CN113185629A - L-borneol-based antibacterial polymer and preparation method and application thereof - Google Patents
L-borneol-based antibacterial polymer and preparation method and application thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 60
- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- DTGKSKDOIYIVQL-QXFUBDJGSA-N (-)-borneol Chemical compound C1C[C@]2(C)[C@H](O)C[C@H]1C2(C)C DTGKSKDOIYIVQL-QXFUBDJGSA-N 0.000 title abstract description 29
- 229930006703 (-)-borneol Natural products 0.000 title abstract description 29
- 229940116229 borneol Drugs 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 238000007872 degassing Methods 0.000 claims abstract description 13
- 230000008014 freezing Effects 0.000 claims abstract description 12
- 238000007710 freezing Methods 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 150000001262 acyl bromides Chemical class 0.000 claims abstract description 8
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
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- 241000588724 Escherichia coli Species 0.000 claims description 17
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
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- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 150000003512 tertiary amines Chemical group 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 6
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- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical group CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- LSCYTCMNCWMCQE-UHFFFAOYSA-N n-methylpyridin-4-amine Chemical compound CNC1=CC=NC=C1 LSCYTCMNCWMCQE-UHFFFAOYSA-N 0.000 claims description 5
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- 230000001580 bacterial effect Effects 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
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- 238000001291 vacuum drying Methods 0.000 description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 3
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 3
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 3
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- 238000000926 separation method Methods 0.000 description 3
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
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- 238000009631 Broth culture Methods 0.000 description 2
- GNGSQLYNLOIDAU-UHFFFAOYSA-N C(C(C)C)(=O)Br.[Br] Chemical compound C(C(C)C)(=O)Br.[Br] GNGSQLYNLOIDAU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
- A01N37/04—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof polybasic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Abstract
The invention discloses a levo-borneol-based antibacterial polymer and a preparation method and application thereof, belonging to the field of polymer synthetic chemistry. The invention takes levo-borneol and halogenated acyl bromide as raw materials, and synthesizes levo-borneol initiator through esterification reaction under inert gas; the L-borneol initiator is dispersed in a solvent, an acrylate monomer containing a tertiary amine group and a catalyst auxiliary agent are sequentially added, the freezing and degassing treatment is carried out, the catalyst is added in a freezing and solidifying state, the oxygen removing treatment is carried out, and then the polymerization reaction is carried out, so as to prepare the L-borneol-based antibacterial polymer. The method for preparing the antibacterial polymer based on the natural product L-borneol expands a new idea for the synthesis of antibacterial materials; the combination of the essential oil and the cationic polymer system exerts respective advantages, the obtained polymer shows good antibacterial activity, is expected to fundamentally reduce the abuse problem of antibiotic drugs, and has wide application prospect in the field of biological antibiosis.
Description
Technical Field
The invention belongs to the field of high-molecular synthetic chemistry, and particularly relates to a levo-borneol-based antibacterial polymer and a preparation method and application thereof.
Background
The use of essential oil in the fields of medicine and food storage has been for thousands of years, and the broad-spectrum antibacterial property of the essential oil is also proved by extensive experimental data. As consumers place more and more emphasis on food safety, they prefer to goods that do not contain synthetic additives. Therefore, much attention has been paid to maximizing the use of natural essential oils. The way of obtaining the essential oil comprises the traditional steam distillation, steam entrainment, organic solvent extraction and low-temperature squeezing, and the ways of supercritical fluid extraction, ultrasonic wave, microwave-assisted extraction and the like are derived along with the technical innovation. With the gradual and deep research on the antibacterial intrinsic mechanism of the essential oil, the main target point of the action is cell membrane, and the purpose of killing microorganisms is achieved by influencing the permeability and integrity of the cell membrane. However, the slow release system of essential oil, which is widely researched, has the serious disadvantages that the release rate is not controllable and the reusability is not enough, so that the antibacterial property is lost in a short time, and the practical application of the essential oil is not facilitated.
The quaternary ammonium salt compound has good antibacterial activity and biocompatibility, so that the quaternary ammonium salt compound becomes an antibacterial material which is widely used except antibacterial drugs. The generally accepted antibacterial mechanism involves the following steps (1) electrostatic attraction of the electropositive quaternary ammonium salt to the surface of the microorganism (2) adsorption and disruption of the cytoplasmic membrane by lipophilic alkyl chain driven diffusion across the cell wall (3), resulting in leakage of cytoplasmic components and death of the microorganism. Compared with micromolecular quaternary ammonium salt, the cationic polymer containing quaternary ammonium groups has obvious advantages of less toxicity to mammalian cells, higher selectivity and longer effective period, and the cationic polymer antibacterial compound has charge density which is several times of that of micromolecular monomers and has larger interaction degree with bacteria, thereby bringing more remarkable antibacterial activity. Polydimethylaminoethyl methacrylate (PDMAEMA) is a common cationic polymer, the protonation degree of tertiary amine groups on the side chain depends on the pH value of the solution, and PDMAEMA shows good antibacterial effect in an acidic environment or after quaternization, but the antibacterial performance of PDMAEMA still needs to be improved (see Reactive and Functional Polymers,2007,67(4): 355-.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a levo-borneol-based antibacterial polymer and a preparation method and application thereof.
According to the invention, the natural product L-borneol is prepared into an atom transfer radical polymerization initiator to initiate DMAEMA polymerization, so that the natural essential oil product is combined with a traditional polymer system, the influence of the synergistic antibacterial property and the molecular weight on the antibacterial activity of the L-borneol-based polymer is explored, and the L-borneol-based polymer is expected to have a larger application value in the field of polymer antibacterial.
Specifically, the natural product and acyl bromide are subjected to simple esterification reaction to synthesize an initiator, cuprous halide/polyamine is used as a catalyst, dimethylaminoethyl methacrylate is used as a polymerization monomer, active polymerization reaction is carried out in an organic solvent medium at the polymerization temperature of 40-60 ℃ for 10-16 hours, and the antibacterial polymer based on the natural product can be obtained through purification treatment after the reaction is finished.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an L-borneol-based antibacterial polymer comprises the following steps:
(1) the levo-borneol initiator is synthesized by esterification reaction of levo-borneol and halogenated acyl bromide serving as raw materials under inert gas;
(2) dispersing the levo-borneol initiator obtained in the step (1) into a solvent, sequentially adding an acrylate monomer containing a tertiary amine group and a catalyst auxiliary agent, carrying out freeze degassing treatment, adding a catalyst in a frozen and solidified state, carrying out oxygen removal treatment, and then carrying out polymerization reaction to prepare the levo-borneol-based antibacterial polymer.
Preferably, the esterification reaction in the step (1) is specifically as follows:
adding levo-borneol, amine and 4-methylamino pyridine into an organic solvent under inert atmosphere, and stirring for dissolving; placing the mixture into an ice water bath, dropwise adding a halogenated acyl bromide solution, condensing and refluxing, then removing the ice water bath, and continuing to condense and reflux at room temperature to obtain the levo-borneol initiator.
Further preferably, the dosage ratio of the levo-borneol, the amine, the 4-methylamino pyridine, the halogenated acyl bromide and the organic solvent is 1 mol: 6-8 mol: 2-3 mol: 10-15 ml: 250-350 ml;
further preferably, the time of the ice-water bath condensation reflux is 1-3 h; the time of condensing reflux at room temperature is 40-60 h;
further preferably, the organic solvent is anhydrous dichloromethane;
further preferably, the amine is triethylamine.
Preferably, after the esterification reaction in the step (1) is finished, the salt generated by the reaction is removed by suction filtration, and then the levoborneol initiator is obtained by rotary evaporation concentration, water washing, acid washing and alkali washing, and finally the saturated salt solution is used for accelerating layering, extraction and drying.
Further preferably, the acid washing, alkali washing and saturated salt solution are 0.1mol/L hydrochloric acid solution, saturated sodium bicarbonate and saturated sodium chloride solution respectively.
Preferably, the haloacyl bromide in step (1) is bromoisobutyryl bromide.
Preferably, the inert atmosphere in step (1) is nitrogen or argon atmosphere.
Preferably, the acrylic ester monomer containing the tertiary amine group in the step (2) is dimethylaminoethyl methacrylate;
preferably, the solvent in the step (2) is methanol;
preferably, the catalyst promoter in the step (2) is pentamethyldiethylenetriamine;
preferably, the catalyst in the step (2) is cuprous bromide.
Preferably, the molar ratio of the acrylate monomer containing the tertiary amine group, the levo-borneol initiator, the catalyst auxiliary agent and the catalyst in the step (2) is (15-120): 1, (1-3): 1-2. Further preferably, the molar ratio of the acrylate monomer containing the tertiary amine group, the levoborneol initiator, the catalyst promoter and the catalyst is 15:1:1: 1.
Preferably, the freeze degassing treatment in the step (2) is at least three times of freeze degassing operation; the catalyst is added within 5-10 s after the freezing and degassing operation; the deoxidization treatment is deoxidization operation 2 ~ 3 times.
Preferably, the temperature of the polymerization reaction is 40-60 ℃ and the time is 10-16 h.
Preferably, the polymerization reaction is atom transfer radical polymerization.
The levo-borneol-based antibacterial polymer prepared by the preparation method.
The application of the L-borneol-based antibacterial polymer as an antibacterial material.
Preferably, the bacteria are gram-negative escherichia coli and gram-positive staphylococcus aureus.
The structural formula of the levo-borneol is as follows:
the structural formula of the bromine isobutyryl bromide is as follows:
the structural general formula of the natural product based cationic polymer is as follows:
wherein n is an integer of 15 to 100;
the method selects and uses the nuclear magnetic resonance hydrogen spectrum (1HNMR) and determining the molecular weight and molecular weight distribution of the copolymer by Gel Permeation Chromatography (GPC).
The following experimental section is provided to illustrate the testing method, but should not be construed as limiting the scope of the invention in any way. The experimental part is as follows:
1the instrument model is Bruker AVANCE III HD 600mHz during H NMR test, and the selected solvent is deuterated chloroform (CDCl)3) And with reference to CDCl3The solvent peak (7.26ppm) of (A) was subjected to chemical shift correction.
The GPC measurement was performed with a Waters 2414 apparatus, THF/Et solvent was used3N, and molecular weight distribution corrections were made using standard curves established with polystyrene standards.
An enzyme-labeling instrument used for measuring optical density in the antibacterial test is American Berton circulation 5, the wavelength of the absorption light is 600nm, and LB broth culture medium is used for gradient dilution of bacterial liquid.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention discloses a method for synthesizing an antibacterial polymer based on a natural product, and provides a new choice for the synthesis of an environment-friendly biological antibacterial material.
(2) The natural product and the polymer system are connected through the covalent bond in the method, and compared with a natural product slow-release system, the natural product slow-release antibacterial agent can achieve longer antibacterial activity and has better antibacterial property.
(3) The antibacterial test used in the method has high feasibility and visual data.
(4) The ATRP reaction has good control on polymerization reaction, and is convenient for subsequent design of polymer molecules.
Drawings
FIG. 1 is a preparation of bromo-levo-borneol initiator prepared in example 11HNMR map.
FIG. 2 is a drawing showing the preparation of L-borneol-based dimethylamino ethyl polymethacrylate prepared in examples 2 to 51HNMR map.
FIG. 3 is a GPC chart of levo-borneol-based poly (dimethylaminoethyl methacrylate) prepared in examples 2-5.
FIG. 4 is a graph showing the growth of L-borneol-based poly (dimethylaminoethyl methacrylate) prepared in example 2 when co-cultured with E.coli.
FIG. 5 is a graph showing the growth of L-borneol-based poly (dimethylaminoethyl methacrylate) prepared in example 2 in coculture with Staphylococcus aureus.
FIG. 6 is a reaction scheme for preparing bromo-L-borneol initiator and L-borneol-based antibacterial polymer.
Detailed Description
The invention will be further described with reference to specific embodiments, but the scope of the invention is not limited thereto.
The method selects and uses the nuclear magnetic resonance hydrogen spectrum (1HNMR) and determining the molecular weight and molecular weight distribution of the copolymer by Gel Permeation Chromatography (GPC).
The following experimental section is provided to illustrate the test method; the experimental part is as follows:
1the instrument model is Bruker AVANCE III HD 600mHz during H NMR test, and the selected solvent is deuterated chloroform (CDCl)3) And with reference to CDCl3The solvent peak (7.26ppm) of (A) was subjected to chemical shift correction.
The GPC measurement was performed with a Waters 2414 apparatus, THF/Et solvent was used3N, and molecular weight distribution corrections were made using standard curves established with polystyrene standards.
An enzyme-labeling instrument used for measuring optical density in the antibacterial test is American Berton circulation 5, the wavelength of the absorption light is 600nm, and LB broth culture medium is used for gradient dilution of bacterial liquid.
Example 1
The preparation of bromo-levo-borneol initiator, the preparation process refers to the route of fig. 6, and comprises the following steps:
adding levo-borneol (3.054g,0.0198mol), triethylamine (18.96mL,0.136mol), 4-methylaminopyridine DMAP (6.0474g, 0.0495mol) and 150mL of anhydrous dichloromethane into a 50mL three-neck flask in turn, and stirring to fully dissolve under the protection of nitrogen; bromoisobutyryl bromide (12.06ml) was added to a constant pressure funnel, diluted with the same volume of anhydrous dichloromethane and placed in a three-necked flask in an ice-water bath. And (3) connecting condensation circulating water, dropwise adding bromine isobutyryl bromide to start reaction for 2 hours, then removing the ice water bath, and reacting for 48 hours at room temperature of 25 ℃. After the reaction is finished, adding a small amount of solvent to scrub the bottle wall, and performing suction filtration, washing, extraction and drying to obtain 4.743g of bromo-levo-borneol initiator, wherein the calculated reaction yield is 79%; it is composed of1The HNMR map is shown in FIG. 1.
Example 2
The preparation process of the levo-borneol-based dimethylamino ethyl polymethacrylate refers to the route of figure 6 and comprises the following steps:
to a 50mL Schlenk bottle were added in sequence bromo-levo-borneol initiator (0.3828g,1.263mmol), dimethylaminoethyl methacrylate (3.193mL,183945mmol) and pentamethyldiethylenetriamine (0.265mL, 1.263mmol) dissolved in 5mL of methanol. And (3) placing the reaction flask into liquid nitrogen to be quickly frozen in a nitrogen-filled environment until the solution is completely solidified, then closing the nitrogen and vacuumizing for 5min, finally introducing the nitrogen, placing the nitrogen into water to completely dissolve the solid, and repeating the freezing and degassing operation for three times. Freezing and solidifying again in liquid nitrogen, adding cuprous bromide powder (0.181g, 1.263mmol) rapidly, then repeating the oxygen removing operation three times, and placing the Schlenk bottle in a 45 ℃ oil bath for reaction for 10 h. After the reaction is finished, adding 5mL of tetrahydrofuran to dilute the reaction solution, removing the catalyst in the reaction system by using a neutral alumina column, carrying out rotary evaporation concentration on the separated filtrate, then precipitating in ice-n-hexane, standing, pouring out the supernatant, and carrying out vacuum drying at room temperature. To obtain 1.6g of levo-borneol-based dimethylamino ethyl polymethacrylate, and the calculated reaction yield is 45.2%. It is composed of1The HNMR chart is shown in FIG. 2, which is a GPC curve corresponding to P16 in FIG. 3, and the number of repeating units in the polymer prepared in this example is 16.
Example 3
The preparation process of the levo-borneol-based dimethylamino ethyl polymethacrylate refers to the route of figure 6 and comprises the following steps:
to a 50mL Schlenk bottle were added bromo-levoborneol initiator (0.4397g,1.45mmol), dimethylaminoethyl methacrylate (7.34mL,43.5mmol) and pentamethyldiethylenetriamine (0.265mL, 1.45mmol) in that order, dissolved in 5mL of methanol. And (3) placing the reaction flask into liquid nitrogen to be quickly frozen in a nitrogen-filled environment until the solution is completely solidified, then closing the nitrogen and vacuumizing for 5min, finally introducing the nitrogen, placing the nitrogen into water to completely dissolve the solid, and repeating the freezing and degassing operation for three times. Freezing and solidifying again in liquid nitrogen, adding cuprous bromide powder (0.208g, 1.45mmol) rapidly, and removing oxygen repeatedlyAnd thirdly, placing the Schlenk bottle in a 45 ℃ oil bath kettle for reaction for 11 hours. After the reaction is finished, 10mL of tetrahydrofuran is added to dilute the reaction solution, a neutral alumina column is used for removing the catalyst in the reaction system, the filtrate obtained by separation is subjected to rotary evaporation and concentration, then the precipitate is precipitated in n-hexane, the supernatant is poured out by standing, and vacuum drying is carried out at room temperature. 3.748g of levo-borneol-based dimethylamino ethyl polymethacrylate is obtained, and the calculated reaction yield is 51.5%. It is composed of1The HNMR chart is shown in FIG. 2, which is a GPC curve corresponding to P30 in FIG. 3, and the number of repeating units in the polymer prepared in this example is 30.
Example 4
The preparation process of the levo-borneol-based dimethylamino ethyl polymethacrylate refers to the route of figure 6 and comprises the following steps:
to a 50mL Schlenk bottle were added bromo-levoborneol initiator (0.4g,1.32mmol), dimethylaminoethyl methacrylate (6.67mL,39.6mmol) and pentamethyldiethylenetriamine (0.276mL, 1.33mmol) in that order, dissolved in 5mL of methanol. And (3) placing the reaction flask into liquid nitrogen to be quickly frozen in a nitrogen-filled environment until the solution is completely solidified, then closing the nitrogen and vacuumizing for 5min, finally introducing the nitrogen, placing the nitrogen into water to completely dissolve the solid, and repeating the freezing and degassing operation for three times. Freezing and solidifying again in liquid nitrogen, adding cuprous bromide powder (0.189g, 1.33mmol) rapidly, then repeating the oxygen removing operation three times, and placing the Schlenk bottle in a 45 ℃ oil bath for reaction for 12 h. After the reaction is finished, 10mL of tetrahydrofuran is added to dilute the reaction solution, a neutral alumina column is used for removing the catalyst in the reaction system, the filtrate obtained by separation is subjected to rotary evaporation and concentration, then the precipitate is precipitated in n-hexane, the supernatant is poured out by standing, and vacuum drying is carried out at room temperature. 3.564g of levo-borneol-based dimethylamino ethyl polymethacrylate is obtained, and the calculated reaction yield is 34.3 percent. It is composed of1The HNMR chart is shown in FIG. 2, which is a GPC curve corresponding to P50 in FIG. 3, and the number of repeating units in the polymer prepared in this example is 50.
Example 5
The preparation process of the levo-borneol-based dimethylamino ethyl polymethacrylate refers to the route of figure 6 and comprises the following steps:
to 50mL of SchlenkBromo-levo-borneol initiator (0.1427g,0.471mmol), dimethylaminoethyl methacrylate (9.52ml,56.5mmol) and pentamethyldiethylenetriamine (0.099ml, 0.473mmol) were added in order to a vial, and dissolved in 10ml of methanol. And (3) placing the reaction flask into liquid nitrogen to be quickly frozen in a nitrogen-filled environment until the solution is completely solidified, then closing the nitrogen and vacuumizing for 5min, finally introducing the nitrogen, placing the nitrogen into water to completely dissolve the solid, and repeating the freezing and degassing operation for three times. Freezing and solidifying again in liquid nitrogen, adding cuprous bromide powder (0.0675g, 0.471mmol) rapidly, then repeating the deoxidization operation three times, and placing the Schlenk bottle in a 45 ℃ oil bath for reaction for 13 h. After the reaction is finished, 10mL of tetrahydrofuran is added to dilute the reaction solution, a neutral alumina column is used for removing the catalyst in the reaction system, the filtrate obtained by separation is subjected to rotary evaporation and concentration, then the precipitate is precipitated in n-hexane, the supernatant is poured out by standing, and vacuum drying is carried out at room temperature. 3.54g of levo-borneol-based dimethylamino ethyl polymethacrylate is obtained, and the calculated reaction yield is 47%. It is composed of1The HNMR chart is shown in FIG. 2, the GPC curve of which corresponds to P100 in FIG. 3, and the number of repeating units of the polymer prepared in this example is 100.
Example 6
MIC is an effective method for evaluating antibacterial performance. The test was performed on representative gram-positive Staphylococcus aureus and gram-negative Escherichia coli by gradient dilution, and the culture broth was prepared by adding 2.1g of LB broth per 100ml of distilled water, and all operations related to bacteria were performed on a sterile bench. First, a single strain of bacteria was extracted from a solid medium containing bacteria and co-cultured with LB broth overnight at 37 ℃ on a shaker at 150 rpm. Then, 30. mu.L of the culture broth was taken out from the culture tube, transferred to 3mL of fresh LB medium, and cultured under the same conditions until the half-exponential growth phase, and the polymer was dissolved in deionized water to prepare an antibacterial sample with a concentration of 4.0mg/mL, and was subjected to gradient dilution through a 96-well plate. Finally, 20 μ L of the bacterial solution is added, mixed with the polymer solution uniformly, and placed into a constant temperature incubator for 24 h. In the MIC test, each sample was run in triplicate to ensure reliability of data for each bacterium, and the polymer-free broth was set as a positive control and pure LB medium as a negative control.
TABLE 1(-) MICs data of Borneol-PDMAEMA against Staphylococcus aureus (S. aureus)
TABLE 2(-) MICs data of Borneol-PDMAEMA on E.coli (E.coli)
As can be seen from the data in Table 1/2, the characteristic of the L-borneol that is difficult to dissolve in water results in that the MIC value of the L-borneol is dozens of times higher than that of the polymer, and the antibacterial efficiency is limited. Meanwhile, the PDMAEMA homopolymer without the essential oil active ingredients shows partial antibacterial effect, and a certain distance is required to participate in practical application. The L-borneol is prepared into an initiator, the two components play a synergistic antibacterial effect after DMAEMA polymerization is initiated, the polymer with the repeating unit number of 16 shows good antibacterial activity, the growth and the propagation of escherichia coli are inhibited under the concentration of 0.125mg/mL of the polymer, and the minimum inhibitory concentration for staphylococcus aureus is 0.25 mg/mL. And it is difficult to see that the activity of the L-borneol-based dimethylamino ethyl polymethacrylate for inhibiting escherichia coli is higher than that of staphylococcus aureus, the antibacterial activity is reduced along with the increase of the molecular weight, the larger the molecular weight of the obtained polymer is, the smaller the mole fraction of the L-borneol is, the polymer structure is similar to pure PDMAEMA, and the understanding that the antibacterial effect is reduced on the contrary along with the continuous increase of the molecular weight is also difficult.
Example 7
The minimum bactericidal concentration is the minimum concentration required for the polymer sample to kill planktonic cultured bacteria. First, a solid medium was prepared by adding 1.5g of agar powder per 100ml of LB broth medium, and was used for drop plating to determine whether or not a clear coculture sample also contained viable bacteria. And taking out 10 mu L of the turbid co-culture solution in the MIC test, dripping the turbid co-culture solution into an LB solid culture medium, repeatedly dripping the co-culture solution with each concentration three times, putting the dried solid culture medium into a constant temperature incubator for culturing for 24 hours, and finding out the concentration corresponding to the growth of the bacterial colony as the minimum bactericidal concentration of the polymer sample.
TABLE 3(-) Borneol-PDMAEMA MBCs data for Staphylococcus aureus (S. aureus)
TABLE 4(-) Borneol-PDMAEMA data on MBCs of E.coli (E.coli)
As shown in table 3/4, the MBC value is substantially consistent with the MIC value, which indicates that the cationic polymer directly kills microorganisms rather than inhibits the growth of microorganisms, and the trend is that the antibacterial activity decreases with the increase of molecular weight, so that the ratio of cationic and hydrophobic components should have a parabolic trend on the antibacterial activity when designing the polymer, and there is an optimal range in which the degree of synergy between the cationic and hydrophobic components is the greatest, the obtained polymer has the highest antibacterial activity, and the molecular weight is too high, which would rather hinder the penetration of the polymer into cell membranes, and similarly, the hydrophobicity is too strong (taking levo-borneol as an example), which greatly reduces the solubility of the polymer in water, and the antibacterial performance decreases obviously. More importantly, the MBC data can reflect the synergistic effect of the combination of the essential oil active ingredients and the cationic polymer in the antibacterial direction.
Example 8
The microorganisms (E.coli and Staphylococcus aureus) were cultured in LB medium overnight at 37 ℃. Then, the obtained bacterial liquid was transferred to a fresh medium and subjected to scale-up culture for 4 hours. (L) Borneol, (L) B-PDMAEMA (example 2, number of repeating unit 16) and MP (dimethylamino ethyl methacrylate homopolymer without L-Borneol) were prepared in advance at 0.125mg/ml (test species is Escherichia coli) and 0.25mg/ml (test species is Staphylococcus aureus or Escherichia coli), and the medium without polymer was used as a blank. Adding the expanded bacteria into the culture tube, placing in a shaking table at 37 deg.C and 150rpm, collecting 200 μ L of co-culture solution each time, and measuring OD with microplate reader600Value, OD, in time as abscissa600Values are plotted as ordinate and the effect of levo-borneol polymer on bacterial growth is observed.
FIG. 4 shows the growth profile of Escherichia coli in cocultivation;
the growth profile of Staphylococcus aureus co-cultures is shown in FIG. 5; wherein, control is blank control, MP is polymer without natural borneol component, and L) B is commercial natural product L-borneol.
As shown in fig. 4/5, the optical density of the blank control group remained unchanged after increasing, and the MP without L-Borneol and pure essential oil (L) Borneol tended to be the same as the control group, showing partial antibacterial effect. While only the sample of L-borneol-based poly (dimethylaminoethyl methacrylate) with the concentration of 0.125mg/mL (1 × MIC) is added, on the growth curve of escherichia coli, the optical density value is always kept near the initial value (the small jump of the optical density value at 30min is caused by the dissolution process of the polymer), no large fluctuation exists, the optical density value of the same sampling point is lower than that of an MP sample and an L-borneol sample, and as can be seen from the figure, within 2h, the optical density values of the other control groups began to increase rapidly, while the optical density values of the levo-borneol-based polymer group tended to plateau instead, then gradually starts to decrease, which shows that the L-borneol-based polymer of the experimental group completely inhibits the propagation of the Escherichia coli, even in the overnight culture, the optical density remained unchanged, indicating that E.coli had been completely cleared by L-borneol-based PDMAEMA. Similar trends were also shown for Staphylococcus aureus, and the optical density values of the experimental groups consistently showed a decreasing trend, meaning that the polymer was able to completely inhibit bacterial propagation. In the growth curve chart, the MP and the L-Borneol have partial antibacterial effects, but the (L) Borneol-PDMAEMA obtained by organically combining the MP and the L-Borneol through ATRP shows more excellent antibacterial effects, and the antibacterial synergistic effect between the MP and the L-Borneol is intuitively explained.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the levo-borneol-based antibacterial polymer is characterized by comprising the following steps:
(1) the levo-borneol initiator is synthesized by esterification reaction of levo-borneol and halogenated acyl bromide serving as raw materials under inert gas;
(2) dispersing the levo-borneol initiator obtained in the step (1) into a solvent, sequentially adding an acrylate monomer containing a tertiary amine group and a catalyst auxiliary agent, carrying out freeze degassing treatment, adding a catalyst in a frozen and solidified state, carrying out oxygen removal treatment, and then carrying out polymerization reaction to prepare the levo-borneol-based antibacterial polymer.
2. The preparation method according to claim 1, wherein the esterification reaction in step (1) is specifically:
adding levo-borneol, amine and 4-methylamino pyridine into an organic solvent under inert atmosphere, and stirring for dissolving; placing the mixture into an ice water bath, dropwise adding a halogenated acyl bromide solution, condensing and refluxing, then removing the ice water bath, and continuing to condense and reflux at room temperature to obtain the levo-borneol initiator.
3. The preparation method according to claim 2, wherein the dosage ratio of the levoborneol, the amine, the 4-methylaminopyridine, the halogenated acyl bromide and the organic solvent is 1 mol: 6-8 mol: 2-3 mol: 10-15 ml: 250-350 ml; the time of ice-water bath condensation reflux is 1-3 h; the time of condensing reflux at room temperature is 40-60 h; the organic solvent is anhydrous dichloromethane; the inert atmosphere is nitrogen or argon atmosphere.
4. The method according to claim 1, wherein the acrylic monomer containing a tertiary amine group in the step (2) is dimethylaminoethyl methacrylate; the solvent is methanol; the catalyst auxiliary agent is pentamethyl diethylenetriamine; the catalyst is cuprous bromide.
5. The preparation method of claim 1, wherein the molar ratio of the acrylate monomer containing the tertiary amine group in the step (2), the levoborneol initiator, the catalyst auxiliary and the catalyst is (15-120): 1 (1-3): 1-2.
6. The method according to claim 1, wherein the freeze degassing treatment of the step (2) is at least three times of freeze degassing; the catalyst is added within 5-10 s after the freezing and degassing operation; the deoxidization treatment is deoxidization operation 2 ~ 3 times.
7. The method according to claim 1, wherein the polymerization in step (2) is carried out at a temperature of 40 to 60 ℃ for a time of 10 to 16 hours.
8. The levo-borneol-based antibacterial polymer prepared by the preparation method of any one of claims 1 to 7.
9. The use of the levo-borneol-based antibacterial polymer of claim 8 as an antibacterial material.
10. Use according to claim 9, wherein the bacteria are gram-negative escherichia coli and gram-positive staphylococcus aureus.
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