CN103734133B - A kind of amino acid composite biomembrane remover - Google Patents

A kind of amino acid composite biomembrane remover Download PDF

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CN103734133B
CN103734133B CN201310419818.2A CN201310419818A CN103734133B CN 103734133 B CN103734133 B CN 103734133B CN 201310419818 A CN201310419818 A CN 201310419818A CN 103734133 B CN103734133 B CN 103734133B
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biomembrane
remover
amino acid
bactericide
composite
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CN103734133A (en
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刘宏芳
秦双
陈碧
顾停月
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Huazhong University of Science and Technology
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Abstract

The present invention relates to bactericide and biomembrane remover field.Amino acid composite biomembrane remover of the present invention comprises one or more amino acid compositions and traditional Non-oxidized quaternary ammonium salt bactericide and solvent and is composited, wherein in composite biomembrane remover, amino acid whose percentage by weight consists of 1 ~ 10%, one or both in amino acid bag D-Tyrosine or TYR; In composite biomembrane remover, the percentage by weight of quaternary ammonium salt bactericide consists of 40 ~ 49%; The percentage by weight of solvent consists of 41 ~ 59%.This composite biomembrane remover has broken the action pathway of conventional sterilants to bacterium under biomembrane, greatly can promote that quaternary ammonium salt bactericide is to the suppression of bacterium under biomembrane and to biomembranous stripping ability, and material is conveniently easy to get, biomembranous stripping and biomembrane corrosion control in the closed systems such as industrial circulating water, oil field extracted water and naval vessels cabin are with a wide range of applications.

Description

A kind of amino acid composite biomembrane remover
Technical field
The invention belongs to bactericide and biomembrane remover field, be specifically related to the amino acid composite biomembrane remover for biomembrane stripping and corrosion control in the closed systems such as industrial circulating water, oil field extracted water and naval vessels cabin.
Background of invention
Research shows, microbiologic(al) corrosion, main and equipment installation and surface the biomembrane of the relevant problem such as fouling and biological clay are closely related.
Bacterial biof iotalm refers to that bacterium is attached to body surface and the film sample many bacteriums complex be made up of the aqueous polymerization matrix (being mainly exocellular polysaccharide) etc. of bacterial cell and secretion thereof formed in process of growth.Bacterial biof iotalm is bacterium is the special existence form that reform of nature environment is formed, it is the existence form corresponding with wandering cell, most bacterium defines meticulous adherence mechanism during evolution gradually, secretion matrix inter-adhesive formation membranoid substance is attached to material surface, thus form biomembranous complicated group, and borrow signaling molecule mutually to exchange the behavior coordinating them, its biochemical composition is Alginate polysaccharides and albumen composition, its basic structure is made up of mushroom Yang Huozhuyang subunit, subunit is divided into head, neck, root three part, aquaporin is formed between each several part, complete various transportation function, maintain bacteria live in film to need.
There is multiple-microorganism in industrial circulating water closed system, as sulfate reducing bacteria (SRB), iron bacteria, produces foundry loam bacterium, saprophytic bacteria etc.These microorganism adherings at material, on the inner surface of normally tube wall or tank skin and propagation dross growth.In biomembrane, microorganism lives in one with the diverse micro-ecological environment of free suspended state, and microorganism is motionless substantially, is wrapped up in the organic matter of aquation.Cell density in biomembrane is higher than suspended state, sometimes even exceeds 5 ~ 6 orders of magnitude, may produce physiology and interact, cause collaborative microbial action between the cell of adjacent position by Long contact time.In addition, biomembranously be formed as the anaerobism enclosed environment that microorganism under biomembrane provides " safety ", anaerobic bacteria amount reproduction under biomembrane, in addition under biological metabolic product causes film, microorganism is " protected " in the environment of reproducibility, traditional oxidizing bactericide produces little effect to microorganism under film, the respiration of the bacterium surface anti-bacteria that non oxidizing bactericide is as electronegative in the sterilization mechanism of quaternary ammonium salt etc. is mainly adsorbed on and then suppression or kill bacterium, but it is mainly effective for free (plantonic) bacterium in water system, for set (sessile) bacterium under biomembrane because the infiltration capacity of bactericide is limited and run into bottleneck, the generation of the environmental pollution that the increase as chemical feeding quantity causes and drug tolerant bacteria.Therefore, increasing researcher explores the Method and Technology suppressing pest film from the biology angle of bacterium itself.
Research in recent years finds, the bacterium in biomembrane has the gene regulation active mechanism of height.In bacterial biof iotalm, peptidoglycans contains D-alanineterminus, the disappearance of this material can go out a kind of biofilm dispersion signal to Microbiological release, under the effect of this signal, bacterium can become free state (planktoniccells) [Kolodkin-Galetal. by set state (sessilecelles), Science328:627-629,2010].Bacterium under the protection of some biomembrane is as promoted the dispersion of bacterium further after the interpolation bactericide such as SRB.Some amino acid can replace the D-alanineterminus on biomembrane as D-Tyrosine and TYR, and then cause the disappearance of bacterial cell D-alanineterminus, promote biomembranous dispersion, suppression [the Xuetal. of bacterial growth under biomembranous stripping and film obviously can be promoted after composite bactericide, WorldJMicrobBiot.28,3067-3074,2012].
Summary of the invention
Task of the present invention is to provide a kind of amino acid composite biomembrane remover, is difficult to suppress the problem such as a series of environmental pollutions, the wasting of resources that microorganism brings under biomembrane to overcome existing industrial bactericide.
Realizing technical scheme of the present invention is:
This amino acid composite biomembrane remover provided by the invention, is made up of following weight percent composition: the amino acid of 1 ~ 10%, the quaternary ammonium salt bactericide of 40 ~ 49%, the solvent of 41 ~ 59%.Described amino acid is D-Tyrosine or TYR, or the mixture of D-Tyrosine and TYR; Described solvent is water or alcohol, or the mixture of water and alcohol; Described quaternary ammonium salt bactericide possesses one in the compound of following structure or mixture of more than two kinds:
Wherein, n=8 ~ 18; R is H, benzyl or alkyl chain; X=Cl or Br.
The present invention starts with from the gene regulation active mechanism of bacterium itself, utilizes to add medicament and intervene the signal representation of bacterium, promotes that bacterium is from the separation biomembrane, and then the corrosion that inhibit the growth and breeding of bacterium in biomembrane to bring and water pollution issue.
Amino acid composite biomembrane remover of the present invention comprises one or more amino acid compositions and traditional Non-oxidized quaternary ammonium salt bactericide and solvent and is composited, wherein in composite biomembrane remover, amino acid whose percentage by weight consists of 1 ~ 10%, amino acid comprise in D-Tyrosine or TYR one or both; In composite biomembrane remover, the percentage by weight of quaternary ammonium salt bactericide consists of 40 ~ 49%; The percentage by weight of solvent consists of 41 ~ 59%.It is extensive that composite biomembrane remover provided by the invention has raw material, with low cost, environmental friendliness and the advantage such as to economize on resources.The bactericide input amount in current oil field can be greatly reduced and improve biomembranous stripping ability.Existing industrial bactericide can be overcome be difficult to suppress the problem such as a series of environmental pollutions, the wasting of resources that microorganism brings under biomembrane.This composite biomembrane remover has broken the action pathway of conventional sterilants to bacterium under biomembrane, greatly can promote that quaternary ammonium salt bactericide is to the suppression of bacterium under biomembrane and to biomembranous stripping ability, and material is conveniently easy to get, biomembranous stripping and biomembrane corrosion control in the closed systems such as industrial circulating water, oil field extracted water and naval vessels cabin are with a wide range of applications.
Accompanying drawing explanation
Fig. 1: the AC impedance Nyquist after biomembrane and four kinds of sample contacts schemes (a) and Bode schemes (b).
EIS collection of illustrative plates equivalent circuit diagram in Fig. 2: Fig. 1.
Fig. 3: SRB biomembrane is through contacting 4 hours rear surface microscopic appearances with four kinds of Sample Reagents, in Fig. 3: A is blank; B sample one; C sample two; D sample three; E sample four.Fig. 3 can find out, the biofilm surface do not contacted with medicament is compact and complete, contacts rear surface biomembrane occur a small amount of crack with bactericide, and with several sample contacts provided by the invention after, strip biomembrane all start be full of cracks, there is slight crack, be easy to come off.
Below for SRB biomembrane modal in industrial circulating water and oil field produced water system, the invention will be further described.
Embodiment 1
Amino acid, quaternary ammonium salt and solvent are acted on free SRB by after the composite mixing of table 1.And contrast with simple quaternary ammonium salt bactericide.Stunt dilution method is adopted to be undertaken by the method specified in SY/T5890-1993, the following condition of its condition determination.
At room temperature in water sample, inject bactericide, sterilization 3h.Water sample after sterilization and blank sample are injected in test bottle, and cultivate in 37 DEG C of insulating boxs.Experiment employing 3 tube method.The calculating of sterilizing rate adopts following formula:
Several formula of table 1 composite biomembrane remover is to the sterilizing ability of free SRB
As can be seen from Table 1, amino acid whose adding can not affect the sterilizing ability of bactericide to free bacteria, and can reach 99.99% to the germicidal efficiency of bacterium in water system after amino acid compound disinfectant.
Embodiment 2
Amino acid composite biomembrane remover is to the rejection ability of bacterium in biomembrane
Under biomembrane bacterium bacterium amount specific ionization medium in much higher, for evaluating combined biomembrane remover is to the rejection ability of SRB under biomembrane, laboratory cultures is with the biomembranous test piece of ripe SRB, after four kinds of component medicaments contact 4h in table 1, dilution-to-extinction method is adopted to detect the quantity of bacterium in biomembrane.The results are shown in Table shown in 2.
Several formula of table 2 composite biomembrane remover is to the sterilizing ability of free SRB
As seen from Table 2, much more in bacterial number specific ionization medium under biomembrane, after adding amino acid composite biomembrane remover, simple bactericide is better than to the rejection ability of bacterium under film.Due to the biomembrane mainly bacterium extracellular polymeric that metabolism produces under biomembrane and corrosion product, the mineral ion etc. in aqueous systems, therefore, inhibits the growth of SRB in biomembrane, just indirectly inhibits the biomembranous development of SRB and adhesive ability.
Embodiment 3
Amino acid composite biomembrane remover is to biomembrane stripping ability electrochemical evaluation
AC impedance electrochemical technology is utilized to act on to evaluate bactericide biomembranous stripping, its principle is carbon steel material surface is by loose biological membranous layer, the multilayer labyrinth of the compositions such as fine and close corrosion scales, by applying the alternating current of different frequency, obtain the information such as the biomembranous electric capacity of steel surface and resistance, can biomembranous stripping be acted on Indirect evaluation bactericide.Experiment adopts three-electrode system, and to contact the biomembranous test piece of the covering after 12 respectively as working electrode with different samples, take saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, utilizes the EIS collection of illustrative plates of CS electrochemical workstation test system.With 3%NaCl solution for test medium, after system corrosion potential is stable, start monitoring.Fig. 1 is shown in by EIS collection of illustrative plates after biomembrane and four kinds of sample contacts.Fig. 1 is that the AC impedance Nyquist after biomembrane and four kinds of sample contacts schemes (a) and Bode schemes (b), Fig. 1 (a) front end (illustration) shows steel disc surface SRB biomembrane resistance and capacitive properties, can find out that sample 3 synergy is that semicircular ring is maximum, maximum corresponding to Fig. 1 (b) front end phase angle; Fig. 1 (a) low frequency end shows charge-transfer resistance and electric double layer capacitance between steel disc surface and medium.Therefore can use as Fig. 2 Equivalent Circuit Fitting AC impedance curve, fitting result is as table 3.
EIS parametric data table after several formula composite biomembrane remover of table 3 and biofilm contact
Rs represents the solution resistance of medium, and in five kinds of systems, solution resistance difference is little.And add medicament artifact membrane capacitance and compare remarkable reduction with blank, in general biomembrane electric capacity shows that more greatly biomembranous structure sheaf is thicker, biomembrane is generally made up of the outer high polymer of born of the same parents and corrosion product, there is loose porous feature, multiple charged ion can be held, therefore the reduction of membrane capacitance fully reflects steel disc surface biological film suppresses bacterium in film growth at the effect further aspect of composite biomembrane remover, promotes biomembranous stripping and comes off on the other hand.In addition, electric double layer capacitance value Cdl also sharply declines, and illustrates that the film layer structure on steel disc surface is by originally loose porous corrosion product ferrous sulfide and SRB biomembrane, becomes fine and close film.Dispersion coefficient (n-dl) increase of electric double layer illustrates that rete is more homogeneous.From corrosion rate, the data of electrode surface electrochemical measurement reflection also illustrate, amino acid composite biomembrane remover provided by the invention effectively can reduce the material corrosion that bacterial metabolism under the biomembranous attachment of material surface and film causes, and this result has important directive significance in the anticorrosion application of industrial pipeline.
Embodiment 4 amino acid composite biomembrane remover application artifact film and material surface morphology observation
See Fig. 3, Fig. 3 can find out, the biofilm surface do not contacted with medicament is compact and complete, contact rear surface biomembrane with bactericide and occur a small amount of crack, and with several sample contacts provided by the invention after, strip biomembrane all start be full of cracks, there is slight crack, be easy to come off.
Above the technical scheme that the embodiment of the present invention provides is described in detail, apply specific case herein to set forth the principle of the embodiment of the present invention and embodiment, the explanation of above embodiment is only applicable to the principle helping to understand the embodiment of the present invention; Meanwhile, for one of ordinary skill in the art, according to the embodiment of the present invention, embodiment and range of application all will change, in sum, this description should not be construed as limitation of the present invention.

Claims (1)

1. an amino acid composite biomembrane remover, is characterized in that, is made up of following weight percent composition: the amino acid of 1 ~ 10%, the quaternary ammonium salt bactericide of 40 ~ 49%, the solvent of 41 ~ 59%;
Described amino acid is D-Tyrosine or TYR, or the mixture of D-Tyrosine and TYR;
Described quaternary ammonium salt bactericide possesses one in the compound of following structure or mixture of more than two kinds:
Wherein, n=8 ~ 18;
R is H, benzyl or alkyl chain;
X=Cl or Br;
Described solvent is water or alcohol, or the mixture of water and alcohol.
CN201310419818.2A 2013-09-13 2013-09-13 A kind of amino acid composite biomembrane remover Active CN103734133B (en)

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CN104198543A (en) * 2014-09-09 2014-12-10 中国石油化工股份有限公司 Method for quickly evaluating stripping capability of bactericide to biofilm
CN106621824B (en) * 2017-01-03 2019-08-13 东北电力大学 The disintegration agent of Biofilm contamination in a kind of alleviation membrane bioreactor
CN109221240A (en) * 2018-11-01 2019-01-18 西安石油大学 A kind of water system inhibits the high efficiency composition disinfecting corrosion inhibitor of simultaneously decomposing organism film

Citations (3)

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Publication number Priority date Publication date Assignee Title
US20110070376A1 (en) * 2002-09-09 2011-03-24 Reactive Surfaces, Ltd. Anti-fouling Paints & Coatings
WO2013032961A1 (en) * 2011-08-26 2013-03-07 Ohio University Compositions and methods for treating biofilms
CN103109850A (en) * 2013-01-30 2013-05-22 武汉华科特新技术有限公司 Composite bactericide for efficiently inhibiting iron bacteria

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110070376A1 (en) * 2002-09-09 2011-03-24 Reactive Surfaces, Ltd. Anti-fouling Paints & Coatings
WO2013032961A1 (en) * 2011-08-26 2013-03-07 Ohio University Compositions and methods for treating biofilms
CN103109850A (en) * 2013-01-30 2013-05-22 武汉华科特新技术有限公司 Composite bactericide for efficiently inhibiting iron bacteria

Non-Patent Citations (1)

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