Trachycarpi oil under 60 ℃.Final products are cooled to room temperature.
Obtain Petiolus Trachycarpi oil from Vandermoortele company.
With Oleum Glycines emulsifying LAE (LAE+emSy)
20g LAE is dissolved in the 60g hot water, uses Ultra Turrax
Stir, stir down slowly adding 20g Oleum Glycines, final products cool off as quick as thought.
Obtain Oleum Glycines from Mateo company.
LAE in the lecithin (LAE+leci)
Under 30 ℃ 10g LAE and 10g lecithin are dissolved among the THF, evaporate THF down at 70 ℃, dispersed mixture in water is by 200nm film extruding 5 times.
Obtain lecithin from Aldrich.
LAE and tween (tween) 20 (LAE+T20)
20g LAE Cl and 20g polysorbas20 are dissolved in the 60g water.
Obtain tween from Panreac.
Embodiment 9
The salt of cationic surfactant
Application in Food
As method of testing, select to measure the antisepsis in the pigeon chest.
Handle
The preparation of the product that uses among this embodiment has been documented among the embodiment 1~4.
1. contrast (being untreated): Bl
2.LAE 0.2g/kg: LAE
3.LAE acetate 0.2g/kg:LAE Ac
4.LAE lactate 0.2g/kg:LAE La
5.LAE glutamate, Glu 0.2g/kg:LAE Gl
What all concentration in the above-mentioned processing all related to is the amount of anticorrosion cationic surfactant in every kilogram of final products.
The result
Experimental data is listed in table 1.Graphic representation is shown in Fig. 1.
Chicken meat sample its counting of handling with LAE when 5 weeks of cooking is lower than 4.0 log cfu/g.
Simultaneously, control sample is 6.7log cfu/g, can think corrupt.
Comparatively speaking, with acetate, lactate or glutamate, Glu and LAE
+Even combined treatment chicken meat sample 8 whens week its counting also be lower than 4.0log cfu/g (than with late 3 weeks of LAE).
When 8 weeks, the chicken meat sample of using acetate, lactate or glutamate, Glu and the combined treatment of LAE is than the low 1.5log cfu/g of the chicken meat sample of handling with LAE.
When experiment finished, all processing samples all had intact and correct outward appearance.
Control sample in 8 whens week has reached 8.3log cfu/g, its abnormal smells from the patient extreme difference, and detect and have thick liquid.
Table 1
The result of total aerobic bacteria
All results represent by log cfu/g
The salt of cationic surfactant
Application in the cosmetics
As method of testing, select to be used for to measure the said method of the antisepsis of cosmetics.
O/w emulsion
The make-up preparation that contains in the O/w emulsion of non-ionic surface active agent consists of (g):
Sorbitol stearate 2.00
Hexadecanol 1.00
Hard paraffin 3.00
Myristic acid isopropyl esters 3.00
Sad-caproic acid triglyceride 3.00
Dimethicone 0.50
Propylene glycol 3.00
Cellulose gum 0.25
Acritamer 940 0.10
Triethanolamine 0.10
Water 100 c.s.p.
Used product is obtained from following source: polysorbate 60:Uniqema; Sorbitol stearate: Uniqema; Hexadecanol: Degussa; Hard paraffin: Impex; Myristic acid isopropyl esters: Degussa; Sad-caproic acid triglyceride: Degussa; Dimethicone: Degussa; Propylene glycol: Quimidroga; Cellulose gum: Hercules; Acritamer 940: Degussa; And triethanolamine: Quimidroga.
Being prepared as follows of O/w emulsion: oil component (polysorbate 60, sorbitol stearate, hexadecanol, hard paraffin, myristic acid isopropyl esters, sad-the caproic acid triglyceride, dimethicone) is mixed, and 75 ℃ of heating down.Water (by propylene glycol, cellulose gum, Acritamer 940 and water constitute) also be heated to 75 ℃.
Using Ultraturrax under about 5000rpm stirs, oil phase is added to aqueous phase.Being emulsified in 2 minutes finishes.Emulsion is quickly cooled to room temperature, under low speed 20rpm, stirs simultaneously.Add triethanolamine with pH regulator to 6-7.
Finish preparation with different protective systems, and, estimate their antiseptic power with respect to the preparation that does not have LAE (contrast).
1. contrast (being untreated): Bl
2.LAE 0.2g/kg:LAE
3.LAE acetate 0.2g/kg:LAE Ac
4.LAE lactate 0.2g/kg:LAE La
5.LAE glutamate, Glu 0.2g/kg:LAE Gl
Shown in concentration by the g/kg O/w emulsion.
The results are shown in following table 2.
Table 2
Microorganism | Bl | LAE | LAE Ac | LAE La | LAE Gl | |
0 day | Aerobic bacteria | 6.5 | 6.2 | 6.0 | 6.1 | 6.1 |
Mycete | 4.4 | 4.3 | 4.1 | 4.2 | 4.1 | |
Yeast | 5.5 | 5.6 | 5.3 | 5.4 | 5.6 | |
7 days | Aerobic bacteria | 6.9 | 3.5 | 2.5 | 2.2 | 2.3 |
Mycete | 3.1 | <2.0 | <2.0 | <2.0 | <2.0 | |
Yeast | 4.9 | 3.4 | 2.1 | 2.2 | 2.4 | |
14 days | Aerobic bacteria | 7.3 | 3.0 | <2.0 | <2.0 | <2.0 |
Mycete | 3.4 | <2.0 | <2.0 | <2.0 | <2.0 | |
Yeast | 4.7 | 2.6 | <2.0 | <2.0 | <2.0 |
The result is by log cfu/g.
In the time of 28 days, the counting during with 14 days is compared and is not detected increase.
Therefore, obviously use LAE and LAE
+X
-(X wherein
-Being acetate, lactate and/or glutamate) O/w emulsion handled can be anticorrosion effectively.
Change counter ion Cl for other aniones (as acetate, lactate or glutamate)
-The log that improves the microorganism of inoculation is reduced above 1log cfu/ml.
Compare with LAE, use LAE
+X
-(X wherein
-Be acetate, lactate and/or glutamate) improved anticorrosion.
Embodiment 11
Combination with the salt of organic acid/mineral acid
Application in Food
Use the method for testing of measuring the antisepsis in the bratwurst sausage.
Handle
1. contrast (being untreated) contrast
2.LAE 0.2g/kg LAE
3.LAE 0.2g/kg+ sodium citrate 3.0g/kg LAE+NaC
4.LAE 0.2g/kg+ sodium hexameta phosphate 3.0g/kg LAE+NaP
Obtain sodium citrate from Quimidroga, obtain sodium hexameta phosphate from BK Giulini Chemie.
What all concentration in the above-mentioned processing all related to is the amount of corrosion preventive compound during every kg of oil fries the sausages.
The microorganism result
Showing in table 3 and corresponding Fig. 2, surpass 4 log cfu/g at the counting again of the 45th day control sample, yet the sample of handling with LAE is 2.8log cfu/g, is 2.0log cfu/g with the sample of the combined treatment of LAE and sodium citrate and sodium hexameta phosphate.
At the 75th day, it is corrupt that control sample is considered to, and the counting again of the sample of handling with LAE has surpassed 4log cfu/g, and if with the combined treatment sample of LAE and sodium citrate and sodium hexameta phosphate, it is counted again and rises to 3log cfu/g so.
Therefore, handle more effective with LAE with LAE separately with the processing ratio of the combination of salt.
When surpassing 90 days, all have good color, outward appearance and color with LAE or with all samples of combined treatment separately, still in control sample, at the bratwurst sausage surface observation to thick liquid.
Table 3
The total aerobic bacteria result
The result represents by log cfu/g
The physical chemistry result
In 90 days, the pH that analyzes four processing changes.The difference of not observing in sample and the control sample between the pH value of where managing in office.Therefore, add the pH characteristic that does not influence bratwurst sausage with the LAE of salt combination.
Embodiment 12
Combination with the salt of organic acid/mineral acid
Application in the cosmetics
As method of testing, select to be used for to measure the said method of the antisepsis of cosmetics.
Bathe gel
Be used to prepare the preparation of bathing gel (g) composed as follows:
Sodium lauryl sulphate (solution 27%) 14.00
Cocoyl amine CAB 6.00
Cocos nucifera oil acyl both sexes guanidine-acetic acid disodium 6.00
Lactic acid 0.25
Sodium chloride 0.50
Water 100c.s.p.
Said preparation is applied in bathes in the gel.
Used product is obtained from following source: sodium lauryl sulphate: Cognis; Cocoyl amine CAB: Degussa; Cocos nucifera oil acyl both sexes guanidine-acetic acid disodium: Impex; Lactic acid: Purac and sodium chloride: Panreac.
With the different preparations of finishing dealing with, and, estimate their antiseptic power with respect to the preparation that does not have LAE (contrast).
1. contrast (being untreated) contrast
2.LAE 0.2g/kg LAE
3.LAE 0.2g/kg+ sodium citrate 3.0g/kg LAE+NaC
4.LAE 0.2g/kg+ sodium hexameta phosphate 3.0g/kg LAE+NaP
The microorganism result
Experimental data is listed in table 4.
Table 4
Microorganism | Contrast | LAE | LAE+NaC | LAE+NaP | |
0 day | Aerobic bacteria | 6.6 | 6.2 | 6.3 | 6.3 |
Mycete | 4.7 | 4.5 | 4.6 | 4.7 | |
Yeast | 4.9 | 4.3 | 4.7 | 4.5 | |
7 days | Aerobic bacteria | 7.0 | 4.2 | 2.5 | 2.5 |
Mycete | 4.3 | 2.3 | <2.0 | <2.0 | |
Yeast | 5.1 | 2.8 | <2.0 | <2.0 | |
14 days | Aerobic bacteria | 7.7 | 3.0 | <2.0 | <2.0 |
Mycete | 3.9 | <2.0 | <2.0 | <2.0 | |
Yeast | 5.4 | <2.0 | <2.0 | <2.0 |
The result represents by log cfu/g
Do not observe aerobic bacteria, mycete and yeast counting at the 28th day.According to result of study, if bathe gel with the combined treatment of LAE and sodium citrate and sodium hexameta phosphate, can be anticorrosion effectively.
Bathing gel with citrate or phosphate treated reduces above 2log cfu/ml the microorganism logarithm of inoculation.The antiseptic of combination has better effect as antiseptic than the LAE that does not have salt.
The physical chemistry result
In 28 days, the pH that analyzes four processing changes.The difference of all not observing in sample or the control sample between the pH value of where managing in office.Therefore, add the pH characteristic that does not influence the bath gel with the LAE of salt combination.
Embodiment 13
The combination of cationic surfactant and another kind of ester compounds
Application in Food
The antisepsis in the use mensuration chickpea and the method for testing of concentration.
Handle
1. contrast (being untreated) Bl
2. in soaking water, add LAE 0.2g/kg LAE
3. in soaking water, add LAE 0.2g/kg+ triethyl citrate 1.0g/kgLAE+tECit
4. in soaking water, add LAE 0.2g/kg+ arginine ethyl ester 1.0g/kg
LAE+EtAr
The LAE concentration results
In Fig. 3 and table 5, the initial concentration data of representing by % have been shown.
Data can be observed from accompanying drawing and table, and the hydrolysis of LAE is near 10% of original doses after 24 hours.
On the other hand, the combination of LAE and triethyl citrate and with the combination of arginine ethyl ester in, hydrolysis delays.In the time of 24 hours, two kinds of processing have all kept predose.
Table 5
Concentration data (HPLC method) is represented by the % of predose
Aerobic bacteria result in the chickpea
Experimental data is listed in table 6.Graphic representation is shown in Fig. 4.
The immersion chickpea sample of handling with LAE soaked its counting of back a little more than 4.0log cfu/g at 24 hours.
Simultaneously, control sample is 8.4log cfu/g, can think corrupt.
Comparatively speaking, use the chickpea sample of LAE and arginine ethyl ester or triethyl citrate combined treatment to soak the about 3.0log cfu/g of its counting of back (than hanging down 1log) at 24 hours with LAE.
After 24 hours, the chickpea sample of the LAE processing of using the LAE that mixes arginine ethyl ester or mixing triethyl citrate is than the low 1.0log cfu/g of chicken meat sample with the LAE processing.
When experiment finished, all processing samples all had intact and correct outward appearance.
Reached 7.3log cfu/g at 16 hours control samples, its abnormal smells from the patient extreme difference, outward appearance does not have captivation usually.
Table 6
The total aerobic bacteria result
The result represents by log cfu/g
The combination of cationic surfactant and cationic molecule
Application in Food
As method of testing, select the assay method of the antisepsis in the pigeon chest.
Handle
1. contrast (being untreated): Bl
2.LAE 0.2g/kg: LAE
3.LAE 0.2g/kg+ arginine ethyl ester 1.0g/kg:LAE+EtAr
Obtain arginine ethyl ester from Aldrich.
What all concentration in the above-mentioned processing all related to is the corrosion preventive compound of every kilogram of meat.
The result
The results are shown in following table 7.Graphic representation is shown in Fig. 5.
Chicken meat sample its counting of handling with LAE when 5 weeks of cooking is lower than 4.0log cfu/g.
Simultaneously, control sample is 6.9log cfu/g, can think corrupt.
Comparatively speaking, even the chicken meat sample of handling with the LAE that mixes arginine ethyl ester its counting when 8 weeks also is lower than 4.0log cfu/g (than with late 3 weeks of LAE).
When 8 weeks, use the chicken meat sample of the LAE processing that mixes arginine ethyl ester to hang down 1.5log cfu/g than the chicken meat sample of handling with LAE.
When experiment finished, all processing samples all had intact and correct outward appearance.
Control sample in 8 whens week has reached 8.5log cfu/g, and its abnormal smells from the patient extreme difference detects and has thick liquid.
Table 7
The total aerobic bacteria result
The result represents by log cfu/g
Embodiment 15
The combination of cationic surfactant and cationic molecule
Application in the cosmetics
As method of testing, select to be used for to measure the said method of the antisepsis of cosmetics.
Bathe gel
Be used to prepare the preparation of bathing gel (g) composed as follows:
Sodium lauryl sulphate (solution 27%) 14.00
Cocoyl amine CAB 6.00
Cocos nucifera oil acyl both sexes guanidine-acetic acid disodium 6.00
Lactic acid 0.25
Sodium chloride 0.50
Water 100c.s.p.
Used product is obtained from following source: sodium lauryl sulphate: Cognis; Cocoyl amine CAB: Degussa; Cocos nucifera oil acyl both sexes guanidine-acetic acid disodium: Impex; Lactic acid: Purac and sodium chloride: Panreac.
Said preparation is applied in to bathe in the gel and obtains aqueous solution.
Finish preparation by adding different antiseptic, and, estimate their antiseptic power with respect to the preparation that does not have LAE (contrast).
1. contrast (being untreated) Bl
2.LAE 0.2g/kg LAE
3.LAE 0.2g/kg+ arginine ethyl ester 1.0g/kg LAE+EtAr
Shown in the formulation concentrations of concentration for representing with g/kg.
The results are shown in following table 8.
Table 8
Microorganism | Bl | LAE | LAE+EtAr | |
0 day | Aerobic bacteria | 6.6 | 6.1 | 6.3 |
Mycete | 4.0 | 4.1 | 4.2 | |
Yeast | 4.5 | 4.3 | 4.5 | |
7 days | Aerobic bacteria | 7.4 | 3.0 | 2.5 |
Mycete | 3.1 | <2.0 | <2.0 | |
Yeast | 4.3 | 3.3 | 2.1 | |
14 days | Aerobic bacteria | 7.9 | 2.6 | <2.0 |
Mycete | 3.4 | <2.0 | <2.0 | |
Yeast | 4.6 | 2.6 | <2.0 |
The result represents by log cfu/g
In the time of 28 days, compare with the counting after 14 days and not detect increase.
Therefore, obviously use the bath gel of LAE and arginine ethyl ester combined treatment can be anticorrosion effectively.
Adding arginine ethyl ester reduces above 1log cfu/mL the logarithm of the microorganism of inoculation.
The anticorrosion of LAE that mixes arginine ethyl ester improved.
Embodiment 16
The encapsulation of cationic surfactant
Application in Food
Cook pigeon chest
Handle
1. contrast (being untreated) Bl
2.LAE 0.2g/kg LAE
3. with the LAE 0.20g LAE/kg LAE+palm of brown tung oil encapsulation
4. the LAE emulsion 0.20g LAE/kg LAE+emSy that contains Oleum Glycines
5. the LAE 0.20g LAE/kg LAE+leci in the lecithin
6. the LAE 0.20g LAE/kg LAE+t20 that contains polysorbas20
The result
Experimental data is listed in table 9.Graphic representation is shown in Fig. 6.
Chicken meat sample its counting of handling with LAE when 5 weeks of cooking is lower than 4.0log cfu/g.
Simultaneously, control sample is 6.9log cfu/g, can think corrupt.
Comparatively speaking, even the chicken meat sample that the LAE that encapsulates with different technologies handles its counting when 8 weeks also is lower than 4.0log cfu/g (than using late 3 weeks of LAE).
When experiment finished, all processing samples all had intact and correct outward appearance.
Control sample in 8 whens week has reached 8.5log cfu/g, and its abnormal smells from the patient extreme difference detects and has thick liquid.
Table 9
The total aerobic bacteria result
The result represents by log cfu/g
Embodiment 17
The encapsulation of cationic surfactant
Application in the cosmetics
The O/w emulsion that contains ionic emulsifying agent
Consist of (g) as the O/w emulsion that contains ionic emulsifying agent of make-up preparation:
Stearic acid 1.90
Tristerin S.E. 2.80
Hexadecanol 1.80
Hard paraffin 3.10
Myristic acid isopropyl esters 3.00
Sad-caproic acid triglyceride 3.00
Dimethicone 0.40
Propylene glycol 3.00
Cellulose gum 0.50
Triethanolamine 1.05
Water 100c.s.p.
Used product is obtained from following source: stearic acid: Uniqema; Tristerin: Degussa; Hexadecanol: Degussa; Hard paraffin: Impex; Myristic acid isopropyl esters: Degussa; Sad-caproic acid triglyceride: Degussa; Dimethicone: Degussa; Propylene glycol: Quimidroga; Cellulose gum: Hercules and triethanolamine: Quimidroga.
The O/w emulsion that contains ionic emulsifying agent is prepared as follows: with oil component (stearic acid, tristerin S.E. hexadecanol, hard paraffin, the myristic acid isopropyl esters, sad-the caproic acid triglyceride, dimethicone) mix, and 75 ℃ of heating down.Water (by propylene glycol, cellulose gum, triethanolamine and water constitute) also be heated to 75 ℃.
Utilize Ultraturrax under about 5000rpm stirs, oil phase is added to aqueous phase.Be emulsified in 2 minutes and finish.Emulsion is quickly cooled to room temperature, under low speed 20rpm, stirs simultaneously.Add triethanolamine with pH regulator to 6-7.
With the different described preparations of finishing dealing with, and, estimate their antiseptic power with respect to the preparation that does not have LAE (contrast).
1. contrast (being untreated) Bl
2.LAE 0.2g/kg LAE
3. with the LAE 0.20g LAE/kg LAE+palm of Petiolus Trachycarpi oil encapsulation
4. the LAE emulsion 0.20g LAE/kg LAE+emSy that contains Oleum Glycines
5. the LAE 0.20g LAE/kg LAE+leci in the lecithin
6. the LAE 0.20g LAE/kg LAE+t20 that contains polysorbas20
Experimental data is listed in table 10.
Table 10
Microorganism | Bl | LAE | LAE+ palm | LAE+ emSy | LAE+ leci | LAE+ t20 | |
0 day | Aerobic bacteria | 6.4 | 6.1 | 6.1 | 6.3 | 6.2 | 6.0 |
Mycete | 4.4 | 4.1 | 4.2 | 4.1 | 4.3 | 4.3 | |
Yeast | 5.5 | 5.3 | 5.5 | 5.2 | 5.4 | 5.3 | |
7 days | Aerobic bacteria | 7.2 | 4.0 | 2.9 | 2.5 | 2.4 | 2.7 |
Mycete | 4.1 | 2.9 | <2.0 | <2.0 | <2.0 | <2.0 | |
Yeast | 5.9 | 3.8 | 2.0 | <2.0 | 2.5 | 3.1 | |
14 days | Aerobic bacteria | 8.0 | 2.9 | <2.0 | <2.0 | <2.0 | <2.0 |
Mycete | 5.9 | <2.0 | <2.0 | <2.0 | <2.0 | <2.0 | |
Yeast | 6.6 | 2.5 | <2.0 | <2.0 | <2.0 | <2.0 |
The result represents by log cfu/g
In the time of 28 days, compare with 14 days counting and not detect increase.
√ therefore, obviously, with LAE 0.2g/kg (LAE), with the LAE 0.20g LAE/kg (LAE+palm) of Petiolus Trachycarpi oil encapsulation, contain the LAE emulsion 0.20g LAE/kg (LAE+emSy) of Oleum Glycines, in the lecithin LAE 0.20g LAE/kg (LAE+leci) and contain the O/w emulsion that contains ionic emulsifying agent of LAE 0.20g LAE/kg (LAE+t20) processing of polysorbas20 can be anticorrosion effectively.
With the LAE of covering/encapsulation (with the LAE 0.20g LAE/kg (LAE+palm) of Petiolus Trachycarpi oil encapsulation, contain the LAE emulsion 0.20g LAE/kg (LAE+emSy) of Oleum Glycines, in the lecithin LAE 0.20g LAE/kg (LAE+leci) and contain the LAE 0.20gLAE/kg (LAE+t20) of polysorbas20) processing the carried out microorganism logarithm that improved inoculation reduces above 1log cfu/mL.
Therefore, the processing of carrying out with the LAE of covering/encapsulation causes the better result than LAE.
Embodiment 18
Cationic surfactant and with the encapsulation of the combination of salt and ester compounds
Application in Food
Cook pigeon chest
Handle
1. contrast (being untreated) Bl
2.LAE 0.2g/kg LAE
3. the LAE acetate 0.2g LAE/kg+ arginine ethyl ester 1.0g/kg+ sodium citrate 3.0g/kg+ triethyl citrate 1.0g/kg LAE+SYN in the lecithin
The results are shown in following table 11.
Table 11
The result represents by log cfu/g
Chicken meat sample its counting of handling with LAE when 5 weeks of cooking is lower than 4.0log cfu/g.
Simultaneously, control sample is 7.1log cfu/g, can think corrupt.
Comparatively speaking, even the chicken meat sample of handling with LAE+SYN its counting when 8 weeks also is lower than 2.5log cfu/g.
When 8 weeks, the chicken meat sample of handling with LAE+SYN hangs down 3.5log cfu/g than the chicken meat sample of handling with LAE.
When experiment finished, all processing samples all had intact and suitable outward appearance.
Control sample in 8 whens week has reached 8.6log cfu/g, and its abnormal smells from the patient extreme difference detects and has thick liquid.
Embodiment 19
Application in the cosmetics
As method of testing, select to be used for to measure the said method of the antisepsis of cosmetics.
Bathe gel
Be used to prepare the preparation of bathing gel (g) composed as follows:
Sodium lauryl sulphate (solution 27%) 14.00
Cocoyl amine CAB 6.00
Cocos nucifera oil acyl both sexes guanidine-acetic acid disodium 6.00
Lactic acid 0.25
Sodium chloride 0.50
Water 100c.s.p.
Used product is obtained from following source: sodium lauryl sulphate: Cognis; Cocoyl amine CAB: Degussa; Cocos nucifera oil acyl both sexes guanidine-acetic acid disodium: Impex; Lactic acid: Purac and sodium chloride: Panreac.
Said preparation is applied in to bathe in the gel and obtains aqueous solution.
Finish said preparation by adding different antiseptic, and, estimate their antiseptic power with respect to the preparation that does not have LAE (contrast).
1. contrast (being untreated) Bl
2.LAE 0.2g/kg LAE
3. the LAE acetate 0.2g LAE/kg+ arginine ethyl ester 1.0g/kg+ sodium citrate 3.0g/kg+ triethyl citrate 1.0g/kg LAE+SYN in the lecithin
Experimental data is listed in table 12.Graphic representation is shown in Fig. 7.
Table 12
Microorganism | Bl | LAE | LAE+SYN | |
0 day | Aerobic bacteria | 6.3 | 6.0 | 6.1 |
Mycete | 4.3 | 4.1 | 4.3 | |
Yeast | 4.1 | 4.5 | 4.5 | |
7 days | Aerobic bacteria | 7.2 | 3.3 | <2.0 |
Mycete | 3.5 | 2.0 | <2.0 | |
Yeast | 4.8 | 3.5 | <2.0 | |
14 days | Aerobic bacteria | 8.2 | 2.9 | <2.0 |
Mycete | 3.8 | <2.0 | <2.0 | |
Yeast | 5.4 | 2.3 | <2.0 |
The result represents by log cfu/g
In the time of 28 days, compare with 14 days counting and not detect increase.
Therefore, obviously the bath gel of handling with LAE+SYN can be anticorrosion effectively, because:
√ reached at 14 days apart from the bacterial population of initial calculation and surpasses 2.0 logarithmic reductions, and detected the not increase of counting apart from 14 days at 28 days
√ does not observe increase apart from the counting of the initial calculation of yeast and mycete.The microorganism logarithm that LAE+SYN has improved inoculation reduces above 1log cfu/mL.Compare with independent LAE, improved with the anticorrosion of LAE+SYN.
Claims (19)
1. the protective system that comprises cationic surfactant, described cationic surfactant be derived from fatty acid and esterification binary amino acid condensation and have the following formula structure:
Wherein:
X
-Be the anion that is derived from organic acid or mineral acid, described mineral acid does not comprise hydrochloric acid, hydrobromic acid and sulphuric acid;
R
1: be the straight chained alkyl that has 8~14 carbon atoms and be connected to alpha-amino satisfied fatty acid or hydroxy acid through amido bond;
R
2: the straight or branched alkyl or the aromatic group that are 1~18 carbon atom;
R
3: be
-NH
3
Wherein n can be 0~4.
2. protective system as claimed in claim 1, wherein said anion X
-Be derived from lactic acid, glutamic acid, acetic acid, citric acid, fumaric acid, maleic acid, gluconic acid, lauric acid, phosphoric acid, tert-butyl hydroquinone or propyl p-hydroxybenzoate.
3. the protective system that comprises cationic surfactant, described cationic surfactant be derived from fatty acid and esterification binary amino acid condensation and have the following formula structure:
Wherein:
X
-Be Br
-, Cl
-Or HSO
4 -The anion that other are fit to,
R
1: be the straight chained alkyl that has 8~14 carbon atoms and be connected to alpha-amino satisfied fatty acid or hydroxy acid through amido bond;
R
2: the straight or branched alkyl or the aromatic group that are 1~18 carbon atom;
R
3: be
-NH
3
Wherein n can be 0~4, and
The salt of at least a organic acid or mineral acid,
Condition is that the salt of organic acid or mineral acid is not the salt of sorbic acid.
4. protective system as claimed in claim 3, wherein said at least a salt are the hydrochlorate of sodium citrate, sodium acetate, sodium glutamate, fumaric acid sodium, natrium malicum, gluconic acid sodium salt, sodium laurate, sodium lactate, sodium hexameta phosphate, tert-butyl hydroquinone sodium, Sodium Propyl Hydroxybenzoate, glucamine or the hydrochlorate of ethanolamine.
5. the protective system that comprises cationic surfactant, described cationic surfactant be derived from fatty acid and esterification binary amino acid condensation and have the following formula structure:
Wherein:
X
-Be Br
-, Cl
-, HSO
4 -Or other aniones that are fit to;
R
1: be the straight chained alkyl that has 8~14 carbon atoms and be connected to alpha-amino satisfied fatty acid or hydroxy acid through amido bond;
R
2: the straight or branched alkyl or the aromatic group that are 1~18 carbon atom;
R
3: be
-NH
3
Wherein n can be 0~4, and
At least a ester compounds, amide or enzyme inhibitor.
6. protective system as claimed in claim 5, wherein said at least a ester compounds are the sugar and the peptides of arginine ethyl ester, triethyl citrate, glyceryl triacetate, diacetine, arginic acetamide, genistein or lupin.
7. the protective system that comprises cationic surfactant, described cationic surfactant be derived from fatty acid and esterification binary amino acid condensation and have the following formula structure:
Wherein:
X
-Be Br
-, Cl
-, HSO
4 -Or other aniones that are fit to;
R
1: be the straight chained alkyl that has 8~14 carbon atoms and be connected to alpha-amino satisfied fatty acid or hydroxy acid through amido bond;
R
2: the straight or branched alkyl or the aromatic group that are 1~18 carbon atom;
R
3: be
-NH
3
Wherein n can be 0~4, and
At least a cationic molecule.
8. protective system as claimed in claim 7, oligomer or glutamic acid that wherein said at least a cationic molecule is arginine ethyl ester, glucamine, chitosan, chitosan.
9. the protective system that comprises cationic surfactant, described cationic surfactant be derived from fatty acid and esterification binary amino acid condensation and have the following formula structure:
Wherein:
X
-Be Br
-, Cl
-Or HSO
4 -The anion that other are fit to,
R
1: be the straight chained alkyl that has 8~14 carbon atoms and be connected to alpha-amino satisfied fatty acid or hydroxy acid through amido bond;
R
2: the straight or branched alkyl or the aromatic group that are 1~18 carbon atom;
R
3: be
-NH
3
Wherein n can be 0~4, wherein
Described cationic surfactant is packing forms.
10. protective system as claimed in claim 9, wherein said at least a packing forms is an O/w emulsion.
11. as claim 9 or 10 described protective systems, wherein used oil is Petiolus Trachycarpi oil (35-80 ℃ of fusing point), Oleum Glycines or Oleum helianthi.
12. protective system as claimed in claim 1 or 2, further with claim 3~9 in one or more combinations.
13. as the described protective system of claim 1~12, wherein said cationic surfactant is the ethyl ester of arginic lauramide.
14. as the described protective system of claim 3~12, wherein said cationic surfactant is the ethyl ester of arginic lauramide, and X is a chloride ion.
15. be used for the purposes of food antiseptic as each described protective system in the claim 1~14.
16. purposes as claimed in claim 15 is used for the anticorrosion of meat, poultry prod, fish, shell-fish, vegetable, green plants, emulsion, soy sauce, confection, bread, milk product, egg products, fruit jam, soft sweet, beverage, fruit juice, wine and medicated beer.
17. be used for the antiseptical purposes of cosmetics as claim 1 and 14 described protective systems.
18. purposes as claimed in claim 17, be used to make cosmetics anticorrosion, described cosmetics contain fatty compound, as mineral oil, animal oil, synthetic vegetable oil and silicon also contain alcohol, fatty acid and wax, organic solvent, surfactant, solubilizing agent, ion and nonionic emulsifier, thickening agent and gelling hydrophilizing agent such as CVP Carbopol ETD2050 (for example carbomer), acrylic copolymer (for example esters of acrylic acid and alkylacrylate), polyacrylamide, polysaccharide, natural gum (for example xanthan gum), the clay of thickening agent and agent of gelling oleophylic such as modification (for example bentonite), fatty acid metal salts, hydrophobic silicon oxide and polyethylene, spice and quintessence oil, softening agent, excipient, antioxidant, chelating agen, opacifier, filtering agent, coloring compound, pigment and hydrophilic or oleophylic active component.
19. the make-up composition of skin nursing, mouth care and body odour control usefulness comprises each defined protective system in the claim 1~13.
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