CN105385056B - A kind of biological antibiotic plastics - Google Patents

A kind of biological antibiotic plastics Download PDF

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Publication number
CN105385056B
CN105385056B CN201511008566.XA CN201511008566A CN105385056B CN 105385056 B CN105385056 B CN 105385056B CN 201511008566 A CN201511008566 A CN 201511008566A CN 105385056 B CN105385056 B CN 105385056B
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biological antibiotic
particle
bioactivity
antibiotic plastics
polymer nano
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CN105385056A (en
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薛奇
李翔
王晓亮
周东山
徐洁
滕超
李林玲
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Nanjing University
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Nanjing University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a kind of biological antibiotic plastics, which is made by following preparation methods:Bioactivity antimicrobial molecule is soluble in water, it is configured to mixed solution system, polymer nano-particle is added into the system, drains after mixing, and puts it into mold, suppresses under room temperature, obtains biological antibiotic plastics.Advantage is the present invention by using polymer nano-particle as carrier, (0~40 DEG C) composite natral bioactivity antimicrobial molecule at ambient temperature, to which a kind of biological antibiotic plastics be made, which has good bactericidal activity, slow release characteristic, does not easily cause environmental pollution and be harmful to human health;Meanwhile preparation method is simple and environmentally-friendly, can be widely used in various biological antibiotic molecular systems and various Polymer Systems.

Description

A kind of biological antibiotic plastics
Technical field
The invention belongs to plastic applications more particularly to a kind of biological antibiotic plastics.
Background technology
Antibiotic plastic be it is a kind of having antibacterial or bactericidal property special plastic, be typically by plastic matrix with it is a certain amount of Antiseptic be blended to be granulated and obtain, various industrial products can be made by the techniques such as being molded or being blow molded.Existing antibiotic plastic at present In common bacteriostatic agent be broadly divided into two major classes, one kind is inorganic antiseptic, and another kind of is organic antibacterial agent.But these are changed Antiseptic is learned often to easily cause environmental pollution or have the health of human body certain harm.
Natural bio-antimicrobial agents have the advantages such as efficient, harmless and environmental-friendly, with the enhancing of people's environmental consciousness With the raising to health requirements, natural bio-antimicrobial agents will be as the first choice of the following antibiotic plastic.Natural bio-antimicrobial agents are main It is divided into animal class antiseptic and plant antiseptic, animal class antiseptic includes mainly chitin, chitosan and some antibacterials Protein, enzyme;Plant antiseptic mainly has the extract of the plants such as juniper, argy wormwood and aloe.However, at present on the market It seldom sees using natural bioactive molecule as the antibiotic plastic of active ingredient, this is because the processing of conventional thermoplastic's plastics It is molded under high temperature (usually more than 100 DEG C) and carries out, these antiseptics is also required to be resistant to high temperature and be denaturalized without decomposing, but It is since mutability inactivates bioactive molecule in the high temperature environment, is difficult to find a kind of method of universality to produce this Kind antibiotic plastic.
Invention content
Goal of the invention:The object of the present invention is to provide one kind being compounded with bioactivity antimicrobial molecule, and with good sterilization Active biological antibiotic plastics.
Technical solution:The biological antibiotic plastics of the present invention are made by following steps:Bioactivity antimicrobial molecule is dissolved in In water, it is configured to the mixed solution system of 0.1~10wt%, polymer nano-particle is added into the system, after mixing It drains, and puts it into mold, after pressure is 100~250MPa, suppresses 1~20min under room temperature, pressure release, demoulding, Obtain the biological antibiotic plastics, wherein the mass ratio of polymer nano-particle and bioactivity antimicrobial molecule is 5~1000: 1。
Furtherly, bioactivity antimicrobial molecule of the invention preferably can be lyase bacterium, chitosan, antimicrobial peptide or kill Bacterium-infiltration enhances albumen, and the mixed solution system of preparation preferably can be 0.1~17wt%, and polymer nano-particle is lived with biology Property antimicrobial molecule mass ratio be 5~500:1, the grain size of polymer nano-particle is 40~1500nm, preferably can be 40~ 1000nm further preferably can be 40~500nm.
According to " going congestion " principle, in withstanding pressure, macromolecular chain flows polymer nano-particle, so as to Enough further wrapping biological active antimicrobial molecules, form a kind of relatively uniform appearance structure, it is preferred that pressure applied For 120~230MPa, room temperature is 0~40 DEG C.
Advantageous effect:Compared with prior art, remarkable advantage of the invention be by using polymer nano-particle as carrier, (0~40 DEG C) composite natral bioactivity antimicrobial molecule at ambient temperature, to which a kind of novel biological antibiotic plastics be made, The plastics have many advantages, such as good bactericidal activity, slow release characteristic and do not easily cause environmental pollution and be harmful to human health; Meanwhile preparation method is simple and environmentally-friendly, can be widely used in various biological antibiotic molecular systems and various Polymer Systems.
Description of the drawings
Fig. 1 is polystyrene and beta galactosidase made from preparation method of the invention and traditional thermoplastic processing method The bioactivity compares figure of composite plastic;
Fig. 2 is polystyrene-lysozyme composite plastic bactericidal activity curve graph;
Fig. 3 is the sustained release measured by filtrate of the polystyrene-lysozyme composite plastic after a large amount of sterile waters repeatedly washing Performance diagram.
Specific implementation mode
Technical scheme of the present invention is further described below in conjunction with the accompanying drawings.
The new bio bactericidal plastic of the present invention is made by following steps:Bioactivity antimicrobial molecule is soluble in water, It is configured to the mixed solution system of 0.1~10wt%, polymer nano-particle is added into the system, drains after mixing, And put it into mold, after pressure is 100~250MPa, suppresses 1~20min under room temperature, pressure release, demoulding are made Obtain the biological antibiotic plastics wherein, the mass ratio of polymer nano-particle and bioactivity antimicrobial molecule is 5~1000:1.
Generally when handling biomolecule, water that be Jing Guo aseptic process, and the inside is tried not containing too many inorganic salts Particle, in order to avoid destroy bioactivity, it is preferred that the water used can be sterile distilled water.The bioactivity antimicrobial molecule of the present invention It is preferred that can be lyase bacterium, chitosan, antimicrobial peptide or sterilization-infiltration enhances albumen, the mixed solution system of preparation preferably may be used For 0.1~7wt%, wherein the mass ratio of polymer nano-particle and bioactivity antimicrobial molecule is 5~500:1, polymer nano The grain size of rice corpuscles is 40~1500nm, preferably can be 40~1000nm, can be further preferably 40~500nm, be applied Pressure is 120~230MPa, and room temperature is 0~40 DEG C.
Embodiment 1
Polystyrene is prepared with beta galactosidase composite plastic:It is the poly- of 150nm to prepare grain size using emulsion polymerization 10 grams of styrene nanometer bead, after washing 5 times respectively with absolute ethyl alcohol, distilled water successively, vacuum drying is spare.By 10 milligrams of β- Galactosidase is dissolved in 10ml sterile distilled waters, is sufficiently stirred, is dissolved to uniform system.10 grams of polystyrene spheres are added In system, quickly stirring forms it into uniform suspension, and is put into mold and paves after the suspension is drained, and is put through mold Enter in forcing press, applies the pressure of 250MPa under the conditions of 40 DEG C, and by after pressure holding 20min, pressure release, demoulding can get Polystyrene and beta galactosidase composite plastic.
Embodiment 2
Comparison of design is tested, prepared by the preparation method at room temperature that traditional thermoplastic processing method and the present invention is respectively adopted Polystyrene and β -- galactosidase composite material utilizes β -- galactosidase can catalyzing hydrolysis β-D galactopyranosides (RBG) property with red fluorescence product is generated, whether is maintained in the activity of verification enzyme, test result such as Fig. 1 institutes Show, wherein ordinate is the fluorescence intensity of enzymic catalytic reaction product, and abscissa is the reaction time.
As shown in Figure 1, using composite material catalyzing hydrolysis β-D galactopyranoses made from traditional thermoplastic processing method When glycosides (RBG), since the activity of enzyme disappears, reaction can not carry out, therefore its fluorescence intensity is always held at a lower number Be worth it is constant, and use the present invention under room temperature composite material catalyzing hydrolysis β-D galactopyranosides (RBG) obtained when, β -- Galactosidase maintains good activity in the composite, and constantly catalyzing hydrolysis β-D galactopyranosides (RBG) are raw At the product of hyperfluorescence, the form of expression in figure increases with the reaction time for the fluorescence intensity of product and constantly increases, most After tend to a stationary value.
Embodiment 3
The preparation of polyvinyl chloride and bovine serum albumin (BSA) composite plastic:Grain size is prepared using nano-particle sedimentation about For 5 grams of the polyvinyl chloride nano bead of 40nm, after washing 5 times respectively with absolute ethyl alcohol, distilled water successively, vacuum drying is spare. 1 gram of bovine serum albumin is dissolved in 10ml sterile distilled waters, is sufficiently stirred, is dissolved to uniform system, by 5 grams of polyvinyl chloride nanos Bead is added in the system, and quickly stirring forms it into uniform suspension, and mold middle berth is put into after the suspension is drained It is flat, it is put into forcing press through mold, applies the pressure of 100MPa under the conditions of 0 DEG C, and by after pressure holding 1min, pressure release takes off Mould can get the composite plastic of polyvinyl chloride and bovine serum albumin.
Embodiment 4
The preparation of polystyrene-lysozyme composite plastic:The polyphenyl for using emulsion polymerization that grain size is prepared as 600nm Ethylene nanometer bead 350g, successively after absolute ethyl alcohol and sterile distilled water wash 5 times respectively, vacuum drying is spare.It will 0.7g lysozymes are dissolved in 10ml sterile distilled waters, are configured to the mixed solution of 7wt%, are sufficiently stirred, are dissolved to uniform system, By in 350g polystyrene sphere addition systems, quickly stirring forms it into uniform suspension, and after the suspension is drained It is put into mold and paves, be put into forcing press through mold, apply the pressure of 220MPa under the conditions of 30 DEG C, and pressure is kept After 20min, pressure release, demoulding, you can obtain the sterilization polystyrene plastics for being compounded with bioactivity antimicrobial molecule lysozyme, kill For bacterium activity curve as shown in Fig. 2, by the curve of Fig. 2 it is found that when composite plastic is put into micrococcus lysodeikticus suspension, bacterium is fast Speed is killed, and system clarity quickly increases, and the absorbance corresponded in figure quickly reduces.
After polystyrene-lysozyme composite material is vigorously stirred 10min in a large amount of aseptic deionized waters, 1ml is gone to filter Liquid carries out the measurement of bactericidal effect, washs 15 times repeatedly, the slow release characteristic curve graph measured is as shown in figure 3, can by Fig. 3 Know, during a large amount of water washing, lysozyme content gradually reduces in filtrate, however to 10~15 times this stage, Content is but basically unchanged, and thus can be explained, and composite plastic prepared by this method has slow release characteristic, and protects in a certain range More uniform rate of release is held.
Embodiment 5
The preparation of polyvinyl chloride and lysozyme composite plastic:Use the nano-particle precipitation method that grain size is prepared as 40nm's Polyvinyl chloride nano bead 5g, successively after absolute ethyl alcohol and sterile distilled water wash 5 times respectively, vacuum drying is spare.It will 1g lysozymes are dissolved in 10ml water, are configured to the mixed solution of 10wt%, are sufficiently stirred, are dissolved to uniform system, by 5g polychlorostyrene In ethylene bead addition system, quickly stirring forms it into uniform suspension, and is put into mold after the suspension is drained Pave, be put into forcing press through mold, under the conditions of 0 DEG C apply 100MPa pressure, and by pressure keep 1min after, pressure release, Demoulding, you can obtain the sterilization igelite for being compounded with bioactivity antimicrobial molecule lysozyme.
Embodiment 6
The preparation of polystyrene and Chitosan Composites:Use emulsion polymerization that grain size is prepared as the poly- of 1500nm Styrene nanometer bead 10g, successively after absolute ethyl alcohol and sterile distilled water wash 5 times respectively, vacuum drying is spare.It will 10mg chitosans are dissolved in 10ml water, are configured to the mixed solution of 0.1wt%, are sufficiently stirred, are dissolved to uniform system, 5g is gathered In styrene bead addition system, quickly stirring forms it into uniform suspension, and is put into mold after the suspension is drained In pave, be put into forcing press through mold, under the conditions of 40 DEG C apply 250MPa pressure, and by pressure keep 20min after, let out Pressure, demoulding, you can obtain the sterilization polystyrene plastics for being compounded with bioactive molecule lysozyme.
Polymer nano-particle is polymerize in addition to using the polyvinyl chloride and polystyrene in above-described embodiment using others Object nano-particle can equally prepare the bactericidal plastic of composite bio-active antimicrobial molecule.
Embodiment 7
Design 7 groups of parallel laboratory tests, the mass ratio of macromolecule and bioactive molecule is respectively 1:1、5:1、10:1、100:1、 500:1、1000:1、1100:1, bioactive molecule is bioactive molecule antimicrobial peptide, remaining step and 6 phase of embodiment Together, the performance of composite material obtained is as shown in table 1.
The performance table of comparisons of composite material made from the different macromolecule addition of table 1
As shown in Table 1, the bactericidal activity of composite material made from the 2nd~6 group and slow release characteristic are due to the 1st and 7 group of reality It tests, wherein with the addition of macromolecule and bioactivity biocide molecule for 10~500:1 is best, this is because bioactivity is killed Bacterium molecule with it is high molecular than it is bigger when, bactericidal activity is stronger, and when the ratio of the two is excessive, and biocide molecule is by fast quick-release It puts, and can not be sustained;And when the ratio of the two is smaller, although the activity of the biomolecule kept is strong, composite wood obtained Expect unstable, biocide molecule will be fettered closely, can not be discharged.
Embodiment 8
Design 6 groups of parallel laboratory tests, the mass percent of the mixed solution system of preparation be respectively 0.05wt%, 0.1wt%, 3wt%, 7wt%, 10wt%, 11wt%, bioactivity antimicrobial molecule enhance albumen, remaining step and reality using sterilization-infiltration Apply that example 6 is identical, the performance of bactericidal plastic obtained is as shown in table 2.
Table 2 prepares the performance table of comparisons of bactericidal plastic made from different quality volumetric concentration
As shown in Table 2, composite wood made from experiment of the bactericidal activity of composite material made from the 2nd~6 group better than the 1st group The bactericidal activity of material, slow release characteristic are better than the slow release characteristic of composite material made from the 6th group of experiment, this is because the mixing prepared When the mass fraction of system is too small, the inactivation ratio of bioactive molecule can be caused to increase, and prepare mass fraction it is excessive when, Bioactive molecule will be unable to equably be adsorbed on macromolecule, so that composite material obtained is uneven, slow release characteristic Difference.
Embodiment 9
Design 6 groups of parallel laboratory tests, the grain size of the polymer nano-particle of preparation be respectively 40nm, 100nm, 500nm, 1000nm, 1500nm, 1600nm, remaining step is same as Example 6, and the performance of composite material obtained is as shown in table 3.
The performance table of comparisons of composite material made from 3 high molecular different-grain diameter of table
Group number 1 2 3 4 5 6
Grain size/nm 40 100 500 1000 1500 1600
Bactericidal activity By force By force It is relatively strong It is medium Preferably It is poor
Slow release characteristic It is good It is good It is medium It is medium Preferably It is poor
As shown in Table 3, better than the 6th group experiment of the bactericidal activity of composite material made from the 1st~5 group and slow release characteristic is made Composite material bactericidal activity and slow release characteristic, this is because high molecular grain size is bigger, the composite material of preparation is more uneven It is even, and bioactive molecule is wrapped, the poor activity of composite material, meanwhile, slow release speed also can not be uniform.
Embodiment 10
Design 6 groups of parallel laboratory tests, the pressure of setting be respectively 50MPa, 100MPa, 120MPa, 230MPa, 250MPa, 300MPa, remaining step is same as Example 6, and the performance of composite material obtained is as shown in table 4.
The performance table of comparisons of composite material obtained under the different pressure condition of table 4
Group number 1 2 3 4 5 6
Pressure/MPa 50 100 120 230 250 300
Bactericidal activity It is relatively strong It is relatively strong It is relatively strong It is medium It is medium It is poor
Slow release characteristic It is poor Preferably Preferably Preferably Preferably Preferably
As shown in Table 4, the bactericidal activity of composite material made from the 2nd~5 group is better than the 6th experiment composite material obtained Bactericidal activity, slow release characteristic are better than the slow release characteristic of composite material made from the 1st group, this is because when pressure is excessive, are easy The activity of biomolecule is destroyed, and when pressure is too small, composite material obtained is unstable, and slow release speed is also unstable.

Claims (7)

1. a kind of biological antibiotic plastics, it is characterised in that:The biological antibiotic plastics are made by following steps:Bioactivity is resisted Bacterium molecule is soluble in water, is configured to the mixed solution system of 0.1~10wt%, and polymer nano-particle is added into the system, It drains, and is put it into mold after mixing, after pressure is 100~250MPa, suppresses 1~20min under room temperature, let out Pressure, demoulding, obtain the biological antibiotic plastics, wherein the mass ratio of polymer nano-particle and bioactivity antimicrobial molecule is 5 ~1000:1, the grain size of the polymer nano-particle is 40~1500nm.
2. biological antibiotic plastics according to claim 1, it is characterised in that:The bioactivity antimicrobial molecule is bacteriolyze Enzyme, chitosan, antimicrobial peptide or sterilization-infiltration enhance albumen.
3. biological antibiotic plastics according to claim 1, it is characterised in that:The mass percent of the mixed solution system For 0.1~7wt%.
4. biological antibiotic plastics according to claim 1, it is characterised in that:The grain size of the polymer nano-particle is 40 ~1000nm.
5. biological antibiotic plastics according to claim 1, it is characterised in that:The grain size of the polymer nano-particle is 40 ~500nm.
6. biological antibiotic plastics according to claim 1, it is characterised in that:The polymer nano-particle and bioactivity The mass ratio of antimicrobial molecule is 10~500:1.
7. biological antibiotic plastics according to claim 1, it is characterised in that:The pressure is 120~230MPa.
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CN110451617A (en) * 2019-07-11 2019-11-15 石狮市星火铝制品有限公司 Sterilizing deodoring device and the method sterilized using the sterilizing deodoring device
CN111363270A (en) * 2020-03-31 2020-07-03 常德集智生物科技有限公司 Broad-spectrum antiviral bactericidal plastic and application thereof
CN111561743A (en) * 2020-06-01 2020-08-21 福建优净星环境科技有限公司 Sterilizing air conditioner indoor unit and sterilizing method adopting same

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CN101629004A (en) * 2009-07-30 2010-01-20 上海交通大学 Preparation method of rare earth modified nano TiO2/polytetrafluoroethylene composite
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