CN1505480A - Methods of using hop acids to control organisms - Google Patents
Methods of using hop acids to control organisms Download PDFInfo
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- CN1505480A CN1505480A CNA018231039A CN01823103A CN1505480A CN 1505480 A CN1505480 A CN 1505480A CN A018231039 A CNA018231039 A CN A018231039A CN 01823103 A CN01823103 A CN 01823103A CN 1505480 A CN1505480 A CN 1505480A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
- A01N65/08—Magnoliopsida [dicotyledons]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
- D21H21/04—Slime-control agents
Abstract
Methods of inhibiting the growth of organisms in aqueous systems such as papermaking systems, cooling systems and process waters of various types, comprises adding to the aqueous system a hop acid. Compositions comprising hop acids and papermaking suspensions or slurries, and/or additives, such as paper making additives, are also provided.
Description
Technical field
It is biological as method of microorganism to the present invention relates to control, particularly adopts lupulic acid (hopacid) inhibition biological growth and/or kills biological control method.Only illustrate, the present invention as paper manufacturing systems and industrial water system, particularly relates to the system of circulation and/or recirculation water, as concrete application is arranged in the cooling water system at water system herein.
Background technology
For water system, as contain the circulation and/or the system of recirculation water, as paper manufacturing systems and industrial water system, the control of the biology in the cooling water system, particularly microorganism is one and is of long duration and insoluble problem.These microorganisms biofoulings, as microorganism or microbial product (as metabolite) deposition, that these depositions produce is membranaceous, bulk and other forms of deposition, can cause adverse consequencess such as hole embolism, flow reduction, heat exchanger effectiveness reduction, obstruction.
For example, generate problems such as biological clay, formation deposition and generation mold fungi and caused special concern.
For example, deposition in the papermaking equipment and the dirt majority in the cooling system are caused by mold fungi (as sphaerotilus natans bacterium (Sphaerotilus natans)).Multiple mold fungi is grown on the immersed surface, is the strand shape, is wrapped among the structure that is called " sheath ".Sheath is considered to a kind of protective structures, and this structure has improved the viability of organism.For example, the sheath structure is considered to protect organism to avoid the infringement of biocide, and this is because this protective structures has for example hindered entering of biocide.Be grown in by the lip-deep mold fungi of papermaking liquid stream submergence and can cause big deposition to form, the inert raw material (particulate, powder, fiber etc.) that contains cell and stumbled in these depositions by mycelia.Hyphomycetic " rectangular " and big deposition piece might drop out, and cause in paper such as hole, problem such as other are damaged and break, and therefore make the papermaking cost obviously improve.Mold fungi also can make cooling tower break down.For example, in cooling device, immersed surface is made dirty by the bacterium of mold fungi and other type, makes the cooling system heat exchange efficiency reduce, in addition, a large amount of living beings drop out and in industrial equipment circulation also can bring some other problem.
The multiple microorganism of in fact causing the problems referred to above is for their means of control, as the means that suppress its growth and/or kill them have resistivity, makes the control of these microorganisms difficulty more that becomes.For example, cause the microorganism of the industrial system that makes water such as industrial water system and paper manufacturing systems fault can resist the condition and the material of wide spectrum, therefore under the condition of wide region, can survive.So now begun to adopt biocide to control these microorganisms.Yet, conventional biocide valency is high and environmentally friendly degree is not high, show unwished-for broad spectrum of activity (promptly, there is no the ability of specific killing for specific objective microbe), must use with big concentration, and/or harmful and/or human body had harm and/or even poisonous to the people.In addition, in water system that needs controlling microbial or medium, also need to consider the compatibility of composition therefor and method.Therefore, still need to have the biocide that above-mentioned usefulness does not show above-mentioned shortcoming simultaneously again.
Based on above-mentioned various reasons, make improvements in this regard and have long-term demand property.
As everyone knows, in brewery industry, some lupulic acid can suppress to cause the microbial growth of beer spoilage.For example, the fact that lupulic acid-hexahydrolupulon can suppress certain lactobacillus (Lactobacillus) growth is disclosed in the 5th, 082, No. 975 United States Patent (USP)s.This patent and then think, owing to have lupulic acid in brewer's wort and the beer, so golden hop has the bacterial infection that helps control in the brewing room.Owing in beer, do not find β-lupulic acid, therefore,, then think because the reason of α-lupulic acid or different α-lupulic acid if there is this control action really.As everyone knows, β-lupulic acid height instability is oxidized to the golden hop letones of bitter taste in the brewer's wort of boiling, and its crystallization can be rotten voluntarily in a couple of days or a few hours.Have now found that and convert it into the shortcoming that hexahydrolupulon (six hydrogen β-acid) can overcome poor stability.Lupulones is as derelict waste material in the brewing process, and its output is superfluous greatly, makes it become a potential cheap raw material.The 4th, 918, No. 240 United States Patent (USP) is the 5th, 082, the relevant patent of No. 975 United States Patent (USP)s.Quote in full these patents herein as a reference.
The 5th, 455, lupulic acid is disclosed in No. 038 United States Patent (USP), tetrahydro-iso-humulone and hexahydrolupulon (being respectively α and β-lupulic acid), as the product of brewery industry, be proved to be to suppress the compound of food borne causal agent such as Listera (Listeria), staphylococcus (Staphylococcus), bacillus (Bacillus) and clostridium (Clostridium).In addition, the 5th, 286, No. 506 U.S. Patent Publications in solid food, mix the β-acid that from golden hop, extracts and can protect these food to avoid the food borne causal agent, comprise the erosion of Listeriamonocytogenes.The 5th, 455, No. 038 U.S. Patent Publication α and β-lupulic acid inhibitory action for Listera (Listeria).Quote in full these patents herein as a reference.
The derivative of β-hydrogenated lupulone can suppress and kill cancer cell (WO 97/31630 and WO98/11883) and have drug-fast bacterial strain such as Staphylococcus aureus (Staphylococcus aureus), Much's bacillus (Mycobacterium tuberculosis) and avian tuberculosis mycobacterium compound (Mycobacterium avian Complex) or enterococcus spp (enterococcus) (" antimicrobial acivity of semi-synthetic compound-hexahydrolupulon " for antibiotic; The people such as StenhanJournal of Antimicrobial Chemotheraphy(1998) 41,519-522).Quote in full these documents herein as a reference.In addition, α and β-lupulic acid have been confirmed as having for the methicillin medicine (Japan Patent JP 9067250) of drug-fast Staphylococcus aureus (Staphylococcus aureus).Quote in full this patent herein as a reference.
The 5th, 370, No. 863 U.S. Patent Publications contain the oral care composition of lupulic acid and salt thereof, can effectively suppress to cause the grampostive bacteria of dental plaque and periodontal disease, comprise sphaerotilus natans bacterium (Strepococcus mutans), be incorporated by reference in this text herein and examine.Its representational composition is a kind of toothpaste that contains tetrahydro-iso-humulone.
It is selective to grampostive bacteria that lupulic acid has been considered to, for example, and referring to above WO 98/11883 as a reference.
Summary of the invention
The invention provides a kind of in water system or medium, as paper manufacturing systems and industrial water system, the system that particularly relates to circulation and/or recirculation water, as the biological method as microorganism, particularly bacterium of control in the cooling water system, this method has adopted and has been easy to obtain from renewable resources and effective raw material.
The invention provides a kind of method of controlling described biology in described water system, the raw material that this method adopts is relatively cheap.
The invention provides a kind of method of controlling described biology in described water system, this method is effective to multiple microorganism, and the microorganism for the described water system of influence has specificity simultaneously.
The invention provides a kind of method of in water system, controlling biological growth, its grey water system is selected from the industrial water system that paper manufacturing systems, cooling system and industrial water do not contact with finished product, or its combined system, this method comprises in described water system adds lupulic acid.
Preferably, lupulic acid is selected from α or β-lupulic acid and composition thereof.
In preferred embodiments, this method comprises the interpolation lupulic acid, and wherein lupulic acid is selected from one or more compounds of following molecular formula representative:
Wherein, "----" represents optional two keys,
R
1Be selected from OH; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom, be preferably about 1 to 10 carbon atom, more preferably from about 1 to 5 carbon atom;
R
2Be selected from-OH;=O;-SH;=S; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom, be preferably about 1 to 10 carbon atom, more preferably from about 1 to 5 carbon atom;
R
3Be selected from-OH;=O;-SH;=S and-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10, and is preferred about 2 to 7, more preferably from about 2 to 5;
R
4Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom, be preferably about 1 to 10 carbon atom, more preferably from about 1 to 5 carbon atom; The ketone group that contains about 1 to 20 carbon atom is preferably and contains about 1 to 10 carbon atom, more preferably contains about 1 to 4 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10, and is preferred about 2 to 7, more preferably from about 2 to 5; And-OOR, wherein R is selected from C
nH
2n+1And H, and n is as mentioned above;
And/or
R wherein
5For general formula is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10, and is preferred about 2 to 7, more preferably from about 2 to 5;
R
6Be selected from-OH;-SH; With-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10, and is preferred about 2 to 7, more preferably from about 2 to 5; With
R
7Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom, be preferably about 1 to 10 carbon atom, more preferably from about 1 to 5 carbon atom;
R
8Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom, be preferably about 1 to 10 carbon atom, more preferably from about 1 to 5 carbon atom; The ketone group that contains about 1 to 20 carbon atom is preferably and contains about 1 to 10 carbon atom, more preferably contains about 1 to 4 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10, preferred about 2 to 7, more preferably about 2 to 5;
And/or
R wherein
9Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom, be preferably about 1 to 10 carbon atom, more preferably from about 1 to 5 carbon atom; With
R
10Be selected from the ketone group that contains about 1 to 20 carbon atom, be preferably and contain about 1 to 10 carbon atom, more preferably contain about 1 to 4 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10, and is preferred about 2 to 7, more preferably from about 2 to 5;
R wherein
11Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom, be preferably about 1 to 10 carbon atom, more preferably from about 1 to 5 carbon atom; With
R
12Be selected from the ketone group that contains about 1 to 20 carbon atom, be preferably and contain about 1 to 10 carbon atom, more preferably contain about 1 to 4 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10, and is preferred about 2 to 7, more preferably from about 2 to 5.
Preferably, R
4The substituting group that comprises the following formula representative:
R wherein
13Comprise C
3-C
8Alkyl.
Preferably, R
13Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3
Preferably, this method comprises the interpolation lupulic acid, and wherein lupulic acid is selected from hexahydrolupulon (hexahydrolupulone), six hydrogen class lupulones (hexahydrocolupulone), the poly-lupulones (hexahydroadlupulone) of six hydrogen and composition thereof.
Preferably, lupulic acid comprises six hydrogen class lupulones.
Preferably, R
8The substituting group that comprises the following formula representative:
R wherein
14Comprise C
3-C
8Alkyl.
Preferably, R
14Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2,-(CH
2)
2CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3And composition thereof.
Preferably, lupulic acid comprises tetrahydro-iso-humulone.
Biology can comprise the microorganism that is selected from gram-negative bacteria, grampostive bacteria and composition thereof.
Microorganism can be selected from sphaerotilus natans bacterium (Sphaerotilus natans), clostridium butyricum (Clostridium butyrium), pseudomonas aeruginosa (Pseudomononas aeruginosa), wilting bacillus pumilis (Curtobacterium flaccumfaciens), onion bulkholderia cepasea (Burkholderia cepacia), Pseudomonas glathei (Pseudomonas glathi), Morocco bacillus (Bacillus maroccanus), bacillus licheniformis (Bacillus licheniformis), Bacillus sphaericus (Bacillus sphaericus), bacillus subtilis (Bacillus subtilis) and composition thereof.
Microorganism can comprise gram-negative bacteria.
Microorganism can be selected from different zygosaccharomyces (Altermonas), Aquaspirillum (Aquaspirillum), campylobacter (Campylobacter), screw rod Pseudomonas (Helicobacter), acinetobacter (Acinetobacter), Agrobacterium (Agrobacterium), Alcaligenes (Alcaligenes), replace zygosaccharomyces (Alteromonas), Flavobacterium (Flavobacterium), pseudomonas (Pseudomnas), Xanthomonas (Xanthomonas), mycoplasmas (Mycoplasma), Methanococcus (Methanococcus) and composition thereof.
Microorganism can comprise grampostive bacteria.
Microorganism can be selected from bacillus (Bacillus), enterococcus spp (Enterococcus), Planococcus (Planococcus), staphylococcus (Staphylococcus), streptococcus (Streptococcus), fusobacterium (Clostridium), lactobacillus (Lactobacillus), Listera belongs to (Listeria), actinomyces (Actinomyces), Arthrobacter (Arthrobacter), Corynebacterium (Corynebacterium), Curtobacterium (Curtobacterium), Nocard's bacillus (Norcardia), actinoplanes (Actinoplanes), mycobacterium (Mycobacterium) and composition thereof.
Water system can comprise paper manufacturing systems.
Water system can comprise the industrial water system.
Water system can comprise cooling system.
Preferably, the lupulic acid consumption is between about 0.001 to 1000ppm.
Preferably, the lupulic acid consumption is between about 0.1 to 250ppm.
Preferably, the lupulic acid consumption is between about 0.1 to 100ppm.
Preferably, lupulic acid and antifreeze add together.
The present invention also comprises a kind of method that suppresses biological growth in paper manufacturing systems, and it comprises the above-mentioned lupulic acid of interpolation in paper manufacturing systems.
The present invention also provides a kind of composition, and said composition comprises aforesaid lupulic acid and a kind of composition that is selected from following group: from papermaking suspension, defoamer, alum, adhesive, papermaking paint, graining paste, starch, pitch control agent (pitch control agent), antisludging agent, sizing agent and composition thereof.
Preferably, the papermaking suspension is selected from refining or unpurified slurry, refining or unpurified paper pulp, paper making pulp and composition thereof.
The present invention also provides a kind of cellulosics, is selected from paper and cardboard.
Paper can be selected from stationery, paper handkerchief and toilet paper.
Description of drawings
With a large amount of accompanying drawings among the non-demarcation embodiment in the illustrative embodiments of the invention as a reference, present invention will be further described in following detailed Description Of The Invention, and wherein similarly label has similar implication in each accompanying drawing, wherein:
Fig. 1 demonstrates the inhibitory action that lupulic acid is grown for sphaerotilus natans bacterium (S.natans) in following examples; With
Fig. 2 has shown with the result of lupulic acid for the bacterium that forms spore.
Embodiment
The present invention is based on lupulic acid can control biology, and as suppressing and/or kill biological this discovery, wherein biology comprises grampostive bacteria and gram-negative bacteria.The term of Cai Yonging " control biological " and " suppressing biological " mean and comprise the inhibition biological growth or kill biology herein, or both have both at the same time, and will be understood that these terms can exchange in this article.
The present invention is specially adapted at water system, and as paper manufacturing systems and industrial water, as cooling water, or control is biological in other water systems.The purpose of employing " water system " and " aqueous medium " is to comprise any part in the relevant water system herein, and is included in internal system or outside any point adding lupulic acid, wherein particularly becomes the situation of the part of water system at lupulic acid.Therefore, the invention is intended to clearly, intention is to be covered by upstream and/or downstream and/or directly and/or add the situation of lupulic acid indirectly in relevant water system.Adopt term " water system " and " aqueous medium " purpose to be to contain any situation and environment that has water simultaneously, for example include but not limited to slurry and solution.
Method of the present invention is applicable to handle anyly needs to suppress biological as microbial growth and/or kill their water system or medium.As described in other places of this paper, in certain embodiments, method of the present invention relate to water system that finished product directly contacts in, as adding lupulic acid in the water system relevant with papermaking.In other embodiments, method of the present invention relates in the water system that does not directly contact finished product and adds lupulic acid.The example water system exemplary, non-demarcation that does not directly contact finished product comprises the industrial water of recycle, and as cooling water, it is equal to finished product by a barrier such as heat exchanger and separates mutually.
Therefore, except that paper manufacturing systems, " water system " refers to industrial water system, and attempts to contain a kind of like this water system, and water in its system such as industrial water do not contact finished product.As the example of non-demarcation, comprising cooling water system, as internal-combustion engine cooling system, power plant cooling system; Heat exchanger is as the cooler etc. that dispels the heat; Be used in the water system in the humidifier; Be used in the water system in heating, the heating ventilation and air-conditioning system; The water of swimming pool; The shower water; Metal-working fluids; Petroleum Production liquid comprises drilling mud; Coating; Bactericide and disinfectant; The combination of plastic working system and these systems, and any other water system.The present invention controls for the biology in these systems by add lupulic acid in paper manufacturing systems or other water systems.
Any lupulic acid all can be used for method of the present invention.Have been found that α one and/or β one lupulic acid are particularly suitables, as following formula (I), (II), (III) with the compound (IV).
When mentioning compound or composition, unless otherwise indicated, refer to compound or composition itself or compound or mixture of ingredients separately, unless otherwise indicated herein.Therefore, for example when mentioning lupulic acid, described lupulic acid comprises the mixture of single lupulic acid and multiple lupulic acid and the mixture that constitutes with various other materials.
When quantity, concentration or other numerical value or parameter provide with preferred ceiling value and preferably low limit value, the content of defined should be considered as hanging down the four corner that limit value is constituted with preferred, and needn't consider that whether these scopes are by separate provision by a pair of preferred ceiling value.
What should particularly point out is the mixture of compound shown in compound shown in the molecular formula (I) and other molecular formula (I), the mixture of compound shown in compound shown in the molecular formula (II) and other molecular formula (II), the mixture of compound shown in compound shown in the molecular formula (III) and other molecular formula (III), the mixture of compound shown in compound shown in the molecular formula (IV) and other molecular formula (IV), and molecular formula (I), (II), (III) and the mixture of compound (IV), and molecular formula (I), (II), (III) and the mixture of one or more formations of compound (IV) all can use.Molecular formula (I) and (III) shown in compound be mainly β-lupulic acid (but also can comprise some α-lupulic acid), and compound shown in the molecular formula (II) is mainly α-lupulic acid (but also can comprise some β-lupulic acid).
The non-demarcation example of α-lupulic acid comprises: humulone, isohumulone, class humulone (cohumulone), poly-humulone (adhumulone), tetrahydro-iso-humulone, tetrahydrochysene deoxidation humulone.
The non-demarcation example of β-lupulic acid comprises: lupulones, class lupulones, six hydrogen class lupulones, the poly-lupulones of six hydrogen.
Compound shown in the particularly preferred molecular formula (I) is R wherein
4In comprise the compound of following group:
R wherein
13Be selected from C
3-C
8Alkyl, as-CH
2CH (CH
3)
2,-CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3Exemplary compound comprises the compound that is disclosed among the WO 98/11883, because it discloses these compounds, so this full patent texts is quoted as a reference, these compounds comprise hexahydrolupulon (R=-CH
2CH (CH
3)
2), six hydrogen class lupulones or " HHC " (R=-CH (CH
3)
2) and the poly-lupulones (R=-CH (CH of six hydrogen
3)
2CH
2CH
3).Six hydrogen class lupulones or " HHC " are the compounds shown in the particularly preferred molecular formula (I).
Compound shown in the particularly preferred molecular formula (II) is R wherein
8The compound that comprises following group:
R wherein
14Be selected from (C
3-C
8) alkyl, as-CH
2CH (CH
3)
2,-CH (CH
3)
2,-(CH
2)
2CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3
Compound shown in the particularly preferred molecular formula (II) is R wherein
8Contain group-(CH
2)
2CH (CH
3)
2Compound, as tetrahydro-iso-humulone.In these compounds, tetrahydro-iso-humulone is particularly preferred.
Compound shown in the particularly preferred molecular formula (III) comprises the class humulone.
Compound shown in the particularly preferred molecular formula (IV) comprises United States Patent (USP) 4,918, and disclosed tetrahydrochysene deoxidation humulone in 240 is incorporated by reference in this text herein and examines.
For above-mentioned molecular formula (I) and the further elaboration of the structure of a plurality of compounds (II) and name can be referring to " by high performance liquid chromatography and NMR (Nuclear Magnetic Resonance) spectrum coupling research golden hop and beer acerbity acid ", people such as Pusecker,
Journnal of Chromatography a, 836 (1999), 245-252 is incorporated by reference in this text herein and examines.
Generally speaking, be preferably the compound shown in the water miscible above-mentioned molecular formula (I) to (IV).In general, few more with carbon atom in " R " group of above-mentioned indicating " n ", then compound dissolution is good more.In preferred embodiments, n is about integer of 1 to 10, more preferably about 2 to 7, more preferably about 2 to 5.
Those skilled in the art can adopt any suitable method to separate and the preparation lupulic acid, for example adopt the disclosed method of above-mentioned list of references, because these documents disclose the preparation method of lupulic acid, quote these documents once more as a reference herein.In the list of references of being quoted, WO98/11883, United States Patent (USP) 4,918,240 and United States Patent (USP) 5,082,975 have directive significance.Be applicable to that lupulic acid of the present invention can be according to TODD, disclosed method is prepared in the United States Patent (USP) 4,844,939 of Jr., owing to disclose the preparation method of lupulic acid, the document of being quoted in this article and this article is incorporated by reference in this text to be examined.For example, this patent disclosure can be prepared according to a plurality of United States Patent (USP)s with the commercially available refining and pre-isomerized golden hop extract of solution form, as United States Patent (USP) 3,448,326,3,798,322,3,965,188 people such as () Westerman; 3,949,092 and 3,973,052 (Mitchell); With 3,486,906 and 4,002,683 (Todd) quotes in full these documents herein as a reference.For overcoming the shortcoming of using artificial organic solvent, begun to adopt liquid and supercritical carbon dioxide to extract lupulic acid.This technology by Kurger describe (MonatsschriftfruBrauerei, 33, Nr.3), be incorporated by reference in this text herein and examine.And, isomerization for the carbon dioxide extract of golden hop can be adopted organic solvent and/or absorption/extraction process (United States Patent (USP) 4 of Lance with the method for separating, 395,431, be incorporated by reference in this text herein and examine, or the Deutsche Bundespatent of Mueller discloses 2920765, be incorporated by reference in this text herein and examine), perhaps " salt out " impurity (United States Patent (USP) 4,298,626 of Laws, be incorporated by reference in this text herein and examine), perhaps in dilute solution, remove the impurity (United States Patent (USP) 4,247,939 of Baker with a large amount of absorbent filterings, be incorporated by reference in this text herein and examine), above-mentioned all methods in the United States Patent (USP) 4,844,939 of the above TODD that quotes, have been quoted.
Lupulic acid can preferably be used with aqueous solution form, as WO the 98/11883, the 4th, 918, No. 240 United States Patent (USP)s and the 5th, disclose the preparation method of the lupulic acid aqueous solution in 082, No. 975 United States Patent (USP), can adopt these methods to prepare the lupulic acid aqueous solution, for this purpose, the present invention quotes these patents as a reference once more.
The commodity of the lupulic acid aqueous solution commodity that are suitable for " HYDROHOPS " by name, from Watertown Hops Company, 1224 American Way, Watertown, Wisconsin, 53094.
Have now found that, needn't further process, can directly add in the water system that needs to handle and directly use for the aqueous solution of commodity by name " HYDROHOPS ".
Can adopt moisture or water-free propane diols, glycerine, similarly stable pure and mild polyalcohol, or the water in its mixture replacing lupulic acid aqueous solution.
The solvability of lupulic acid of the present invention is subjected to Temperature Influence.For example, lupulic acid is being lower than meeting crystallization under the condition of room temperature.Therefore, have been found that it is very favorable using one or more antifreezing agents.Preferably, the consumption of antifreezing agent should effectively reduce the crystalline temperature of composition, to avoid the appearance of lupulic acid cloud and mist or crystallization.Can adopt any antifreezing agent, those of ordinary skills just can easily select.The example of antifreezing agent comprises:
Glycerine (glycerine), poly glycerine are as two polyglycerols, three polyglycerols, four polyglycerols, five polyglycerols, six polyglycerols and higher glycerine oligomer;
Glycol is as ethylene glycol, diethylene glycol, propane diols, dipropylene glycol, tripropylene glycol and higher glycol oligomer;
The trihydroxylic alcohol of poly two alcoholization is as the expoxy propane thing of glycerine, oxirane of glycerine and composition thereof;
Single hydroxyl alcohol, its scope for example can be from methyl alcohol to C
50Alcohol is preferably C
6-C
36Can comprise, as methyl alcohol, ethanol, isopropyl alcohol, butanols, isobutanol, amylalcohol, isoamyl alcohol, hexanol, isohexyl alcohol, enanthol, n-octanol, 2-Ethylhexyl Alcohol, isooctanol, n-nonyl alcohol, isononyl alcohol, n-decyl alcohol, isodecanol, n-laruyl alcohol, tridecanol, n-tetradecanol, n-hexadecanol, isohexadecane alcohol, n-octadecanol, isooctadecane alcohol, eicosanol, archidyl alcohol, octanol, oleyl alcohol, carbon atoms up to C
50, preferred C
36Up to alcohol and the ethoxylate and/or the propoxylate of above-mentioned alcohol, phenoxetol, and the ethyoxyl of above-mentioned alcohol, phenoxetol ethyoxyl and/or propenoxylated nonyl phenol and/or propoxylate (those of ordinary skills just can select other numerous alcohol easily, comprise single hydroxyl alcohol); With
Other antifreezing agents, as single hydroxyl alcohol diester (being used for cosmetics and personal care sectors), pure as jade by pure (2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether), alkyl diol ether (dimerization propylene glycol monomethyl ether), salt (organic and inorganic), polyethylene glycol, alkyl carbitol, peptide class (" antifreezer peptides "), glycopeptide (" antifreeze glycopeptide "), alkylamine etc.
According to the present invention, the consumption of lupulic acid can be the biological consumption of any effective control, and the biological mode of control is to suppress biological growth and/or kill them.Generally speaking, for the water system that the present invention quoted, in the amount of active component (lupulic acid), the content of lupulic acid is about 0.001 to 1 in relevant water system, and 000ppm is preferably about 0.1 to 250ppm, more preferably 0.1 to 100ppm.
Be surprisingly found out that the present invention is applicable to that control comprises the multiple biology of microorganism such as Gram-negative and gram-positive bacteria.Particularly surprisingly lupulic acid can be controlled the Gram-negative microorganism.Other microorganisms also can be suppressed by the present invention, comprise dinoflagellate, microalgae, microfungus, bacterium, protozoa or its mixture.The present invention is particularly effective to control nutrition type microorganism.
The example of the gram-negative bacteria that can be suppressed by the inventive method comprises different zygosaccharomyces, Aquaspirillum, campylobacter, Helicobacterium, acinetobacter, Agrobacterium, Alcaligenes, replace zygosaccharomyces, Flavobacterium, pseudomonas, Xanthomonas, mycoplasma, Methanococcus (Methanococcus) and composition thereof.
The example of the grampostive bacteria that can be suppressed by the inventive method comprises bacillus, enterococcus spp, Planococcus, staphylococcus, streptococcus, fusobacterium, lactobacillus, Listera belongs to, actinomyces, Arthrobacter, Corynebacterium, Curtobacterium, Nocardia, actinoplanes, mycobacterium and composition thereof.
The present invention comprises that for the biology of enterobacteriaceae Escherichia, Enterobacter, Klebsiella and composition thereof are effectively same, for the biology of vibrionaceae, comprises that Aeromonas, vibrio and composition thereof are also effective.
The present invention comprises that for other bacteriums Desulfovibrio, Thiobacterium and composition thereof are also effective.
Quenchable other microorganism of the present invention comprises above-mentioned kind, as seen
Bergev ' s Manual of Determinative Bacteriology.Holt wait people .Williams ﹠amp; Wilkins. the 9th edition (1994) are incorporated by reference in this text herein and examine.Chapters and sections: organized for 2 (comprising the 39th page), organized for 3 (comprising the 71st page), organized for 5 (comprising the 175th page), organized for 12 (comprising the 427th page), organized for 14 (comprising the 477th page), organized for 17 (comprising the 527th page), organized for 182 (comprising the 559th page), because explain in more detail, be incorporated by reference in this text herein and examine for these microorganisms.
Have been found that the inventive method is effective especially for following microorganism, these microorganisms comprise sphaerotilus natans bacterium, clostridium butyricum, pseudomonas aeruginosa, wilting bacillus pumilis, onion bulkholderia cepasea, Pseudomonas glathei, Morocco bacillus, bacillus licheniformis, Bacillus sphaericus, bacillus subtilis and composition thereof.
For example according to the assay method of following examples, those of ordinary skill in the art can determine whether to occur suppressing the phenomenon of growth of microorganism or killing microorganisms, with and effect size.
According to method of the present invention, lupulic acid can add in the pending water system by any way.In most cases, can directly commodity lupulic acid solution such as HYDROHOPS be added in the pending water system, can realize method of the present invention easily like this.Also lupulic acid can be formed mixture or solution in being diluted to or being added into other media, and then this mixture or solution are added in the pending water system.Therefore, lupulic acid can be used as a component to be added in the additive of papermaking or other water systems, and the prescription of these additives also is what what's frequently heard can be repeated in detail for those skilled in the art.
The processing method of paper manufacturing systems
The present invention can be used for any paper manufacturing systems, can be used for any point of system, can be used for need using the place of additive by any way, the additive that can be used for paper industry by any way and adopted.Can be directly and/or use solution indirectly, as the lupulic acid aqueous solution, perhaps lupulic acid and any additive for paper making, the mixture that additive for paper making constituted mentioned as this paper.
As the example of non-demarcation, suitable addition manner comprises:
Homogenate and not homogenate stoste in the storage tank,
The paper pulp homogenate of carrying out in the refiner,
Spare the paper pulp of slurry, placed reserve pit stand-by,
From the raw material for paper grade (stock) of reserve pit taking-up,
Flow box, herein paper making raw material with controlled data rate stream to fourdrinier wire.
Perhaps any suitable position of any point between the upstream of the combination of above-mentioned position, any above-mentioned position or these positions or other or these positions the time or in the combination of different time.
Preferably, lupulic acid of the present invention is taked above-mentioned consumption.
In the time of in being added into paper making compositions such as additive for paper making or paper making pulp or mucilage etc., lupulic acid can become a component of products obtained therefrom.Therefore, the present invention also provides the cellulosics that contains lupulic acid, as paper and paper products.Comprising in the cellulosics of paper and paper products exists lupulic acid to have some benefits, as can effectively controlling the biology in the water system of producing these products, simultaneously can not bring safety, toxicity or relevant problem, and/or the problem of bad physiological reaction.This has the meaning of particular importance for some cellulosics as stationery, paper handkerchief and toilet paper.
The processing method of other industrial waters
The present invention can be used for any industrial water system, can be used for any point of system, can be used for needing to use the place of additive by any way, the additive that can be used for this technology by any way and adopted.As the example of non-demarcation, suitable addition manner comprises the initial liquid in being added into system, or as a composition of initial liquid, adds at the conventional charge door place of system.
Can adopt any combination of said method.
Composition
Can infer, the present invention also comprises the content of Composition Aspects.
Therefore, as non-limiting example, the present invention also provides a kind of composition, it comprises lupulic acid and aqueous medium, this aqueous medium is selected from paper manufacturing systems and other water system, as emulsion, adhesive, industrial water, comprise cooling water system, as internal-combustion engine cooling system, power plant cooling system; Heat exchanger is as the cooler etc. that dispels the heat; Be used in the water system in the humidifier; Be used in the water system in heating, the heating ventilation and air-conditioning system; The water of swimming pool; The shower water; Metal-working fluids; Petroleum Production liquid comprises drilling mud; Coating; Bactericide and disinfectant; Plastics; The mixture of above-mentioned material, and other water system.
Other exemplary application of these compositions exists
Disinfection.Sterilization and Preservation, the 4th edition, Block Lea ﹠amp; Febiger has description in (1991), because it discloses these application, is incorporated by reference in this text herein and examines.Specially the whole of table 56-2 of the document are quoted as a reference herein.
The present invention also provides a kind of composition, and said composition is stored in order to adding in the water system subsequently, as additive for paper making and water treatment additive.Therefore, the present invention also comprises the composition that contains lupulic acid and additive for paper making, and wherein additive for paper making is selected from defoamer, alum, adhesive, papermaking paint, graining paste, starch, pitch control agent, antisludging agent, sizing agent and (comprises alkyl ketene dimer sizing agent (AKD ' s)) and composition thereof.Paper making compositions of the present invention comprises following non-limiting example:
The homogenate in the storage tank or the stoste of homogenate not,
Paper pulp, as the paper pulp in refiner,
Spare the paper pulp of slurry, placed reserve pit stand-by,
From the raw material for paper grade (stock) of reserve pit taking-up,
Flow box, herein paper making raw material with controlled data rate stream to fourdrinier wire.
Perhaps any suitable position of any point between the upstream of the combination of above-mentioned position, any above-mentioned position or these positions or other or these positions the time or in the combination of different time.
For example, about the details of conventional ingredient, prescription and points for attention etc. and optimization method can referring to
Pulp and Paner, Chemistry and Chemical Technology, Casey, James P. (editor), J.Wiley, the 3rd edition (1980) are incorporated by reference in this text for this reason and examine.
Needn't remake further research, utilize above description, believe that those skilled in the art can make full use of the present invention.
Therefore, below preferred specific embodiments only with explaining usefulness, and the remainder that does not limit the present invention in any way.In following examples, all temperature are Celsius temperature, and thermometer is proofreaied and correct; Except as otherwise noted, all umbers and percentage all in weight are.
Embodiment
Embodiment 1: control S.natans
Present embodiment has been described the growth of the derivative controlled mold fungi S.natans of a natural products in the golden hop.Below listed the experimental result that in the S.natans medium, adds selected concentration lupulic acid.In these researchs, lupulic acid (HYDROHOPS with different S.natans bacterial strains (ATCC 15291 and ATCC29329) and selected concentration, come to Watertown Hops, in tetrahydro-iso-humulone be, be diluted to 10,25 and 50ppm) be inoculated in the flask that contains diluted medium (, below will describe in detail) medium incubation 48 and after 96 hours as the CYG broth bouillon, the jolting flask takes out the 1ml sample and does the ATP test.According to untreated in the same old way and the various computing percent inhibition between the medium after handling.It is as follows to test concrete rules:
S.natans (ATCC 15291,29329 and 13925) cultivates in the CYG broth bouillon, wherein consisting of of medium: 0.5g/l junket peptone, 1.0g/l glycerine, 0.1g/l yeast extract.S.natans bacterial strain shaking in the bottle on placing orbital shaker cultivated under the room temperature, and culture volume is 50ml.Taking out equal amounts of S .natans from cultivate 48 to 72 hours cultured solution of broth inoculates to begin experiment the test flask.The active component of selected concentration is added in the flask that contains S.natans.Contrast in all experiments does not all deal with.Quantitatively examine or check the action effect of lupulic acid by measuring ATP to S.natans.(Bridgend, reagent U.K.) and luminometer carry out ATP and analyze to adopt Biotrace Ltd..Carrying out ATP by the following method extracts and tests:
1, uses 10ml suction pipe hybrid test culture fluid with broken flocculate repeatedly, make uniform suspension with this.
2, in vitro 100 μ l culture fluids and 100 μ l extracts are mixed.Test tube left standstill under room temperature 1 minute after shaking.
3, in mixture, add 100 μ l luciferases, shake and be placed in the luminometer.(light unit-rlu), this reading is corresponding to the amount of the ATP that is extracted relatively to note reading.All data all obtain by repeating to extract.
Data analysis:
The rlu reading of each test flask is made the percent inhibition that contrast obtains growing with the contrast reading.
Fig. 1 shows the I of these two kinds of bacterial strains
50Value (concentration that suppresses the required active component of 50% microorganism) is about 10ppm.
Embodiment 2: suppress clostridium butyricum (Clotridium butyricum)
Dull and stereotyped diffusion test research by adopting clostridium butyricum is for the inhibitory action of anaerobic bacteria.The α of employing purifying-and β-lupulic acid (HYDROHOPS).Experiment finds that clostridium butyricum is very responsive for the inhibitory action of α-lupulic acid, but not too responsive for β-lupulic acid.Garbled data shown in the Table I shows that concentration arrives in the 1mg/ plate scope 0.1, and two kinds of compounds of this of equivalent do not have synergy.Adopt the data of the aerobic grampostive bacteria shown in the Table II to prove conclusively to these data.Further dull and stereotyped diffusion test shows that bactericidal activity is 5 to the 50mg/ plate, and bacteriostatic activity is 1mg/ plate (having provided between the inhibition zone in the following Table I).
Biological: clostridium butyricum (ATCC 3627)
Medium: Oxoid, and reinforcement fusobacterium medium (UNIPATH, Ltd.)
Experimental procedure
The experiment beginning will be transferred to fresh RCM agar (Oxoid from the clostridium butyricum (bacterial strain #ATCC 3627) that the American Type Collection obtains in preceding 16 hours, strengthen the fusobacterium medium, from UNIPATH) upward (operation instructions according to UNIPATH prepare medium, and the concentration of DIFCO agar is 12.5g/L's.Water and build up plate and storage under the oxygen free condition that contains carbonic acid gas, hydrogen and nitrogen (concentration is respectively 5,10 and 85%)).Before loading lupulic acid, BBL (blank cardboard (diameter 1/4 ", STN 31039, from Becton DickinsonMicrobiological Systems)) is sterilized.On the plate of each sterilization, load the lupulic acid of predetermined concentration, and before changing the anaerobic chamber over to, dry.Adopt the new RCM agar plate of the clostridium butyricum of active growth inoculation on the RCM plate before, guarantee that with this microorganism is in exponential phase.Under aseptic condition all plates are transferred on the plate, plate was in 35 ℃ of following incubations 48 hours.Aseptic interval is referred to as " between the inhibition zone ", available ruler measurement, record incubation 24 and the value between the inhibition zone after 48 hours.After 48 hours, plate is taken out from the anaerobic chamber and take pictures.The data of clostridium butyricum are expressed as the diameter between the inhibition zone; Diameter between aseptic area is big more, and then product activity is high more or concentration is high more.
Experimental result is listed in the table below in 1.
Should be pointed out that between the inhibition zone and suppress to illustrate that also microorganism has been killed, because these intervals have kept germ-free condition the growth of microorganism except illustrating.It is certain water-soluble that experimental result illustrates that also these active components have at least, and this is necessarily to have dissolved at least a portion (otherwise lupulic acid is can not move on the agar) because be the interval that is inhibited, lupulic acid.
Table I
| α-lupulic acid | β-lupulic acid | α/β-lupulic acid | ||||||
| Concentration (mg/ plate) | Between the inhibition zone (mm) | Concentration (mg/ plate) | Between the inhibition zone (mm) | Concentration (mg/ plate) | Between the inhibition zone (mm) | |||
| ????24hr | ????48hr | ????24hr | ????48hr | ??24hr | ??48hr | |||
| ??1000 | ????23 | ????23 | ????1000 | ????15 | ????15 | ????1000 | ??21 | ??21 |
| ??500 | ????23 | ????23 | ????500 | ????15 | ????15 | ????500 | ??20 | ??20 |
| ??250 | ????23 | ????23 | ????250 | ????12 | ????12 | ????250 | ??21 | ??32 |
| ??100 | ????23 | ????23 | ????100 | ????11 | ????10 | ????100 | ??16 | ??16 |
| ??50 | ????20 | ????24 | ????50 | Do not have | Do not have | |||
| ??25 | ????20 | ????21 | ????25 | Do not have | Do not have | |||
| ??10 | ????18 | ????19.5 | ????10 | Do not have | Do not have | |||
| ??5 | ????15 | ????14.3 | ????5 | Do not have | Do not have | |||
| ??4 | ????15 | ????13 | ????4 | Do not have | Do not have | |||
| ??3 | ????13 | ????11.5 | ????3 | Do not have | Do not have | |||
| ??2 | ????12 | ????12 | ????2 | Do not have | Do not have | |||
| ??1 | ????10 | ????10 | ????1 | Do not have | Do not have | |||
Embodiment 3: the droplet test
Use synthetic plain boiled water solution estimate α-and the droplet test of β-lupulic acid for grampostive bacteria and gram-negative bacteria in, find some gram-negative bacteria to the lupulic acid sensitivity, but desired concn is wanted high a lot (as pseudomonas aeruginosa).The result of screening experiment shows these compounds, promptly α-and β-lupulic acid in wide concentration range, have the obvious suppression effect for multiple microorganism.This stress efficacy shows that these compounds not only can be used among paper pulp and the paper, and might be widely used in the water treatment (such as cooling tower etc.).
Experimental result is listed in the table below among the II.
Table II
| Bacterial isolates | ????pH | Lupulic acid | Time (hrs) | ????I 50(ppm) |
| Friedlander (Klebsiella pneumonia) (ATCC 13883) | ????5.5 | ????α | ???????4??????????????????????????18.07 ???????24?????????????????????????＞40 ???????4??????????????????????????＞40 ???????24?????????????????????????＞40 | |
| ????8.0 | ||||
| ????5.5 | ????β | ???????4??????????????????????????35.79 ???????24?????????????????????????＞40 ???????4??????????????????????????＞40 ???????24?????????????????????????＞40 | ||
| ????8.0 | ||||
| Pseudomonas aeruginosa (Pseudomonas aeruginusa) (ATCC 1542) | ????5.5 | ????α | ???????4??????????????????????????0.357 ???????24?????????????????????????＞2.5 ???????4??????????????????????????＞2.5 ???????24?????????????????????????＞2.5 ???????4??????????????????????????＞2.5 ???????24?????????????????????????＞2.5 | |
| ????7.2 | ||||
| ????8.0 | ||||
| ????5.5 | ????β | ???????4??????????????????????????0.036 ???????24?????????????????????????＞2.5 ???????4??????????????????????????＞2.5 ???????24?????????????????????????＞2.5 ???????4??????????????????????????＞2.5 ???????24?????????????????????????＞2.5 | ||
| ????7.2 | ||||
| ????8.0 | ||||
| Wilting bacillus pumilis (Curtobacterium flaccumfaciens) (BPC 124A) | ????5.5 | ????α | ???????4??????????????????????????0.447 ???????24?????????????????????????0.837 ???????4??????????????????????????＞2.5 ???????24?????????????????????????＞2.5 ???????4??????????????????????????18.72 ???????24?????????????????????????＞2.5 | |
| ????7.2 | ||||
| ????8.0 | ||||
| ????5.5 | ????β | ???????4??????????????????????????0.084 ???????24?????????????????????????0.935 ???????4??????????????????????????0.293 ???????24?????????????????????????1.49 ???????4??????????????????????????0.748 ???????24?????????????????????????1.72 | ||
| ????7.2 | ||||
| ????8.0 | ||||
| Onion bulkholderia cepasea (Burkholderia cepacia) (BPC 124A) | ????5.5 | ????α | ???????4??????????????????????????25.63 ???????24?????????????????????????＞40 ???????4??????????????????????????＞40 ???????24?????????????????????????＞40 | |
| ????8.0 | ||||
| ????5.5 | ????β | ???????4??????????????????????????3.67 ???????24?????????????????????????9.26 ???????4??????????????????????????6.23 ???????24?????????????????????????6.85 | ||
| ????8.0 | ||||
| Pseudomonas glathei (Pseudomonas glathi) (BPC 124A) | ????5.5 | ????α | ???????4??????????????????????????39.86 ???????24?????????????????????????＞40 ???????4??????????????????????????＞40 ???????24?????????????????????????＞40 | |
| ????8.0 | ||||
| ????5.5 | ????β | ???????4??????????????????????????＞40 ???????24?????????????????????????＞40 ???????4??????????????????????????＞40 ???????24?????????????????????????4.41 | ||
| ????8.0 | ||||
Table II, continuous
| Bacterial isolates | ????pH | Lupulic acid | Time (hrs) | ????I 50(ppm) |
| Bacillus cercus (Bacillus cereus) (ATCC 14579) | ????5.5 | ????α | ???????4??????????????????????????0.214 ???????24?????????????????????????0.899 ???????4??????????????????????????＞2.5 ???????24?????????????????????????＞2.5 | |
| ????8.0 | ||||
| ????5.5 | ????β | ???????4??????????????????????????0.033 ???????24?????????????????????????0.230 ???????4??????????????????????????0.404 ???????24?????????????????????????0.758 | ||
| ????8.0 | ||||
| Morocco bacillus (Bacillus maroccanus) (BPC 223A) | ????5.5 | ????α | ???????4??????????????????????????0.535 ???????24?????????????????????????1.66 ???????4??????????????????????????＞2.5 ???????24?????????????????????????＞2.5 ???????4??????????????????????????17.32 ???????24?????????????????????????33.11 | |
| ????7.2 | ||||
| ????8.0 | ||||
| ????5.5 | ????β | ???????4??????????????????????????0.091 ???????24?????????????????????????1.46 ???????4??????????????????????????0.579 ???????24?????????????????????????＞2.50 ???????4??????????????????????????0.922 ???????24?????????????????????????1.60 | ||
| ????7.2 | ||||
| ????8.0 | ||||
| Bacillus licheniformis (Bacillus licheniformis) (ATCC 12759) | ????5.5 | ????α | ???????4??????????????????????????0.281 ???????24?????????????????????????0.513 ???????4??????????????????????????＞2.5 ???????24?????????????????????????＞2.5 | |
| ????8.0 | ||||
| ????5.5 | ????β | ???????4??????????????????????????0.026 ???????24?????????????????????????0.324 ???????4??????????????????????????0.257 ???????24?????????????????????????0.734 | ||
| ????8.0 | ||||
| Bacillus sphaericus (Bacillus sphaericus) (ATCC 4525) | ????5.5 | ????α | 4 do not grow 24 does not grow 4＞2.5 24＞2.5 | |
| ????8.0 | ||||
| ????5.5 | ????β | 4 do not grow 24 does not grow 4 0.099 24 0.194 | ||
| ????8.0 | ||||
| Bacillus subtilis (Bacillus subtilis) (ATCC 23059) | ????5.5 | ????α | ???????4??????????????????????????0.479 ???????24?????????????????????????0.795 ???????4??????????????????????????＞2.5 ???????24?????????????????????????＞2.5 | |
| ????8.0 | ||||
| ????5.5 | ????β | ???????4??????????????????????????0.026 ???????24?????????????????????????0.09 ???????4??????????????????????????0.175 ???????24?????????????????????????0.116 | ||
| ????8.0 | ||||
Embodiment 4: lupulic acid is to the influence of spore
Experiment:
The Bacillus cercus spore preparation is adopted in experiment.In nutrient medium with the Bacillus cercus culture in 37 ℃ of following overnight incubation with the preparation spore.Centrifugal results culture also is suspended in the sterile purified water again.Place 80 ℃ to amount to 15 minutes then.After the thermal treatment, spore preparation in 4 ℃ of storages, is stored 48 hours at least before the use.
Test the action effect of L-alanine and lupulic acid as follows.The Bacillus cercus spore suspension is added in the aqua sterilisa to obtain concentration is about 10
4To 10
5The spore liquid storage of individual spore/ml.The equal portions that then the spore liquid storage are divided into 1.0ml are in order to test.The concentration of used L-alanine is 1 or 2.5mM.After adding the L-alanine, spore was placed one hour down in 37 ℃.After the L-alanine was handled, (HYDROHOPS from Watertown Hops, Wisconsion) added in the spore with lupulic acid.Expose after 20 minutes, spore is placed on the nutrient agar plate through a series of dilutions.Plate is incubated overnight under 37 ℃, after this counts the bacterium colony number.
With the spore preparation that does not contact the L-alanine is contrast, estimates the action effect of L-alanine.For conclusive evidence L-alanine can effectively be induced spore germination, the spore sample is handled with the L-alanine and is placed 80 ℃ to amount to 15 minutes down.
Experimental result:
Shown in Fig. 2 and Table III, control sample A and B show that the L-alanine can induce spore-germination, but the situation that lupulic acid is killed the cell of sprouting do not occur.This may be because compare with other compounds of testing with the L-alanine (as two mercaptan, sulfone/quat mixture, glutaraldehyde etc.) with heating, and lupulic acid is a kind of more " gentleness " or act on the slower reagent of killing.Shown in the following Table III of the critical data of Fig. 2:
| Table III |
| Sample number L-alanine biocidal processing method CFU SD (mM) |
| -80 ℃ of A 1 heating; 15min.-80 ℃ of 72 6 B, 2.5 heating; 15min.-80 ℃ of 85 1.4 C, 0 lupulic acids (50ppm), 220 9.5 D, 0 lupulic acids (25ppm), 180 8.2 E, 1.0 lupulic acids (50ppm), 200 11.9 F, 2.5 lupulic acids (50ppm), 180 16.5 G, 1.0 lupulic acids (25ppm), 176 34.5 H, 2.5 lupulic acids (25ppm), 205 14.3 I, 0 heating, 15min. 162 13.4 |
Embodiment 5: the antifungal effect evaluation experimental that uses lupulic acid
Estimate the control effect of lupulic acid by the dull and stereotyped diffusion test that uses lupulic acid for two kinds of fungi-aspergillus nigers (Aspergillus nigre) and Chaetomium globosum growth.The agar medium plate that is used for this experiment is potato glucose (PDA).Contain in interpolation before the flat board of lupulic acid, earlier fungal spore is placed on the PDA with the lawn form.This concentration of testing used flat board is 100,200,500 and 1000ppm.
Cultivate 35 ℃ of incubations of plank, and observe every day.Experiment was ended after 8 days, and experimental result shows after adding spore all observes conk (being the unrestraint interval) on each plate.Illustrate that lupulic acid does not have control action to these two kinds of fungi growth.
Conclusion
The foregoing description explanation lupulic acid is invalid for the bacterium possibility that some forms spore, but effective for the nutrition type bacterium.
According to above description, those skilled in the art can easily determine spiritual essence of the present invention, and under the situation that does not deviate from spirit and scope of the invention, can make multiple changes and improvements to be adapted to multiple purposes and condition.
Claims (97)
1, a kind ofly control in the water system biological method, its grey water system is selected from paper manufacturing systems, cooling system or the industrial water system that does not directly contact with final products or the combination of these water systems, and described method comprises adds lupulic acid in water system.
2, the method for claim 1, wherein lupulic acid is selected from α-and β-lupulic acid and composition thereof.
3, the method for claim 1, wherein lupulic acid is selected from the compound of following one or more molecular formula representatives:
Wherein, "----" represents optional two keys,
R
1Be selected from OH; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
2Be selected from-OH;=O;-SH;=S; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
3Be selected from-OH;=O;-SH;=S and-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10;
R
4Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; The ketone group that contains about 1-20 carbon atom; General formula is C (O) H or C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10; And-OOR, wherein R is selected from C
nH
2n+1And H, wherein n is about integer of 2 to 10;
And/or
R wherein
5For general formula is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
R
6Be selected from-OH;-SH; With-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10; With
R
7Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
8Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
And/or
R wherein
9Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; With
R
10Be selected from the ketone group that contains about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
And/or
R wherein
11Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; With
R
12Be selected from the ketone group that contains about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10.
4, method as claimed in claim 3, wherein R
4The substituting group that comprises the following formula representative:
R wherein
13Comprise C
3-C
8Alkyl.
5, method as claimed in claim 4, wherein R
13Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3
6, method as claimed in claim 5, wherein lupulic acid is selected from hexahydrolupulon, six hydrogen class lupulones, the poly-lupulones of six hydrogen and composition thereof.
7, method as claimed in claim 6, wherein lupulic acid comprises six hydrogen class lupulones.
8, method as claimed in claim 3, wherein R
8The substituting group that comprises the following formula representative:
R wherein
14Comprise C
3-C
8Alkyl.
9, method as claimed in claim 8, wherein R
14Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2,-(CH
2)
2CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3And composition thereof.
10, method as claimed in claim 9, wherein lupulic acid comprises tetrahydro-iso-humulone.
11, the method for claim 1, wherein said biology comprises the microorganism that is selected from gram-negative bacteria, grampostive bacteria and composition thereof.
12, method as claimed in claim 11, wherein said microorganism is selected from sphaerotilus natans bacterium (sPhaerotilus natans), clostridium butyricum (Clostridium butyrium), pseudomonas aeruginosa (Pseudomononas aeruginosa), wilting bacillus pumilis (Curtobacteriumflaccumfaciens), onion bulkholderia cepasea (Burholderia cepacia), Pseudomonas glathei (Pseudomonas glathi), Bacillus cercus (Bacillus cereus), Morocco bacillus (Bacillus maroccanus), bacillus licheniformis (Bacilluslicheniformis), Bacillus sphaericus (Bacillus sphaericus), bacillus subtilis (Bacillus subtilis) and composition thereof.
13, method as claimed in claim 11, wherein said microorganism comprises gram-negative bacteria.
14, method as claimed in claim 13, wherein said microorganism is selected from different zygosaccharomyces, Aquaspirillum, campylobacter, Helicobacterium, acinetobacter, Agrobacterium, Alcaligenes replaces zygosaccharomyces, Flavobacterium, pseudomonas, Xanthomonas, mycoplasma, Methanococcus and composition thereof.
15, method as claimed in claim 11, wherein said microorganism comprises grampostive bacteria.
16, method as claimed in claim 15, wherein said microorganism is selected from bacillus, enterococcus spp, Planococcus, staphylococcus, streptococcus, fusobacterium, lactobacillus, Listera belongs to, actinomyces, Arthrobacter, Corynebacterium, Curtobacterium, Nocardia, actinoplanes, mycobacterium and composition thereof.
17, the method for claim 1, wherein said water system comprises paper manufacturing systems.
18, the method for claim 1, wherein said water system comprises industrial water.
19, the method for claim 1, wherein said water system comprises cooling system.
20, the method for claim 1, wherein the lupulic acid consumption is about 0.001 to 1, between the 000ppm.
21, method as claimed in claim 20, wherein the lupulic acid consumption is between about 0.1 to 250ppm.
22, method as claimed in claim 21, wherein the lupulic acid consumption is between about 0.1 to 100ppm.
23, the method for claim 1, wherein lupulic acid and antifreeze add together.
24, method as claimed in claim 17, wherein lupulic acid comprises select a kind of from α and β lupulic acid and mixing thereof.
25, method as claimed in claim 17, wherein lupulic acid is selected from the compound of following one or more molecular formula representatives:
Wherein, "----" represents optional two keys,
R
1Be selected from OH; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
2Be selected from-OH;=O;-SH;=S; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
3Be selected from-OH;=O;-SH;=S and-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10;
R
4Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; The ketone group that contains about 1 to 20 carbon atom; General formula is C (O) H or C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10; And-OOR, wherein R is selected from C
nH
2n+1And H, wherein n is about integer of 2 to 10;
And/or
R wherein
5For general formula is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
R
6Be selected from-OH;-SH; With-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10; With
R
7Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
8Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
And/or
R wherein
9Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; With
R
10Be selected from the ketone group that contains about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
And/or
R wherein
11Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; With
R
12Be selected from the ketone group that contains about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10.
26, method as claimed in claim 25, wherein R
4The substituting group that comprises the following formula representative:
R wherein
13Comprise C
3-C
8Alkyl.
27, method as claimed in claim 26, wherein R
13Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3
28, method as claimed in claim 27, wherein lupulic acid is selected from hexahydrolupulon, six hydrogen class lupulones, the poly-lupulones of six hydrogen and composition thereof.
29, method as claimed in claim 28, wherein lupulic acid comprises six hydrogen class lupulones.
30, method as claimed in claim 25, wherein R8 comprises the substituting group of following formula representative:
R wherein
14Comprise C
3-C
8Alkyl.
31, method as claimed in claim 30, wherein R
14Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2,-(CH
2)
2CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3And composition thereof.
32, method as claimed in claim 31, wherein lupulic acid comprises tetrahydro-iso-humulone.
33, method as claimed in claim 17, wherein said biology comprises the microorganism that is selected from gram-negative bacteria, grampostive bacteria and composition thereof.
34, method as claim 33, wherein said microorganism is selected from sphaerotilus natans bacterium (Sphaerotilus natans), clostridium butyricum (Clostridium butyrium), pseudomonas aeruginosa (Pseudomononas aeruginosa), wilting bacillus pumilis (Curtobacteriumflaccumfaciens), onion bulkholderia cepasea (Burholderia cepacia), Pseudomonas glathei (Pseudomonas glathi), Bacillus cercus (Bacillus cereus), Morocco bacillus (Bacillus maroccanus), bacillus licheniformis (Bacilluslicheniformis), Bacillus sphaericus (Bacillus sphaericus), bacillus subtilis (Bacillus subtilis) and composition thereof.
35, method as claimed in claim 34, wherein said microorganism comprise sphaerotilus natans bacterium (Sphaerotilus natans).
36, method as claimed in claim 34, wherein said microorganism comprise clostridium butyricum (Clostridium butyrium).
37, method as claimed in claim 34, wherein said microorganism comprise pseudomonas aeruginosa (Pseudomononas aeruginosa).
38, method as claimed in claim 34, wherein said microorganism comprise wilting bacillus pumilis (Curtobacterium flaccumfaciens).
39, method as claimed in claim 34, wherein said microorganism comprise onion bulkholderia cepasea (Burholderia cepacia).
40, method as claimed in claim 34, wherein said microorganism comprise Pseudomonas glathei (Pseudomonas glathi).
41, method as claimed in claim 34, wherein said microorganism comprise Bacillus cercus (Bacillus cereus).
42, method as claimed in claim 34, wherein said microorganism comprise Morocco bacillus (Bacillus maroccanus).
43, method as claimed in claim 34, wherein said microorganism comprise bacillus licheniformis (Bacillus lichenformis).
44, method as claimed in claim 34, wherein said microorganism comprise Bacillus sphaericus (Bacillus sphaericus).
45, method as claimed in claim 34, wherein said microorganism comprise bacillus subtilis (Bacillus subtilis).
46, method as claimed in claim 17, wherein the lupulic acid consumption is about 0.001 to 1, between the 000ppm.
47, method as claimed in claim 46, wherein the lupulic acid consumption is between about 0.1 to 250ppm.
48, method as claimed in claim 47, wherein the lupulic acid consumption is between about 0.1 to 100ppm.
49, a kind of cellulosics that adopts method as claimed in claim 17 to produce.
50, cellulosics as claimed in claim 49 is comprising a kind of paper products.
51, a kind of method that suppresses biological growth in the water system, its grey water system is selected from cooling water system; Be used in the water system in the humidifier; Be used in the water system in heating, the heating ventilation and air-conditioning system; The water of swimming pool; The shower water; Metal-working fluids; Petroleum Production liquid; Coating; Plastic working system; The mixture of said system, described method comprise add lupulic acid in water systems.
52, method as claimed in claim 51, wherein lupulic acid is selected from α-and β-lupulic acid and composition thereof.
53, method as claimed in claim 51, wherein lupulic acid is selected from the compound of following one or more molecular formula representatives:
Wherein, "----" represents optional two keys,
R
1Be selected from OH; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
2Be selected from-OH;=O;-SH;=S; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
3Be selected from-OH;=O;-SH;=S and-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10;
R
4Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; The ketone group that contains about 1 to 20 carbon atom; General formula is C (O) H or C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10; And-OOR, wherein R is selected from C
nH
2n+1And H, wherein n is about integer of 2 to 10;
And/or
R wherein
5For general formula is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
R
6Be selected from-OH;-SH; With-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10; With
R
7Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
8Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
And/or
R wherein
9Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; With
R
10Be selected from the ketone group that contains about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
And/or
R wherein
11Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; With
R
12Be selected from the ketone group that contains about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10.
54, method as claimed in claim 53, wherein R
4The substituting group that comprises the following formula representative:
R wherein
13Comprise C
3-C
8Alkyl.
55, method as claimed in claim 54, wherein R
13Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3
56, method as claimed in claim 55, wherein lupulic acid is selected from hexahydrolupulon, six hydrogen class lupulones, the poly-lupulones of six hydrogen and composition thereof.
57, method as claimed in claim 56, wherein lupulic acid comprises six hydrogen class lupulones.
58, method as claimed in claim 53, wherein R8 comprises the substituting group of following formula representative:
R wherein
14Comprise C
3-C
8Alkyl.
59, method as claimed in claim 58, wherein R
14Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2,-(CH
2)
2CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3And composition thereof.
60, method as claimed in claim 59, wherein lupulic acid comprises tetrahydro-iso-humulone.
61, method as claimed in claim 53, wherein said biology comprises the microorganism that is selected from gram-negative bacteria, grampostive bacteria and composition thereof.
62, method as claim 61, wherein said microorganism is selected from sphaerotilus natans bacterium (Sphaerotilus natans), clostridium butyricum (Clostridium butyrium), pseudomonas aeruginosa (Pseudomononas aeruginosa), wilting bacillus pumilis (Curtobacteriumflaccumfaciens), onion bulkholderia cepasea (Burholderia cepacia), Pseudomonas glathei (Pseudomonas gtatni), Bacillus cercus (Bacillus cereus), Morocco bacillus (Bacillus maroccanus), bacillus licheniformis (Bacilluslicheniformis), Bacillus sphaericus (Bacillus sphaericus), bacillus subtilis (Bacillus subtilis) and composition thereof.
63, method as claimed in claim 61, wherein said microorganism comprise sphaerotilus natans bacterium (Sphaerotilus natans).
64, method as claimed in claim 61, wherein said microorganism comprise clostridium butyricum (Clostridium butyrium).
65, method as claimed in claim 61, wherein said microorganism comprise pseudomonas aeruginosa (Pseudomononas aeruginosa).
66, method as claimed in claim 61, wherein said microorganism comprise wilting bacillus pumilis (Curtobacterium flaccumfaciens).
67, method as claimed in claim 61, wherein said microorganism comprise onion bulkholderia cepasea (Burholderia cepacia).
68, method as claimed in claim 61, wherein said microorganism comprise Pseudomonas glathei (Pseudomonas glathi).
69, method as claimed in claim 61, wherein said microorganism comprise Bacillus cercus (Bacillus cereus).
70, method as claimed in claim 61, wherein said microorganism comprise Morocco bacillus (Bacillus maroccanus).
71, method as claimed in claim 61, wherein said microorganism comprise bacillus licheniformis (Bacillus licheniformis).
72, method as claimed in claim 61, wherein said microorganism comprise Bacillus sphaericus (Bacillus sphaericus).
73, method as claimed in claim 61, wherein said microorganism comprise bacillus subtilis (Bacillus subtilis).
74, method as claimed in claim 53, wherein the lupulic acid consumption is about 0.001 to 1, between the 000ppm.
75, as the described method of claim 74, wherein the lupulic acid consumption is between about 0.1 to 250ppm.
76, as the described method of claim 74, wherein the lupulic acid consumption is between about 0.1 to 100ppm.
77, a kind of composition, it comprises lupulic acid and a kind of composition that is selected from papermaking suspension, defoamer, alum, adhesive, papermaking paint, graining paste, starch, pitch control agent, antisludging agent, sizing agent and composition thereof.
78, as the described composition of claim 77, wherein lupulic acid is selected from α-and β-lupulic acid and composition thereof.
79, as the described composition of claim 77, wherein lupulic acid is selected from the compound of following one or more molecular formula representatives:
Wherein, "----" represents optional two keys,
R
1Be selected from OH; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
2Be selected from-OH;=O;-SH;=S; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
3Be selected from-OH;=O;-SH;=S and-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10;
R
4Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; The ketone group that contains about 1 to 20 carbon atom; General formula is C (O) H or C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10; And-OOR, wherein R is selected from C
nH
2n+1And H, wherein n is about integer of 2 to 10;
And/or
R wherein
5For general formula is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
R
6Be selected from-OH;-SH; With-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10; With
R
7Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
8Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
And/or
R wherein
9Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; With
R
10Be selected from the ketone group that contains about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
And/or
R wherein
11Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; With
R
12Be selected from the ketone group that contains about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10.
80, as the described method of claim 79, wherein R
4The substituting group that comprises the following formula representative:
R wherein
13Comprise C
3-C
8Alkyl.
81, as the described composition of claim 80, wherein R
13Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3
82, as the described composition of claim 81, wherein lupulic acid is selected from hexahydrolupulon, six hydrogen class lupulones, the poly-lupulones of six hydrogen and composition thereof.
83, as the described composition of claim 82, wherein lupulic acid comprises six hydrogen class lupulones.
84, as the described composition of claim 83, wherein R
8The substituting group that comprises the following formula representative:
R wherein
14Comprise C
3-C
8Alkyl.
85, as the described composition of claim 84, wherein R
14Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2,-(CH
2)
2CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3And composition thereof.
86, as the described composition of claim 77, wherein the papermaking suspension is selected from refining or unpurified batching liquid storage, refining or unpurified paper pulp, papermaking batching and their combination.
87, a kind of cellulosics that comprises lupulic acid and cellulosic fibre.
88, as the described cellulosics of claim 87, wherein lupulic acid is selected from α-and β-lupulic acid and composition thereof.
89, as the described cellulosics of claim 87, wherein lupulic acid is selected from the compound of following one or more molecular formula representatives:
Wherein, "----" represents optional two keys,
R
1Be selected from OH; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
2Be selected from-OH;=O;-SH;=S; And saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
3Be selected from-OH;=O;-SH;=S and-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10;
R
4Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; The ketone group that contains about 1 to 20 carbon atom; General formula is C (O) H or C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10; And-OOR, wherein R is selected from C
nH
2n+1And H, wherein n is about integer of 2 to 10;
And/or
R wherein
5For general formula is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
R
6Be selected from-OH;-SH; With-OOR, wherein R is selected from H and C
nH
2n+1, wherein n is about integer of 2 to 10; With
R
7Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom;
R
8Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
And/or
R wherein
9Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; With
R
10Be selected from the ketone group that contains about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10;
And/or
R wherein
11Be selected from saturated or unsaturated (contain approximately 1 to 5 two keys), the straight or branched alkyl or alkenyl, wherein comprise about 1 to 20 carbon atom; With
R
12Be selected from the ketone group that contains about 1 to 20 carbon atom; General formula is that aldehyde radical or the general formula of C (O) H is C (O) C
nH
2n+1Ketone group, wherein n is about integer of 2 to 10.
90, as the described cellulosics of claim 89, wherein R
4The substituting group that comprises the following formula representative:
R wherein
13Comprise C
3-C
8Alkyl.
91, as the described cellulosics of claim 90, wherein R
13Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3
92, as the described cellulosics of claim 91, wherein lupulic acid is selected from hexahydrolupulon, six hydrogen class lupulones, the poly-lupulones of six hydrogen and composition thereof.
93, as the described cellulosics of claim 92, wherein lupulic acid comprises six hydrogen class lupulones.
94, as the described cellulosics of claim 93, wherein R
8The substituting group that comprises the following formula representative:
R wherein
14Comprise C
3-C
8Alkyl.
95, as the described cellulosics of claim 94, wherein R
14Be selected from-CH
2CH (CH
3)
2,-CH (CH
3)
2,-(CH
2)
2CH (CH
3)
2With-CH (CH
3)
2CH
2CH
3And composition thereof.
96, as the described cellulosics of claim 97, it comprises paper and cardboard.
97, as the described cellulosics of claim 96, wherein said paper bag is drawn together stationery, paper handkerchief and toilet paper.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2001/010005 WO2002078450A1 (en) | 2001-03-28 | 2001-03-28 | Methods of using hop acids to control organisms |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1505480A true CN1505480A (en) | 2004-06-16 |
| CN1306875C CN1306875C (en) | 2007-03-28 |
Family
ID=21742450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018231039A Expired - Fee Related CN1306875C (en) | 2001-03-28 | 2001-03-28 | Methods of using hop acids to control organisms |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1372399A1 (en) |
| CN (1) | CN1306875C (en) |
| AU (1) | AU2001251073B2 (en) |
| BR (1) | BR0116950A (en) |
| CA (1) | CA2441074A1 (en) |
| MX (1) | MXPA03008614A (en) |
| WO (1) | WO2002078450A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003270103B2 (en) | 2002-05-17 | 2007-01-25 | S.S. Steiner, Inc. | Improved application for hop acids as anti-microbial agents |
| US20030228814A1 (en) * | 2002-06-07 | 2003-12-11 | Barney Michael C. | Antibacterial packaging material including hop acids |
| FI116030B (en) | 2002-11-06 | 2005-09-15 | Kemira Oyj | Inhibition of biofilm formation of thermophilic microbes in paper and board machines |
| FI115502B (en) * | 2002-11-06 | 2005-05-31 | Kemira Oyj | Prevention of deposition caused by bacteria on surfaces of paper and cardboard machines |
| FI119903B (en) | 2006-03-16 | 2009-05-15 | Kemira Oyj | Inhibition of bacterial spores in the board machine wreck system |
| CL2008003653A1 (en) | 2008-01-17 | 2010-03-05 | Mitsubishi Tanabe Pharma Corp | Use of a glucopyranosyl-derived sglt inhibitor and a selected dppiv inhibitor to treat diabetes; and pharmaceutical composition. |
| US9489981B2 (en) | 2012-03-15 | 2016-11-08 | Echostar Technologies L.L.C. | Successive initialization of television channel recording |
| EP2777395A1 (en) | 2013-03-14 | 2014-09-17 | S.S. Steiner, Inc. | Plant wash |
| CA2912767A1 (en) | 2013-05-20 | 2014-11-27 | BiOWiSH Technologies, Inc. | Microbial-based waste water treatment compositions and methods of use thereof |
| WO2017079211A1 (en) * | 2015-11-02 | 2017-05-11 | BiOWiSH Technologies, Inc. | Compositions and methods of use for reducing evaporative loss from swimming pools and spas |
| US11116240B2 (en) | 2018-05-29 | 2021-09-14 | BiOWiSH Technologies, Inc. | Compositions and methods for improving survivability of aquatic animals |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL223035A (en) * | 1957-09-23 | 1900-01-01 | Buckman Labor Inc | |
| US4855296A (en) * | 1988-09-12 | 1989-08-08 | Betz Laboratories, Inc. | Biocidal compositions and use thereof |
| US5827895A (en) * | 1996-02-27 | 1998-10-27 | Regents Of The University Of Minnesota | Hexahydrolupulones useful as anticancer agents |
| DE19909827A1 (en) * | 1999-03-05 | 2000-09-07 | Betatec Hopfenprodukte Gmbh | Process for controlling microorganisms in a sugar-containing, aqueous process medium |
| AU3721300A (en) * | 1999-03-05 | 2000-09-21 | Haas Hop Products, Inc. | Process for controlling micro-organisms in an aqueous process medium |
| EP1202640A1 (en) * | 1999-07-27 | 2002-05-08 | Rhodia Inc. | Hops acid antibacterial compositions |
| AU2001241774A1 (en) * | 2000-03-08 | 2001-09-17 | Hercules Incorporated | Control of spore forming bacteria |
| US6379720B1 (en) * | 2000-07-18 | 2002-04-30 | Nalco Chemical Company | Compositions containing hops extract and their use in water systems and process streams to control biological fouling |
-
2001
- 2001-03-28 AU AU2001251073A patent/AU2001251073B2/en not_active Ceased
- 2001-03-28 BR BR0116950A patent/BR0116950A/en not_active IP Right Cessation
- 2001-03-28 MX MXPA03008614A patent/MXPA03008614A/en not_active Application Discontinuation
- 2001-03-28 EP EP20010924417 patent/EP1372399A1/en not_active Withdrawn
- 2001-03-28 CA CA 2441074 patent/CA2441074A1/en not_active Abandoned
- 2001-03-28 CN CNB018231039A patent/CN1306875C/en not_active Expired - Fee Related
- 2001-03-28 WO PCT/US2001/010005 patent/WO2002078450A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002078450A1 (en) | 2002-10-10 |
| AU2001251073B2 (en) | 2006-12-21 |
| BR0116950A (en) | 2006-02-21 |
| CN1306875C (en) | 2007-03-28 |
| CA2441074A1 (en) | 2002-10-10 |
| MXPA03008614A (en) | 2003-12-08 |
| EP1372399A1 (en) | 2004-01-02 |
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