CN110818624A - Pyridine quaternary ammonium salt hydrazone compound, preparation method and application in antibacterial or perfume slow release - Google Patents
Pyridine quaternary ammonium salt hydrazone compound, preparation method and application in antibacterial or perfume slow release Download PDFInfo
- Publication number
- CN110818624A CN110818624A CN201911152808.0A CN201911152808A CN110818624A CN 110818624 A CN110818624 A CN 110818624A CN 201911152808 A CN201911152808 A CN 201911152808A CN 110818624 A CN110818624 A CN 110818624A
- Authority
- CN
- China
- Prior art keywords
- compound
- pyridinium
- hydrogen
- hydrazone compound
- ammonium salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/65—One oxygen atom attached in position 3 or 5
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/507—Compounds releasing perfumes by thermal or chemical activation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a pyridine quaternary ammonium salt type hydrazone compound, which has the following structure:
the definition of each substituent group in the formula is shown in the specification. The pyridinium quaternary ammonium salt hydrazone compound with the long carbon chain has good water solubility, can release aromatic aldehyde ketone substances in an acidic aqueous solution by water, and achieves the aim of slowly releasing perfume through dynamic balance. At the same time, pyridine remaining in the solution system after hydrolysisThe quaternary ammonium salt type hydrazide compound still has good surface activity and antibacterial capability, is a multifunctional surfactant, and has certain positive significance in practical application.
Description
Technical Field
The invention belongs to the technical field of synthesis of novel pyridyl quaternary ammonium salt hydrazone compounds, and particularly relates to a pyridyl quaternary ammonium salt hydrazone compound, a preparation method and application in antibacterial or perfume slow release.
Background
With the continuous development of society and the continuous progress of science and technology, the living standard of people is continuously improved, and people begin to pursue higher-quality life after meeting the basic material living requirements. The essence and flavor are widely existed in daily life, such as food additives, daily chemical products, and the like, and the essence and flavor are ubiquitous. In recent years, the continuous emergence of aromatic wallpaper, aromatic high-grade seats and aromatic textiles proves that the traditional spices of the people are not satisfied any more, and people desire the spices with more functionality and more lasting fragrance. Meanwhile, the essence is not limited to releasing fragrance to be pleasant, and can play a plurality of roles such as sterilization, antibiosis and disease treatment. The essence has such wide use value, and the research on the essence is also a subject with great economic value and social significance. However, the perfume molecules have the characteristics of high saturated vapor pressure, high volatility and unstable oxidation, so that the perfume molecules cannot keep lasting fragrance retention time. In order to solve this problem, various methods have also been proposed in recent years (review: Quellet, C, Schudel, M, Ringgenberg, R.Chimia 2001; 55: 421-; among them, research on designing and preparing highly effective chemical latent fragrances has received extensive attention and research.
There are many methods for fragrance release, and the method of using latent fragrance to delay fragrance release is that volatile fragrance molecules and non-volatile precursors are combined together by covalent bonds by chemical means, and chemical bond breakage occurs selectively under specific conditions to release fragrance active molecules, and the process is controllable and continuous. The conditions for breaking chemical bonds include light, oxidation, heating, hydrolysis, pH change, enzyme catalysis, etc., and are widely present in the natural world and in the daily life of human beings. Water is a common solvent commonly used in a variety of perfumed products, and the control of the release of perfume molecules by hydrolysis or by changing the pH has been reported in many documents. Hydrazone compounds, like schiff bases, can give off aldo-ketone perfume molecules in aqueous acidic solutions. Meanwhile, compared with Schiff base, the hydrazone compound has better stability and can not be rapidly hydrolyzed. The pyridine quaternary ammonium salt hydrazide compound reacts with aromatic aldehyde ketone to obtain the pyridine quaternary ammonium salt hydrazone compound, and the aromatic aldehyde ketone molecules can be released under the acidic condition through water interpretation. The compounds which are remained in the aqueous solution system after the latent aroma body hydrolyzes to release aroma molecules are mostly useless, so that the synthesis of the latent aroma body compound which has better water solubility and has the same multiple functions as the substances remained in the aqueous solution system after the aroma is released becomes a technical problem to be solved.
Disclosure of Invention
The invention provides a pyridyl quaternary ammonium salt hydrazone compound.
The second purpose of the invention is to provide a preparation method of the quaternary pyridinium hydrazone compound.
The third purpose of the invention is to provide an application of the pyridinium quaternary ammonium salt hydrazone compound in antibacterial or perfume slow release.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a pyridinium quaternary ammonium salt hydrazone compound, which has the following structure:
R1selected from hydrogen, C1-C20An alkyl group;
R2selected from hydrogen, substituted or unsubstituted aryl, C1-C20An alkenyl-substituted aryl group, a substituted or unsubstituted cycloalkyl group, or a heterocyclic group;
R3selected from hydrogen, C1-C20An alkyl group;
R4selected from hydrogen, C1-C20An alkyl group;
x is halogen (F, Cl, Br or I).
More preferably, in the pyridinium quaternary ammonium salt type hydrazone compound,
R1selected from hydrogen, C5-C18An alkyl group;
R2selected from hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted benzoheterocycle, C1-C20Alkenyl-substituted phenyl, substituted or unsubstituted cyclohexene, substituted or unsubstituted cycloalkyl;
R3selected from hydrogen, C5-C18An alkyl group;
R4selected from hydrogen, C5-C18An alkyl group;
x is Cl or Br.
More preferably, in the pyridinium quaternary ammonium type hydrazone compound,
R1selected from hydrogen, C5-C18An alkyl group;
R2selected from hydrogen,
R3Selected from hydrogen, methyl;
R4selected from hydrogen, methyl;
and X is Br.
Most preferably, the pyridinium quaternary hydrazone compound is one of the following structures:
the second aspect of the present invention provides a method for preparing a pyridinium quaternary hydrazone compound, comprising the following steps:
dissolving 3-hydroxypyridine in a solvent, adding alkali, reacting for 0.1-48 h at the temperature of 20-60 ℃, dropwise adding alkyl halide, wherein the molar ratio of the 3-hydroxypyridine to the alkali to the alkyl bromide is 1 (2-30) to 1, and obtaining an intermediate pyridine compound after the reaction is completed;
dissolving an intermediate pyridine compound in a solvent, adding halogenated ethyl acetate, wherein the molar ratio of the intermediate pyridine compound to the halogenated ethyl acetate is 1 (1.1-2), and reacting at 20-60 ℃ for 0.1-48 h to obtain a pyridine quaternary ammonium salt compound;
dissolving hydrazine hydrate in a solvent, dissolving a quaternary pyridinium salt compound in the solvent, slowly adding the solution of the hydrazine hydrate, wherein the molar ratio of hydrazine hydrate to the quaternary pyridinium salt compound is (5-15) to 1, and reacting for 0.1-48 h at the temperature of 20-60 ℃ to obtain the quaternary pyridinium salt hydrazide compound;
dissolving a pyridine quaternary ammonium salt type hydrazide compound and aldehyde or ketone spices in a solvent according to a molar ratio of 1 (1.1-2), and performing reflux reaction to obtain the pyridine quaternary ammonium salt type hydrazone compound.
The solvent is dimethyl sulfoxide, ethyl acetate and ethanol.
The alkali is potassium hydroxide or sodium hydroxide.
The alkyl halide is bromododecane, bromooctane, bromodecane, bromotetradecane, bromohexadecane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane and bromononane.
The halogenated ethyl acetate is ethyl bromoacetate.
The aldehyde or ketone perfume is cinnamaldehyde, heliotropin, β -ionone, cyclamen aldehyde, benzaldehyde, anisaldehyde, vanillin, citronellal, ionone, methyl ionone, carvone, damascenone.
The third aspect of the invention provides an application of the pyridinium quaternary ammonium salt hydrazone compound in antibacterial or perfume slow release.
The fourth aspect of the invention provides an application of the pyridinium quaternary hydrazone compound as an antibacterial agent or a perfume slow-release agent.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the pyridinium quaternary ammonium salt hydrazone compound with the long carbon chain is subjected to a series of performance tests and representations, has good water solubility, can release aromatic aldehyde ketone substances in an acidic aqueous solution by water, and achieves the aim of slowly releasing perfume through dynamic balance. Meanwhile, the pyridine quaternary ammonium salt type hydrazide compound remained in the solution system after hydrolysis still has good surface activity and antibacterial capability, is a multifunctional surfactant, and has certain positive significance in practical application.
Drawings
FIG. 1 is a graphical representation of the surface tension-concentration curve for a quaternized pyridinium hydrazide compound.
FIG. 2 is a graphical representation of the time-peak area curves for fragrance release from a quaternized pyridinium hydrazone compound A and a neat fragrance material.
FIG. 3 is a graphical representation of the time-peak area curves for fragrance release from a quaternized pyridinium hydrazone compound B and a neat fragrance material.
FIG. 4 is a graphical representation of the time-peak area curves for fragrance release from a quaternized pyridinium hydrazone compound C and a neat fragrance material.
FIG. 5 is a graphical representation of the time-peak area curves for fragrance release from a quaternized pyridinium hydrazone compound D and a neat fragrance material.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
The preparation method of the pyridyl quaternary ammonium salt hydrazone compound comprises the following steps:
(1) 10mmol of 3-hydroxypyridine was placed in a flask, and 10mL of dimethyl sulfoxide was added to dissolve it. Adding 2.7g of KOH into a flask, stirring for 30 minutes at the temperature of 35 ℃, dropwise adding 10mmol of bromododecane, reacting overnight, adding a saturated ammonium chloride aqueous solution after the reaction is finished, washing with water, extracting with dichloromethane, combining extract liquids, performing column chromatography by using petroleum ether/ethyl acetate as an eluent to obtain a light yellow solid intermediate pyridine compound, wherein the yield is 53%.
(2) And (3) putting 1mmol of the intermediate pyridine compound into a flask, adding 10mL of ethyl acetate to dissolve the intermediate pyridine compound, adding 1.2mmol of ethyl bromoacetate, refluxing at 50 ℃ for 24 hours, cooling to separate out a solid after the reaction is finished, filtering, and recrystallizing by using n-hexane to obtain a white solid product, namely the pyridine quaternary ammonium salt compound, wherein the yield is 96%.
(3) 10mmol of hydrazine hydrate was placed in a flask and dissolved by adding 15mL of anhydrous ethanol. 1mmol of the above quaternary ammonium salt pyridine compound is dissolved in 10mL of absolute ethanol, and slowly added into the above hydrazine hydrate ethanol solution, and reacted for four hours at the temperature of 50 ℃. After the reaction is finished, distilling under reduced pressure to spin off part of ethanol, cooling in a refrigerator overnight, precipitating crystals, filtering the crystals, and washing with glacial ethanol to obtain the pyridine quaternary ammonium salt hydrazide compound which is a white solid with the yield of 63%.
(4) Adding 0.8mmol of pyridine quaternary ammonium salt hydrazide compound into a round-bottom flask, adding 1.2mmol of cinnamaldehyde, adding 15mL of ethanol as a solvent, refluxing for 4h, cooling to room temperature after the reaction is finished, and performing column chromatography by using dichloromethane/methanol as an eluent to obtain a light yellow target product (the structure is shown in formula A), wherein the yield is 50%.
1H NMR(400MHz,CDCl3)δ12.40(s,1H),9.03(s,1H),8.82(d,J＝5.4Hz,1H),8.19(d,J＝8.7Hz,1H),7.82(dd,J＝13.9,8.3Hz,2H),7.34–7.29(m,2H),7.24(d,J＝7.5Hz,3H),6.82(m,J＝16.0,12.4Hz,2H),5.90(s,2H),4.12(t,J＝6.3Hz,2H),1.75–1.68(m,2H),1.18(s,18H),0.80(t,J＝6.8Hz,3H).
13C NMR(101MHz,CDCl3)δ159.29,157.07,151.59,140.81,137.39,134.58,131.27,131.21,128.28,127.81,127.01,126.27,123.45,76.39,76.07,75.75,70.36,60.55,30.89,28.63,28.61,28.56,28.47,28.33,28.27,27.67,24.73,21.67,13.12.
HRMS(ESI-TOF)m/z:[M-Br]+Calcd for C28H40N3O2450.3115；Found 450.3120.
Example 2
The preparation method of the pyridyl quaternary ammonium salt hydrazone compound comprises the following steps:
the same conditions as in example 1 were repeated except that cinnamaldehyde was changed to helional in the step (4) of example 1, to obtain a compound represented by the formula B.
1H NMR(400MHz,CDCl3)δ12.28(s,1H),9.07(s,1H),8.83(s,1H),7.87(d,J＝2.3Hz,2H),7.83(d,J＝6.2Hz,1H),6.67(d,J＝7.8Hz,1H),6.60(d,J＝1.4Hz,1H),6.56(m,J＝7.9,1.5Hz,1H),5.87(s,2H),5.82(d,J＝6.9Hz,2H),4.21(t,J＝6.2Hz,3H),2.81(m,J＝13.5,5.9Hz,2H),2.70–2.59(m,2H),2.44(m,J＝13.6,8.7Hz,2H),1.80(m,J＝14.6,6.6Hz,2H),1.23(s,18H),1.01–0.98(d,3H),0.85(t,J＝6.8Hz,3H).
13C NMR(101MHz,CDCl3)δ158.92,158.24,157.14,146.50,144.87,137.17,132.28,131.95,131.24,131.17,126.94,121.15,108.46,107.14,99.78,76.40,76.08,75.76,70.38,60.47,38.88,37.97,30.89,28.63,28.61,28.55,28.47,28.33,28.25,27.67,24.74,21.67,15.85,13.12.
HRMS(ESI-TOF)m/z:[M-Br]+Calcd for C30H44N3O4510.3326；Found 510.3333.
Example 3
The preparation method of the pyridyl quaternary ammonium salt hydrazone compound comprises the following steps:
the same conditions as in example 1 were repeated except that the cinnamic aldehyde in step (4) of example 1 was changed to β -ionone, to give a compound represented by formula C.
1H NMR(400MHz,CDCl3)δ11.29(s,1H),9.29(s,1H),8.93(s,1H),7.89–7.80(d2H),6.62(d,J＝16.5Hz,1H),6.23(d,J＝16.5Hz,1H),6.13(s,2H),4.22(t,J＝6.3Hz,2H),2.33(s,3H),1.97(t,J＝6.1Hz,2H),1.85–1.76(m,3H),1.63(s,3H),1.60–1.54(m,2H),1.44–1.42(m,2H),1.23(s,18H),0.97(s,6H),0.84(t,J＝6.8Hz,3H).
13C NMR(101MHz,CDCl3)δ159.89,157.61,157.13,137.25,135.62,134.76,131.45,131.31,131.17,130.89,126.79,76.41,76.09,75.77,70.44,60.34,38.52,33.09,32.06,30.90,28.63,28.61,28.55,28.47,28.33,28.24,27.81,27.67,24.74,21.67,20.67,18.02.
HRMS(ESI-TOF)m/z:[M-Br]+Calcd for C32H52N3O2510.4054；Found510.4059.
Example 4
The preparation method of the pyridyl quaternary ammonium salt hydrazone compound comprises the following steps:
the same conditions as in example 1 were repeated except that cinnamaldehyde was changed to galbanum aldehyde in the step (4) of example 1, to obtain a compound represented by the formula D.
1H NMR(400MHz,CDCl3)δ12.29(s,1H),9.10(s,1H),8.84(s,J＝2.8Hz,1H),7.87(d,J＝6.5Hz,2H),7.85(d,J＝0.9Hz,1H),7.11(d,J＝8.0Hz,2H),7.04(d,J＝8.1Hz,2H),5.85(d,J＝6.7Hz,2H),4.22(t,J＝6.3Hz,2H),2.92–2.78(m,3H),2.74–2.65(m,1H),2.47(m,J＝13.5,9.1Hz,1H),1.81(m,J＝14.7,6.6Hz,2H),1.24(s,18H),1.20(d,J＝6.9Hz,6H),1.00(d,J＝6.8Hz,3H),0.86(t,J＝6.8Hz,3H).
13C NMR(101MHz,CDCl3)δ158.87,158.54,157.16,145.67,137.11,135.45,131.25,131.14,128.10,126.91,125.40,76.40,76.08,75.76,70.40,60.46,38.70,37.78,32.65,30.89,28.63,28.61,28.55,28.47,28.33,28.24,27.66,24.74,23.00,21.67,15.85,13.12.
HRMS(ESI-TOF)m/z:[M-Br]+Calcd for C32H50N3O2508.3898；Found 508.3904.
Example 5
The preparation method of the pyridyl quaternary ammonium salt hydrazone compound comprises the following steps:
the same conditions as in example 1 were repeated except that bromododecane in step (1) in example 1 was changed to bromooctane and cinnamaldehyde in step (4) in example 1 was changed to helional, to obtain a compound represented by formula E.
1H NMR(400MHz,CDCl3)δ12.32(s,1H),9.10(s,1H),8.83(s,1H),7.86(d,J＝3.0Hz,2H),7.83(d,J＝6.2Hz,1H),6.67(d,J＝7.8Hz,1H),6.60(d,J＝1.4Hz,1H),6.56(dd,J＝7.9,1.5Hz,1H),5.87(s,2H),5.82(d,J＝7.3Hz,2H),4.21(t,J＝6.2Hz,2H),2.81(m,J＝13.6,5.8Hz,1H),2.65(m,J＝10.6,4.2Hz,1H),2.43(m,J＝13.6,8.7Hz,2H),1.80(m,J＝14.7,6.6Hz,2H),1.25(s,J＝1.8Hz,10H),0.99(d,J＝6.8Hz,3H),0.89–0.76(t,3H).
13C NMR(101MHz,CDCl3)δ158.88,158.24,157.16,146.50,144.87,137.09,131.94,131.24,131.17,126.94,121.14,108.45,107.14,99.77,76.40,76.08,75.77,70.40,60.45,38.88,37.96,30.72,28.68,28.17,28.11,27.65,24.72,21.61,15.85,13.08.
HRMS(ESI-TOF)m/z:[M-Br]+Calcd for C26H36N3O4454.2700；Found 454.2707.
Example 6
The preparation method of the pyridyl quaternary ammonium salt hydrazone compound comprises the following steps:
the same conditions as in example 1 were repeated except that bromododecane in step (1) in example 1 was changed to bromodecane and cinnamaldehyde in step (4) in example 1 was changed to helional, thereby obtaining a compound represented by formula F.
1H NMR(400MHz,CDCl3)δ12.30(s,1H),9.09(s,1H),8.83(s,1H),7.86(d,J＝3.1Hz,2H),7.83(d,J＝6.2Hz,1H),6.67(d,J＝7.8Hz,1H),6.60(d,J＝1.4Hz,1H),6.56(m,J＝7.9,1.5Hz,1H),5.87(s,2H),5.83(d,J＝7.3Hz,2H),4.22(t,J＝6.2Hz,3H),2.82(m,J＝13.6,5.9Hz,1H),2.64(m,J＝13.9,7.3Hz,1H),2.44(m,J＝13.6,8.7Hz,1H),1.87–1.75(m,2H),1.24(s,14H),1.00(d,J＝6.8Hz,3H),0.85(t,J＝6.8Hz,3H).
13C NMR(101MHz,CDCl3)δ158.88,158.25,157.16,146.51,144.87,137.11,131.94,131.24,131.17,126.92,121.15,108.46,107.14,99.78,76.40,76.08,75.76,70.40,60.46,38.88,37.97,30.85,28.49,28.46,28.28,28.23,27.66,24.73,21.65,15.86,13.11.
HRMS(ESI-TOF)m/z:[M-Br]+Calcd for C28H40N3O4482.3013；Found 482.3020.
Example 7
The preparation method of the pyridyl quaternary ammonium salt hydrazone compound comprises the following steps:
the same conditions as in example 1 were repeated except that bromododecane in step (1) in example 1 was changed to bromotetradecane and cinnamaldehyde in step (4) in example 1 was changed to helional, to obtain a compound represented by formula G.
1H NMR(400MHz,CDCl3)δ12.28(s,1H),9.08(s,1H),8.83(s,1H),7.86(d,J＝3.1Hz,2H),7.83(d,J＝6.2Hz,1H),6.67(d,J＝7.8Hz,1H),6.59(d,J＝1.5Hz,1H),6.55(m,J＝7.9,1.6Hz,1H),5.87(s,2H),5.83(d,J＝7.2Hz,2H),4.21(t,J＝6.2Hz,3H),2.81(m,J＝13.5,5.9Hz,1H),2.64(m,J＝19.3,6.4Hz,1H),2.43(m,J＝13.6,8.7Hz,1H),1.87–1.67(m,2H),1.23(s,22H),0.99(d,J＝6.8Hz,3H),0.85(t,J＝6.8Hz,3H).
13C NMR(101MHz,CDCl3)δ158.92,158.20,157.13,146.50,144.87,137.15,131.94,131.23,131.18,126.93,121.15,108.45,107.14,99.78,76.41,76.09,75.78,70.39,60.45,38.88,37.97,30.90,28.67,28.64,28.56,28.48,28.34,28.25,27.67,24.74,21.67,15.86,13.12.
HRMS(ESI-TOF)m/z:[M-Br]+Calcd for C32H48N3O4538.3639；Found 538.3646.
Example 8
The preparation method of the pyridyl quaternary ammonium salt hydrazone compound comprises the following steps:
the same conditions as in example 1 were repeated except that bromododecane in step (1) in example 1 was changed to bromohexadecane and cinnamaldehyde in step (4) in example 1 was changed to helional, to obtain a compound represented by formula H.
1H NMR(400MHz,CDCl3)δ12.29(s,1H),9.09(s,1H),8.83(s,1H),7.86(d,J＝3.1Hz,2H),7.83(d,J＝6.2Hz,1H),6.67(d,J＝7.8Hz,1H),6.60(d,J＝1.4Hz,1H),6.56(dd,J＝7.9,1.5Hz,1H),5.88(s,2H),5.83(d,J＝7.4Hz,2H),4.22(t,J＝6.2Hz,3H),2.82(m,J＝13.5,5.9Hz,1H),2.65(m,J＝12.9,6.4Hz,1H),2.44(m,J＝13.6,8.7Hz,1H),1.87–1.76(m,2H),1.23(s,26H),1.00(d,J＝6.8Hz,3H),0.85(t,J＝6.8Hz,3H).
13C NMR(101MHz,CDCl3)δ160.01,159.35,158.25,147.59,145.96,138.21,133.02,132.33,132.24,127.99,122.24,109.54,108.23,100.86,77.48,77.16,76.84,71.44,61.55,39.97,39.06,31.99,29.77,29.73,29.65,29.57,29.43,29.34,28.76,25.83,22.76,16.95,14.20.
HRMS(ESI-TOF)m/z:[M-Br]+Calcd for C34H52N3O4566.3952；Found 566.3959.
Example 9
Measurement of surface tension of pyridine quaternary ammonium salt hydrazide compound:
the pyridine quaternary ammonium salt hydrazide compounds with carbon chain lengths of 8 (structural formula 4 a), 10 (structural formula 4 b), 12 (structural formula 4 c), 14 (structural formula 4 d) and 16 (structural formula 4 e) were synthesized according to the methods (1), (2) and (3) in example 1, and all of these compounds have good solubility in water. In the process of testing the surface tension, 20mL of water is taken as a reference, a prepared sample solution to be tested with the concentration of 0.005mol/L is gradually added, and finally, logC of the added sample concentration is taken as an abscissa and the surface tension value of the water is taken as an ordinate to be plotted to obtain a schematic diagram of a surface tension-concentration curve. The specific test results are shown in fig. 1.
The specific test results are shown in fig. 1, and fig. 1 is a surface tension-concentration curve diagram of the pyridine quaternary ammonium salt hydrazide compound. As can be seen from the figure, when the carbon chain length is 8-16, the surface tension of water is reduced after the sample to be tested is added, which shows that the pyridine quaternary ammonium salt hydrazide compound can effectively reduce the surface tension of water. The effect of the compound on reducing the surface tension of water increases gradually as the carbon chain length increases from 8 to 12, but conversely, the surface activity decreases as the carbon chain length increases from 14 to 16. When the carbon chain length is 12, the surface tension of water can be reduced to about 25.5mN/m, which shows that the surfactant is a very good surfactant. The hydrazone compound is used as a matrix to react with various fragrances, aldehyde and ketone to generate corresponding hydrazone compounds, and then the performances of antibiosis and fragrance release are tested.
Example 10
And (3) testing the bacteriostatic properties of the pyridine quaternary ammonium salt hydrazone compound and the pyridine quaternary ammonium salt hydrazide compound:
8 quaternary pyridinium hydrazone compounds prepared in examples 1 to 8 and the quaternary pyridinium hydrazide compound prepared in example 9 were mixed: the method comprises the following steps of weighing 12.8mg of the compound respectively, placing the compound in a volumetric flask, adding water to dilute the compound until the concentration is 1280 mu g/mL, and filtering the compound by using a 0.45 mu m organic phase filter head to ensure that no bacteria exists in a product water solution, wherein the carbon chain length is 8 (the structure is shown in a formula 4 a), 10 (the structure is shown in a formula 4 b), 12 (the structure is shown in a formula 4 c), 14 (the structure is shown in a formula 4 d) and 16 (the structure is shown in a formula 4 e).The aqueous solution was then diluted sequentially to a concentration of: 640,320,160,80,40,20,10,5,2.5, 1.25. mu.g/mL. Pipette 10. mu.L of the above solutions at different concentrations into 96-well plates and add 90. mu.L of 10-concentrated solution to each plate5And (3) after the cfu/mL bacterial culture medium is added, placing the 96-well plate in a 37 ℃ thermostat for 24 hours, and observing the growth condition of the bacteria to obtain the lowest concentration for inhibiting the growth of the bacteria, namely the MIC value. The lower the MIC value, the better the bacteriostatic properties of the compound, and the specific data results are shown in table 1.
TABLE 1
As can be seen from Table 1, the pyridylquaternary hydrazone compound or the pyridylquaternary hydrazide compound has broad-spectrum antibacterial activity against gram-positive bacteria and gram-negative bacteria, and can kill and inhibit the growth of bacterial cells at a certain concentration. The premise that the pyridyl quaternary ammonium salt hydrazone compound plays a role is as follows: the compound with positive electrode head group is selectively adsorbed on the surface of bacteria through electrostatic interaction with the bacterial cell membrane with negative charge on the surface, the permeability of the bacterial cell plasma membrane is changed, important enzyme and nutrient substance in bacteria flow out, and bacterial cells die, thereby achieving the purpose of sterilization. Therefore, the longer the carbon chain length is, the better the antibacterial performance is, and when the carbon chain length is increased to a certain extent, the adsorption force is reduced, and the decisive condition for the contact of the quaternary ammonium salt hydrazone compound with bacteria is directly influenced, so that the antibacterial effect is influenced. As can be seen from the data in Table 1, the compounds with 12 or 14 carbons in the structure have better bacteriostatic effect than the compounds with 8, 10 or 16 carbons, whether they are pyridiniumhydrazone compounds or pyridiniumhydrazide compounds. Also, since gram-positive bacteria have only one cell wall not closely associated with the cell membrane, most compounds have a stronger bacteriostatic effect on gram-positive bacteria than on gram-negative bacteria.
From the MIC values of A, B, C, D in Table 1, which show that the quaternary pyridinium hydrazone compounds have the same long carbon chain but react with different aromatic aldehyde ketones, the bacteriostatic activity of the series of compounds on bacterial cells is related to the long carbon chain. The pyridine quaternary ammonium salt hydrazone compound contains an imine bond (-CONHN ═ CH-) which is an active functional group, and oxygen and nitrogen atoms contained in the pyridine quaternary ammonium salt hydrazone compound can participate in the formation of hydrogen bonds in organisms, so that the generation of a plurality of biochemical processes is inhibited, and the pyridine quaternary ammonium salt hydrazone compound has good antibacterial activity.
Example 11
And (3) detecting aldehyde ketone perfume substances released by hydrolyzing the pyridine quaternary ammonium salt hydrazone compounds:
solid phase microextraction-gas chromatography is utilized to detect hydrolysis of the pyridinium quaternary ammonium salt hydrazone compound in an acidic aqueous solution and volatilization of equimolar amount of pure perfume molecules under the same experimental conditions, and comparison of the two groups of peak area data shows that the pyridinium quaternary ammonium salt hydrazone compound has the function of controlling and delaying release of perfume substances.
The specific test method comprises the following steps: 0.04mmol of the quaternized pyridinium hydrazone compound was added to a sealed headspace bottle, 0.5mL of absolute ethanol (to better dissolve the sample by taking advantage of the mutual solubility of water and ethanol) and 0.5mL of citric acid-sodium citrate buffer were added, and then the headspace bottle was placed in an oil bath and heated at 60 ℃. After heating for 10 minutes, the extraction fibers were inserted into the headspace of the headspace bottle for 10 minutes of extraction. The needle was quickly inserted into the back sample port of the GC, and the perfume components adsorbed on the fibers were desorbed at high temperature and smoothly entered the gas phase for analysis. The desorption time was 5 minutes while the gas chromatograph was started for data acquisition. For reference, pure fragrance molecules are treated the same.
Solid phase micro-extraction operating conditions: the aldehyde/ketone fragrance release performance was assessed by Solid Phase Microextraction (SPME), which consists of a SPME holder and a needle with fibers. The fibers were coated with a carboxyl/polydimethylsiloxane (CAR/PDMS) adsorbing coating, 75 μm in diameter. Before use, the SPME needle with extraction fibers was inserted into the back sample port of the GC and pre-treated at 250 ℃ for 30 minutes with the flow rate of carrier gas (helium) maintained at 1.0 mL/min.
Fig. 2 to 5 show headspace release properties of various pyridinium quaternary hydrazone compounds, where time is abscissa and peak area of released fragrance is ordinate to obtain time-peak area curve, fig. 2 is a schematic diagram of time-peak area curve of releasing fragrance of pyridinium quaternary hydrazone compound a and pure fragrance material, fig. 3 is a schematic diagram of time-peak area curve of releasing fragrance of pyridinium quaternary hydrazone compound B and pure fragrance material, fig. 4 is a schematic diagram of time-peak area curve of releasing fragrance of pyridinium quaternary hydrazone compound C and pure fragrance material, and fig. 5 is a schematic diagram of time-peak area curve of releasing fragrance of pyridinium quaternary hydrazone compound D and pure fragrance material.
As can be seen from the figure, the release of all the pure perfume materials is greater than the hydrolysis release of the pyridylquaternary hydrazone compounds. Under the condition of acidic aqueous solution, the imine bond of the pyridyl quaternary ammonium salt hydrazone compound is broken, and the pyridyl quaternary ammonium salt hydrazone compound is hydrolyzed to form hydrazide and aromatic aldehyde ketone. As the reaction proceeds, the hydrolysis gradually approaches dynamic equilibrium, the aromatic gas phase components volatilized to the upper space of the headspace bottle under heating gradually become stable, and the pure perfume material shows a rapid and large-scale release trend with time due to no constraint of chemical force.
The release rates and the release amounts of different aromatic aldehyde ketone molecules are different by comparing the graphs, wherein the release amount of the compound C and the corresponding β -ionone is the largest because the boiling point of β -ionone is only 126 ℃ and is lower than that of the other three aromatic aldehydes, in addition, the release conditions of the four pyridinium quaternary ammonium salt hydrazone compounds with different chemical structures are also obviously different, the ratio of the pure release amounts of the cinnamaldehyde and the β -ionone to the mass of the aromatic substances released by the hydrolysis of the respectively formed pyridinium quaternary ammonium salt hydrazone compounds is larger than that of the heliotropin and the laggeral (18 times of A:18 times, 17 times of C: 8 times compared with B: 6 times and D:6 times), which is attributed to the existence of the conjugated structure in the compound A, C so as to ensure that the chemical structures are more stable, and the different structures of the pyridinium quaternary ammonium salt hydrazone compounds and the different boiling points of the aromatic substances can cause different aroma release behaviors.
The synthesized pyridinium quaternary ammonium salt hydrazone compound can hydrolyze in an aqueous solution to release aldehyde ketone perfume substances, and the pyridinium quaternary ammonium salt hydrazide compound remained in a solution system after hydrolysis also has good surface activity and antibacterial capacity. If the water-soluble aromatic amine compound is applied to some weakly acidic washing products, the water surface tension can be reduced, the clothes can be sterilized and bacteriostatic, and meanwhile, the fragrance in the washing products can be kept for a longer time, so that the water-soluble aromatic amine compound has certain market application prospect.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A pyridinium quaternary hydrazone compound having a structure represented by the following formula:
R1selected from hydrogen, C1-C20An alkyl group;
R2selected from hydrogen, substituted or unsubstituted aryl, C1-C20An alkenyl-substituted aryl group, a substituted or unsubstituted cycloalkyl group, or a heterocyclic group;
R3selected from hydrogen, C1-C20An alkyl group;
R4selected from hydrogen, C1-C20An alkyl group;
x is halogen.
2. The pyridinium quaternary hydrazone compound according to claim 1, wherein the pyridinium quaternary hydrazone compound is characterized in that,
R1selected from hydrogen, C5-C18An alkyl group;
R2selected from hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted benzoheterocycle, C1-C20Alkenyl-substituted phenyl, substituted or unsubstituted cyclohexene, substituted or unsubstituted cycloalkyl;
R3selected from hydrogen, C5-C18An alkyl group;
R4selected from hydrogen, C5-C18An alkyl group;
x is Cl or Br.
3. The pyridinium quaternary hydrazone compound according to claim 2, wherein the pyridinium quaternary hydrazone compound is characterized in that,
R1selected from hydrogen, C5-C18An alkyl group;
R2selected from hydrogen,
R3Selected from hydrogen, methyl;
R4selected from hydrogen, methyl;
and X is Br.
4. The quaternary pyridinium hydrazone compound of claim 3, wherein the quaternary pyridinium hydrazone compound is one of the following structures:
5. a method for preparing a hydrazone compound of any one of claims 1 to 4, comprising the steps of:
dissolving 3-hydroxypyridine in a solvent, adding alkali, reacting for 0.1-48 h at the temperature of 20-60 ℃, dropwise adding alkyl halide, wherein the molar ratio of the 3-hydroxypyridine to the alkali to the alkyl bromide is 1 (2-30) to 1, and obtaining an intermediate pyridine compound after the reaction is completed;
dissolving an intermediate pyridine compound in a solvent, adding halogenated ethyl acetate, wherein the molar ratio of the intermediate pyridine compound to the halogenated ethyl acetate is 1 (1.1-2), and reacting at 20-60 ℃ for 0.1-48 h to obtain a pyridine quaternary ammonium salt compound;
dissolving hydrazine hydrate in a solvent, dissolving a quaternary pyridinium salt compound in the solvent, slowly adding the solution of the hydrazine hydrate, wherein the molar ratio of hydrazine hydrate to the quaternary pyridinium salt compound is (5-15) to 1, and reacting for 0.1-48 h at the temperature of 20-60 ℃ to obtain the quaternary pyridinium salt hydrazide compound;
dissolving a pyridine quaternary ammonium salt type hydrazide compound and aldehyde or ketone spices in a solvent according to a molar ratio of 1 (1.1-2), and performing reflux reaction to obtain the pyridine quaternary ammonium salt type hydrazone compound.
6. The method of claim 5, wherein the solvent is selected from the group consisting of dimethylsulfoxide, ethylacetate, and ethanol;
the alkali is potassium hydroxide or sodium hydroxide.
7. The method of claim 5, wherein the alkyl halide is bromododecane, bromooctane, bromodecane, bromotetradecane, bromohexadecane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, and bromononane.
8. The method of claim 5, wherein the ethyl haloacetate is ethyl bromoacetate;
the aldehyde or ketone perfume is cinnamaldehyde, heliotropin, β -ionone, cyclamen aldehyde, benzaldehyde, anisaldehyde, vanillin, citronellal, ionone, methyl ionone, carvone, damascenone.
9. Use of the pyridinium quaternary hydrazone compound according to any one of claims 1 to 4 in an antibacterial or perfume slow release.
10. Use of a hydrazone compound of the quaternary pyridinium type according to any one of claims 1 to 4 as an antibacterial agent or a perfume slow-release agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911152808.0A CN110818624B (en) | 2019-11-22 | 2019-11-22 | Pyridine quaternary ammonium salt hydrazone compound, preparation method and application in antibacterial or perfume slow release |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911152808.0A CN110818624B (en) | 2019-11-22 | 2019-11-22 | Pyridine quaternary ammonium salt hydrazone compound, preparation method and application in antibacterial or perfume slow release |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110818624A true CN110818624A (en) | 2020-02-21 |
| CN110818624B CN110818624B (en) | 2022-11-22 |
Family
ID=69558197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911152808.0A Active CN110818624B (en) | 2019-11-22 | 2019-11-22 | Pyridine quaternary ammonium salt hydrazone compound, preparation method and application in antibacterial or perfume slow release |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110818624B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5750088A (en) * | 1993-03-30 | 1998-05-12 | The Dupont Merck Pharmaceutical Company | Stable hydrazones linked to a peptide moiety as reagents for the preparation of radiopharmaceuticals |
| CN1373747A (en) * | 1999-07-09 | 2002-10-09 | 宝洁公司 | Process for making amine componds |
| US20060111270A1 (en) * | 2002-08-02 | 2006-05-25 | Sergey Selifonov | Ketocampholenic acid derivatives and their use in fragrance applications |
| WO2006100647A1 (en) * | 2005-03-24 | 2006-09-28 | Firmenich Sa | Hydrogels for the controlled release of bioactive materials |
| CN101001832A (en) * | 2004-08-05 | 2007-07-18 | 弗门尼舍有限公司 | Use of dynamic mixtures for a controlled release of fragrances |
| US20190276469A1 (en) * | 2016-11-25 | 2019-09-12 | Henkel Ag & Co. Kgaa | Cyclic Ketals As Fragrance Precursor Compounds |
-
2019
- 2019-11-22 CN CN201911152808.0A patent/CN110818624B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5750088A (en) * | 1993-03-30 | 1998-05-12 | The Dupont Merck Pharmaceutical Company | Stable hydrazones linked to a peptide moiety as reagents for the preparation of radiopharmaceuticals |
| CN1373747A (en) * | 1999-07-09 | 2002-10-09 | 宝洁公司 | Process for making amine componds |
| US20060111270A1 (en) * | 2002-08-02 | 2006-05-25 | Sergey Selifonov | Ketocampholenic acid derivatives and their use in fragrance applications |
| CN101001832A (en) * | 2004-08-05 | 2007-07-18 | 弗门尼舍有限公司 | Use of dynamic mixtures for a controlled release of fragrances |
| WO2006100647A1 (en) * | 2005-03-24 | 2006-09-28 | Firmenich Sa | Hydrogels for the controlled release of bioactive materials |
| US20190276469A1 (en) * | 2016-11-25 | 2019-09-12 | Henkel Ag & Co. Kgaa | Cyclic Ketals As Fragrance Precursor Compounds |
Non-Patent Citations (4)
| Title |
|---|
| BARBARA LEVRAND,ET AL: "Controlled Release of Volatile Aldehydes and Ketones from Dynamic Mixtures Generated by Reversible Hydrazone Formation", 《HELVETICA CHIMICA ACTA》 * |
| 李银涛: "吡啶季铵盐表面活性剂的杀菌活性研究", 《长治医学院学报》 * |
| 许同桃等: "香草醛缩2,4-二硝基苯腙的合成和抑菌性研究", 《化工时刊》 * |
| 韩建伟 等: "基于纳米尺寸低聚硅倍半氧烷潜香体的合成、表征及其香料醛分子缓释性能研究", 《中国科学: 化学》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110818624B (en) | 2022-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109651621B (en) | Zirconium-based metal organic framework composite material and preparation method and application thereof | |
| Fasulo et al. | Structural and mechanistic investigation of a cationic hydrogen-substituted ruthenium silylene catalyst for alkene hydrosilation | |
| Hess et al. | Inversion of enantioselectivity in the platinum-catalyzed hydrogenation of substituted acetophenones | |
| Xu et al. | Polyoxometalate-modified fabrics: New catalytic materials for low-temperature aerobic oxidation | |
| CN105385439A (en) | Reaction type Rhodamine-class fluorescence probe for mercury ion detection and preparation as well as application thereof | |
| CN109232781A (en) | A kind of preparation method of nitrogenous porous organic polymer | |
| CN108982631A (en) | A kind of monatomic metal/composite material of graphene and its preparation method and application | |
| CN107486562A (en) | Plant-derived polyoses extract reducing metal salt prepares method and the application of metal nano material | |
| CN109459475B (en) | Preparation and application of Au NPs/zinc oxide nanocone array/foam graphene electrode | |
| CN110818624B (en) | Pyridine quaternary ammonium salt hydrazone compound, preparation method and application in antibacterial or perfume slow release | |
| Ho et al. | Copper-catalyzed amination of alkenes and ketones by phenylhydroxylamine | |
| Schmitt et al. | 2, 4, 6, 8‐Tetracyanoazulene: A New Building Block for “Organic Metals” | |
| CN113087698A (en) | Preparation method and antifungal application of nicotine benzoate solid | |
| CN108456188A (en) | A kind of 7- lignocaines -4- methytal coumarins derivative, preparation method and the application as nanometer fragrance precursor | |
| Trachsel et al. | Slow release of fragrance aldehydes and ketones in functional perfumery from dynamic mixtures generated with N‐heteroarylmethyl‐substituted secondary diamines | |
| CN104650358A (en) | Porphyrin-based heteronuclear double-metal polymer, and preparation method and applications thereof | |
| CN109254049B (en) | Preparation method and application of ampicillin sensor | |
| CN109096314A (en) | (-) -4,5- firpene-bipy 2,2' bipyridyl copper nitrate monokaryon chiral coordination compound and preparation method thereof | |
| Tovrog et al. | Oxidation of ruthenium coordinated alcohols by molecular oxygen to ketones and hydrogen peroxide | |
| CN107880269B (en) | Polyhedral oligomeric silsesquioxane-containing compound and use thereof | |
| CN105482047B (en) | A kind of preparation method of imidazole salt high-molecular anti-bacteria film | |
| CN109307695B (en) | Preparation method and application of chlordimeform electrochemiluminescence sensor | |
| CN104255777B (en) | A kind of graft on polyolefin-based materials surface antibacterial agent, its preparation method and application | |
| Fantin et al. | Stereochemical Control in Bakers' Yeast Redox Biotransformations of Aryl Methyl Ketones and Carbinols | |
| Wang et al. | Imide-functionalized Cu-MOF: Biomimetic peroxidase activity and detection of hydrogen peroxide and ascorbic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |