CN113632787B - Slow-release bactericide suitable for hospital environment and preparation method thereof - Google Patents
Slow-release bactericide suitable for hospital environment and preparation method thereof Download PDFInfo
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- CN113632787B CN113632787B CN202111041989.7A CN202111041989A CN113632787B CN 113632787 B CN113632787 B CN 113632787B CN 202111041989 A CN202111041989 A CN 202111041989A CN 113632787 B CN113632787 B CN 113632787B
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- benzene sulfonate
- hydrotalcite
- apramycin
- release
- slow
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 37
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 134
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 134
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 134
- 229950006334 apramycin Drugs 0.000 claims abstract description 105
- XZNUGFQTQHRASN-XQENGBIVSA-N apramycin Chemical group O([C@H]1O[C@@H]2[C@H](O)[C@@H]([C@H](O[C@H]2C[C@H]1N)O[C@@H]1[C@@H]([C@@H](O)[C@H](N)[C@@H](CO)O1)O)NC)[C@@H]1[C@@H](N)C[C@@H](N)[C@H](O)[C@H]1O XZNUGFQTQHRASN-XQENGBIVSA-N 0.000 claims abstract description 104
- 229940077388 benzenesulfonate Drugs 0.000 claims abstract description 51
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims abstract description 51
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims abstract description 50
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011229 interlayer Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000010410 layer Substances 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 10
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 238000013268 sustained release Methods 0.000 claims 3
- 239000012730 sustained-release form Substances 0.000 claims 3
- 238000009830 intercalation Methods 0.000 abstract description 18
- 238000002156 mixing Methods 0.000 abstract description 6
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000001954 sterilising effect Effects 0.000 description 21
- 238000004659 sterilization and disinfection Methods 0.000 description 17
- 230000002687 intercalation Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 11
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 10
- 239000012266 salt solution Substances 0.000 description 10
- 229940092714 benzenesulfonic acid Drugs 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 206010011409 Cross infection Diseases 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 239000005794 Hymexazol Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- KGVPNLBXJKTABS-UHFFFAOYSA-N hymexazol Chemical compound CC1=CC(O)=NO1 KGVPNLBXJKTABS-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 206010029803 Nosocomial infection Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- 241001478240 Coccus Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 239000005574 MCPA Substances 0.000 description 1
- 241000204031 Mycoplasma Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- 241000194017 Streptococcus Species 0.000 description 1
- 241000187747 Streptomyces Species 0.000 description 1
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 description 1
- 241000589886 Treponema Species 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940126574 aminoglycoside antibiotic Drugs 0.000 description 1
- 239000002647 aminoglycoside antibiotic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 230000000249 desinfective effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Classifications
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- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the technical field of organic-inorganic composite materials, and particularly relates to a slow-release bactericide suitable for hospital environment and a preparation method thereof. The slow-release bactericide suitable for hospital environment is apramycin, dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite. Firstly, preparing hydrotalcite precursor, intercalating dodecylbenzene sulfonate and benzene sulfonate into the hydrotalcite precursor according to a certain proportion to obviously enlarge the interlayer spacing of the hydrotalcite, mixing the hydrotalcite and apramycin aqueous solution, and diffusing apramycin into the interlayer of the hydrotalcite to obtain the apramycin intercalated hydrotalcite, namely the slow-release bactericide. The invention can realize the function of regulating the slow release rate of apramycin by adjusting the proportion of dodecyl benzene sulfonate and benzene sulfonate between layers.
Description
Technical Field
The invention belongs to the technical field of organic-inorganic composite materials, and particularly relates to a slow-release bactericide suitable for hospital environment and a preparation method thereof.
Background
Hospital infection is also known as nosocomial infection or nosocomial infection, and refers to infection acquired by patients, staff and accompanying persons in a hospital. The hospital is a place where various patients gather, various bacteria are easy to breed, and hospital infection becomes a prominent public health problem faced by the hospital, so that the sterilization and killing work of the bacteria in public places in the hospital has extremely important practical significance. At present, two methods of hydrogen peroxide disinfectant and ultraviolet rays are mainly adopted for inhibiting and killing bacteria in hospital environment. The hydrogen peroxide disinfectant can kill intestinal pathogenic bacteria, pyogenic coccus and pathogenic yeast, and is generally used for disinfecting the surfaces of objects. Ultraviolet lamps are installed mainly in the air duct at the front end of the coil or on a shelf fixed to a wall, and when air passes through, microorganisms in the air are killed and become harmless. In addition, the ultraviolet sterilization has strong sterilization effect but weak penetration capacity to objects, and is suitable for sterilizing the space between an operating room, a burn ward, an infection ward and a sterile room and sterilizing the surfaces of thermolabile articles and table tops. However, the two disinfection methods have obvious limitations when applied to sterilization of walls and floors of hospitals, hydrogen peroxide disinfectant needs to be frequently and regularly sprayed when used, and hydrogen peroxide is not stable enough and is easy to rapidly decompose in high-temperature, acid and alkali environments; ultraviolet lamps require high intensity for long periods of time to achieve sterilization and are not suitable for direct irradiation of the body.
The slow-release bactericide is a material which is formed by attaching the bactericide in a cross-linked network structure of a carrier material and has the function of slowly releasing the bactericide. Generally, the bactericide carrier material mainly includes synthetic polymer materials and various inorganic adsorbing materials. The research and development of novel environment-friendly slow-release bactericide realizes high drug-loading rate by controlling the structure of carrier materials and adjusting the interaction between the carrier and the bactericide, and the controllable loading and release of the bactericide is developed into a hot topic of bactericide slow release.
Apramycin, also known as apramycin, is an aminoglycoside antibiotic produced by Streptomyces nigreus, an important antibiotic commonly used as its sulfate salt, with the molecular formula C 21 H 41 N 5 O 11 ·2.5H 2 SO 4 . The apramycin is yellowish or tawny powder, is easy to dissolve in water, has hygroscopicity, is characterized by wide antibacterial spectrum, has quite strong antibacterial action on gram-negative bacteria, particularly pathogenic bacteria such as escherichia coli, salmonella and the like with other antibiotic resistance, and also has better antibacterial action on gram-positive bacteria (certain streptococcus), treponema and certain mycoplasma.
Layered Double Hydroxides (LDHs) are a general term for Hydrotalcite (HT) and Hydrotalcite-Like Compounds (HTLCs), and a series of supramolecular materials intercalated and assembled from these Compounds are called Hydrotalcite-Like intercalation materials (LDHs). LDHs are compounds assembled by interaction of positively charged host lamellae and interlayer anions through noncovalent bonds, and have a structure similar to brucite Mg (OH) 2 Made of MgO 6 The octahedron share the prism to form a unit layer. The chemical composition of LDHs is [ M ] 2+ 1-x M 3+ x (OH) 2 ] x+ (An – ) x/n ·mH 2 And O. The material is composed of parallel plates with a permanent positive charge. M 2+ ，M 3+ I.e. divalent and trivalent metal cations, with exchangeable anions A between the layers n- To maintain charge balance. The elements between the hydrotalcite laminates have strong covalent bond, the anions between the laminates attract each other by electrostatic attraction, and the whole crystal is electrically neutral. Due to the controllability of the metal ions and the anions between the layers of the laminate, the hydrotalcite materials are widely applied to the fields of catalysis, absorption, drug slow release, ion exchange and the like.
Chinese patent CN 110663683A discloses a slow-release type weeding and sterilizing double-effect pesticide and a preparation method thereof, wherein dimethyltetrachlorate is intercalated into hydrotalcite precursorThen, the hymexazol is inserted into the hydrotalcite precursor, and finally the hymexazol is put into the mixed solution containing hydrogen peroxide, isopropanol and water for treatment to obtain the slow-release type weeding and sterilizing double-effect pesticide; the chemical formula is: [ (M) 2+ ) 1-x (M 3+ ) x (OH) 2 ] x+ (MCPA - ) x (hym) y ·mH 2 O, wherein x is 0.25-0.33, y is 0.12-0.20, M is 3-6, M is the number of interlayer crystalline water molecules, M is 2+ Is a divalent metal ion, M 3+ Is trivalent metal ion, MCPA-is dimethyltetrachlorate, hym is hymexazol. The pesticide in the patent can only be slowly released at a single speed, and the release speed of the pesticide in different environments cannot be artificially adjusted.
Although apramycin is widely applied in the field of sterilization, sterilization directly applied to hospital environment has many defects, such as instability, need of regular spraying and the like, and the application of apramycin is limited. If the apramycin is intercalated between hydrotalcite layers, when the apramycin intercalated hydrotalcite suspension is sprayed on the wall surface of a hospital, apramycin can slowly diffuse out of hydrotalcite to play a role in slowly releasing a bactericide and achieve the long-time sterilization effect. At present, the literature and the patent of the apramycin intercalated hydrotalcite are not disclosed in China.
Disclosure of Invention
The invention aims to provide a slow-release bactericide suitable for hospital environment, which is apramycin intercalated hydrotalcite, the apramycin intercalated structure is stable, light-resistant, high-temperature resistant and acid and alkali resistant, the slow-release bactericide is soaked in water or in a humid environment and can release apramycin for a long time to play the effects of sterilization and bacteriostasis, and in addition, the slow-release speed of apramycin can be adjusted by adjusting the proportion of dodecyl benzene sulfonate and benzene sulfonate between layers; the invention also provides a preparation method of the slow-release bactericide suitable for hospital environment, which is scientific, reasonable, simple and feasible.
The slow release type bactericide applicable to hospital environment is apramycin, dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite, and has the chemical formula as follows:
[(M 2+ ) 1-x (M 3+ ) x (OH) 2 ] x+ (DBS - ) y (BS - ) x-y (APR) z ·mH 2 O
wherein x is 0.25-0.34, y is 0.05-0.28, z is 0.05-0.14, M is 3-6, M is the number of interlayer crystal water molecules, M is 2+ Is a divalent metal ion, M 3+ Being trivalent metal ions, DBS - Is dodecyl benzene sulfonate, BS - Is benzene sulfonate and APR is apramycin.
Said M 2+ Is Zn 2+ 、Mg 2+ Or Ni 2+ Is preferably Zn 2+ 。
Said M 3+ Is Al 3+ 。
The preparation method of the slow-release bactericide suitable for the hospital environment comprises the following steps:
(1) preparing a hydrotalcite precursor;
(2) preparing dodecyl benzene sulfonate and benzene sulfonate co-intercalated hydrotalcite:
dissolving sodium dodecyl benzene sulfonate and sodium benzene sulfonate in water to remove CO 2 Obtaining a solution by deionized water, adding the hydrotalcite precursor obtained in the step (1) into the solution, and N 2 Reacting under protective heating and stirring, centrifugally washing and drying a product to obtain dodecyl benzene sulfonate and benzene sulfonate co-intercalated hydrotalcite DBS/BS-LDHs;
(3) the apramycin is fixed between layers of dodecyl benzene sulfonate and benzene sulfonate co-intercalated hydrotalcite:
dissolving apramycin in CO 2 Adding the dodecyl benzene sulfonate and benzene sulfonate co-intercalated hydrotalcite DBS/BS-LDHs obtained in the step (2) into the deionized water, and adding the mixture into the deionized water in the presence of N 2 Protecting and stirring for co-heating, centrifugally washing the product, and drying to obtain apramycin, dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite APR/DBS/BS-LDHs.
The hydrotalcite precursor in the step (1) is formed by taking NO as interlayer anion 3 － Or Cl － Layer ofMole ratio M of divalent and trivalent metal ions in the plate 2+ /M 3+ Hydrotalcite precursor NO 2-3 3 -LDHs or Cl-LDHs.
The preparation method of the hydrotalcite precursor in the step (1) is as follows:
will M 2+ Soluble salts of (A) and (B) 3+ Preparing a salt mixed solution from the soluble salt of (2), wherein M 2+ /M 3+ The molar ratio is 2-3, M 2 + In a molar concentration of 0.1-1.0M, M 3+ The molar concentration of (A) is 0.05-0.5M; using NaOH aqueous solution with the molar concentration of 1.0-3.0M as alkali solution in N 2 Under the protection condition, simultaneously adding the salt mixed solution and the alkali solution into a four-mouth bottle by adopting a double-dropping method, after the dropwise addition is finished, adjusting the pH value to 6-10 by using 0.1-3.0M NaOH solution, crystallizing the obtained slurry for 12-72h at the temperature of 60-80 ℃, and centrifugally washing for 3-5 times; taking out a sample, and drying at 50-70 ℃ for 20-48h to obtain a hydrotalcite precursor;
wherein M is 2+ The soluble salt of (A) is a hydrochloride or nitrate thereof, M 3+ The soluble salt of (A) is hydrochloride or nitrate; in the salt mixture solution, M 2+ Soluble salts of (A) and (B) 3+ The soluble salts of (a) are of the same kind.
The mol ratio of the sodium dodecyl benzene sulfonate and the sodium benzene sulfonate in the step (2) is 0.2-5.
The heating temperature in the step (2) is 50-70 ℃.
The reaction time in the step (2) is 12-48 h.
The washing times in the step (2) are 3-5 times.
The drying temperature in the step (2) is 50-70 ℃, and the drying time is 20-48 h.
The co-heating temperature in the step (3) is 40-45 ℃, and the co-heating time is 48-96 h.
The number of washing times in the step (3) is 2 to 3.
The drying temperature in the step (3) is 50-70 ℃, and the drying time is 20-48 h.
Firstly, preparing hydrotalcite precursor, intercalating dodecylbenzene sulfonate and benzene sulfonate into the hydrotalcite precursor according to a certain proportion to obviously enlarge the interlayer spacing of the hydrotalcite, mixing the hydrotalcite and apramycin aqueous solution, and diffusing apramycin into the interlayer of the hydrotalcite to obtain the apramycin intercalated hydrotalcite, namely the slow-release bactericide.
When the slow-release bactericide (apramycin intercalated hydrotalcite) prepared by the invention is used for sterilizing the inner walls of hospitals, a mixed solution (the volume ratio is 1: 1-3) of glycerol and water is prepared, then the apramycin intercalated hydrotalcite is dispersed in the mixed solution, and finally the slow-release bactericide is sprayed on the wall surfaces. The glycerol can play a role in moisture retention and absorption, can keep the surface of the hydrotalcite moist for a long time, and improves the slow release rate of the apramycin. In the using process, in order to ensure that the apramycin can be continuously released, the water content of the hydrotalcite is kept to be 10-25%, and if the water content is lower than 10%, a small amount of clear water can be lightly sprayed on the surface of the hydrotalcite for wetting by using a spraying device. If the limit of the release amount of the bactericide is reached, a large amount of clear water can be used for washing the wall surface, and a new apramycin intercalated hydrotalcite product (APR/DBS/BS-LDHs) is sprayed after the hydrotalcite is washed.
The invention has the following beneficial effects:
the invention uses the interlayer ion exchangeability, laminate controllability and laminate structure positioning effect of hydrotalcite to insert dodecyl benzene sulfonate and benzene sulfonate into hydrotalcite interlayer to prepare organic-inorganic nano composite material; after the dodecyl benzene sulfonate and the benzene sulfonate are intercalated, the hydrotalcite interlayer supporting function is realized, a higher space distance can be formed between hydrotalcite layers, and the hydrophilic apramycin can be conveniently inserted into the hydrotalcite layers, so that the layered composite material containing the high-dispersion apramycin intercalation is prepared. Because the apramycin has a plurality of hydroxyl groups and amino groups and can form hydrogen bonds with dodecyl benzene sulfonate, benzene sulfonate and a hydrotalcite laminate, the prepared hydrotalcite material intercalated with the apramycin has a stable intercalation structure. The apramycin can be released for a long time by soaking the material in water or in a humid environment, and has the effects of sterilization and bacteriostasis.
According to the invention, the hydrotalcite interlamination is expanded by utilizing dodecyl benzene sulfonate and benzene sulfonate which play a role of pillaring, and then the hydroxyl of the dodecyl benzene sulfonate and the polar group of the benzene sulfonate and the hydroxyl of the hydrotalcite laminate can be utilized to assemble apramycin rich in hydroxyl and amino into the hydrotalcite interlamination, so that the immobilization and high dispersion of apramycin are realized. In the prepared apramycin intercalated hydrotalcite material, the interaction force of apramycin, dodecylbenzene sulfonate, benzene sulfonate and a hydrotalcite laminate is strong, and the intercalation structure is stable; meanwhile, a series of apramycin intercalated hydrotalcite materials can be prepared by changing the type of divalent trivalent metal ions of the hydrotalcite laminate, the materials can release apramycin for a long time to play a role in slow release of a bactericide, and the preparation method is simple and easy to implement and easy to realize.
In the invention, the dodecyl benzene sulfonate and benzene sulfonate are jointly intercalated into the hydrotalcite, so that the hydrotalcite not only has the function of forming a hydrogen bond between a pillared hydrotalcite layer plate and the apramycin, but also can realize the function of regulating the slow release rate of the apramycin by changing the proportion of the dodecyl benzene sulfonate and the benzene sulfonate between layers. Experimental research shows that the release time of apramycin can be obviously prolonged by increasing the proportion of dodecyl benzene sulfonate, and the release time of apramycin can be obviously shortened by increasing the proportion of benzene sulfonate, because dodecyl benzene sulfonate has longer alkyl chain and has a cross phenomenon between hydrotalcite layers, the movement of macromolecular apramycin between hydrotalcite layers is not facilitated, and the release speed of apramycin is delayed; and the benzene sulfonate does not contain a longer molecular chain, so the fixing effect on the apramycin is weaker, and the apramycin is released more quickly when the content of the benzene sulfonate in the interlayer is higher.
XRD characterization is carried out on the hydrotalcite material prepared by the method, and the result shows that the hydrotalcite co-intercalated with apramycin, dodecylbenzene sulfonate and benzene sulfonate is successfully prepared. The XRD structure parameters show that apramycin adopts a flat-laying single-layer arrangement mode between hydrotalcite layers. The molecular width of apramycin is small, the interlamellar spacing is basically kept unchanged after the apramycin enters an interlayer, and the unit cell parameter a value of the apramycin is similar to that of other hydrotalcite, so that a product has a complete layered structure. From the condition that the apramycin is released from the intercalation product in the aqueous solution, more than 0.0800 g of apramycin can be released from each gram of apramycin intercalation hydrotalcite, and the release time lasts more than 25 days; the intercalated product can also continuously release apramycin in a humid environment, the release amount is more than 0.0500 g, the release time is more than 130 days, and the sterilization rate on the surface of the hydrotalcite is more than or equal to 90 percent.
The apramycin intercalation structure is stable, light-resistant, high-temperature resistant, acid-resistant and alkali-resistant, and has a slow release effect. Therefore, the hydrotalcite intercalated with the apramycin can be used as a medical slow-release bactericide and has high application value.
Drawings
FIG. 1 is a schematic diagram of the structure of hydrotalcite intercalated with apramycin, dodecylbenzene sulfonate and benzene sulfonate.
FIG. 2 is an X-ray powder diffraction pattern of apramycin, dodecylbenzene sulfonate and benzene sulfonate intercalated hydrotalcite prepared in example 1;
in the figure: a-a hydrotalcite precursor; b-dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite; c-apramycin, dodecyl benzene sulfonate and hydrotalcite with benzene sulfonate intercalation.
FIG. 3 is a graph of the release profile of apramycin from hydrotalcite intercalated with apramycin, dodecylbenzenesulfonate, and benzenesulfonate prepared in example 1; in the figure, a-release in water; b-release in a humid environment.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
(1) 29.75g Zn (NO) are weighed out 3 ) 2 ﹒6H 2 O and 18.76g Al (NO) 3 ) 3 ﹒9H 2 O dissolved in 200ml to remove CO 2 Preparing mixed salt solution with water, dissolving 8.0g NaOH in 100ml to remove CO 2 Preparing aqueous alkali solution in water, N at room temperature 2 The protection adopts a double-dropping method to add the salt solution and the alkali solution into a four-mouth bottle and strongly stir. The pH was adjusted to 7 with 0.1mol/L NaOH solution. Crystallizing the obtained slurry at 60 ℃ for 72h, and centrifugally washing for 3 times; taking out a sample, drying for 48h at 50 ℃, and then characterizing to obtain ZnAl-NO 3 LDHs in a molar ratio Zn 2+ /Al 3+ ＝2。
(2) 17.4g of sodium dodecylbenzenesulfonate and 9.0g of sodium benzenesulfonate are dissolved in 150mL of a solution to remove CO 2 Then transferring the deionized water into a four-mouth bottle, and then adding 10g of hydrotalcite precursor ZnAl-NO 3 -LDHs，N 2 Heating to 50 ℃ under protection, and reacting for 48h under stirring. And centrifuging and washing the product for 3 times, and drying the product for 48 hours at 50 ℃ to obtain the dodecyl benzene sulfonic acid and benzenesulfonic acid co-intercalated hydrotalcite DBS/BS-LDHs.
(3) Mixing 10.0g apramycin [ C ] 21 H 41 N 5 O 11 ·2.5H 2 SO 4 ]The solid is dissolved in 150mL to remove CO 2 Transferring the deionized water into a four-mouth bottle, adding the dodecyl benzene sulfonic acid and benzene sulfonic acid co-intercalated hydrotalcite DBS/BS-LDHs10g obtained in the step (2), and adding the deionized water into the four-mouth bottle 2 Under protection and stirring, heating for 96h at 40 ℃, centrifuging and washing the product for 2 times, and drying for 48h at 50 ℃ to obtain apramycin, dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite APR/DBS/BS-LDHs.
In this example, the product has the formula: [ (Zn) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (DBS - ) 0.15 (BS - ) 0.18 (APR) 0.09 ·3H 2 And O. The X-ray powder diffraction pattern of the product is shown in figure 2. As can be seen from fig. 2, hydrotalcite has an ideal hexagonal layered structure, a single crystal phase, and a good crystallinity. D of dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite DBS/BS-LDHs 003 Interlayer spacing of 2.68nm, ZnAl-NO as intercalation precursor 3 The interlayer spacing of the LDHs increases by 1.79 nm. The expansion phenomenon of the layer plate shows that dodecyl benzene sulfonate and benzene sulfonate are successfully inserted between LDHs layers. After apramycin has entered the hydrotalcite bed, d 003 The interlayer spacing remains substantially unchanged. In addition, 1g of the hydrotalcite is soaked in 100mL of distilled water, apramycin can be continuously released, the release balance is basically realized after 33 days, and the total release amount is 0.0836 g; the hydrotalcite can continuously release apramycin in a humid environment, basically releases balance after 139 days, has a total release amount of 0.0517 g, achieves a sterilization rate of 93% on the surface of the hydrotalcite, and has a release curve shown in figure 3.
Example 2
(1) 25.63g Mg (NO) are weighed 3 ) 2 ﹒6H 2 O and 18.76g Al (NO) 3 ) 3 ﹒9H 2 O dissolved in 200ml to remove CO 2 Preparing mixed salt solution with water, dissolving 8.0g NaOH in 200ml to remove CO 2 Preparing aqueous alkali solution in water, N at room temperature 2 The protection adopts a double-dropping method to add the salt solution and the alkali solution into a four-mouth bottle and strongly stir. The pH was adjusted to 10 with 1.0mol/L NaOH solution. Crystallizing the obtained slurry at 80 ℃ for 12h, and centrifugally washing the product for 5 times; taking out a sample, drying for 20h at 70 ℃, and then characterizing to obtain MgAl-NO 3 LDHs in a molar ratio of Mg 2+ /Al 3+ ＝2。
(2) 7.0g of sodium dodecylbenzenesulfonate and 18.0g of sodium benzenesulfonate are dissolved in 150mL of a solution of sodium dodecylbenzenesulfonate to remove CO 2 The deionized water is transferred into a four-mouth bottle, and then 10g of hydrotalcite precursor MgAl-NO is added 3 -LDHs，N 2 Heating to 70 ℃ under protection, and reacting for 12h under stirring. And centrifuging and washing the product for 5 times, and drying at 70 ℃ for 20h to obtain the dodecyl benzene sulfonic acid and benzene sulfonic acid co-intercalated hydrotalcite DBS/BS-LDHs.
(3) Mixing 10.0g apramycin [ C ] 21 H 41 N 5 O 11 ·2.5H 2 SO 4 ]The solid is dissolved in 150mL to remove CO 2 The deionized water is transferred into a four-mouth bottle, and then the dodecyl benzene sulfonic acid and benzene sulfonic acid co-intercalated hydrotalcite DBS/BS-LDHs10g obtained in the step (2) is added in the bottle in the presence of N 2 Under protection and stirring, heating at 45 ℃ for 48h, centrifuging and washing the product for 3 times, and drying at 70 ℃ for 20h to obtain apramycin, dodecylbenzene sulfonate and benzene sulfonate intercalated hydrotalcite APR/DBS/BS-LDHs.
In this example, the product has the formula: [ (Mg) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (DBS - ) 0.05 (BS - ) 0.28 (APR) 0.08 ·3H 2 And O. The product is known to have a more ideal hexagonal layered structure, a single crystal phase and better crystallinity through X-ray powder diffraction. D of dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite DBS/BS-LDHs 003 Interlayer spacing of 2.67nm, insertLayer precursor MgAl-NO 3 The interlayer spacing of the LDHs increases by 1.78 nm. The expansion phenomenon of the layer plate shows that dodecyl benzene sulfonate and benzene sulfonate are successfully inserted between LDHs layers. After apramycin has entered the hydrotalcite bed, d 003 The interlayer spacing remains substantially unchanged. In addition, 1g of the hydrotalcite is soaked in 100mL of distilled water, apramycin can be continuously released, the release balance is basically realized after 25 days, and the total release amount is 0.0812 g; the intercalation product can also continuously release apramycin in a humid environment, the apramycin is basically released and balanced after the release lasts for 131 days, the total release amount is 0.0502 g, and the sterilization rate on the surface of the hydrotalcite reaches 91%.
Example 3
(1) Weighing 29.08g Ni (NO) 3 ) 2 ﹒6H 2 O and 18.76g Al (NO) 3 ) 3 ﹒9H 2 Dissolving O in 250ml to remove CO 2 Preparing mixed salt solution with water, dissolving 8.0g NaOH in 200ml to remove CO 2 Preparing aqueous alkali solution in water, N at room temperature 2 The protection adopts a double-dropping method to add the salt solution and the alkali solution into a four-mouth bottle and strongly stir. The pH was adjusted to 7 with 3mol/L NaOH solution. Crystallizing the obtained slurry at 70 ℃ for 36h, and centrifuging and washing the product for 4 times; taking out a sample, drying for 36h at 60 ℃, and then characterizing to obtain NiAl-NO 3 LDHs in a molar ratio Zn 2+ /Al 3+ ＝2。
(2) 34.8g of sodium dodecylbenzenesulfonate and 3.6g of sodium benzenesulfonate are dissolved in 150mL of a solution to remove CO 2 The deionized water is transferred into a four-mouth bottle, and then 10g of hydrotalcite precursor NiAl-NO is added 3 -LDHs，N 2 Heating to 60 ℃ under protection, and reacting for 36h under stirring. And centrifuging and washing the product for 4 times, and drying at 60 ℃ for 36h to obtain the dodecyl benzene sulfonic acid and benzene sulfonic acid co-intercalated hydrotalcite DBS/BS-LDHs.
(3) Mixing 10.0g apramycin [ C ] 21 H 41 N 5 O 11 ·2.5H 2 SO 4 ]The solid is dissolved in 150mL to remove CO 2 The deionized water is transferred into a four-mouth bottle, and then the dodecyl benzene sulfonic acid and benzene sulfonic acid co-intercalated hydrotalcite DBS/BS-LDHs10g obtained in the step (2) is added in the bottle in the presence of N 2 Under protection and stirring, heating at 42 deg.C for 72 hr, centrifuging and washing the product for 2 times, and drying at 60 deg.C for 36 hr to obtain apramycin,Dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite APR/DBS/BS-LDHs.
In this example, the product has the formula: [ (Ni) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (DBS - ) 0.28 (BS - ) 0.05 (APR) 0.09 ·6H 2 And O. The product is known to have a more ideal hexagonal layered structure, a single crystal phase and better crystallinity through X-ray powder diffraction. D of dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite DBS/BS-LDHs 003 Interlayer spacing of 2.71nm, ZnAl-NO as intercalation precursor 3 The interlayer spacing of the LDHs increases by 1.82 nm. The expansion phenomenon of the layer plate shows that the dodecyl benzene sulfonate and the benzene sulfonate are successfully inserted into the LDHs layer. After apramycin has entered the hydrotalcite bed, d 003 The interlayer spacing remains substantially unchanged. In addition, 1g of the hydrotalcite is soaked in 100mL of distilled water, apramycin can be continuously released, the release balance is basically realized after 49 days, and the total release amount is 0.0896 g; the intercalation product can also continuously release apramycin in a humid environment, the apramycin is basically released and balanced after 167 days, the total release amount is 0.0541 g, and the sterilization rate on the surface of the hydrotalcite reaches 94%.
Example 4
(1) 27.26g of ZnCl was weighed 2 And 24.13g AlCl 3 ﹒6H 2 O dissolved in 200ml to remove CO 2 Preparing mixed salt solution with water, dissolving 16.0g NaOH in 200ml to remove CO 2 Preparing aqueous alkali solution in water, N at room temperature 2 The protection adopts a double-dropping method to add the salt solution and the alkali solution into a four-mouth bottle and strongly stir. The pH was adjusted to 7 with 1.5mol/L NaOH solution. Crystallizing the obtained slurry at 65 ℃ for 60h, and centrifuging and washing the product for 3 times; taking out a sample, drying for 48h at 50 ℃, and then characterizing to obtain ZnAl-Cl-LDHs with the molar ratio of Zn 2+ /Al 3+ ＝2。
(2) 17.4g of sodium dodecylbenzenesulfonate and 9.0g of sodium benzenesulfonate are dissolved in 150mL of a solution to remove CO 2 Then transferring the deionized water into a four-mouth bottle, and then adding 10g of hydrotalcite precursor ZnAl-Cl-LDHs, N 2 Heating to 50 ℃ under protection, and reacting for 48h under stirring. Centrifuging and washing the product for 5 times, and drying at 55 deg.C for 60hTo obtain the dodecyl benzene sulfonic acid and benzene sulfonic acid co-intercalated hydrotalcite DBS/BS-LDHs.
(3) Mixing 10.0g apramycin [ C ] 21 H 41 N 5 O 11 ·2.5H 2 SO 4 ]The solid is dissolved in 150mL to remove CO 2 The deionized water is transferred into a four-mouth bottle, and then the dodecyl benzene sulfonic acid and benzene sulfonic acid co-intercalated hydrotalcite DBS/BS-LDHs10g obtained in the step (2) is added in the bottle in the presence of N 2 Under protection and stirring, heating at 40 ℃ for 96h, centrifuging and washing the product for 3 times, and drying at 50 ℃ for 48h to obtain apramycin, dodecylbenzene sulfonate and benzene sulfonate intercalated hydrotalcite APR/DBS/BS-LDHs.
In this example, the product has the formula: [ (Zn) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (DBS - ) 0.16 (BS - ) 0.17 (APR) 0.09 ·3H 2 And O. The product is known to have a more ideal hexagonal layered structure, a single crystal phase and better crystallinity through X-ray powder diffraction. D of dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite DBS/BS-LDHs 003 Interlayer spacing of 2.69nm, ZnAl-NO as intercalation precursor 3 The interlayer spacing of the LDHs increases by 1.80 nm. The expansion phenomenon of the layer plate shows that dodecyl benzene sulfonate and benzene sulfonate are successfully inserted between LDHs layers. After apramycin has entered the hydrotalcite bed, d 003 The interlayer spacing remains substantially unchanged. In addition, 1g of the hydrotalcite is soaked in 100mL of distilled water, apramycin can be continuously released, the release balance is basically released after 27 days, and the total release amount is 0.0829 g; the intercalation product can also continuously release apramycin in a humid environment, the apramycin is basically released and balanced after being continuously released for 135 days, the total release amount is 0.0522 g, and the sterilization rate on the surface of the hydrotalcite reaches 93%.
Example 5
(1) 29.75g Zn (NO) are weighed out 3 ) 2 ﹒6H 2 O and 12.50g Al (NO) 3 ) 3 ﹒9H 2 O dissolved in 200ml to remove CO 2 Preparing mixed salt solution with water, dissolving 8.0g NaOH in 100ml to remove CO 2 Preparing aqueous alkali solution in water, N at room temperature 2 The protection adopts a double-dropping method to mix the salt solution and the alkali solutionAdding into a four-mouth bottle, and stirring intensively. The pH value was adjusted to 7 with 0.1mol/L NaOH solution. Crystallizing the obtained slurry at 70 ℃ for 48h, and centrifugally washing the product for 5 times; taking out a sample, drying for 48h at 50 ℃, and then characterizing to obtain ZnAl-NO 3 LDHs in a molar ratio Zn 2+ /Al 3+ ＝3。
(2) 17.4g of sodium dodecylbenzenesulfonate and 9.0g of sodium benzenesulfonate are dissolved in 150mL of a solution to remove CO 2 Then transferring the deionized water into a four-mouth bottle, and then adding 10g of hydrotalcite precursor ZnAl-NO 3 -LDHs，N 2 Heating to 70 ℃ under protection, and reacting for 20h under stirring. And centrifuging and washing the product for 3 times, and drying at 50 ℃ for 48h to obtain the dodecyl benzene sulfonic acid and benzene sulfonic acid co-intercalated hydrotalcite DBS/BS-LDHs.
(3) 10.0g of apramycin [ C ] 21 H 41 N 5 O 11 ·2.5H 2 SO 4 ]The solid is dissolved in 150mL to remove CO 2 The deionized water is transferred into a four-mouth bottle, and then the dodecyl benzene sulfonic acid and benzene sulfonic acid co-intercalated hydrotalcite DBS/BS-LDHs10g obtained in the step (2) is added in the bottle in the presence of N 2 Under protection and stirring, heating for 96h at 40 ℃, centrifuging and washing the product for 2 times, and drying for 48h at 50 ℃ to obtain apramycin, dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite APR/DBS/BS-LDHs.
In this example, the product has the formula: [ (Zn) 2+ ) 0.75 (Al 3+ ) 0.25 (OH) 2 ] 0.25+ (DBS - ) 0.12 (BS - ) 0.13 (APR) 0.10 ·4H 2 And O. The product is known to have a more ideal hexagonal layered structure, a single crystal phase and better crystallinity through X-ray powder diffraction. D of dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite DBS/BS-LDHs 003 Interlayer spacing of 2.70nm, ZnAl-NO as intercalation precursor 3 The interlayer spacing of the LDHs increases by 1.81 nm. The expansion phenomenon of the layer plate shows that dodecyl benzene sulfonate and benzene sulfonate are successfully inserted between LDHs layers. After apramycin has entered the hydrotalcite bed, d 003 The interlayer spacing remains substantially unchanged. In addition, 1g of the hydrotalcite is soaked in 100mL of distilled water, apramycin can be continuously released, and the release balance and total release amount are basically balanced after 28 days0.0858 g; the intercalation product can also continuously release apramycin in a humid environment, the apramycin is basically released and balanced after the apramycin lasts for 134 days, the total release amount is 0.0542 g, and the sterilization rate on the surface of the hydrotalcite reaches 92%.
Comparative example 1
The procedure of example 1 was repeated except that sodium dodecylbenzenesulfonate was used alone in the step (2).
1g of the hydrotalcite is soaked in 100mL of distilled water, apramycin can be continuously released, the release balance is basically realized after 72 days, and the total release amount is 0.0414 g; the hydrotalcite can continuously release apramycin in a humid environment, the release balance is basically kept after 283 days, and the total release amount is 0.0271 g.
Comparative example 2
The procedure of example 1 was repeated except that sodium benzenesulfonate was used in step (2).
1g of the hydrotalcite is soaked in 100mL of distilled water, apramycin can be continuously released, the release is basically balanced after the hydrotalcite is continuously released for 15 days, and the total release amount is 0.0985 g; the hydrotalcite can also continuously release apramycin in a humid environment, basically releases balance after 68 days, and has total release amount of 0.0629 g.
Claims (7)
1. The slow-release bactericide suitable for hospital environment is characterized by being apramycin, dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite with the chemical formula as follows:
[(M 2+ ) 1-x (M 3+ ) x (OH) 2 ] x+ (DBS - ) y （BS - ) x-y (APR) z •mH 2 O
wherein x =0.25-0.34, y =0.05-0.28, z =0.05-0.14, M is 3-6, M is the number of interlayer crystal water molecules, M is 2 + Is a divalent metal ion, M 3+ Being trivalent metal ions, DBS - Is dodecyl benzene sulfonate, BS - Is benzene sulfonate and APR is apramycin;
the preparation method of the slow-release bactericide suitable for hospital environment comprises the following steps:
(1) preparing a hydrotalcite precursor;
(2) preparing dodecyl benzene sulfonate and benzene sulfonate co-intercalated hydrotalcite:
dissolving sodium dodecyl benzene sulfonate and sodium benzene sulfonate in water to remove CO 2 Obtaining a solution by deionized water, adding the hydrotalcite precursor obtained in the step (1) into the solution, and N 2 Reacting under protective heating and stirring, centrifugally washing and drying a product to obtain dodecyl benzene sulfonate and benzene sulfonate co-intercalated hydrotalcite DBS/BS-LDHs;
(3) the apramycin is fixed between the layers of dodecyl benzene sulfonate and benzene sulfonate co-intercalated hydrotalcite:
dissolving apramycin in CO 2 Adding the dodecyl benzene sulfonate and benzene sulfonate co-intercalated hydrotalcite DBS/BS-LDHs obtained in the step (2) into the deionized water, and adding the mixture into the deionized water in the presence of N 2 Protecting and stirring for co-heating, centrifugally washing the product, and drying to obtain apramycin, dodecyl benzene sulfonate and benzene sulfonate intercalated hydrotalcite APR/DBS/BS-LDHs;
the mol ratio of the sodium dodecyl benzene sulfonate to the sodium benzene sulfonate in the step (2) is 0.2-5;
said M 2+ Is Zn 2+ 、Mg 2+ Or Ni 2+ One of (1), M 3+ Is Al 3+ 。
2. The sustained-release bactericide suitable for hospital environment according to claim 1, characterized in that said hydrotalcite precursor in step (1) is such that the interlayer anion is NO 3 － Or Cl － Layer plate divalent, trivalent metal ion molar ratio M 2+ /M 3+ Hydrotalcite precursor NO of =2-3 3 -LDHs or Cl-LDHs.
3. The sustained-release bactericide suitable for hospital environment according to claim 1, characterized in that said hydrotalcite precursor in step (1) is prepared as follows:
will M 2+ Soluble salts of (A) and (B) 3+ Preparing a salt-forming mixed solution from the soluble salt of (A), wherein M 2+ /M 3+ The molar ratio is 2-3, M 2+ In a molar concentration of 0.1-1.0M, M 3+ The molar concentration of (A) is 0.05-0.5M; using NaOH aqueous solution with the molar concentration of 1.0-3.0M as alkali solution in N 2 Under the protection condition, simultaneously adding the salt mixed solution and the alkali solution into a four-mouth bottle by adopting a double-dropping method, after the dropwise addition is finished, adjusting the pH value to 6-10 by using 0.1-3.0M NaOH solution, crystallizing the obtained slurry for 12-72h at the temperature of 60-80 ℃, and centrifugally washing for 3-5 times; taking out a sample, and drying at 50-70 ℃ for 20-48h to obtain a hydrotalcite precursor;
wherein M is 2+ The soluble salt of (A) is hydrochloride or nitrate thereof, M 3+ The soluble salt of (A) is hydrochloride or nitrate; in the salt mixture solution, M 2+ Soluble salts of (A) and (B) 3+ The soluble salts of (a) are of the same kind.
4. The slow-release bactericide suitable for hospital environments according to claim 1, wherein said heating temperature in step (2) is 50-70 ℃ and the reaction time is 12-48 h.
5. The slow-release bactericide suitable for hospital environments according to claim 1, characterized in that in step (2) the washing times are 3-5, the drying temperature is 50-70 ℃ and the drying time is 20-48 h.
6. The slow-release bactericide suitable for hospital environment according to claim 1, characterized in that said co-heating temperature in step (3) is 40-45 ℃ and co-heating time is 48-96 h.
7. The sustained-release bactericide suitable for use in a hospital environment according to claim 1, wherein the washing in step (3) is conducted 2 to 3 times at a drying temperature of 50 to 70 ℃ for 20 to 48 hours.
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