CN110327888A - Difunctional sulfydryl schiff base metal organogel-nanocomposite and its preparation method and application - Google Patents
Difunctional sulfydryl schiff base metal organogel-nanocomposite and its preparation method and application Download PDFInfo
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- A—HUMAN NECESSITIES
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of difunctional sulfydryl schiff base metal organogel-nanocomposites and its preparation method and application, the difunctional sulfydryl schiff base metal organogel-nanocomposite AgNPs@Ag (I)-MTMP, AgNPs@Ag (the I)-MTMP contains Nano silver grain AgNPs, Ag (I)-MTMP and solvent, the AgNPs is adsorbed on the Ag (I)-MTMP, and Ag (the I)-MTMP wraps up solvent with hydrogen bond and molecular force;The chemical formula of Ag (I)-MTMP is [Ag (MTMP)]n(L)n, [Ag (MTMP)]n n+Structure it is shown in formula I, wherein L is negative univalent anion, and n is positive integer, and MTMP is 2- ((5- sulfydryl -1,3,4- thiadiazoles -2- imino group) methyl) phenol;Double composite materials efficiently Adsorption acidic organic dye molecule and can have both antibacterial functions;
Description
Technical field
The present invention relates to organogel-nanocomposites, and in particular, to a kind of difunctional sulfydryl schiff base metal has
Machine gel-nanocomposite and its preparation method and application.
Background technique
It is well known that water is the most important component part of life on earth.With the development of modern society, world population is in
Geometric growth greatly increases the demand of clean water.However, industrialized production and rural activity generate a large amount of give up
Water causes serious environment water pollution, so that water quality constantly deteriorates, the whole world faces serious water resource and lacks problem.
Organic dyestuff is widely used in weaving, leather, process hides, papermaking, food processing, plastics, cosmetics, rubber, printing
Etc. industries, be the major pollutants of industrial wastewater.The carcinogen that dyestuff generates in degradation process is to the ecosystem and the mankind
Life causes harm.Therefore, the organic dye pollutant in water is effectively removed to environmental protection and human health with important
Meaning.
The chemical property of organic dyestuff is stablized, and is difficult to degrade.Being used the various methods for removing dye discolorations includes
Flocculence, electrochemical treatment, absorption method, membrane separation process etc..In the above-mentioned methods, absorption method has adsorption efficiency height, recycling
Rate is high, at low cost and be widely used.Currently used adsorbent has shallow lake powder/polyaniline, porous silicon, guar gum, active carbon, gold
Belong to organic frame (MOFs) and hollow inorganic spheres etc..However, these traditional common adsorbents also have many deficiencies, including to perhaps
The removal effect of mostly hydrophilic pollutant is poor, too low to the adsorption capacity of macromolecular stabilizer pollutant, and physically activated needs are longer
Time, chemical activation need thoroughly cleaning etc..
Summary of the invention
The object of the present invention is to provide a kind of difunctional sulfydryl schiff base metal organogel-nanocomposite and its systems
Preparation Method and application, the difunctional sulfydryl schiff base metal organogel-nanocomposite can efficiently Adsorption acid
Property organic dye molecule simultaneously has both antibacterial functions so that the composite material can be applied in water process, while the preparation side
Method have the advantages that easily prepare, it is at low cost.
To achieve the goals above, the present invention provides a kind of difunctional sulfydryl schiff base metal organogel-nanometer is multiple
Condensation material AgNPs@Ag (I)-MTMP, AgNPs@Ag (the I)-MTMP contain Nano silver grain AgNPs, Ag (I)-MTMP and molten
Agent, the AgNPs are adsorbed on the Ag (I)-MTMP, and Ag (the I)-MTMP wraps up solvent with hydrogen bond and molecular force;
The chemical formula of Ag (I)-MTMP is [Ag (MTMP)]n(L)n, [Ag (MTMP)]n n+Structure it is shown in formula I, wherein L is negative monovalence
Anion, n are positive integer, and MTMP is 2- ((5- sulfydryl -1,3,4- thiadiazoles -2- imino group) methyl) phenol;
The present invention also provides a kind of such as above-mentioned difunctional sulfydryl schiff base metal organogel-nanocomposite
The preparation method of AgNPs@Ag (I)-MTMP, the preparation method include: that silver salt AgL, MTMP are placed in solvent to mix and adjust
Haptoreaction is carried out after pH, is then allowed to stand, is dried to obtain AgNPs Ag (I)-MTMP.
Invention further provides a kind of such as above-mentioned difunctional sulfydryl schiff base metal organogel-nano combined material
Expect application of AgNPs@Ag (the I)-MTMP in adsorbed water body in acidic organic dye and/or water sterilization.
Through the above technical solutions, the present invention uses schiff bases MTMP and silver salt containing sulfydryl to exist by in-situ synthetic method
It is reacted in solvent, has synthesized AgNPs@Ag (I)-MTMP metal organogel-nanocomposite, metal organogel has hole
The advantages that gap rate height, large specific surface area, therefore there is good adsorption effect;By silver salt can in gel-type vehicle shape in situ
At Nano silver grain, metal organogel-nanocomposite is formed, makes material while there is anti-microbial property.The preparation simultaneously
Method is easy to operate, yield is high and solves the problems, such as that dyestuff is difficult to degrade.
Experiment show the material Adsorption aqueous acid medium dyestuff for example naphthol green B (NG), acid fuchsin (AF),
Congo red (CR), methyl orange (MO) etc. show extraordinary performance.The absorption of dyestuff meet quasi- first order kinetics process and
Freundlich isotherm adsorption model, show to carry out is chemisorption.In addition, the composite material is to Escherichia coli, withered grass bar
Bacterium and staphylococcus aureus have good anti-microbial property.Therefore, resulting materials have absorption and antibacterial dual function, can be with
It is disposably solved two problems in environment water treatment procedure, provides reference to obtain field direct drink processing material.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings: in Fig. 2-5, used in a
Raw material is AgNO3, b raw materials used is AgClO4。
Fig. 1 is that AgNPs@Ag (I)-MTMP synthesizes schematic diagram in embodiment 1;
Fig. 2-1 is the SEM figure of AgNPs@Ag (I)-MTMP in embodiment 1;
Fig. 2-2 is the SEM figure of AgNPs@Ag (I)-MTMP in embodiment 4;
Fig. 3-1 is the TEM figure of AgNPs@Ag (I)-MTMP in embodiment 1;
Fig. 3-2 is the TEM figure of AgNPs@Ag (I)-MTMP in embodiment 4;
Fig. 4-1 is the XRD diagram of AgNPs@Ag (I)-MTMP in embodiment 1;
Fig. 4-2 is the XRD diagram of AgNPs@Ag (I)-MTMP in embodiment 4;
Fig. 5-1 is the BET figure of AgNPs@Ag (I)-MTMP in embodiment 1;
Fig. 5-2 is the BET figure of AgNPs@Ag (I)-MTMP in embodiment 4;
Fig. 6 is the absorptance statistical chart that AgNPs@Ag (I)-MTMP adsorbs dyestuff naphthol green in embodiment 1;
Fig. 7 is that AgNPs@Ag (I)-MTMP adsorbs the Congo red absorptance statistical chart of dyestuff in embodiment 1;
Fig. 8 is the absorptance statistical chart that AgNPs@Ag (I)-MTMP adsorbs methyl orange in embodiment 1;
Fig. 9 is the absorptance statistical chart that AgNPs@Ag (I)-MTMP adsorbs dyestuff acid fuchsin in embodiment 1;
Figure 10 be in embodiment 1 AgNPs@Ag (I)-MTMP to the saturated extent of adsorption of four kinds of dyestuffs;
Figure 11 is that AgNPs@Ag (I)-MTMP changes with time figure to four kinds of Dye Adsorption efficiency in embodiment 1;
Figure 12 is the antibacterial effect figure of AgNPs@Ag (I)-MTMP in embodiment 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of difunctional sulfydryl schiff base metal organogel-nanocomposite AgNPs@Ag (I)-
MTMP, AgNPs@Ag (the I)-MTMP contain Nano silver grain AgNPs, Ag (I)-MTMP and solvent, and the AgNPs is adsorbed in institute
It states on Ag (I)-MTMP, Ag (the I)-MTMP wraps up solvent with hydrogen bond and molecular force;The chemical formula of Ag (I)-MTMP is
[Ag(MTMP)]n(L)n, [Ag (MTMP)]n n+Structure it is shown in formula I, wherein L is negative univalent anion, and n is positive integer,
MTMP is 2- ((5- sulfydryl -1,3,4- thiadiazoles -2- imino group) methyl) phenol;
In above-mentioned difunctional sulfydryl schiff base metal organogel-nanocomposite, difunctional sulfydryl schiff bases gold
Belonging to organogel-nanocomposite specific structure can select in a wide range, in order to further increase organogel-
The absorption of nanocomposite and antibacterial effect, it is preferable that Ag (I)-MTMP is linear fiber structure.
In above-mentioned difunctional sulfydryl schiff base metal organogel-nanocomposite, the specific type of L can be in width
In the range of select, in order to further increase silver ion in-situ reducing efficiency so that improve composite material antibacterial effect, it is excellent
Selection of land, L are selected from least one of nitrate anion, perchlorate.
In above-mentioned difunctional sulfydryl schiff base metal organogel-nanocomposite, the specific type of solvent can be with
It selects in a wide range, improves composite material antibacterial effect in turn to further increase the efficiency of in-situ reducing of silver ion
Fruit, it is preferable that solvent is selected from CH3OH、CH3CH2OH、DMSO/H2O mixed solution, DMF/H2At least one of O mixed solution;
It is highly preferred that solvent is DMF, H2The mixed solution of O.
The present invention also provides a kind of such as above-mentioned difunctional sulfydryl schiff base metal organogel-nanocomposite
The preparation method of AgNPs@Ag (I)-MTMP, the preparation method include: that silver salt AgL, MTMP are placed in solvent to mix and adjust
Haptoreaction is carried out after pH, is then allowed to stand, is dried to obtain AgNPs Ag (I)-MTMP.
In the above preparation method, the one-dimensional linear structure heap formed by Ag (I)-MTMP coordination polymer is come with hydrogen
Key and molecular force and solvent DMF, H2The effects of O, package mixed solvent form metal organogel;Excessive silver salt is in warm
Silver nano-grain can be formed in situ after processing to be attached on the linear fiber network of Ag (I)-MTMP coordination polymer formation.It is one-dimensional
Linear polymer fiber accumulations form space, and resulting materials is made to have strong adsorption capacity.
In the above preparation method, silver salt, MTMP molar ratio can select in a wide range, but in order to further mention
The absorption of high AgNPs@Ag (I)-MTMP and antibacterial effect, it is preferable that silver salt, MTMP molar ratio are 0.6-1.2:1.0;When
AgNO3When/MTMP is between 1.2-0.6, Ag (I)-MTMP metal organogel can be formed, when greater than 1.2 or less than 0.6,
Gel cannot be effectively formed.
In the above preparation method, the dosage of solvent can select in a wide range, but anti-in order to further increase
Answer efficiency, it is preferable that silver salt, solvent amount ratio be 1.2mmol:15-30mL.
In the above preparation method, the condition of haptoreaction and standing can select in a wide range, but in order into
One step improves reaction efficiency and yield, it is preferable that haptoreaction meets the following conditions: carrying out with stirring, reaction temperature 45-
55 DEG C, reaction time 10-20min;Preferably, stand and meet the following conditions: dwell temperature is 20-30 DEG C, and time of repose is
8-12min。
In the above preparation method, dry condition can select in a wide range, but in order to further increase
The absorption property of AgNPs@Ag (I)-MTMP, it is preferable that drying meets the following conditions: drying temperature is -45~-55 DEG C, dry
Time is 48-72h.Freeze-drying time is too long, and solvent loses excessively, and gelatinous fibre accumulation is closer, causes under Dye Adsorption effect
Drop.
In the above preparation method, the type of solvent can select in a wide range, but in order to further increase
The absorption property of AgNPs@Ag (I)-MTMP, it is preferable that solvent is selected from CH3OH、CH3CH2OH、DMSO/H2O mixed solution, DMF/
H2At least one of O mixed solution;Preferably, solvent DMF, H2The mixed solution of O;It is highly preferred that DMF, H2The volume of O
Than for 1:0.9-1.1.Wherein, MTMP dissolubility in DMF solvent is good, therefore can be complete with silver salt polymerization reaction, at gel
Effect it is good, and DMF has reproducibility, and silver salt can be reduced to Ag nanoparticle, therefore forms more silver nano-grains.
In the above preparation method, the type of silver salt can select in a wide range, but taking cost into account, preferably
Ground, silver salt are selected from AgNO3、AgClO4At least one of.
In the above preparation method, pH can be selected in a wide range when haptoreaction starts, but in order to further
Improve absorption and the anti-microbial property of AgNPs@Ag (I)-MTMP obtained, it is preferable that pH is 5.0- when the haptoreaction starts
8.0, preferably 6-7.
In the above preparation method, MTMP can be commercially available product, can also be by voluntarily preparing, in order to further mention
The purity of high MTMP, it is preferable that MTMP is prepared by the following method and obtains: by 2- sulfydryl -5- amido-1,3,4-thiadiazoles
(AMTD) it is reacted in ethanol with salicylide according to the molar ratio of 1:1, after flowing back 3 hours at 80 DEG C, by the yellow mercury oxide of generation
It is washed respectively using excessive water, methanol, ether, it is spare to obtain yellow powder for vacuum drying.
Invention further provides a kind of such as above-mentioned difunctional sulfydryl schiff base metal organogel-nano combined material
Expect application of AgNPs@Ag (the I)-MTMP in adsorbed water body in acidic organic dye and/or water sterilization.
In above-mentioned application, the specific type of acidic organic dye can select in a wide range, but in order into one
Step improve AgNPs@Ag (I)-MTMP adsorption effect, it is preferable that acidic organic dye be selected from NG naphthol green B, acid fuchsin AF,
At least one of Congo red CR, methyl orange MO.
In above-mentioned application, the scope of restraining fungi of AgNPs@Ag (I)-MTMP can select in a wide range, but in order to
The fungistatic effect of AgNPs@Ag (I)-MTMP is further increased, it is highly preferred that AgNPs@Ag (I)-MTMP large intestine bar in water body
Application in the inhibition of bacterium, hay bacillus and staphylococcus aureus.
The present invention will be described in detail by way of examples below.Salicylide, dehydrated alcohol, DMF, NaOH, naphthol green B
For the commercially available product of Sinopharm Chemical Reagent Co., Ltd.;The Congo red, acid fuchsin (city of Aladdin experiment reagent Co., Ltd
Sell product;Methyl orange is the commercially available product of Tianjin recovery fine chemistry reagent research institute;Beef extract, peptone are Shanghai experiment reagents
The commercially available product of Co., Ltd;2- sulfydryl -5- amino -1,3,4- thiadiazoles, agar are the commercially available products of lark prestige Science and Technology Ltd.;
Secondary distilled water is by the dual pure water distiller preparation of Shanghai Yarong Biochemical Instrument Plant SZ-93.
The detecting instrument that test in following embodiment and test case uses are as follows: X-ray powder diffraction instrument (Cu target, XRD-
6000, Hitachi, Japan);Field emission scanning electron microscope (FESEM, S-8100, Hitachi, Japan);120KV transmission
Electron microscope (TEM, HT-7700, Hitachi, Japan);Infrared spectrometer (FT-IR, XECTOR22, Hitachi, Japan,
KB tabletting sample preparation);Ultraviolet specrophotometer (the upper Nereid's promise scientific instrument Co., Ltd of UV-1800).
Preparation example 1
The preparation of MTMP:
AMTD (1.0mmol), salicylide (1.0mmol), 20mL dehydrated alcohol is taken to carry out magnetic agitation, it is anti-in 80 DEG C of reflux
3h is answered, yellow mercury oxide is obtained;Filtering filters out solid and uses water, methanol, ether washing, then vacuum drying 5 hours to constant weight respectively.
Obtained solid powder is carried out1HNMR detection, the data obtained are1H NMR(500MHz,d6-DMSO):δ14.5
(d, 1H, SH) 11.21 (d, 1H, OH), 8.80, (d, 1H, C=N), 7.88 (d, 1H, NH), 7.5,7.0 (d, 4H, phenyl ring H).
Embodiment 1
Take MTMP (1.0mmol), AgNO3(1.2mmol)、10mL DMF、10mLH2O mixing, while pH to 6.5 is adjusted,
Heating stirring 10min obtains orange solution at 50 DEG C, obtains orange gel after standing 10min at 25 DEG C;It is freeze-dried at -50 DEG C
AgNPs@Ag (I)-MTMP metal organogel-nanocomposite is obtained to constant weight after 48h.
Embodiment 2
Take MTMP (1.0mmol), AgNO3(0.6mmol)、10mL DMSO、10mLH2O mixing, while pH to 5 is adjusted,
Heating stirring 15min obtains orange solution at 45 DEG C, obtains orange gel after standing 12min at 20 DEG C;It is freeze-dried at -45 DEG C
AgNPs@Ag (I)-MTMP metal organogel-nanocomposite is obtained to constant weight after 72h.
Embodiment 3
Take MTMP (1.0mmol), AgNO3(0.8mmol)、20mL CH3CH2OH mixing, while pH to 8 is adjusted, at 45 DEG C
Lower heating stirring 15min obtains orange solution, obtains orange gel after standing 8min at 30 DEG C;After being freeze-dried 48h at -55 DEG C
AgNPs@Ag (I)-MTMP metal organogel-nanocomposite is obtained to constant weight.
Embodiment 4
The procedure of Example 1 was followed except that by AgNO3It is changed to silver perchlorate.
Comparative example 1
The preparation of precursor A g (I)-MTMP- gel:
It carries out according to the method for embodiment 1, except that not carrying out freeze-drying process.
Detect example 1
AgNPs@Ag (I)-MTMP metal organogel made from embodiment 1 and embodiment 4-nanocomposite is carried out
SEM, TEM, XRD and BET detection, testing result are shown in Fig. 2-1, Fig. 2-2, Fig. 3-1, Fig. 3-2, Fig. 4-1, Fig. 4-2, Fig. 5-1 and figure
(a represents raw materials used for AgNO 5-23, b represents raw materials used for AgClO4), as seen from the figure: SEM can be seen that gained composite wood
Material is mainly formed by the one-dimensional linear fiber accumulations that Ag (I)-MTMP coordination polymer is formed, and TEM can be seen that in linear fiber
On adhere to partial size between 30-70nm, average grain diameter is about the silver nano-grain of 50nm, XRD and standard card JCPDS04-
Known to 0783 comparison 38.09 °, 44.28 °, 64.54 ° and 77.42 ° of peak respectively correspond (111) of Ag, (200), (220),
(311) crystal face illustrates that there are AgNPs in resulting materials;The surface area of resulting materials known to BET is 365.3539m2·g-1,
Aperture is about in the meso-hole structure of 25nm.
Test case 2
AgNPs@Ag (I)-MTMP metal organogel-nanocomposite to various dyestuffs be adsorbed at 25 DEG C into
Row:
It same amount dyestuff will not be dissolved in 50mL second distillation pure water, it is molten to form a series of dyestuff that concentration are 0-100mg/L
Liquid measures a certain amount of dye solution respectively, tests absorbance.Then it is multiple 10mg to be obtained into AgNPs@Ag (I)-MTMP gel nanometer
Condensation material (made from embodiment 1) is put into beaker, stirs at 25 DEG C, adsorbs it sufficiently.Then it is taken out every 10min a certain amount of
Liquid after absorption, centrifuging and taking supernatant, the absorbance of dyestuff after measurement absorption.
The removal efficiency of dyestuff is obtained according to following calculation formula:
Wherein C0For the initial concentration for adsorbing preceding dyestuff, CfFor the dye strength after absorption.
Absorption detection is carried out to naphthol green B, Congo red, methyl orange and acid fuchsin according to the method described above, testing result is shown in
Fig. 6-9,11.As seen from the figure, after 3 hours, composite material to dyestuff naphthol green B, acid fuchsin, methyl orange, Congo red go
Except efficiency respectively is: 95%, 90%, 89%, 90%.
Test case 2
The adsorption capacity of AgNPs@Ag (I)-MTMP gel nanocomposites detects:
It same amount dyestuff will not be dissolved in 50mL second distillation pure water, it is molten to form a series of dyestuff that concentration are 0-100mg/L
Liquid measures a certain amount of dye solution respectively, tests absorbance.By 10mg metal organogel-nanocomposite (embodiment
Made from 1) it is put into beaker, it is stirred at 25 DEG C, reaches adsorption equilibrium.Liquid after then taking out a certain amount of absorption, centrifugation
Supernatant is taken, the absorbance of dyestuff after measurement absorption.The saturated extent of adsorption q of gel nanocompositesePass through following formula meter
It calculates:
Wherein C0For the initial concentration of dye solution, CeFor dyes concentration after adsorption equilibrium, W is gel complex material
The quality of adsorbent, V are the volume of solution.
Adsorbance q is balanced to naphthol green B, Congo red, methyl orange and acid fuchsin according to the method described aboveeDetection, inspection
The result is shown in Figure 10 is surveyed, as seen from the figure, composite material is to dyestuff naphthol green B, acid fuchsin, methyl orange, Congo red maximum adsorption
Amount is respectively as follows: 225mgg-1、172mg·g-1、168mg·g-1、165mg·g-1;Composite material can reach after 100min
To adsorption equilibrium.
Test case 3
PH, temperature adsorb AgNPs@Ag (I)-MTMP metal organogel-nanocomposite (made from embodiment 1)
The influence of acid dyes performance:
It uses PBS buffer solution (phosphate buffer solution, pH=2-12);Use 0.1molL-1HCl solution and 0.1mol
L-1NaOH solution adjusts pH value, and the pH value of each solution is measured with pH meter.
According to embodiment 2 method carry out, change pH, test dye absorption property with pH variation;Concrete outcome is shown in Table
1。
It is carried out according to the method for embodiment 2, changes temperature, by temperature control between 300-360K, test dye absorption
Performance variation with temperature;Concrete outcome is shown in Table 2.
It is learnt by above-mentioned detection, AgNPs@Ag (I)-MTMP pH condition optimal to Dye Adsorption is: 6-7;Best temperature
Degree condition is: 300K.
Table 1
Table 2
Test case 4
De-adsorption cycle:
Metal organogel-nanocomposite (made from embodiment 1) after absorption dyestuff is added to 50mL
(2mol·L-1) NaCl solution in, stirring 48h is desorbed, and then 7000rpm is centrifuged 2min for gel-nanocomposite
It takes out, is respectively washed three times with deionized water and dehydrated alcohol.Material after desorption is dried under the conditions of 50 DEG C;Then batch process
Its adsorption capacity is tested, is tested 5 times repeatedly;Concrete outcome is shown in Table 3, and as seen from table, resulting materials can regenerate repetition and follow
Ring uses multiple.
Table 3
Test case 5
The preparation of culture medium: beef extract 3g, peptone 10g, NaCl 5g, agar 18g are weighed and is dissolved in 50 DEG C of hot water, then
Use 0.2molL-1NaOH solution adjust pH to 7.2-7.4, then by culture solution high-temp steam sterilizing 3h.By the training after sterilizing
Nutrient solution is uniformly applied on culture medium, and natural cooling forms solid medium.
Antibacterial experiment: by Escherichia coli, staphylococcus aureus, hay bacillus is uniformly applied on solid medium, so
Oxford cup is placed in culture medium central afterwards, 10mg metal organogel-nanocomposite (embodiment 1 is added into Oxford cup
It is obtained), it is then placed at 37 DEG C of incubator and cultivates the inhibition zone for measuring culture medium for 24 hours;The result is shown in Figure 12.
AgNPs@Ag (I)-MTMP gel nanocomposites are judged by measurement solid medium antibacterial circle diameter
Anti-microbial property.Specifically: by AgNPs@Ag (I)-MTMP gel (Xerogel) nanocomposite, MTMP, AgNO3And forerunner
Body Ag (I)-MTMP- gel (gel) is respectively to Escherichia coli (E.coli), hay bacillus (B.subtilis), golden yellow grape
Coccus (S.aureus) carries out antibacterial detection, and concrete outcome is shown in Table 4, shows that gained gel nanocomposites are thin to above-mentioned three kinds
Bacterium shows good anti-microbial property, especially has high antibacterial activity to hay bacillus.
Table 4
The product of embodiment 2-4 is detected according to detection example 2-5 identical method, testing result and embodiment 1
The testing result of product is almost the same.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of difunctional sulfydryl schiff base metal organogel-nanocomposite AgNPs@Ag (I)-MTMP, feature exist
In AgNPs@Ag (the I)-MTMP contains Nano silver grain AgNPs, Ag (I)-MTMP and solvent, and the AgNPs is adsorbed in institute
It states on Ag (I)-MTMP, Ag (the I)-MTMP wraps up solvent with hydrogen bond and molecular force;The chemistry of Ag (the I)-MTMP
Formula is [Ag (MTMP)]n(L)n, [Ag (MTMP)]n n+Structure it is shown in formula I, wherein L is negative univalent anion, and n is positive whole
Number, MTMP are 2- ((5- sulfydryl -1,3,4- thiadiazoles -2- imino group) methyl) phenol;
2. difunctional sulfydryl schiff base metal organogel according to claim 1-nanocomposite AgNPs@Ag
(I)-MTMP, wherein Ag (the I)-MTMP is linear fiber structure;
Preferably, the L is selected from least one of nitrate anion, perchlorate;
It is highly preferred that the solvent is selected from CH3OH、CH3CH2OH、DMSO/H2O mixed solution, DMF/H2In O mixed solution extremely
Few one;
It is further preferred that the solvent is DMF, H2The mixed solution of O.
3. a kind of difunctional sulfydryl schiff base metal organogel-nanocomposite AgNPs@Ag as described in claim 1
(I) preparation method of-MTMP, which is characterized in that the preparation method include: by silver salt AgL, MTMP be placed in solvent mixing and
Haptoreaction is carried out after adjusting pH, is then allowed to stand, dries to obtain AgNPs Ag (the I)-MTMP.
4. preparation method according to claim 3, wherein the silver salt, MTMP molar ratio are 0.6-1.2:1.0;
Preferably, it is described state silver salt, solvent amount ratio be 1.2mmol:15-30mL.
5. preparation method according to claim 3, wherein the haptoreaction meets the following conditions: it carries out with stirring,
Reaction temperature is 45-55 DEG C, reaction time 10-20min;
Preferably, the standing meets the following conditions: dwell temperature is 20-30 DEG C, time of repose 8-12min;
It is highly preferred that the drying meets the following conditions: drying temperature is -45~-55 DEG C, drying time 48-72h.
6. preparation method according to claim 3, wherein the solvent is selected from CH3OH、CH3CH2OH、DMSO/H2O mixing
Solution, DMF/H2At least one of O mixed solution;
Preferably, the solvent is DMF, H2The mixed solution of O;
It is highly preferred that described DMF, H2The volume ratio of O is 1:0.9-1.1.
7. preparation method according to claim 3, wherein the silver salt is selected from AgNO3、AgClO4At least one of;
Preferably, pH is 5.0-8.0, preferably 6-7 when the haptoreaction starts.
8. a kind of difunctional sulfydryl schiff base metal organogel-nanocomposite AgNPs@as claimed in claim 1 or 2
Application of Ag (the I)-MTMP in adsorbed water body in acidic organic dye and/or water sterilization.
9. application according to claim 8, wherein the acidic organic dye be selected from NG naphthol green B, acid fuchsin AF,
At least one of Congo red CR, methyl orange MO.
10. application according to claim 8, wherein AgNPs@Ag (I)-MTMP Escherichia coli, withered grass in water body
The application of inhibition in bacillus and staphylococcus aureus.
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