CN110961030A - Morpholine head-based cationic gemini surfactant and preparation and application thereof - Google Patents
Morpholine head-based cationic gemini surfactant and preparation and application thereof Download PDFInfo
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- C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
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Abstract
The invention relates to a morpholine head group cation gemini surfactant, which has the following structural formula:
or
Wherein m is 10, 12,14 or 16, and X is Cl or Br. The preparation method comprises the following steps: (1) carrying out substitution reaction on morpholine and 1-bromoalkane to obtain N-alkyl morpholine; (2) by reacting N-alkylmorpholine with biphenyl dihalobenzyl or p-diThe benzyl halide is subjected to quaternization. The morpholine head-based cationic gemini surfactant has stronger bactericidal performance and excellent molecular solubility and surface activity; can be used for sterilization; the preparation raw materials are cheap and easy to obtain, the reaction condition is mild, the operation is simple, and the yield and the purity of the obtained product are high. The morpholine head group and biphenyl coupling group cationic gemini surfactant has better sterilization performance on escherichia coli and bacillus subtilis than that of a commercially available bactericide benzalkonium bromide, and can reduce the dosage of the bactericide, reduce the cost and reduce the pollution in use. The CMC value is 1-2 orders of magnitude lower than that of the corresponding traditional surfactant, and the efficiency of reducing the surface tension of the aqueous solution is higher than that of the traditional surfactant.
Description
Technical Field
The invention belongs to the field of surfactant science and application, and particularly relates to a morpholine head group cationic gemini surfactant as well as preparation and application thereof.
Background
The traditional single-chain cationic surfactant has the functions of antibiosis and sterilization, and has a wide application range, such as the commonly used bactericide of benzalkonium chloride (dodecyl dimethyl benzyl ammonium chloride). However, when the surfactant is used for sterilization for a long time, microorganisms can generate certain drug resistance to the surfactant, so that the drug effect is continuously reduced, the adding amount is gradually increased, the use cost is increased year by year, and the environmental pollution is caused, so that the search for a novel efficient bactericide is urgent.
Cationic Gemini (Gemini) surfactants are a new class of surfactants that have emerged in recent years and are formed by linking two hydrophilic head groups and two hydrophobic tail chains at or near their hydrophilic head groups via a linking group. Compared with the traditional surfactant, the cationic Gemini surfactant has the advantages of higher surface activity, lower critical micelle concentration, stronger interface adsorption capacity and the like in an aqueous solution. Compared with the traditional single-chain bactericide, the cationic Gemini surfactant has higher head group positive charge density and hydrophobic chain density due to the advantages of the molecular structure, can be better adsorbed on the surface of bacteria, and has strong hydrophobic effect with a lipoid layer of cells, thereby obtaining better sterilization effect. Due to the excellent stability and the synthesis simplicity of Gemini surfactant molecules, groups with a sterilization function can be introduced into the surfactant molecules in the molecular design process, and the sterilization performance of the Gemini surfactant molecules is improved in a targeted manner.
Researches show that biphenyl is a group with good bactericidal effect, but the derivative of biphenyl has poor water solubility due to the larger rigidity of biphenyl group, which seriously influences the application of biphenyl bactericides.
Disclosure of Invention
The invention aims to provide a morpholine head group cationic gemini surfactant and preparation and application thereof, and aims to solve the problems that the derivative of the morpholine head group cationic gemini surfactant is poor in water solubility due to high rigidity of biphenyl groups, application of biphenyl bactericides is seriously affected and the like.
Morpholine head group cation gemini surfactant has the following structural formula:
wherein m is 10-16, and X is Cl and Br. Preferably, m is 10, 12,14 or 16. The morpholine head-based cationic gemini surfactant can be used for sterilization, has better surface activity and sterilization performance than the traditional single-chain cationic surfactant, can reduce the dosage of the bactericide in practical application, reduces the cost and pollution, and has great significance for environmental protection and economic energy conservation.
The structural formula of the morpholine head group cationic gemini surfactant is as follows:
the synthetic route is as follows:
for convenience of description, according to the molecular structure and the contained groups, the Morpholine head group and the biphenyl coupling group cationic gemini surfactant are marked as Mor-BP-m, wherein Mor represents a Morpholine (morpholinone) head group, BP represents a biphenyl (biphenyl) coupling group, and m represents the number of carbon atoms on a hydrocarbon chain.
M ═ 10, 12,14, or 16, X ═ Cl, Br; the method mainly comprises the following steps:
(1) carrying out substitution reaction on morpholine and 1-bromoalkane to obtain N-alkyl morpholine;
(2) the N-alkyl morpholine and biphenyl dihalogen benzyl are subjected to quaternization reaction.
Preferably, the preparation of N-alkyl morpholine in step (1) essentially comprises: mixing 1-bromoalkane, morpholine and ethanol, heating for substitution reaction, removing ethanol by a rotary evaporator after the reaction is finished, neutralizing the residue with sodium hydroxide aqueous solution, extracting the obtained oil-water mixture with ethyl acetate, and combining organic phases, and drying with anhydrous magnesium sulfate overnight; after filtration, ethyl acetate was removed by a rotary evaporator to obtain a pale yellow oily liquid, which was finally distilled under reduced pressure.
Preferably, the quaternization reaction of the N-alkyl morpholine and the biphenyl dihalogen benzyl in the step (2) mainly comprises the following steps: mixing N-alkyl morpholine and biphenyl dihalogen benzyl, adding a solvent, heating for quaternization, removing the solvent by using a rotary evaporator after the reaction is finished, and recrystallizing by using an acetone/ethanol mixed system.
Preferably, the molar ratio of the 1-bromoalkane to the morpholine in the step (1) is 1 (1-6); the temperature of the substitution reaction is 75-90 ℃ and the time is 10-24 h.
Preferably, the molar ratio of the N-alkyl morpholine to the biphenyl dihalogen benzyl in step (2) is 1: (2-10); the temperature of the quaternization reaction is 70-100 ℃ and the time is 24-48 h.
Preferably, the 1-bromoalkane is 1-bromodecane, 1-bromododecane, 1-bromotetradecane or 1-bromohexadecane.
Preferably, the solvent is one or more of acetone, ethyl acetate, absolute ethyl alcohol, isopropyl alcohol or n-propyl alcohol.
The structural formula of the morpholine head group cationic gemini surfactant is as follows:
the synthetic route is as follows:
wherein m is 10, 12,14,16, X is Cl, Br, mainly including two steps:
(3) carrying out substitution reaction on morpholine and 1-bromoalkane to obtain N-alkyl morpholine;
(4) the N-alkyl morpholine and p-benzyl dihalide are subjected to quaternization reaction to obtain the heterocyclic head group and rigid linking group cationic gemini surfactant.
For convenience of description, the gemini surfactant is recorded as Mor-P-m according to the molecular structure and the contained groups, wherein Mor represents a Morpholine (morpholinone) head group, P represents a benzene ring (phenyl) linking group, and m represents the number of carbon atoms on a hydrocarbon chain.
According to the scheme, the specific steps in the step (1) are as follows: mixing 1-bromoalkane and morpholine ring, heating with ethanol as solvent for substitution reaction, removing solvent with rotary evaporator after reaction, neutralizing residue with sodium hydroxide water solution, extracting the obtained oil-water mixture with ethyl acetate, and combining organic phases, and drying with anhydrous magnesium sulfate overnight; filtering, removing ethyl acetate by using a rotary evaporator to obtain light yellow oily liquid, and finally carrying out reduced pressure distillation to obtain the high-purity N-alkyl morpholine.
Preferably, the 1-bromoalkane is 1-bromodecane, 1-bromododecane, 1-bromotetradecane or 1-bromohexadecane.
Preferably, the specific steps in step (2) are: mixing N-alkyl morpholine and p-benzyl dihalide, adding a solvent, heating for quaternization, removing the solvent by using a rotary evaporator after the reaction is finished, recrystallizing by using an acetone/ethanol mixed system to obtain white solid powder, and removing the residual solvent to obtain the high-purity heterocyclic head group and rigid linking group cationic gemini surfactant.
Preferably, the molar ratio of the 1-bromoalkane to the morpholine in the step (1) is 1 (1-6); the reaction temperature is 75-90 ℃ and the reaction time is 10-24 h.
Preferably, the molar ratio of the p-dichlorobenzyl to the N-alkyl morpholine in the step (2) is 1 (2-10); the reaction temperature is 75-100 ℃ and the reaction time is 24-48 h.
Preferably, the solvent used is acetone, ethyl acetate, absolute ethanol, isopropanol or n-propanol.
Preferably, the 1-bromoalkane, morpholine, p-dihalobenzyl and the like are all commercially available chemical reagents.
The morpholine head group cationic gemini surfactant is applied to sterilization and wetting. The invention uses gram-negative bacteria escherichia coli and gram-positive bacteria bacillus subtilis as indicator bacteria, and the Minimum Inhibitory Concentration (MIC) of the prepared gemini surfactant to the two bacteria is determined by a plate coating method. Experiments prove that the morpholine head-based cationic gemini surfactant has good surface performance and sterilization effect.
Compared with the prior art, the invention has the following advantages:
(1) the morpholine head group cationic gemini surfactant synthesized by the method takes 1-bromoalkane, morpholine and biphenyl dihalogen benzyl as raw materials, is cheap and easy to obtain, has mild reaction conditions and simple operation, and obtains products with higher yield and purity.
(2) According to the invention, morpholine and biphenyl groups are simultaneously introduced into cationic gemini surfactant molecules for the first time, and morpholine is introduced into a hydrophilic head group, so that on one hand, the sterilization performance of the molecules can be enhanced, and on the other hand, oxygen atoms on a ring can form hydrogen bonds with water molecules, thereby being beneficial to improving the solubility and surface activity of the molecules; biphenyl group is introduced into the linking group, the defect of extremely poor water solubility of biphenyl is overcome by utilizing good water solubility of the surfactant, and the sterilization performance of biphenyl is fully utilized. The introduction of two functional groups pertinently improves the bactericidal performance of molecules, the bactericidal performance to escherichia coli and bacillus subtilis is superior to that of a commercially available bactericide benzalkonium bromide, and the bactericide adding amount, the cost and the pollution can be reduced in use.
(3) The morpholine head group and biphenyl coupling group cationic gemini surfactant prepared by the method has good surface activity, the CMC value of the surfactant is 1-2 orders of magnitude lower than that of a corresponding traditional surfactant, and the efficiency of reducing the surface tension of an aqueous solution is higher than that of the traditional surfactant.
(4) In the invention, morpholine heterocycle is introduced on the head group of the gemini surfactant, benzene ring rigid group is introduced on the linking group, and the molecular structure is not reported. Compared with a methyl head group, the oxygen atom on the morpholine ring can form a hydrogen bond with water molecules, so that the hydration effect is enhanced, and the surface performance and the water solubility at low temperature of the surfactant are improved; the morpholine heterocycle has smaller polarity, is more favorable for surfactant molecules to aggregate in an aqueous solution to form micelles, has a lower CMC value, has lower MIC (minimum inhibitory concentration) on gram-negative bacteria escherichia coli and gram-positive bacteria bacillus subtilis, can improve the bacteriostatic efficiency in practical application, reduces the investment of a bactericide, reduces the cost and is favorable for environmental protection.
Drawings
FIG. 1 is a schematic synthesis scheme of a morpholino head group cationic gemini surfactant of the present invention;
FIG. 2 is a curve of surface tension of the aqueous solution of the gemini surfactant Mor-BP-m synthesized by the invention at 25 ℃ along with the change of concentration;
FIGS. 3-6 are graphs showing the variation of conductivity with concentration of the aqueous solution of the gemini surfactant Mor-BP-m synthesized at different temperatures;
FIG. 7 is a graph showing the variation of contact angle of the synthesized gemini surfactant Mor-BP-m aqueous solution on a polytetrafluoroethylene plate along with the concentration;
FIG. 8 is a nuclear magnetic hydrogen spectrum of the gemini surfactant Mor-BP-10 synthesized in example 1;
FIG. 9 is a nuclear magnetic hydrogen spectrum of the gemini surfactant Mor-BP-12 synthesized in example 2;
FIG. 10 is a nuclear magnetic hydrogen spectrum of the gemini surfactant Mor-BP-14 synthesized in example 3;
FIG. 11 is a nuclear magnetic hydrogen spectrum of the gemini surfactant Mor-BP-16 synthesized in example 4;
FIG. 12 is a graph showing the surface tension of the aqueous solution of the gemini surfactant Mor-P-m synthesized at 25 ℃ as a function of concentration;
FIGS. 13-16 are graphs showing the variation of conductivity with concentration of the aqueous solutions of the gemini surfactant Mor-P-m synthesized at different temperatures;
FIG. 17 is a graph showing the change of contact angle of the synthesized gemini surfactant Mor-P-m aqueous solution on a polytetrafluoroethylene plate according to concentration;
FIG. 18 is a nuclear magnetic hydrogen spectrum of the synthesized gemini surfactant Mor-P-10;
FIG. 19 is a nuclear magnetic hydrogen spectrum of the synthesized gemini surfactant Mor-P-12;
FIG. 20 is a nuclear magnetic hydrogen spectrum of the synthesized gemini surfactant Mor-P-14;
FIG. 21 is a nuclear magnetic hydrogen spectrum of the synthesized gemini surfactant Mor-P-16.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
A morpholine head group cationic gemini surfactant, wherein m is 10, and the preparation method of Mor-BP-10 is shown in figure 1, and comprises the following steps:
(1) intermediate product alkyl substituted morpholine C4H8NO-C10H21The synthesis steps are as follows: mixing 1-bromodecane and morpholine according to a molar ratio of 1:3, and reacting for 24 hours at 75 ℃ by using absolute ethyl alcohol as a solvent; after the reaction is finished, removing the solvent by using a rotary evaporator, and neutralizing the residue by using a sodium hydroxide solution; extracting the mixed solution with ethyl acetate for 3 times, combining organic phases, adding anhydrous magnesium sulfate, and drying overnight; filtering, removing ethyl acetate with rotary evaporator to obtain light yellow oily liquid, and vacuum distilling to obtain high purity alkyl substituted morpholine C4H8NO-C10H21The yield was 93.9%.
(2) The synthesis of Mor-BP-10 comprises the following steps: biphenyl dichlorobenzyl and alkyl substituted morpholine C4H8NO-C10H21According to the following steps of 1: 2.2, reacting for 48 hours at 75 ℃ by taking absolute ethyl alcohol as a solvent, cooling to room temperature after the reaction is finished, recrystallizing for 3 times by using an acetone/ethanol mixed system, filtering to obtain white solid powder, and removing a small amount of residual solvent to obtain the gemini surfactant Mor-BP-10, wherein the yield is 78.1%, the nuclear magnetic hydrogen spectrum diagram is shown in figure 8, and the obtained gemini surfactant Mor-BP-10 is high in purity as can be seen from figure 8.
Example 2
A morpholine head group cationic gemini surfactant, wherein m is 12, and the preparation method of Mor-BP-12 is shown in figure 1, and comprises the following steps:
(1) intermediate product alkyl substituted morpholine C4H8NO-C12H25The synthesis steps are as follows: mixing 1-bromododecane and morpholine according to a molar ratio of 1:3, and reacting for 20 hours at 80 ℃ by taking absolute ethyl alcohol as a solvent; after the reaction is finished, removing the solvent by using a rotary evaporator, and neutralizing the residue by using a sodium hydroxide solution; extracting the mixed solution with ethyl acetate for 3 times, combining organic phases, adding anhydrous magnesium sulfate, and drying overnight; filtering, removing ethyl acetate with rotary evaporator to obtain light yellow oily liquid, and vacuum distilling to obtain high purity alkyl substituted morpholine C4H8NO-C12H25Yield 92.6%.
(2) The synthesis step of Mor-BP-12 comprises the following steps: biphenyl dichlorobenzyl and alkyl substituted morpholine C4H8NO-C12H25According to the following steps of 1: 2.2, reacting at 80 ℃ for 36h by taking absolute ethyl alcohol as a solvent, cooling to room temperature after the reaction is finished, recrystallizing for 3 times by using an acetone/ethanol mixed system, filtering to obtain white solid powder, and removing a small amount of residual solvent to obtain the gemini surfactant Mor-BP-12, wherein the yield is 66.4%, a nuclear magnetic hydrogen spectrum diagram is shown in figure 9, and the obtained gemini surfactant Mor-BP-12 is high in purity as can be seen from figure 9.
Example 3
A morpholine head group cationic gemini surfactant, wherein m is 14, and the preparation method of Mor-BP-14 is shown in figure 1, and comprises the following steps:
(1) intermediate product alkyl substituted morpholine C4H8NO-C14H29The synthesis steps are as follows: mixing 1-bromotetradecane and morpholine according to a molar ratio of 1:4, and reacting for 16h at 85 ℃ by using absolute ethyl alcohol as a solvent; after the reaction is finished, removing the solvent by using a rotary evaporator, and neutralizing the residue by using a sodium hydroxide solution; extracting the mixed solution with ethyl acetate for 3 times, combining organic phases, adding anhydrous magnesium sulfate, and drying overnight; filtering, and removing ethyl acetate by rotary evaporatorObtaining light yellow oily liquid, and obtaining high-purity alkyl substituted morpholine C by reduced pressure distillation4H8NO-C14H29The yield was 90.1%.
(2) The synthesis step of Mor-BP-14 comprises the following steps: biphenyl dichlorobenzyl and alkyl substituted morpholine C4H8NO-C14H29According to the following steps of 1:6, using isopropanol as a solvent, reacting at 90 ℃ for 32 hours, cooling to room temperature after the reaction is finished, recrystallizing for 3 times by using an acetone/ethanol mixed system, filtering to obtain white solid powder, removing a small amount of residual solvent to obtain the gemini surfactant Mor-BP-14, wherein the yield is 60.1%, the nuclear magnetic hydrogen spectrum diagram is shown in figure 10, and the obtained gemini surfactant Mor-BP-14 has high purity as can be seen from figure 10.
Example 4
A morpholine head group cationic gemini surfactant, wherein m is 16, and the preparation method of Mor-BP-16 is shown in figure 1, and comprises the following steps:
(1) intermediate product alkyl substituted morpholine C4H8NO-C16H33The synthesis steps are as follows: mixing 1-bromohexadecane and morpholine according to a molar ratio of 1:6, and reacting for 10 hours at 90 ℃ by using absolute ethyl alcohol as a solvent; after the reaction is finished, removing the solvent by using a rotary evaporator, and neutralizing the residue by using a sodium hydroxide solution; extracting the mixed solution with ethyl acetate for 3 times, combining organic phases, adding anhydrous magnesium sulfate, and drying overnight; filtering, removing ethyl acetate with rotary evaporator to obtain light yellow oily liquid, and vacuum distilling to obtain high purity alkyl substituted morpholine C4H8NO-C16H33Yield 86.5%.
(2) The synthesis step of Mor-BP-16 comprises the following steps: biphenyl dichlorobenzyl and alkyl substituted morpholine C4H8NO-C16H33According to the following steps of 1: 10, reacting at 100 ℃ for 24 hours by taking n-propanol as a solvent, cooling to room temperature after the reaction is finished, recrystallizing for 3 times by using an acetone/ethanol mixed system, filtering to obtain white solid powder, removing a small amount of residual solvent to obtain the gemini surfactant Mor-BP-16, wherein the yield is 63.0%, the nuclear magnetic hydrogen spectrum diagram is shown in figure 11, and the obtained gemini table can be seen from figure 11The surfactant Mor-BP-16 has higher purity.
Example 5
Surface property test: the four gemini surfactants obtained in examples 1 to 4 were prepared as a series of aqueous solutions of different concentrations, and the surface tension of the samples was measured by the ring method on a surface tensiometer at 25 ℃ and the curve of the surface tension as a function of the concentration is shown in FIG. 2, giving cmc of the surfactants and their efficiency pC for reducing the surface tension of the aqueous solution20. For the convenience of comparison, the surface activity parameters of the four gemini surfactants synthesized by the invention and the corresponding traditional single-chain surfactant alkyl dimethyl benzyl ammonium chloride (BAC-m, m is 12,14 and 16) are simultaneously listed in Table 1, and from Table 1, the cmc value of Mor-BP-m is 1 to 2 orders of magnitude smaller than that of BAC-m, and pC can be found out that when the lengths of the hydrophobic tail chains are consistent20Is higher than BAC-m, which shows that the surface activity of the synthesized gemini surfactant is far better than that of the traditional single-chain surfactant.
TABLE 1 surface Properties of various surfactants
| Surface active agent | Mor-BP-10 | Mor-BP-12 | Mor-BP-14 | Mor-BP-16 | BAC-12* | BAC-14* | BAC-16* |
| cmc(mmol/L) | 2.86 | 0.55 | 0.15 | 0.05 | 9.1 | 1.9 | 0.4 |
| pC20 | 3.298 | 4.285 | 4.535 | 5.704 | 2.850 | 3.368 | 4.134 |
Injecting: surfactant parameters of the BAC-m series are cited from the literature
Example 6
And (3) conductivity test: the four gemini surfactants obtained in examples 1-4 were formulated into a series of aqueous solutions of different concentrations and tested for their conductivity at different temperatures, as shown in fig. 3-6. As can be seen from the graph, the conductivity curve shows an inflection point with the concentration change, and the concentration corresponding to the inflection point is the cmc of the surfactant. As can be seen from fig. 3-6, the conductivity measured cmc values are very close to the results in example 5, further demonstrating the accuracy of the measured cmc values.
Example 7
And (3) testing the wetting property: the four gemini surfactants obtained in examples 1-4 were formulated into a series of aqueous solutions of different concentrations, and the contact angle of the sample on the polytetrafluoroethylene surface was measured on a contact angle meter, and the curve of the contact angle as a function of the concentration is shown in fig. 7. The contact angle of the aqueous solution without the added surfactant (i.e., the blank) on the teflon plate was confirmed to be 114 °. As can be seen from FIG. 7, the contact angle of the Mor-BP-m aqueous solution on the polytetrafluoroethylene plate can be reduced to 54 degrees at the lowest within the tested concentration range, and good wetting performance is shown.
Example 8
The morpholine head-based cationic gemini surfactants Mor-BP-10, Mor-BP-12, Mor-BP-14 and Mor-BP-16 prepared in examples 1-4 were tested for bacteriostatic properties. The Minimum Inhibitory Concentrations (MIC) of the surfactants were determined by plate coating method for E.coli (ATCC8739) and Bacillus subtilis (ATCC 6633). The experimental method is as follows:
(1) preparation of a culture medium: weighing 10g of peptone, 5g of yeast extract and 10g of sodium chloride, adding 1000ml of distilled water for dissolving, adjusting the pH value to 7.0, and performing steam sterilization at 121 ℃ for 20min to obtain a sterile liquid culture medium; adding 15g of agar powder into the formula, heating for dissolving, adjusting the pH value to 7.0, subpackaging, performing steam sterilization at 121 ℃ for 20min under pressure, pouring the sterilized agar culture medium into a sterile culture dish while the agar is hot, and turning over the culture medium after the agar is solidified to obtain the sterile solid culture medium.
(2) Preparation of sterile water: the distilled water was filled in a test tube and a triangular flask, plugged with a stopper, and steam-sterilized at 121 ℃ under pressure for 20min for use.
(3) Preparation of a sterilizing liquid: weighing a certain amount of gemini surfactant, uniformly spreading in a super clean bench, sterilizing under an ultraviolet lamp for 30min, and respectively dissolving the four surfactants in sterile water under sterile environment.
(4) Preparing a bacterial liquid: taking a proper amount of bacteria-containing materials by using an inoculating loop on a standard second generation inclined plane of the two strains under an aseptic environment, washing in a liquid culture medium, and placing in a shaker at 37 ℃ for culturing for 18-24 h.
Adding gemini surfactant sterilizing solution into the original bacteria solution to obtain bacteria solution containing different surfactant concentrations, wherein the bacterial colony number in the bacteria solution of each experiment is 1 × 107-9×107cfu/ml. Culturing the bacterial solutions containing different bactericide concentrations in a 37 ℃ shaking table for 1h, taking out, diluting the bacterial solutions by adopting a 10-fold dilution method respectively, namely transferring liquidInjecting 100 mul of bacterial liquid into 900 mul of blank sterile water for dilution, fully mixing to obtain bacterial liquid with the first dilution, and so on; sucking 200 mul of the fifth diluted bacterial liquid by a pipette, coating the fifth diluted bacterial liquid on a sterile solid culture medium, making two parallel samples, culturing the samples in an incubator at 37 ℃ for 18-24h, counting, determining the number of bacterial colonies under the condition of different bactericide concentrations, taking the number of bacterial colonies without bactericide as a control, and obtaining the experimental results shown in table 2.
The calculation formula of the sterilization rate is as follows:
percent Sterilization (%) (average number of colonies in control dish-average number of colonies in test dish)/average number of colonies in control dish
TABLE 2 MIC of various surfactants for E.coli and B.subtilis
Injecting: data for BAC-12 are cited in the literature
In table 2, the traditional bactericide benzalkonium chloride (i.e. dodecyl dimethyl benzyl ammonium chloride, BAC-12) is added for comparison of bactericidal performance, and it can be found that MIC values of the gemini surfactant synthesized by the invention on gram-negative bacteria escherichia coli and gram-positive bacteria bacillus subtilis are both lower than BAC-12, especially the MIC values of the gemini surfactant with 10 and 12 carbon atoms in tail chains are far lower than BAC-12, and the gemini surfactant is proved to have efficient antibacterial performance.
Example 9
A heterocyclic head group and rigid linking group quaternary ammonium salt gemini surfactant is disclosed, wherein m is 10, and the preparation method of Mor-P-10 comprises the following steps:
(1) intermediate product alkyl substituted morpholine C4H8NO-C10H21The synthesis steps are as follows: mixing 1-bromodecane and morpholine according to a molar ratio of 1:3, and reacting for 24 hours at 75 ℃ by using absolute ethyl alcohol as a solvent; after the reaction is finished, removing the solvent by using a rotary evaporator, and neutralizing the residue by using a sodium hydroxide solution; extracting the mixed solution with ethyl acetate for 3 times, combining organic phases, adding anhydrous magnesium sulfate, and drying overnight; filtered and removed by a rotary evaporatorRemoving ethyl acetate to obtain light yellow oily liquid, and distilling under reduced pressure to obtain high-purity alkyl substituted morpholine C4H8NO-C10H21The yield was 93.9%.
(2) The synthesis of Mor-P-10 comprises the following steps: p-dichlorobenzyl and alkyl are substituted for morpholine C4H8NO-C10H21According to the following steps of 1: 2.2, reacting at 75 ℃ for 48h by using absolute ethyl alcohol as a solvent, cooling to room temperature after the reaction is finished, recrystallizing for 3 times by using an acetone/ethanol mixed system, filtering to obtain white solid powder, and removing a small amount of residual solvent to obtain the gemini surfactant with the yield of 74.3%.
Example 10
A heterocyclic head group and rigid linking group quaternary ammonium salt gemini surfactant is disclosed, wherein m is 12, and the preparation method of Mor-P-12 comprises the following steps:
(1) intermediate product alkyl substituted morpholine C4H8NO-C12H25The synthesis steps are as follows: mixing 1-bromododecane and morpholine according to a molar ratio of 1:3, and reacting for 20 hours at 80 ℃ by taking absolute ethyl alcohol as a solvent; after the reaction is finished, removing the solvent by using a rotary evaporator, and neutralizing the residue by using a sodium hydroxide solution; extracting the mixed solution with ethyl acetate for 3 times, combining organic phases, adding anhydrous magnesium sulfate, and drying overnight; filtering, removing ethyl acetate with rotary evaporator to obtain light yellow oily liquid, and vacuum distilling to obtain high purity alkyl substituted morpholine C4H8NO-C12H25Yield 92.6%.
(2) And (3) synthesis of Mor-P-12: p-dichlorobenzyl and alkyl are substituted for morpholine C4H8NO-C12H25According to the following steps of 1: 2.2, reacting at 80 ℃ for 36 hours by taking absolute ethyl alcohol as a solvent, cooling to room temperature after the reaction is finished, recrystallizing for 3 times by using an acetone/ethanol mixed system, filtering to obtain white solid powder, and removing a small amount of residual solvent to obtain the gemini surfactant with the yield of 65.6%.
Example 11
A heterocyclic head group and rigid linking group quaternary ammonium salt gemini surfactant is disclosed, wherein m is 14, and the preparation method of Mor-P-14 comprises the following steps:
(1) intermediate product alkyl substituted morpholine C4H8NO-C14H29The synthesis steps are as follows: mixing 1-bromotetradecane and morpholine according to a molar ratio of 1:4, and reacting for 16h at 85 ℃ by using absolute ethyl alcohol as a solvent; after the reaction is finished, removing the solvent by using a rotary evaporator, and neutralizing the residue by using a sodium hydroxide solution; extracting the mixed solution with ethyl acetate for 3 times, combining organic phases, adding anhydrous magnesium sulfate, and drying overnight; filtering, removing ethyl acetate with rotary evaporator to obtain light yellow oily liquid, and vacuum distilling to obtain high purity alkyl substituted morpholine C4H8NO-C14H29The yield was 90.1%.
(2) And (3) synthesis of Mor-P-14: p-dichlorobenzyl and alkyl are substituted for morpholine C4H8NO-C14H29According to the following steps of 1:6, reacting at 90 ℃ for 32 hours by taking isopropanol as a solvent, cooling to room temperature after the reaction is finished, recrystallizing for 3 times by using an acetone/ethanol mixed system, filtering to obtain white solid powder, and removing a small amount of residual solvent to obtain the gemini surfactant with the yield of 60.6%.
Example 12
A heterocyclic head group and rigid linking group quaternary ammonium salt gemini surfactant is disclosed, wherein m is 16, and the preparation method of Mor-P-16 comprises the following steps:
(1) intermediate product alkyl substituted morpholine C4H8NO-C16H33The synthesis steps are as follows: mixing 1-bromohexadecane and morpholine according to a molar ratio of 1:6, and reacting for 10 hours at 90 ℃ by using absolute ethyl alcohol as a solvent; after the reaction is finished, removing the solvent by using a rotary evaporator, and neutralizing the residue by using a sodium hydroxide solution; extracting the mixed solution with ethyl acetate for 3 times, combining organic phases, adding anhydrous magnesium sulfate, and drying overnight; filtering, removing ethyl acetate with rotary evaporator to obtain light yellow oily liquid, and vacuum distilling to obtain high purity alkyl substituted morpholine C4H8NO-C16H33Yield 86.5%.
(2) And (3) Mor-P-16 synthesis: p-dichlorobenzyl and alkyl are substituted for morpholine C4H8NO-C16H33According to the following steps of 1: 10, reacting at 100 ℃ for 24 hours by taking n-propanol as a solvent, cooling to room temperature after the reaction is finished, recrystallizing for 3 times by using an acetone/ethanol mixed system, filtering to obtain white solid powder, and removing a small amount of residual solvent to obtain the gemini surfactant with the yield of 58.1%.
The invention can be realized by the upper and lower limit values and interval values of the process parameters (such as the molar ratio of reactants, the temperature, the time and the like), and the examples are not listed.
Example 13
Surface property test: the four gemini surfactants obtained in examples 9 to 12 were prepared as a series of aqueous solutions of different concentrations, and the surface tension of the samples was measured by the flying ring method on a surface tensiometer at 25 ℃ to obtain the cmc of the surfactant from the surface tension curve (FIG. 12) as a function of the concentration. For comparison, the cmc of the series of heterocyclic head groups, rigid linking group quaternary ammonium salt gemini surfactants (Mor-P-m) synthesized in the patent and the methyl head group, rigid linking group quaternary ammonium salt gemini surfactants (Me-P-m) reported in the literature are simultaneously listed in Table 3. From Table 3, it can be seen that, in addition to the equalization of the cmc value of Mor-P-12 with that of Me-P-12, the cmc value of Mor-P-m is lower than that of Me-P-m, and particularly when the number of carbon atoms in the tail chain is 14 and 16, the cmc value of Mor-P-m is about 1 order of magnitude smaller than that of Me-P-m. This shows that the series of surfactants synthesized by the invention have excellent surface properties.
TABLE 3 surface Properties of various surfactants
Injecting: the surfactant parameters of the Me-P-m series are cited from the literature (DOI: 10.3390/molecules22111810)
Example 14
And (3) conductivity test: the four gemini surfactants obtained in examples 9-12 were formulated into a series of aqueous solutions of different concentrations and tested for their conductivity at different temperatures, as shown in fig. 13-16. As can be seen from the graph, the conductivity curve shows an inflection point with the concentration change, and the concentration corresponding to the inflection point is the cmc of the surfactant. As can be seen from fig. 13-16, the conductivity measured cmc values were close to those of example 13, further demonstrating the accuracy of the measured cmc values.
Example 15
And (3) testing the wetting property: the four gemini surfactants obtained in examples 9-12 were formulated into a series of aqueous solutions of different concentrations, and the contact angle of the samples on the polytetrafluoroethylene surface was measured on a contact angle meter, and the curve of the contact angle as a function of the concentration is shown in FIG. 17. The contact angle of the aqueous solution without the added surfactant (i.e., the blank) on the teflon plate was confirmed to be 114 °. As can be seen from FIG. 18, the contact angle of the aqueous Mor-P-m solution on the PTFE plate decreases with the increase of the surfactant concentration, and can be reduced to about 50 ℃ at the lowest, showing good wetting performance.
Example 16
The bacteriostatic properties of the heterocyclic head group, rigid linker quaternary ammonium salt gemini surfactants Mor-P-10, Mor-P-12, Mor-P-14 and Mor-P-16 prepared in examples 9-12 were determined. The Minimum Inhibitory Concentrations (MIC) of the surfactants were determined by plate coating method for E.coli (ATCC8739) and Bacillus subtilis (ATCC 6633). The experimental method is as follows:
(1) preparation of a culture medium: weighing 10g of peptone, 5g of yeast extract and 10g of sodium chloride, adding 1000ml of distilled water for dissolving, adjusting the pH value to 7.0, and performing steam sterilization at 121 ℃ for 20min to obtain a sterile liquid culture medium; adding 15g of agar powder into the formula, heating for dissolving, adjusting the pH value to 7.0, subpackaging, performing steam sterilization at 121 ℃ for 20min under pressure, pouring the sterilized agar culture medium into a sterile culture dish while the agar is hot, and turning over the culture medium after the agar is solidified to obtain the sterile solid culture medium.
(2) Preparation of sterile water: the distilled water was filled in a test tube and a triangular flask, plugged with a stopper, and steam-sterilized at 121 ℃ under pressure for 20min for use.
(3) Preparation of a sterilizing liquid: weighing a certain amount of gemini surfactant, uniformly spreading in a super clean bench, sterilizing under ultraviolet rays for 30min, and respectively dissolving the four surfactants in sterile water under sterile environment.
(4) Preparing a bacterial liquid: taking a proper amount of bacteria-containing materials by using an inoculating loop on a standard second generation inclined plane of the two strains under an aseptic environment, washing in a liquid culture medium, and placing in a shaker at 37 ℃ for culturing for 18-24 h.
Adding gemini surfactant sterilizing solution into the original bacteria solution to obtain bacteria solution containing different surfactant concentrations, wherein the colony count in the mixture is 1 × 107-9×107cfu/ml. Putting the bacterial liquids containing different bactericide concentrations into a shaking table at 37 ℃ for culturing for 1h, then taking out the bacterial liquids, respectively diluting the bacterial liquids by adopting a 10-time dilution method, namely taking 100 mu l of the bacterial liquids by using a liquid transfer machine, injecting the bacterial liquids into 900 mu l of blank sterile water for dilution, fully mixing to obtain the bacterial liquid with the first dilution, and so on; sucking 200 mul of the fifth diluted bacterial liquid by a pipette, coating the fifth diluted bacterial liquid on a sterile solid culture medium, culturing for 18-24h in an incubator at 37 ℃ after two parallel samples are made, counting, determining the number of bacterial colonies under the condition of different bactericide concentrations, taking the number of bacterial colonies without bactericide as a control, and obtaining the experimental results shown in table 4.
The calculation formula of the sterilization rate is as follows:
percent Sterilization (%) (average number of colonies in control dish-average number of colonies in test dish)/average number of colonies in control dish
TABLE 4 MIC of various surfactants for E.coli and B.subtilis
Injecting: the data for Me-P-m are cited in the literature (DOI: 10.3390/molecules22111810)
In Table 4, by adding Me-P-m for comparison of bactericidal performance, it can be found that the gemini surfactant Mor-P-m synthesized by the invention has lower MIC value than Me-P-m, especially when the number of carbon atoms on the tail chain is 14 and 16, the MIC value of Mor-P-m is about 1 to 2 orders of magnitude smaller than that of Me-P-m, which indicates that Mor-P-m has higher bacteriostatic efficiency.
Gemini surfactants prepared by replacing biphenyl dichlorobenzyl in examples 1-4 with biphenyl dibromide benzyl and p-dichlorobenzyl in examples 9-12 with p-dibromide benzyl were similar to examples 1-4 and examples 9-12, respectively.
Claims (10)
1. A morpholine head group cationic gemini surfactant is characterized in that the structural formula is as follows:
wherein m is 10, 12,14 or 16, and X is Cl or Br.
2. The method for preparing the morpholino headgroup cationic gemini surfactant as claimed in claim 1, essentially comprising the steps of:
(1) carrying out substitution reaction on morpholine and 1-bromoalkane to obtain N-alkyl morpholine;
(2) the N-alkyl morpholine and biphenyl dihalogen benzyl or p-dihalogen benzyl are subjected to quaternization reaction.
3. The process according to claim 2, wherein the preparation of N-alkylmorpholine in step (1) comprises: mixing 1-bromoalkane, morpholine and ethanol, heating for substitution reaction, removing ethanol by a rotary evaporator after the reaction is finished, neutralizing the residue with sodium hydroxide aqueous solution, extracting the obtained oil-water mixture with ethyl acetate, and combining organic phases, and drying with anhydrous magnesium sulfate overnight; after filtration, ethyl acetate was removed by a rotary evaporator to obtain a pale yellow oily liquid, which was finally distilled under reduced pressure.
4. The method according to claim 2, wherein the quaternization of the N-alkyl morpholine with the biphenyl dihalobenzyl in step (2) mainly comprises: mixing N-alkyl morpholine and biphenyl dihalogen benzyl or p-dihalogen benzyl, adding a solvent, heating for quaternization, removing the solvent by using a rotary evaporator after the reaction is finished, and recrystallizing by using an acetone/ethanol mixed system.
5. The preparation method according to claim 2, wherein the molar ratio of the 1-bromoalkane to the morpholine in the step (1) is 1 (1-6); the temperature of the substitution reaction is 75-90 ℃ and the time is 10-24 h.
6. The method according to claim 2, wherein the molar ratio of N-alkyl morpholine to biphenyl dichlorobenzyl in step (2) is 1: (2-10); the temperature of the quaternization reaction is 70-100 ℃ and the time is 24-48 h.
7. The method according to claim 2, wherein the molar ratio of p-dichlorobenzyl to N-alkylmorpholine in step (2) is 1 (2-10); the reaction temperature is 75-100 ℃ and the reaction time is 24-48 h.
8. The method of claim 2, wherein the 1-bromoalkane is one of 1-bromodecane, 1-bromododecane, 1-bromotetradecane, or 1-bromohexadecane.
9. The method according to claim 2, wherein the solvent is one or more of acetone, ethyl acetate, absolute ethanol, isopropanol, or n-propanol.
10. Use of the morpholino headgroup cationic gemini surfactant according to claim 1 for disinfecting and moisturizing.
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