CN1466423A - Antimicrobial agent - Google Patents

Antimicrobial agent Download PDF

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CN1466423A
CN1466423A CNA018163017A CN01816301A CN1466423A CN 1466423 A CN1466423 A CN 1466423A CN A018163017 A CNA018163017 A CN A018163017A CN 01816301 A CN01816301 A CN 01816301A CN 1466423 A CN1466423 A CN 1466423A
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alkyl
present
arbitrary aforementioned
compound
spore
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D・埃泽尔
D·埃泽尔
莫甘
A·J·莫甘
托马斯
L·V·托马斯
于书坤
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DuPont Nutrition Biosciences ApS
Danisco US Inc
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Danisco AS
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Priority claimed from GB0023686A external-priority patent/GB0023686D0/en
Priority claimed from GB0023687A external-priority patent/GB0023687D0/en
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
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    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
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    • A—HUMAN NECESSITIES
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    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances

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Abstract

An antimicrobial composition comprising a cyclic compound having Formula I, wherein R1 and R2 are independently selected from -OH, =O, and -OC(O)R', wherein R' is a hydrocarbyl group; wherein R3 is selected from -OH, =O, a substitutent comprising an -OH group and -OC(O)R', wherein R' is a H or a hydrocarbyl group, wherein R4 and R5 are each independently selected from a hydrocarbyl group, H, OH, =O, and -OC(O)R', wherein R' is a H or a hydrocarbyl group or wherein R4 and R5 represent a bond with an adjacent atom on the ring of the cyclic compound; and wherein said compound comprises at least one ester group. Also disclosed a process for preventing and/or inhibiting the growth of, and/or killing, micro-organisms in a material, and the use of a cyclic compound having Formula I.

Description

Antimicrobial
The present invention relates to antimicrobial.More precisely, the present invention relates to the antimicrobial acivity of a series of anhydrofructose derivatives.
The food spoilage that a variety of causes causes sees in the document, and known various chemicals can suppress the degraded of the each side that a kind of reason causes.The forfeiture of known degraded and fresh incised wound plant part color or fragrance is owing to oxidation, enzyme, microorganism and metal ion cause.For example, known acidulant can prevent microbial degradation by keeping low relatively pH environment, but its validity only is temporary.
Monocyte hyperplasia listeria spp (Listeria monocytogenes) is an example that can pollute the biology of some food, and described bacterium shows has resistance to multiple physics and chemistry processing.The monocyte hyperplasia listeria spp is a kind of Gram-positive bacillus that mainly causes severe infections in immuno-compromised patients and neonate.Meningitis and bacteremia all are the most common forms of expression of listeriosis.
Bacillus cercus (Bacillus cereus) be food poisoning another kind of common disease because of.Identified two kinds of different clinical syndromes, first kind has about 4 hours short delitescence, and be about 17 hours second kind incubation period.Bacillus cercus food poisoning does not take place when sporogenesis have the cooking to kill and when allowing contaminated food reach to allow the temperature of described spore germination and release enterotoxin.
The Salmonella (Salmonella) that more than 2000 kind of different strains wherein arranged is another cause of disease that human foods is poisoned.Salmonella is a genus in the bar-shaped Gram-negative enterobacteriaceae (Enterobacteriaceae), and it is settled down in intestines and causes various infection for example gastroenteritis and typhoid fever.When invading, they can cause typhoid fever (for example, typhoid fever that is caused by salmonella typhi (Salmonella typhi) or the paratyphoid that is caused by salmonella paratyphi (Salmonellaparatyphi)).Other bacterial strain in the Salmonella relevant with food poisoning (normally salmonella typhimurium (Salmonella Typhimurium), moscow' panama (Salmonella panama) or Bacterium enteritidis (Salmonella Enteritidis), the latter is well-known poultry pollutant) and in non-intestinal tissue, cause septicemia once in a while.
It is well known in the art that Salmonella can not breed under the pH value is lower than 4.5 situation.Therefore, for example purified diet and non-fermentation meat product are especially responsive to the attack of Salmonella for the faintly acid goods.
For meat products, use nitrite usually as anticorrisive agent.Yet the interpolation of nitrite is restricted (because its acute toxicity and have with nitrosamine generate relevant danger) owing to it is poisonous.Because Salmonella only surpasses 1 at nitrite concentration, 000ppm just is suppressed, and this is considerably beyond the restriction of rules.
Yet the combination that has shown nitrite and sorbic acid can increase validity to Salmonella, and [natrium nitrosum and potassium sorbate can suppress Salmonella, are stated from: Frankfurters, Journal of Food Science, the 47,1982, the 1615th ff page or leaf].When surpassing the nitrite coupling 2600ppm sorbic acid of 50ppm, concentration observed inhibitory action.
Can not suppress Salmonella in the food such as other reagent of bacteriocin (Nisin), and benzoic acid is not too suitable owing to can only observe depression effect in acid goods.Also tested from the depression effect of the plant component (" natural materials ") of difference such as the oil extract that derives from different spices, but proof reaches too high to the desired concn of the depression effect of Salmonella once more, and too strong to the organoleptic effects of food.
Therefore, up to now, the application of chemical substance is because following former thereby seriously limited: on the one hand, they must be safe according to the toxicology viewpoint, and on the other hand, they must not influence described product on sense organ.
The present invention tries hard to solve the problem relevant with the prior art chemical substance, and the novel antimicrobial composition based on anhydrofructose derivatives is provided.Specifically, the present invention tries hard to provide the antimicrobial that is suitable for foods/feeds.
Aspect first, the invention provides the antimicrobial compositions that comprises cyclic compound with formula I,
Figure A0181630100121
R wherein 1And R 2Be independently selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl; R wherein 3Be selected from-OH ,=substituting group of O, comprise-OH group and-OC (O) R ', wherein R ' is H or alkyl; R wherein 4And R 5Be selected from independently of one another alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl or R wherein 4And R 5The chemical bond of adjacent atom on representative and the described cyclic compound ring; Wherein said compound comprises at least one ester group.
Second aspect of the present invention provides a kind of and prevents and/or suppress in certain material growth of microorganism and/or kill described method of microorganism, and described method comprises the step that described material is contacted with the cyclic compound with formula I,
Figure A0181630100122
R wherein 1And R 2Be independently selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl; R wherein 3Be selected from-OH ,=substituting group of O, comprise-OH group and-OC (O) R ', wherein R ' is H or alkyl; R wherein 4And R 5Be selected from independently of one another alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl or R wherein 4And R 5The chemical bond of adjacent atom on representative and the described cyclic compound ring; Wherein said compound comprises at least one ester group.
Aspect the 3rd, the compound that the present invention relates to have formula I preventing and/or suppressing growth of microorganism in certain material and/or kill application in the described microorganism,
Figure A0181630100123
R wherein 1And R 2Be independently selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl; R wherein 3Be selected from-OH ,=substituting group of O, comprise-OH group and-OC (O) R ', wherein R ' is H or alkyl; R wherein 4And R 5Be selected from independently of one another alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl or R wherein 4And R 5The chemical bond of adjacent atom on representative and the described cyclic compound ring; Wherein said compound comprises at least one ester group.
People will recognize that term " ester group " is meant the group of formula X-C (O) O-Y, and wherein X and Y are alkyl.
Described material is food or feed preferably.Therefore, one preferred aspect, the present invention relates to be suitable for the antimicrobial material in food and/or the feed, with the spoilage organisms that suppresses food poisoning and wherein contained.
In another preferred embodiment, described material is a for example floral water of household wares, body nursing product or cosmetics.
As definition, term " antimicrobial " is meant the material that kills or prevent or suppress growth of microorganism or breeding.Antimicrobial is generally classified according to the microorganism type that they are effectively resisted.For example, the antibacterium material is effectively resisted bacterium, and antimycotic material is effectively resisted the fungi that comprises yeast, and antiviral substance is effectively resisted virus.Some antimicrobial can use for example antibiotics in vivo, but and other antimicrobial external application anticorrisive agent for example only.
Term used herein " alkyl " is meant the group that comprises C and H at least and can chooses wantonly and comprises one or more other suitable substituents.The substituent example of this class can comprise halogen-, alkoxyl-, nitro-, hydroxyl, carboxyl, epoxy radicals, acrylic, alkyl, N-acyl group or cyclic group or the like.Except that described substituting group can be the cyclic group, described substituent combination also can form cyclic group.If alkyl comprises a more than C, then those carbon not necessarily need to interconnect.For example, in the described carbon at least 2 can connect by suitable element or group.Therefore, alkyl can contain hetero atom.Suitable hetero atom will be apparent to those skilled in the art, and comprises for example sulphur, nitrogen and oxygen.
One preferred aspect, cyclic compound of the present invention is the compound with formula II R wherein 1, R 2, R 3, R 4And R 5Limit as mentioned.
Preferred described cyclic compound is the compound with formula III
Figure A0181630100142
R wherein 1, R 2, R 3, R 4And R 5Limit as mentioned.
In a preferred embodiment, described cyclic compound is a formula IV compound,
Figure A0181630100143
R wherein 1And R 2Be independently selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl; R wherein 3Be selected from-OH ,=substituting group of O, comprise-OH group and-OC (O) R ', wherein R ' is H or alkyl; R wherein 4And R 5Be selected from independently of one another alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl or R wherein 4And R 5The chemical bond of adjacent atom on representative and the described cyclic compound ring; R wherein 6And R 7Be selected from independently of one another alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl, perhaps R wherein 4And R 5The chemical bond of adjacent atom on representative and the described cyclic compound ring; Wherein said compound comprises at least one ester group.
More preferably described cyclic compound is a formula V compound,
Figure A0181630100151
R wherein 1, R 2, R 3, R 4, R 5, R 6And R 7Limit as mentioned.
Preferred R 1Be selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl.
Preferred R 2Be selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl.
Preferred R 3Be selected from comprise-substituting group of OH group and-OC (O) R ', wherein R ' is H or alkyl.
Even more preferably R 3For-OC (O) R ', wherein R ' is H or alkyl.
Even more preferably R 3For-OC (O) R ', wherein R ' is an alkyl.
In a preferred embodiment, R 3For-OC (O) R ', wherein R ' is R " group.
Preferred R ' and/or R " be side chain or straight chain, replacement or unsubstituted alkyl.
More preferably R ' and/or R " be (CH 2) pCH 3, wherein p is 1-24.
Even more preferably R ' and/or R " be C 8Alkyl.
In another preferred embodiment, R ' and/or R " be C 12Alkyl.
In another preferred embodiment, R ' and/or R " be C 16Alkyl or C 18Alkyl.
In a preferred embodiment of the invention, R 3Be formula-(CH 2) n-OC (O)-(CH 2) pCH 3, wherein n and p are 1-24 independently of one another.
More preferably R 3Be formula-(CH 2) n-OC (O)-(CH 2) 7CH 3, wherein n is 1-24, preferably 1-20, preferably 1-10,1-5 or preferably 1,2 or 3 preferably.
In an alternative preferred embodiment, R 3Be formula-(CH 2) n-OC (O)-(CH 2) 11CH 3, wherein n is 1-24, preferably 1-20, preferably 1-10,1-5 or preferably 1,2 or 3 preferably.
In a preferred embodiment, R 4Be selected from alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl.
In an especially preferred embodiment, R 4Be selected from alkyl, H, OH and=O.
In a preferred embodiment, R 5Be selected from alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl.
In an especially preferred embodiment, R 5Be selected from alkyl, H, OH and=O.
In a preferred embodiment, R 4And R 5On representative and the described cyclic compound ring with the chemical bond of adjacent atom.
In an especially preferred embodiment, described compound is esterified to be anhydrofructose, and wherein at least one OH group of anhydrofructose is esterified, formation-OC (O) R group, and wherein R is an alkyl.
Preferred R is side chain or straight chain, replacement or unsubstituted alkyl.
Even more preferably R is (CH 2) pCH 3, wherein p is 1-24.
More preferably R is C again 8Alkyl.
In an alternative preferred embodiment, R is C 12Alkyl.
In another preferred embodiment, R is C 16Alkyl or C 18Alkyl.
In a preferred embodiment of the invention, described cyclic compound is a following formula: compound:
In a preferred embodiment of the invention, cyclic compound is a following formula: compound:
More preferably described cyclic compound is selected from following compound: More preferably described cyclic compound is selected from following compound:
Figure A0181630100172
Preferred compound of the present invention is that shell two spore pyrones (Ascopyrone) P, shell two spore pyrroles are fed ketone M, shell two spore pyrones T, shell two spore pyrones T 1, shell two spore pyrones T 2, shell two spore pyrones T 3Derivative and their derivative of mixture.
Even compound more preferably of the present invention is selected from esterification shell two spore pyrones P, esterification shell two spore pyrones M, esterification shell two spore pyrones T, esterification shell two spore pyrones T 1, esterification shell two spore pyrones T 2, esterification shell two spore pyrones T 3With their mixture.
Shell two spore pyrones P, shell two spore pyrones M, shell two spore pyrones T, shell two spore pyrones T 1, shell two spore pyrones T 2With shell two spore pyrones T 3Structure as follows. Shell two spore pyrones M shells two spore pyrones P shells two spore pyrones T Shell two spore pyrones T 1Shell two spore pyrones T 2Shell two spore pyrones T 3Shell two spore pyrones are a kind of compound known.In 1978 and 1981, U.S. scientist group is in order to use shell two spore pyrones P as the raw material of organic synthesis and usually prepare shell two spore pyrones P[Shafizadeh at the Wood of Montana Chemistry laboratory by pyrolysis amylopectin, amylose and fiber, F., Furneaux R.H., Stevenson, T.T. and Cochran, T.G., 1,5-dehydration-4-deoxidation-D-glycerine-oneself-1-alkene-3-ketose and cellulosic other thermal decomposition product, Carbohydr.Res.67 (1978): 433-447; Stevenson, T.T., Stenkmap, R.E., Jensen, L.H., Cochran, T.T., Shafizadeh, F. and FurneauxR.H., 1,5-dehydration-4-deoxidation-D-glycerine-oneself-crystal structure of 1-alkene-3-ketose, Carbohydr.Res.90 (1981): 319-325].They for example pass through 1H and 13C NMR and IR spectroscopy technology have characterized shell two spore pyrones P.The three-dimensional structure of shell two spore pyrones P is provided.The yield of the shell two spore pyrones P that obtain by pyrolysis is lower than 3% and must use complicated separation method.
About existing statement [M.-A.Baute in some kind type of the natural fungi that is present in the considerably less research that derives from Alps of shell two spore pyrones P, G.Deffieux, J.Vercauteren, R.Baute and Badoc A., Pezizale and Tuberale enzymatic activity degraded 1, the 4-alpha-glucans is shell two spore pyrones P and shell two spore pyrones T (Enzymatic activity degrading 1,4-α-glucans toAscopyrones P and T in Pezizales ad Tuberales), Phytochemistry, 33 (1993): 41-45].The shell two spore pyrones P that exist in the fungi make the people propose shell two spore pyrones P at once and can be used as the hypothesis that antibiotic uses.Yet, use also unsatisfactory as antibiotic at disclosed test mesochite two spore pyrones P.
Shell two spore pyrones P and shell two spore pyrones T can adopt cell-free extract from the preparation of following fungi from 1,5-dehydration-D-fructose Production by Enzymes: Pezizale (Pezizales) is Plicaria leiocarpa and Anthracobia melaloma and Tuberale (Tuberales) black truffle (Tuber melanosporum) for example for example.Shell two spore pyrones T 1Be the dihydrate form of shell two spore pyrones T, and shell two spore pyrones T 2With shell two spore pyrones T 3It is the dynamic isomer monohydrate form of shell two spore pyrones T.
Shell two spore pyrones M can be by the EDTA sensitivity of separating from following fungi dehydratase from 1,5-dehydration-D-fructose is produced: hickory chick is Morchella vulgaris, Gyromitra (Gyromitres), cup fungi (pezizes) Peziza echinospora for example for example.
Shell two spore pyrones M, P and T also can be by using alkali treatment 1 under temperate condition, 5-dehydration-D-fructose comes chemical production [to some pentose and 1, the degraded of 5-dehydration-D-fructose, starch degrading enzyme a-1, the research of 4-glucan lyase product (Studies on the degradation of somepentoses and of 1,5-anhydro-D-fructose, the product of the starch-degrading enzyme a-1,4-glucan lyase); Ahmad, the paper of T., The SwedishUniversity of Agricultural Sciences, Sweden, 1995].
When preparing compound of the present invention, can prepare described compound according to arbitrary following method by chemical method:
(1) shell two spore pyrones P can for example pass through with non-water acid treatment 1 down at 70 ℃ under the situation that temperature raises, and 5-dehydration-D-fructose is produced.
(2) shell two spore pyrones (for example shell two spore pyrones P, T and M) can pass through according to Ahmad, T., and 1995 alkali treatment method is from 1, and 5-dehydration-D-fructose is produced.
The structure of all shell two spore pyrones of being produced is all confirmed by the NMR technology.
Compound of the present invention is preferably by as M.-A.Baute etc., and [Phytochemistry, 33 (1993): disclosed enzyme process prepares 41-45).For example can adopt as disclosed enzyme process such as M.-A.Baute from 1,5-dehydration-D-fructose is produced shell two spore pyrones (for example shell two spore pyrones P, T and M).
In an especially preferred embodiment, described compound is selected from following compound or its esterification derivative:
Figure A0181630100201
In a preferred embodiment, the cyclic compound with formula I has the antimicrobial effect at gram-positive bacterium and yeast.
The cyclic compound that preferably has formula I has at the antimicrobial effect that is selected from following microorganism: listeria spp belongs to (Listeria), Salmonella, bacillus (Bacillus), saccharomyces (Saccharomyces), pseudomonas (Pseudomonas), fusobacterium (Clostridium), lactobacillus (Lactobacillus), rope silk Pseudomonas (Brochothrix), Micrococcus (Micrococcus), Yersinia (Yersinia), Enterobacter (Eterobacter) and Zygosaccharomyces belong to (Zygosaccharomyces), staphylococcus (Staphylococcus), Escherichia (Escherichia).
Even the cyclic compound that more preferably has formula I has at the antimicrobial effect that is selected from following microorganism: the monocyte hyperplasia listeria spp, Escherichia coli (E.coli), staphylococcus aureus (Staphylococcus aureus), harmless listeria spp (Listeria innocua), salmonella typhimurium, salmonella (Salmonella sp.), Bacillus cercus, hay bacillus (Bacillus subtilis), saccharomyces cerevisiae (Saccharomyces cerevisiae), the unusual mutation of saccharomyces cerevisiae (Saccharomyces cerevisiae var.paradoxus), saccharomyces carlsbergensis (Saccharomyces carlsbergensis), Pseudomonas fluorescens (Pseudomonasfluorescens), clostridium sporogenes (Clostridium sporogenes), Lactobacillus saki (Lactobacillus sake), heat kill rope silk bacterium (Brochothrix thermosphacta), micrococcus luteus (Micrococcus luteus), yersinia enterocolitica (Yersiniaenterocolitica), clostridium perfringen (Enterobacter aerogenes) and Bayer Zygosaccharomyces (Zygosaccharomyces bailii).
Even the cyclic compound that more preferably has formula I has at the antimicrobial effect that is selected from following microorganism: monocyte hyperplasia listeria spp, Escherichia coli, Bacillus cercus, saccharomyces cerevisiae, saccharomyces carlsbergensis, Pseudomonas fluorescens, clostridium sporogenes, Lactobacillus saki, heat kill rope silk bacterium and micrococcus luteus.
One highly preferred aspect, the derivative of formula I compound is a following formula: compound:
This compound (3; 6-two-O-acetyl group-1; 5-dehydration-4-deoxidation D-glycerine-oneself-3-enol pyranose-2-ketose) can be according to (1998) such as Andersen (1; the structure of 5-dehydration-D-fructose: the X-ray analysis of crystalline state acetylation dimeric forms, J.Carbohydr.Chem.17:1027-1035) described method prepares.
The derivative that this aspect of the present invention particularly preferably is its Chinese style I compound is an ester, because described compound can be for lipophilic and/or can not only have hydrophobic property but also have water-wet behavior.When described compound not only had hydrophobic property but also has water-wet behavior, described compound easily was present in the water/oily interface of emulsion.
Water/oily interface that described compound is present in emulsion can make it work as emulsifying agent.Therefore, the present invention can further provide the compound with difunctional effect.Described compound not only can be used as antimicrobial but also can be used as emulsifying agent.
Many compounds of the present invention can be derived from 1, the 5-anhydrofructose.1, the 5-anhydrofructose is the single ketones sugar that is present in bacterium, red algae, fungi and the mammal.In red algae and fungi, by α-1, the effect of 4-glucan lyase [EC 4.2.2.13] produces 1, the 5-anhydrofructose from floriferous starch and glycogen respectively.
When from 1, when 5-dehydration-D-fructose prepares The compounds of this invention, 1,5-dehydration-D-fructose preferably prepares according to GB-A-2296717.In other words, 1, preferably by comprising with described enzyme α-1, the 4-glucan lyase is handled α-1 to 5-dehydration-D-fructose, and the method for 4-glucan prepares, and it is characterized by the described enzyme of the pure substantially form of use.
Cyclic compound of the present invention preferably comprises five-membered ring or hexatomic ring.
Compound of the present invention comprises at least one ester group.Therefore, term used herein " ester " comprises monoesters, diester, three esters and polyester.
One preferred aspect, formula I compound is a diester, wherein R 1Substituting group is-the OH group, wherein by R 4Substituent-OH group and R 3Substituent-OH group forms described ester bond.
As mentioned above, in a particularly preferred embodiment according to the invention, described compound is a 6-O-acyl group-1 as follows, 5-dehydration-D-fructose.
Figure A0181630100221
6-O-acyl group-1, the preparation of 5-dehydration-D-fructose can be finished by chemical method or by enzyme process according to the method that describes in detail among the WO 00/56745.
Described chemical method can comprise following reaction, with the C of synthetic anhydrofructose 12Ester:
Described reaction is carried out with lauroyl chloride and pyridine.NH is passed through in the acidylate site 2The separation and the NMR of OR derivatization afterproduct determine.Found that described product is
50% 6-O-acyl group-1,5-dehydration-D-fructose
11% 3-O-acyl group-1,5-dehydration-D-fructose
Can use similar method to prepare other ester derivant of anhydrofructose.
Preparation 6-O-acyl group-1, the Enzymology method of 5-dehydration-D-fructose can comprise the application of lipase and protease.In the aqueous solution, lipase and protease can cut ester bond.Lipase is that sugar is specific, and that protease is aliphatic acid is specific.Yet Synthesis 1990, and 112-115 discloses lipase and protease can provide active reverse in non-aqueous solution, thereby form ester bond.Therefore can prepare according to compound of the present invention with lipase in the non-aqueous solution and protease.
According to J.Chem.Soc.Perkin Trans.I, 1995,2203-2222 screens with evaluation lipase and to be used to prepare suitable lipase according to The compounds of this invention.With the pyridine Screening and Identification Candida antarctica, Pseudomonas cepacia (Pseudomonas cepacia), Pseudomonas fluorescens and pig pancreas.Use the tert-butyl alcohol: pyridine be 2: 1 Screening and Identification Candida antarctica, Candida cylindrace, Pseudomonas cepacia, Pseudomonas fluorescens, pig pancreas.
Therefore, prepare according to the most handy lipase that from Candida antarctica, Pseudomonas cepacia, Pseudomonas fluorescens, pig pancreas and Candida cylindrace, obtains of compound of the present invention.
Prepare according to the most handy lipase that from Candida antarctica, obtains of compound of the present invention.Candida antarctica can derive from Novo Nodisk A/S, Denmark, and commodity are called Novozym 435.
Described enzyme process is by using laurate enzymatic acylation 1, and 5-dehydration-D-fructose generates 6-O-acyl group-1, and 5-dehydration-D-fructose is confirmed.
Laurate (mol/mol) Solvent 3 molecular sieves (w/w) Temperature (℃) Reaction time (h) Conversion ratio
1 The tert-butyl alcohol - 40 ?24 ?21％
1 The tert-butyl alcohol 1 (powdery) 40 ?24 ?56％
1 The tert-butyl alcohol 1 (powdery) 40 ?72 ?62％
1 Acetone 1 (powdery) 20 ?24 ?55％
1 The tert-butyl alcohol 5 ?45 ?24 ?56％
1 The tert-butyl alcohol 10 ?45 ?24 ?61％
1 The tert-butyl alcohol 20 ?45 ?24 ?66％
3 The tert-butyl alcohol 20 ?45 ?24 ?73％
3 The tert-butyl alcohol 20 (powderies) 45 ?24 ?78％
3 The tert-butyl alcohol 20 (powderies) 45 ?48 Quantitatively
3 Acetone 20 ?20 ?72 Quantitatively
Described chemical method can comprise with laurate, palmitic acid and stearic acid following with 1, and 5-dehydration-D-fructose Quantitative yield is a 6-O-acyl group-1,5-dehydration-D-fructose:
Described reaction forms the composition that comprises monomer ketone/dimer 1 type/dimer 2 types-1: 3: 1.Described mixture can obtain about 70% yield through the silica gel chromatograph purifying.
Cyclic compound of the present invention can use separately or unite use with other component, and described other component is one or more anticorrisive agents, one or more chelating agents (for example EDTA sodium salt, polyphosphate or citrate) and/or one or more antioxidants (for example ascorbic acid, arabo-ascorbic acid, ascorbyl palmitate, BHA or BHT) for example.
As definition, in a broad sense, term " anticorrisive agent " means the material that comprises that all suppress growth of microorganism or kill described microorganism.In a narrow sense, generally be understood that anticorrisive agent with concentration be 0.5% or lower concentration use.About the food additives except that colouring agent and sweetener, the food additives that allow as anticorrisive agent in the RegulationNo.95/2/EG of the European Parliament and in February 20 nineteen ninety-five Council, have been listed.
The suitable typical food anticorrisive agent with the The compounds of this invention coupling of EU permission comprises sorbic acid, benzoic acid, PHB ester (p-hydroxybenzoate) and sulfur dioxide.The binding mode of these anticorrisive agents and their effective range are as described below. Sorbic acid(E200-203):
Binding mode: suppress the various enzymes in the described microbial cell.
Effective range: main anti-yeast and mould and catalase positive bacteria.Do not suppress catalase negative bacteria and lactic acid bacteria and clostridium.
Valid density: 500-3000ppm.
Maximum permission amount in the food: 2000ppm at the most in potato dough (potato dough), process cheese, packing bread, fine finishining baked product, the emulsification baste etc. Benzoic acid(E210-213):
Binding mode: suppress to pass through the oxygen exchange of cell membrane and influence enzymatic structure.
Effective range: only for acidic products, about at the most pH4.5; Suppress yeast and mould, limited inhibition bacterium (do not have or only very faintly suppress lactic acid bacteria and clostridium).
Maximum permission amount in the food: 500ppm at the most in meat jelly, fruit, the jam etc. The PHB ester(p-hydroxybenzoate) (E214-219)
Binding mode: owing to surface-active is damaged bacterial membrane, owing to protein denaturation and to the toxic effect of plasm.
Effective range: mainly suppress yeast and fungi, but between pH scope 3.0-8.0, also suppress gram-positive bacterium.
Valid density: surpassing at about 0.08% o'clock in concentration has organoleptic effects. Sulfur dioxide(E220-224; E226-227)
Binding mode: depend on pH to a great extent, in fact sulfur dioxide is only effective when acid ph value (＜4,0).Mechanism is very complicated.
Effective range: main antibacterium, especially anti-Gram-negative aerobe.
Valid density: 250-500ppm can suppress aerobic gramnegative bacterium, but 800-2000ppm resisting gram-positive bacterium, yeast and mould.
Maximum permission amount in the food: be used for dry fruit, the maximum 2000ppm of grape juice concentrate of family's wine production, in some cases, maximum permission amount only is 20-30ppm.
For more special application, The compounds of this invention also can be united use with following anticorrisive agent: biphenyl, hexichol, o-phenyl phenol, thiabendazole, streptococcus lactis peptide, Natamycin, hexa, two dimethyl carbonates, boric acid, sodium tetraborate, nitrite, propionic acid and propionate and lysozyme.The binding mode of these anticorrisive agents and their effective range and concrete application are as described below. Biphenyl, hexichol(E230)
Effective range: mould fungus inhibition.
Be used to handle the material of fruit: the surface treatment cedra fruits.
Maximum permission amount: 70ppm O-phenyl phenol(E231/E232)
The same with E230, be limited to processing fruit, as the surface treatment cedra fruits. Thiabendazole(E233)
Surface treatment cedra fruits and banana. Streptococcus lactis peptide(E234)
Binding mode: upset the film function.
Effective range: gram-positive bacterium, do not have influence to gramnegative bacterium.
Maximum permission amount (EU) in the food: red dog pudding and similar products 3ppm, aged cheese and process cheese 12.5ppm (=12.5IU/g), the cream 10ppm that condenses, Maas card friend 10ppm. Natamycin(Korean pine element) (E235)
Binding mode: generally speaking attack cells film specifically wherein interacts with sterol, thereby increases the permeability of film.
Effective range: mould and yeast are invalid to bacterium.Effective dose rate is lower than about 50mg/l.The surface Cmax is 1mg/dm 2, maximum penetration 5mm.
Use: surface treatment hard cheese, semi-hard cheese and semi-soft cheese and saveloy. Hexa(E239)
Hexa forms by ammonia is added in the formalin.Function of killing microorganism is because due to the formaldehyde.
Only permission is used for Italian POLO volt Lip river cheese (25ppm residual quantity). Two dimethyl carbonates(E242)
Only permission is used for non-alcoholic beverage, no pure wine and liquid concentrate. Boric acid, sodium tetraborate(E284/E285)
Only permission is used for caviar. Nitrite(E249 and E250)
Permission is used to handle meat products (" red goods ") with nitrite curing salt form.Be used to pickle can not heat treated dry meat products and be used for the meat products that other is pickled, according to the fixing 150ppm that adds of guide.These concentration demonstrations do not have antisepsis.Mainly due to their technical characteristic (constitute color, taste) and because their antioxidation and with its adding. Propionic acid and propionate(E280, E281, E282 and E283)
Binding mode: similar to sorbic acid, optimal pH＜4.5.
Accumulation causes suppressing various enzymes in cell.
The inhibition scope: at pH5.5, mould fungus inhibition when concentration is 125-12500ppm, in order to suppress bacterium, concentration that must be higher (＞16000ppm).
Use: slice packaging bread.
Maximum permission amount: 3000ppm. Lysozyme(E1105)
Only permission is used for aged cheese.
Maximum permission amount: an amount of.
The applicant tests in the culture medium (Elliker meat soup) of nearly neutral pH (pH6.8) by the The compounds of this invention depression effect is studied, and has shown and can effectively resist gram-positive bacterium and gramnegative bacterium.Above-mentioned multiple anticorrisive agent demonstration depression effect is obviously used The compounds of this invention and has been enlarged potential range of application mainly at low pH.
In principle, following factors is depended in the application of chemical preservation material:
(a) harmless on the toxicology
The effect of described material when short-term, medium and long term application.
Test acute toxicity (LD 50), dynamics and metabolism, pharmacotoxicological effect, genotoxicity etc.
(b) technology/Food Chemistry aspect:
Water-soluble: because microorganism grows at aqueous phase, so that anticorrisive agent is necessary for is water miscible
With the reaction of food composition, peculiar smell problem (sense organ acceptance)
Disturb food composition (for example sulfuric acid destruction vitamin B1)
Therefore, the antimicrobial effect of a series of different factor decision chemical substances in food and feed.Wherein, microorganism composition, food composition (composition, pH, water activity, salt content etc.), packing, time-temperature-condition etc. all are the key factors that influences the inhibition activity of antimicrobial.
Only also the present invention is described with reference to the accompanying drawings now by embodiment, in the accompanying drawing:
Fig. 1 shows the hole diffusion test photo of a width of cloth with micrococcus luteus (top 1 flat board), Bacillus cercus (middle 2 flat boards) and the clostridium sporogenes (following 2 flat boards) of following agent treatment:
Top right-hand component: 3% C 8The anhydrofructose ester;
Middle right-hand component: 0.3% C 8The anhydrofructose ester;
Following right-hand component: 3% C 12The anhydrofructose ester;
Following left-hand component: 0.3% C 12The anhydrofructose ester;
Middle left-hand component: the equivalent methyl alcohol contrast of 25% methyl alcohol;
Top left-hand component: the equivalent methyl alcohol contrast of 2.5% methyl alcohol.
Fig. 2 shows the hole diffusion test photo of a width of cloth with the micrococcus luteus of following agent treatment:
Part 1:3% C 8The anhydrofructose ester;
Part 2:0.3% C 8The anhydrofructose ester;
Part 3:3% C 12The anhydrofructose ester;
Part 4:0.3% C 12The anhydrofructose ester;
The equivalent methyl alcohol contrast of part 5:25% methyl alcohol;
The equivalent methyl alcohol contrast of part 6:2.5% methyl alcohol.
Embodiment Chemical synthesis
The compounds of this invention is according to disclosed universal method preparation, sign and purifying among the WO 00/56745. Material and method Test strain
All microorganisms are taken from-80 ℃ repertory.Most of biological vegetative cell suspensions that derive from the broth culture that spends the night of using are tested.Bacillus and clostridium are with early preparing and preserving in 4 ℃ endospore suspension and test.
For broth culture and Bioscreen test, allow most of bacteriums in brain heart infusion (BHI, Oxoid, pH7.4) middle growth.Allow Lactobacillus saki A10 at de Man, Rogosa, Sharpe culture medium (MRS, Oxoid) middle growth.Allow yeast in Sha Shi liquid medium (SabouraudLiquid medium) (SLM, Oxoid) middle growth.Most of bacteriums are in 30 ℃ of cultivations.Allow lactic acid bacteria be rich in CO 2Environment under on solid medium, grow.Allow clostridium in reinforced clostridial medium (RCM) under oxygen free condition in 37 ℃ of growths.Allow heat kill rope silk bacterium and yeast in 25 ℃ of growths. The Rioscreen test
Adopt automation microorganism readout instrument Bioscreen C to measure at the growth curve that has and do not have described bacterial strain under the situation of test specimen.Bioscreen C can measure dynamics turbidity in the cellular microtiter plate in 200 holes (i.e. growth) simultaneously by vertical photometry.Described system is by Bioscreen C analyzer (it has an incubator and measurement mechanism), integrated PC, software (BioLink v 5.30), printer and ' the cup type porous plate of Honeycomb 2 ' colorimetric is formed.Can output in the program such as Excel with BioLink software analysis growth curve data or with described data. Scheme
In the 14mg sample, add 50 μ l, 100% methyl alcohol.Add 66.7 μ l IMS (industrial methylated spirit, 96% ethanol) then, to prepare 12% (w/v) solution.
For described test, this solution dilutes with 1: 4 with sterile distilled water then.This step is essential, because the concentration of alcohol in the sample can suppress described test microorganism.This makes the whole solution of 3% (w/v).
Described test specimen can not carry out filtration sterilization, because loss can be too big, only can obtain about 470 μ l.Sample is carried out sterile working, wish that this sample is aseptic.Because same cause is not measured the pH of sample.
In Bioscreen, under 0.3% concentration, test described sample then.Yet, will appreciate that at once this has problem, because AF ester 1 test specimen is muddy milky.What something lost was shaken is that in the time of in it being joined each hole of Bioscreen, original turbidity is too high, so that can't offer an explanation any microbial growth.Therefore, in order to prove conclusively whether any inhibition taking place, must carry out count plate to inoculum, then in Bioscreen in 30 ℃ cultivate 24 hours after, the sample in the direct sample test b ioscreen plate.Can estimate inhibition by it is compared with the final viable count of control wells that contains 2.5% ethanol then. Bioscreen BS021100 result
The C of AF ester 1=anhydrofructose 8Ester (structure shown in the claim 32-LHS).Table 1
Test strain First counting (cfu/ml) 30 ℃ of countings (cfu/ml) after 24 hours
The contrast of 2.5% ethanol 0.3%AF ester 1
Bacillus cercus 204 ?1×10 3 ?1.3×10 7 2.4×10 2
Monocyte hyperplasia listeria spp S23 ?1.2×10 3 ?1.1×10 9 ＜10 2
Lactobacillus saki A10 ?＜10 2 ?1.9×10 2 ＜10 2
Escherichia coli S15 ?5.3×10 2 ?1.1×10 9 3.7×10 7
Pseudomonas fluorescens 3756 ?3.6×10 2 ?1.1×10 9 2.3×10 7
Saccharomyces cerevisiae 9763 ?3.6×10 2 ?2.0×10 6 2×10 1
Saccharomyces carlsbergensis 6418 ?5.2×10 2 ?9.7×10 4 1×10 1
Conclusion
Result in the table 1 shows that AF-ester 1 suppresses all tested microorganisms.The order that suppresses activity is as follows: gram-positive bacterium＞yeast＞gramnegative bacterium.This sample is effective especially to the monocyte hyperplasia listeria spp, but also very effective to bacillus.Evidence at monocyte hyperplasia listeria spp bactericidal activity is arranged, and may bactericidal activity be arranged described yeast. Anhydrofructose ester 1: BA
In Bioscreen, confirm that with count plate early the sample of test carries out preliminary sterilization experiment.This shows excellent activity.For described sterilization experiment, selected test organism is monocyte hyperplasia listeria spp S23, because this bacterium shows hypersensitivity in growth inhibition test. Scheme
Equal portions 3 * 890ml 10mM HEPES buffer solution, pH7.In an experimental control, add 100ml water, in another experimental control, add the contrast of 100ml equivalent ethanol, in test specimen, add 100ml AF ester 1.In all tests, add the 10ml overnight culture.Sample was left standstill under the environmental protection temperature 2 hours.Carry out count plate.Please note: AF ester 1 can be precipitated out at duration of test. The result Test Count plate (cfu/ml)Contrast/water 3.1 * 10 8Contrast/ethanol 2.0 * 10 7Test/AF ester 1 2.4 * 10 7
The conclusion that draws according to this result is that AF ester 1 does not have any bactericidal activity. The test of fresh sample:
The C of anhydrofructose ester C8 (AFC8)=anhydrofructose 8Ester (structure shown in the claim 32-LHS)
The C of anhydrofructose ester C12 (AFC12)=anhydrofructose 12Ester (structure shown in the claim 32-RHS)
Glucose ester C8 (GC8)-contrast
Glucose ester C12 (GC12)-contrast
With the AF ester by in 70 ℃ of heating 10-15 minute or in 100 ℃ of heating 5-10 minute and soluble in water.Two kinds of methods are not all achieved success, and the described ester in heating back is finally made 50: 50 methanol/water solution of 0.5% (w/v).AFC8 does not dissolve, but other sample is than good dissolving. The result
Do not observe equivalent methyl alcohol check plot.Table 2
Test strain The diffusion region of surveying at 0.5% (wt/vol) extract, hole (mm)
?AF?C8 ?AF?C12 Glucose C8 Glucose C12
Bacillus cercus 204 ?0 ?6.82 ?0 ?0
Clostridium sporogenes Campden ?3.90 ?11.30 ?0 ?+/-(3.50)
Monocyte hyperplasia listeria spp S23 ?0 ?0 ?0 ?0
Lactobacillus saki A10 ?0 ?0 ?0 ?0
Heat kill rope silk bacterium CRA7883 ?0 ?7.50 ?0 ?0
Micrococcus luteus ?0 ?8.95 ?0 ?0
Escherichia coli S15 ?0 ?0 ?0 ?0
Pseudomonas fluorescens 327 ?0 ?0 ?0 ?0
Saccharomyces cerevisiae ATCC9763 ?0 ?+/-(10.00) ?0 ?0
Saccharomyces carlsbergensis CRA6413 ?0 ?0 ?0 ?0
BS191200 Bioscreen result of the testTable 3
Bacterial strain (contrast: the average OD that does not contain methyl alcohol) Experimental concentration % (wt/vol) 30 ℃ of growths 18 hours or 24 hours the end-min OD
?AFC8 ?AFC12 ?GC8 ?GC12 Contrast: equivalent methanol concentration
Bacillus cercus 204 (0.80) ?0.05 ?0 ?0 ?0.242 ?0 ?0.194
?0.025 * ?0.168 ?0 ?0.785 ?0.561 ?0.619
Bacillus cercus Campden (0.72) ?0.05 ?0 ?0 ?0.882 ?0.437 ?0.75
?0.025 * ?0.8 ?0 ?0.777 ?0.641 ?0.707
Monocyte hyperplasia listeria spp S23 (0.66) ?0.05 ?0 ?0 ?0.242 ?0.19 ?0.27
?0.025 ?0.027 ?0 ?0.514 ?0.379 ?0.537
Lactobacillus saki A10 (0.90) ?0.05 ?0 ?0 ?0.245 ?0.392 ?0.123
?0.025 ?0.535 ?0.376 ?0.81 ?0.785 ?0.477
Escherichia coli S15 (0.95) ?0.05 ?0.573 ?0.478 ?0.654 ?0.745 ?0.716
?0.025 ?0.753 ?0.703 ?0.818 ?0.875 ?0.851
Escherichia coli CRA109 (0.86) ?0.05 ?0 ?0 ?0.285 ?0.149 ?0.187
?0.025 ?0.697 ?0.738 ?0.789 ?0.759 ?0.84
Pseudomonas fluorescens 3756 (1.2) ?0.05 ?0 ?0 ?0 ?0 ?0
?0.025 ?0.068 ?0.192 ?0.82 ?0.953 ?0.973
Pseudomonas fluorescens 327 (0.37) ?0.05 ?0 ?0 ?0 ?0 ?0
?0.025 ?0.12 ?0.178 ?0.21 ?0.354 ?0.219
*AF C12 shows Bc204 and the Bc Campden inhibition fully when minimum experimental concentration 0.0125%.
This takes turns contrast based at the whole OD of equivalent methanol concentration in 30 ℃ of growths 18 hours or 24 hours.Whether hang down the inhibitory action of judging described AF ester according to number of bacteria than methyl alcohol contrast number of bacteria. Conclusion
Hole diffusion result shows that 0.5% AFC8 and AFC12 all have anti-clostridium activity, and AFC12 also has the activity of anti-bacillus, rope silk Pseudomonas, Micrococcus, perhaps also have yeast-resistant activity, but the activity of nonreactive monocyte hyperplasia listeria spp or Gram-negative (GN) bacterium.
Bioscreen result derives from the test of 0.05% sample.
The active order that Bioscreen confirms is as follows: AFC12＞AFC8.Bioscreen also confirms the activity of anti-bacillus, but also observes the activity of active and certain anti-Gram-negative (GN) bacterium of anti-monocyte hyperplasia listeria spp and Lactobacillus saki. The description that Bioscreen analyzes: BS040101
0.3% AF ester is dissolved in 2.5% methyl alcohol.The preparation serial dilution.Test following concentration: 0.3%, 0.15%, 0.075%, 0.038% and 0%.APP is soluble in water.This sample is analyzed (table 4) at 30 ℃ after 24 hours.Table 4
Bacterial strain AF ester C8 AF ester C12
Bc?204 0.15% suppresses 0.075% fully suppresses 0.038% suppresses fully
Lm?S23 0.15% suppresses 0.038% fully suppresses 0.038% suppresses fully
Lbs?A10 0.3% suppresses 0.15% fully suppresses 0.15% suppresses 0.038% fully suppresses
Ec?S15 0.3% does not suppress 0.3% does not suppress
Psf3756 0.3% suppresses 0.3% suppresses
The count plate of BS040101
Whether judge inhibition by the counting eventually in the presence of any AF ester than counting to hang down at the end of 2.5% methyl alcohol (contrast).The results are shown in the table 5.Table 5
Bacterial strain Whole count plate (cfu/ml) after 24 hours
?0.3％?AFE?C8 ?0.3％?AFE?C12 The contrast of 2.5% methyl alcohol
Bc?204 ?1×10 3 ?1.5×10 3 ?1×10 5
Lm?S23 ?2.5×10 3 ?1.5×10 3 ?2.9×10 9
Lbs?A10 ?＜10 5 ?＜10 5 ?3.7×10 7
Ec?S15 ?3.5×10 7 ?1.7×10 9 ?2.3×10 9
Psf?3756 ?1.7×10 8 ?2.7×10 8 ?3.2×10 9
Sce?9763 ?9.4×10 4 ?7.4×10 2 ?4.5×10 6
Sca?6413 ?3.3×10 4 ?nd ?1.4×10 4
The hole diffusion test
Micrococcus luteus, Bacillus cercus 204, Bacillus cercus Campden, clostridium sporogenes 1.221 and clostridium sporogenes Campden the results are shown among Fig. 1 and Fig. 2 and the table 6.The methyl alcohol check experiment does not obtain any diffusion region.Each hole numbering: 1=3% AFEC8,2=0.3%AFEC8,3=3% AFEC12,4=0.3% AFEC12, the equivalent methyl alcohol contrast of 5=25% methyl alcohol, the equivalent methyl alcohol contrast of 6=2.5% methyl alcohol, table 6
Test strain The diffusion region of surveying at 0.3% and 3% (wt/vol) extract, hole (mm)
?AFE?C8 ?3％ ?AFE?C8 ?0.3％ AFE?C12 ?3％ ?AFE?C12 ?0.3％
Bacillus cercus 204 ?2.29 ?0 ?7.75 ?1.27
Bacillus cercus Campden ?＜0.5 ?0 ?3.23 ?＜0.5
Clostridium sporogenes 1.221 ?6.00 ?0 ?16.83 ?5.06
Clostridium sporogenes Campden ?6.15 ?5.05 ?14.15 ?6.15
Monocyte hyperplasia listeria spp S23 ?1.62 ?0 ?2.26 ?+/-
Monocyte hyperplasia listeria spp 272 ?2.36 ?0 ?+/-8.82 ?0
Lactobacillus saki A10 ?+/- ?0 ?+/-(2.8) ?+/-
Heat kill rope silk bacterium CRA7883 ?0.98 ?0 ?7.55 ?+/-
Micrococcus luteus ?3.95 ?0 ?9.42 ?2.33
Escherichia coli S15 ?0 ?0 ?0 ?0
Pseudomonas fluorescens 327 ?0 ?0 ?0 ?0
Pseudomonas fluorescens 3756 ?0 ?0 ?0 ?0
Saccharomyces cerevisiae ATCC 9763 ?E ?E ?+ ?E
Saccharomyces carlsbergensis CRA6413 ?E ?E ?+ ?E
Code (CODE) (yeast): the E=increase of growing; +=observe inhibition zone. The further test of APP
3% o'clock diffusion region, hole (with respect to clostridium sporogenes Campden (4.72) and heat kill rope silk bacterium 7883 (2.96)) The count plate of BS040101Table 7
Bacterial strain The count plate of 0.3% APP
Bc?204 ?7.0×10 1
Lm?S23 ?5.4×10 7
Lbs?A10 ?1.9×10 8
Ec?S15 ?6.2×10 8
Psf?3756 ?＜10 2
Sce?9763 ?3.1×10 5
Sca ?1.1×10 5
The various modifications and variations of described method and system of the present invention under the situation that does not depart from scope and spirit of the present invention are conspicuous to those skilled in the art.Therefore carry out the conspicuous modification of various equivalent modifications and belong to the following claims scope implementing described mode of the present invention.

Claims (42)

1. antimicrobial compositions, described composition comprises formula I cyclic compound,
Figure A0181630100021
R wherein 1And R 2Independently be selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl; R wherein 3Be selected from-OH ,=substituting group of O, comprise-OH group and-OC (O) R ', wherein R ' is H or alkyl; R wherein 4And R 5Independently be selected from separately alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl, perhaps R wherein 4And R 5For with described cyclic compound ring on the chemical bond of adjacent atom; Wherein said compound comprises at least one ester group.
2. one kind prevents and/or suppresses in certain material growth of microorganism and/or kills described method of microorganism, and described method comprises the step that described material is contacted with formula I cyclic compound, R wherein 1And R 2Independently be selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl; R wherein 3Be selected from-OH ,=substituting group of O, comprise-OH group and-OC (O) R ', wherein R ' is H or alkyl; R wherein 4And R 5Independently be selected from separately alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl, perhaps R wherein 4And R 5For with described cyclic compound ring on the chemical bond of adjacent atom; Wherein said compound comprises at least one ester group.
3. formula I compound is preventing and/or is suppressing growth of microorganism in certain material and/or kill application aspect the described microorganism, R wherein 1And R 2Independently be selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl; R wherein 3Be selected from-OH ,=substituting group of O, comprise-OH group and-OC (O) R ', wherein R ' is H or alkyl; R wherein 4And R 5Independently be selected from separately alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl, perhaps R wherein 4And R 5For with described cyclic compound ring on the chemical bond of adjacent atom; Wherein said compound comprises at least one ester group.
4. the present invention of arbitrary aforementioned claim, wherein said material is food or feed.
5. the present invention of arbitrary aforementioned claim, wherein said cyclic compound is a formula II compound
Figure A0181630100032
R wherein 1, R 2, R 3, R 4And R 5With aforementioned claim definition.
6. the present invention of arbitrary aforementioned claim, wherein said cyclic compound is the formula III compound
Figure A0181630100033
R wherein 1, R 2, R 3, R 4And R 5With aforementioned claim definition.
7. the present invention of arbitrary aforementioned claim, wherein said cyclic compound is a formula IV compound, R wherein 1And R 2Independently be selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl; R wherein 3Be selected from-OH ,=substituting group of O, comprise-OH group and-OC (O) R ', wherein R ' is H or alkyl; R wherein 4And R 5Independently be selected from separately alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl, perhaps R wherein 4And R 5For with described cyclic compound ring on the chemical bond of adjacent atom; R wherein 6And R 7Independently be selected from separately alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl, perhaps R wherein 4And R 5For with described cyclic compound ring on the chemical bond of adjacent atom; Wherein said compound comprises at least one ester group.
8. the present invention of arbitrary aforementioned claim, wherein said cyclic compound is a formula V compound,
Figure A0181630100042
R wherein 1, R 2, R 3, R 4, R 5, R 6And R 7Define with claim 7.
9. the present invention of arbitrary aforementioned claim, wherein R 1Be selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl.
10. the present invention of arbitrary aforementioned claim, wherein R 2Be selected from-OH ,=O and-OC (O) R ', wherein R ' is an alkyl.
11. the present invention of arbitrary aforementioned claim, wherein R 3Be selected from comprise-substituting group of OH group and-OC (O) R ', wherein R ' is H or alkyl.
12. the present invention of arbitrary aforementioned claim, wherein R 3For-OC (O) R ', wherein R ' is H or alkyl.
13. the present invention of arbitrary aforementioned claim, wherein R 3For-OC (O) R ', wherein R ' is an alkyl.
13. the present invention of arbitrary aforementioned claim, wherein R 3For-OC (O) R ', wherein R ' is R " group.
14. the present invention of arbitrary aforementioned claim, wherein R ' and/or R " be side chain or straight chain, replacement or unsubstituted alkyl.
15. the present invention of arbitrary aforementioned claim, wherein R ' and/or R " be (CH 2) pCH 3, wherein p is 1-24.
16. the present invention of arbitrary aforementioned claim, wherein R ' and/or R " be C 8Alkyl.
17. the present invention of arbitrary aforementioned claim, wherein R ' and/or R " be C 12Alkyl.
18. the present invention of arbitrary aforementioned claim, R 3Be formula-(CH 2) n-OC (O)-(CH 2) pCH 3, wherein n and p independently are 1-24 separately.
19. the present invention of arbitrary aforementioned claim, R 3Be formula-(CH 2) n-OC (O)-(CH 2) 7CH 3, wherein n and p independently are 1-24 separately.
20. the present invention of arbitrary aforementioned claim, R 3Be formula-(CH 2) n-OC (O)-(CH 2) 11CH 3, wherein n and p independently are 1-24 separately.
21. the present invention of arbitrary aforementioned claim, wherein R 4Be selected from alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl.
22. the present invention of arbitrary aforementioned claim, wherein R 4Be selected from alkyl, H, OH and=O.
23. the present invention of arbitrary aforementioned claim, wherein R 5Be selected from alkyl, H, OH ,=O and-OC (O) R ', wherein R ' is H or alkyl.
24. the present invention of arbitrary aforementioned claim, wherein R 5Be selected from alkyl, H, OH and=O.
25. the present invention of arbitrary aforementioned claim, wherein R 4And R 5For with described cyclic compound ring on the chemical bond of adjacent atom;
25. the present invention of arbitrary aforementioned claim, wherein said compound is the esterification anhydrofructose, at least one OH group esterification formation-OC (O) R group of anhydrofructose wherein, and wherein R is an alkyl.
26. the present invention of claim 25, wherein R is side chain or straight chain, replacement or unsubstituted alkyl.
27. the present invention of claim 25, wherein R is (CH 2) pCH 3, wherein p is 1-24.
28. the present invention of claim 25, wherein R is C 8Alkyl.
29. the present invention of claim 25, wherein R is C 12Alkyl.
30. the present invention of arbitrary aforementioned claim, wherein said cyclic compound is a following formula: compound:
31. the present invention of arbitrary aforementioned claim, wherein said cyclic compound is a following formula: compound:
Figure A0181630100062
32. the present invention of arbitrary aforementioned claim, wherein said cyclic compound is selected from following compound:
Figure A0181630100071
33. the present invention of arbitrary aforementioned claim, wherein said cyclic compound is selected from following compound:
Figure A0181630100072
34. the present invention of arbitrary aforementioned claim, wherein said compound is shell two spore pyrones P, shell two spore pyrones M, shell two spore pyrones T, shell two spore pyrones T 1, shell two spore pyrones T 2, shell two spore pyrones T 3Derivative and their mixture.
35. the present invention of arbitrary aforementioned claim, wherein said compound is selected from esterification shell two spore pyrones P, esterification shell two spore pyrones M, esterification shell two spore pyrones T, esterification shell two spore pyrones T 1, esterification shell two spore pyrones T 2, esterification shell two spore pyrones T 3With their mixture.
36. the present invention of arbitrary aforementioned claim, wherein said compound is selected from following compound or its esterification derivative:
Figure A0181630100081
37. the present invention of arbitrary aforementioned claim, wherein said formula I cyclic compound has at the antimicrobial effect that is selected from following microorganism: listeria spp belongs to (Listeria), Salmonella (Salmonella), bacillus (Bacillus), saccharomyces (Saccharomyces), pseudomonas (pseudomonas), fusobacterium (Clostridium), lactobacillus (Lactobacillus), rope silk Pseudomonas (Brochothrix), Micrococcus (Micrococcus), Yersinia (Yersinia), Enterobacter (Enterobacter) and Zygosaccharomyces belong to (Zygosaccharomyces), staphylococcus (Staphylococcus) and Escherichia (Escherichia).
38. the present invention of arbitrary aforementioned claim, wherein said formula I cyclic compound has at the antimicrobial effect that is selected from following microorganism: monocyte hyperplasia listeria spp (Listeria monocytogenes), Escherichia coli (E.coli), staphylococcus aureus (Staphylococcus aureus), harmless listeria spp (Listeria innocua), salmonella typhimurium (Salmonella Typhimurium), salmonella (Salmonella sp.), Bacillus cercus (Bacillus cereus), hay bacillus (Bacillus subtilis), saccharomyces cerevisiae (Saccharomyces cerevisiae), the unusual mutation of saccharomyces cerevisiae (Saccharomycescerevisiae var.paradoxus), saccharomyces carlsbergensis (Saccharomyces carlsbergensis), Pseudomonas fluorescens (Pseudomonas, uorescens), clostridium sporogenes (Clostridiumsporogenes), Lactobacillus saki (Lactobacillus sake), heat kill rope silk bacterium (Brochothrixthermosphacta), micrococcus luteus (Micrococcus luteus), yersinia enterocolitica (Yersinia enterocolitica), clostridium perfringen (Enterobacter aerogenes) and Bayer Zygosaccharomyces (Zygosaccharomyces bailii).
39. the present invention of arbitrary aforementioned claim, wherein said formula I cyclic compound has at the antimicrobial effect that is selected from following microorganism: monocyte hyperplasia listeria spp, Escherichia coli, Bacillus cercus, saccharomyces cerevisiae, saccharomyces carlsbergensis, Pseudomonas fluorescens, clostridium sporogenes, Lactobacillus saki, heat kill rope silk bacterium and micrococcus luteus.
40. the present invention of arbitrary aforementioned claim wherein unites use with described formula I compound and one or more antioxidants, anticorrisive agent and/or chelating agent.
CNA018163017A 2000-09-27 2001-09-27 Antimicrobial agent Pending CN1466423A (en)

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Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003037906A1 (en) * 2001-10-31 2003-05-08 Danisco A/S Antimicrobial use of anhydrofructose derivatives
WO2003038085A1 (en) * 2001-10-31 2003-05-08 Danisco A/S 1,5-anhydro-d-fructose dehydratase
US7776314B2 (en) 2002-06-17 2010-08-17 Grunenthal Gmbh Abuse-proofed dosage system
WO2004039820A1 (en) * 2002-10-30 2004-05-13 Danisco A/S Material
GB0306312D0 (en) * 2003-03-19 2003-04-23 Danisco Composition
DE10336400A1 (en) 2003-08-06 2005-03-24 Grünenthal GmbH Anti-abuse dosage form
DE102004032051A1 (en) 2004-07-01 2006-01-19 Grünenthal GmbH Process for the preparation of a secured against misuse, solid dosage form
DE10361596A1 (en) 2003-12-24 2005-09-29 Grünenthal GmbH Process for producing an anti-abuse dosage form
US20070048228A1 (en) 2003-08-06 2007-03-01 Elisabeth Arkenau-Maric Abuse-proofed dosage form
DE102005005446A1 (en) 2005-02-04 2006-08-10 Grünenthal GmbH Break-resistant dosage forms with sustained release
CN100582101C (en) 2003-10-28 2010-01-20 日本淀粉工业株式会社 Antitumoral agent
JP4825413B2 (en) * 2003-10-28 2011-11-30 日本澱粉工業株式会社 Antitumor agent
WO2005049599A1 (en) * 2003-11-20 2005-06-02 Nihon Starch Co., Ltd. Method of efficiently producing ascopyrone p
WO2005121114A2 (en) * 2004-06-07 2005-12-22 Glycom Aps 1,5 and 1,4-anhydroketoses, methods for the preparation of 1,5-and 1,4-anhydroketoses, intermediates, and uses of 1,5-and 1,4-anhydroketoses
DE102004032049A1 (en) 2004-07-01 2006-01-19 Grünenthal GmbH Anti-abuse, oral dosage form
DE102005005449A1 (en) 2005-02-04 2006-08-10 Grünenthal GmbH Process for producing an anti-abuse dosage form
JP4825957B2 (en) * 2005-03-29 2011-11-30 国立大学法人 鹿児島大学 Antitumor agent
JP4778723B2 (en) * 2005-04-28 2011-09-21 日本澱粉工業株式会社 Anti-inflammatory agent
RU2493830C2 (en) 2008-01-25 2013-09-27 Грюненталь Гмбх Drug form
BRPI0912014A2 (en) 2008-05-09 2019-03-06 Grünenthal GmbH A process for preparing an intermediate powder formulation and a final solid dosage form using a spray freeze step
KR101747156B1 (en) 2009-07-22 2017-06-27 그뤼넨탈 게엠베하 Oxidation-stabilized tamper-resistant dosage form
TW201105316A (en) 2009-07-22 2011-02-16 Gruenenthal Gmbh Hot-melt extruded pharmaceutical dosage form
PE20131102A1 (en) 2010-09-02 2013-10-12 Gruenenthal Chemie HANDLING RESISTANT DOSAGE FORM INCLUDING INORGANIC SALT
CN103179954A (en) 2010-09-02 2013-06-26 格吕伦塔尔有限公司 Tamper resistant dosage form comprising an anionic polymer
PT2736497T (en) 2011-07-29 2017-11-30 Gruenenthal Gmbh Tamper-resistant tablet providing immediate drug release
MX348491B (en) 2011-07-29 2017-06-15 Gruenenthal Gmbh Tamper-resistant tablet providing immediate drug release.
WO2013127831A1 (en) 2012-02-28 2013-09-06 Grünenthal GmbH Tamper-resistant dosage form comprising pharmacologically active compound and anionic polymer
AU2013248351B2 (en) 2012-04-18 2018-04-26 Grunenthal Gmbh Tamper resistant and dose-dumping resistant pharmaceutical dosage form
US10064945B2 (en) 2012-05-11 2018-09-04 Gruenenthal Gmbh Thermoformed, tamper-resistant pharmaceutical dosage form containing zinc
AR096439A1 (en) 2013-05-29 2015-12-30 Gruenenthal Gmbh DOSAGE METHOD RESISTING TO INDEED USE CONTAINING ONE OR MORE PARTICLES
US10154966B2 (en) 2013-05-29 2018-12-18 Grünenthal GmbH Tamper-resistant dosage form containing one or more particles
EA032465B1 (en) 2013-07-12 2019-05-31 Грюненталь Гмбх Tamper-resistant oral pharmaceutical dosage form containing ethylene-vinyl acetate polymer and process for the production thereof
JP6480936B2 (en) 2013-11-26 2019-03-13 グリュネンタール・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Preparation of powdered pharmaceutical composition by cryomilling
EP3142646A1 (en) 2014-05-12 2017-03-22 Grünenthal GmbH Tamper resistant immediate release capsule formulation comprising tapentadol
CN106456550A (en) 2014-05-26 2017-02-22 格吕伦塔尔有限公司 Multiparticles safeguarded against ethanolic dose-dumping
AU2016251854A1 (en) 2015-04-24 2017-10-19 Grunenthal Gmbh Tamper-resistant dosage form with immediate release and resistance against solvent extraction
EP3346991A1 (en) 2015-09-10 2018-07-18 Grünenthal GmbH Protecting oral overdose with abuse deterrent immediate release formulations
CN105851484A (en) * 2016-03-24 2016-08-17 宋介珍 Microbial feed additive, and preparation process and application thereof

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4521592A (en) * 1981-10-23 1985-06-04 Svenska Sockerfabriks Ab Compounds for therapeutic or diagnostic use, a process and intermediates for their preparation
FR2617502B1 (en) * 1987-06-30 1990-03-09 Elf Aquitaine ENZYMATIC PREPARATION OF 1,5 D ANHYDRO FRUCTOSE
NZ275423A (en) * 1993-10-15 1997-12-19 Danisco Use of pure alpha-1,4-glucan lyase for preparing 1,5-d-anhydrofructose
GB9422157D0 (en) * 1994-10-15 1994-12-21 Danisco Enzyme
JPH08134090A (en) * 1994-11-11 1996-05-28 Fujisawa Pharmaceut Co Ltd Galactosyl kojic acid, its production and tyrosinase-inhibiting agent containing the same
GB9709161D0 (en) * 1997-05-06 1997-06-25 Danisco A process of preparing an anti-oxidant
GB9906457D0 (en) * 1999-03-19 1999-05-12 Danisco Anti-oxidant
GB2348423B (en) * 1999-03-19 2003-10-22 Danisco Novel anhydrofructose antioxidant
JP2001089377A (en) * 1999-09-20 2001-04-03 進 ▲桧▼作 Agent for suppressing or inhibiting bacterial proliferation containing 1,5-d-anhydrofructose
GB2358137B (en) * 2000-01-14 2004-06-09 Danisco Compound
WO2001056408A1 (en) * 2000-01-31 2001-08-09 Asama Chemical Co., Ltd. Process for producing foods having good keeping qualities and food keeping agents
DE60118156D1 (en) * 2000-03-28 2006-05-11 Nihon Starch Co Ltd 1.5-D ANHYDROFRUCTOSIS CONTAINING REGULATORS OR INHIBITORS OF BACTERIAL GROWTH

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