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    • 专利摘要:
    Method for obtaining nanocomposites of copper double salts. The present invention refers to a method for obtaining nanocomposites of double copper salts supported on different supports, such as oxidized graphene and fumed silica, which comprises mixing the starting materials in a solvent, sonicating with ultrasound and irradiating the mixture with microwaves. The nanocomposites of copper salts obtained can be used as catalysts in different chemical reactions and in the biosanitary and food sector as a microbicide. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2802422A1
    申请号:ES201930641
    申请日:2019-07-10
    公开日:2021-01-19
    发明作者:Shabestari Marjan Entezar；Cadiz Olga Martin；Llido Juan Baselga；Ruiz Santiago Gomez；Garcia Diana Diaz；Garcia Gemma Montalvo；Carretero Francisco Guillen；Quintela Diogo Manuel Videira
    申请人:Universidad de Alcala de Henares UAH；Universidad Carlos III de Madrid；Universidad Rey Juan Carlos；
    IPC主号:
    专利说明:

    [0001] METHOD OF OBTAINING NANOCOMPOSITES FROM DOUBLE COPPER SALTS AND
    [0003] FIELD OF THE INVENTION
    [0004] The present invention belongs to the technical field of new materials and, more specifically, to nanomaterials based on double copper salts.
    [0006] BACKGROUND OF THE INVENTION
    [0007] The study and research of new environmentally safe, low-toxic and more effective materials has gained more academic and industrial attention in recent times.
    [0009] Some current proposals are noble metal nanoparticles, specifically silver (AgNPs) and copper (CuNPs) nanoparticles, which are well known for their antibacterial activity against a wide variety of microorganisms [1], and are already applied in devices medical, textile, cosmetic, food, or packaging materials [2].
    [0011] Specifically, particle size, in addition to its shape, can vary the antibacterial properties of metallic nanoparticles [3]. For example, colloidal Ag and Cu nanoparticles with mean particle sizes of 793 and 292 nm, respectively, showed very good minimum inhibitory concentration (MIC) values, specifically 0.793 and 0.469 mg / L for Escherichia coli [4].
    [0013] On the other hand, copper compounds are particularly attractive to the scientific community because they can be a good replacement for palladium compounds in some catalytic reactions and improve efficiency for several reasons: copper is very cheap compared to palladium, it has a higher natural abundance and is less toxic than palladium, especially in large-scale reactions. That is why, in recent years, copper has received increasing attention due to its catalytic activity in oxidation and reduction reactions, and other powerful catalytic reactions, such as cycloaddition, hydrogenation, etc. [5].
    [0015] All catalytic studies have shown that, in general, copper nanoparticles, with small sizes and different shapes, present more interesting catalytic results than complexes of copper or non-nanometric copper-based materials because their surface areas are highly accessible and they show greater reactivity [6].
    [0016] By preventing their aggregation and improving their flexibility in terms of applicability, immobilization can be used on a specific support by preventing their aggregation and improving their flexibility in terms of applicability. Numerous support materials have been described such as metal oxides [7, 8], chitosan [9], graphene oxide [10, 11], mesoporous silicas [12], polymers [13], silica dioxide [14, 15], zeolites [16] and clay [17, 18], among others.
    [0018] For example, at least 2 synthesis routes for copper-based nanocomposites supported with graphene or graphene oxide are known. In the first route, the copper and graphene nanoparticles are synthesized separately and then, the decoration is carried out through different methods such as chemical vapor deposition (CVD) [19], ultrasonication [20] and / or hydrothermal procedures [21].
    [0020] On the other hand, the second route consists of mixing a solution of graphene oxide and a copper salt to subsequently reduce both simultaneously [22].
    [0022] However, in most methods some specific synthetic parameters are required such as high temperature, pH control and long reaction time [23, 24]. Furthermore, most of the resulting mixtures are composed of copper in different oxidation states (Cu (0), Cu (I) and Cu (II) [25]).
    [0024] DESCRIPTION OF THE INVENTION
    [0025] The present invention solves the problems present in the state of the art by means of a method of obtaining double copper salts supported on oxidized graphene and fumed silica in a simple and environmentally clean way that favors their dispersion, subsequent recycling and applicability in the biosanitary sector and food.
    [0027] In one aspect of the invention, a method for obtaining nanocomposites of copper double salts is provided that comprises the following steps:
    [0028] a) add copper nitrate, a support and a solvent,
    [0029] b) sonicate the mixture obtained in step a) with ultrasound, and
    [0030] c) irradiate with microwaves.
    [0032] In this method, thanks to the correct selection of the solvent, the selective transformation of the Cu2 + ions, coming from the copper nitrate, into the desired nanometric structure, CuO, Cu 2 O or double copper salt, Cu2 (OH) 3NO3, is achieved. obtaining pure derivatives, avoiding subsequent purification processes.
    [0033] n e m o o e to present nvenc n, the soncac n process favors minor nanoparticle love by adequately dispersing all the components.
    [0035] Furthermore, microwave radiation focuses the energy supply, favoring nucleation for particle growth on the surface of the support, reducing collateral reactions and reducing reaction time.
    [0037] Ultimately, the reaction yield is increased and the unnecessary use of solvents and purification reagents is avoided.
    [0039] In another aspect of the invention, the support used is selected from graphene oxide or fumed silica.
    [0041] In another aspect of the invention, the solvent is ethanol.
    [0043] In another aspect of the invention, graphene oxide supported copper double salt nanocomposites are suitable for use as a catalyst for oxidation and / or coupling reactions.
    [0045] In a final aspect of the invention, the nanocomposites of double salt of copper supported on fumed silica are suitable for use as a food grade microbicide.
    [0047] BRIEF DESCRIPTION OF THE FIGURES
    [0048] Figure 1. Representation of MIC results in mg / mL of DS / FS, Cu / FS and Ag / FS for E. coli and S. aureus. The MIC is the lowest concentration of an antimicrobial agent that inhibits the growth of a microorganism (bacteriostatic capacity), and is determined by the decrease in OD at 625 nm (turbidity of the bacteriological suspension). In this case, in the samples of DS / FS, Cu / FS, and Ag / FS, the MIC values determined were 8, 4 and 3 mg / mL for E. coli and 24, 12 and 12 mg / mL, for S. aureus, respectively.
    [0050] Figure 2. Representation of CMB results (minimum bactericidal concentration) in mg / mL of DS / FS, Cu / FS and Ag / FS for E. coli and S. aureus. The determination of CMB is the lowest concentration of an antimicrobial agent that causes the death of a microorganism (bactericidal capacity). In this case, in the DS / FS, Cu / FS, and Ag / FS samples, the CMB values determined were 8, 16 and 3 mg / mL for E. coli and 24, 12 and 32 mg / mL, for S. aureus, respectively.
    [0052] DESCRIPTION OF REALIZATION MODES
    [0053] a in or writing to present nvenc n, conamene will be used with me and following examples.
    [0055] Example 1. Method of obtaining a double salt supported in graphene oxide (Cu (OH) 3 NO 3 / Graphene oxide (DS / GO))
    [0056] The synthesis of four Cu / GO nanocomposites was carried out. Initially, a double salt of copper (Cu 2 (OH) 3 NO 3 , DS) was synthesized using graphene oxide (GO) as a support and later other nanocomposites were synthesized with the same support, which are not the object of the invention. but they are used to demonstrate the activity and improved properties of the double salt compared to other copper nanomaterials.
    [0058] 1. Synthesis of Cu 2 (OH) 3 NO 3 / Graphene oxide (DS / GO)
    [0059] 100 mg of GO in ethanol (50 mL) and 100 mL of Cu (NO 3 ) 2 (0.1-1) M were added and the mixture was sonicated with ultrasound for 5 min. Subsequently, it was heated in a 1450 W microwave (Sharp R-742 (IN) W) for a total time of 2-3 minutes in steps of 5 to 10 seconds of heating and 10 seconds of cooling.
    [0061] After cooling to room temperature, the mixture was filtered and the solid obtained was washed with deionized water and hot ethanol, at least 5 times, and finally dried in a vacuum oven at 60mmHg / 90 ° C overnight.
    [0063] 2. Synthesis of Cu 2 O / GO
    [0064] By changing the solvent to ethylene glycol under the same conditions as mentioned above, nanoparticles of cuprous oxide (Cu 2 O) were obtained in GO instead of the double salt.
    [0066] 3. Synthesis of Cu / GO
    [0067] 50 mL of a 0.5-2 M ascorbic acid solution in 1 g of DS / GO was added and stirred for 30 minutes. The color of the mixture changed from blue-green to reddish-brown, indicating the formation of Cu / GO particles. When the reaction was complete, the final product was filtered off.
    [0069] 4. Synthesis of CuO / GO
    [0070] Copper oxide on graphene oxide (CuO / GO) was prepared by heating 1 g of DS / GO in an oven at 250 ° C for 10 min in an air atmosphere.
    [0072] Example 2. Application of the double salt of copper supported on graphene oxide (Cu (OH) 3 NO 3 / Graphene oxide (DS / GO)) as a catalyst in oxidation reactions
    [0073] This is how the reactions were carried out in an atmosphere of dry nitrogen. The solvents were distilled from the appropriate drying agents and degassed prior to use. Reagents for catalytic reactions: benzyl alcohol (Fluorochem), iodobenzene (Sigma-Aldrich), phenyl boronic acid (Sigma-Aldich), 3,5-dimethylthiophenol (Fluorochem), benzylamine (Fluorochem) and methylamine (30% in water, Sigma-Aldrich) and H 2 O 2 (Sigma-Aldrich) were used directly without further purification.
    [0075] In this example it was carried out in the selective oxidation of benzyl alcohol using H 2 O 2 as an oxidizing agent in dimethyl formamide, DMF.
    [0077] The catalytic activity in the oxidation reaction of benzyl alcohol was studied to determine the preliminary catalytic activity and selectivity towards benzaldehyde formation of the Cu-containing materials synthesized in Example 1 (DS / GO, Cu / GO, CuO / GO and Cu 2 O / GO).
    [0079] In a typical catalytic experiment, 108 mg (1.0 mmol) of benzyl alcohol was dissolved in DMF (5 mL), 0.15 mL (4.4 mmol) of hydrogen peroxide solution 30% (w / w) in H 2 O and 25 mg of copper-containing material. they were added under a nitrogen atmosphere to a Schlenk tube. The mixture was stirred at 110 ° C for 24 hours. Subsequently, the reaction mixture was filtered through a nylon filter (0.45 pm) and the filtrate was analyzed by gas chromatography with a flame ionization detector or GC-FID (GC Clarus 580 from Perkin-Elmer) with a Velocity® column (dimethylpolysiloxane, 30m, 0.25mm, 1.00 pm) to quantify the conversion to benzaldehyde. The temperature program for the column for detection and quantification was 90 ° C (5 minutes), heating for 3 minutes (ramp 20 ° C / min) to 150 ° C (5 minutes), heating for 4 minutes (ramp 25 ° C / min) to 250 ° C (6 minutes) and heating for 2 minutes (ramp 20 ° C / min) to 290 ° C. The gas chromatograph had an injection temperature of 240 ° C and the detector temperature was 300 ° C.
    [0081] The study was carried out at 110 ° C for 24 hours and the results are shown in Table 1.
    [0083] Table 1. Results of the catalytic oxidation at 24 hours using as
    [0084] catalysts: DS / GO, Cu / GO, CuO / GO and Cu 2 O / GO.
    [0088] a Data in square brackets refer to selectivity towards benzaldehyde.
    [0089] urnover num er: e convers n an aes os ac vos e ca a za or
    [0091] The catalytic study shows a much higher oxidation conversion for the DS / GO material with conversions of up to 85% compared to the conversion of the other materials ranging from 47 to 69%, indicating that the oxidation capacity of DS supported is very high, considering that this material shows the value of TON = (% conversion / amount of catalyst active sites). The 4.72 value obtained for DS / GO is much higher than all the others, ranging between 1.46 and 2.27. In all cases, the systems are quite selective since the amount of benzaldehyde obtained is greater than 98% and only traces of benzoic acid and benzyl benzoate were obtained. These latter materials present similar TON values to other compatible systems based on Pd nanoparticles [26].
    [0093] Example 3. Application of the double salt of copper supported on graphene oxide (Cu (OH) 3 NO 3 / Graphene oxide (DS / GO)) as a catalyst in CC coupling reactions
    [0094] The versatility of copper-based compounds supported on graphene oxide was studied by evaluating their catalytic activity in different coupling reactions. First, the C-C coupling reactions were analyzed.
    [0096] The reaction studied was the coupling of iodobenzene (Ph-I) with phenylboronic acid (Ph-Bor) at 110 ° C for 24 h. The coupling reaction was carried out in 5 mL of a 95: 5 DMF: H 2 O mixture. Iodobenzene was used as a limiting reagent and with a molar ratio between halide and boronic acid of 1: 1.2. Furthermore, the molar ratio between halide and base (Cs 2 CO 3 ) was 1: 1 and the amount of catalyst was 25mg in all cases.
    [0097] All reactions were carried out using degassed solvents and under a nitrogen atmosphere. To prepare the iodobenzene solution, 153 mg (0.75 mmol) of iodobenzene was dissolved in 5.0 ml of a degassed solvent mixture (DMF: H 2 O 95: 5) under nitrogen in a Schlenk tube. Subsequently, a Schlenk flask was filled with phenylboronic acid (110 mg, 0.90 mmol) and Cs 2 CO 3 (244 mg, 1.50 mmol) and copper-based materials as catalyst (25 mg) and three cycles of vacuum / N 2 (10 min / 1 min) were carried out to remove oxygen from the reaction atmosphere and reduce the hypothetical amount of water adsorbed from the solids.
    [0099] Subsequently, the 1-iodobenzene solution was transferred under N 2 to the Schlenk flask containing the solid mixture and the resulting suspension was heated to 110 ° C and stirred for 24 hours. After this time, the solution was cooled to room temperature and filtered over a nylon filter (0.4 µm). The filtered reaction mixture was then injected into a chromatograph e gases with e ecor e onzac ne ama o - er n- mer arus with the same column, temperature program, injection temperature and detector temperature as those described in example 2.
    [0101] Results are shown in table 2.
    [0103] Table 2. Results of the C-C coupling reaction at 24 hours using as catalysts: DS / GO, Cu / GO, CuO / GO and Cu 2 O / GO.
    [0107] TON ( Turnover number): % conversion / Amount of catalyst active sites
    [0109] The nanocomposites studied show a moderate catalytic activity with very similar conversion values of around 40%, without significant differences in conversion between the different materials studied. However, again, as happened in the oxidation reactions, higher TON values are observed for DS / GO, which point towards a higher catalytic activity than their Cu, CuO or Cu 2 O analogues.
    [0111] Example 4. Application of the double salt of copper supported on graphene oxide (Cu 2 (OH) 3 NO 3 / GO (DS / GO)) as a catalyst in CS coupling reactions
    [0112] The versatility of copper-based compounds supported on graphene oxide was studied by evaluating their catalytic activity in a C-S coupling reaction.
    [0114] The reaction studied was the coupling of iodobenzene (Ph-I) and 3,5-dimethylthiophenol (Me 2 PhSH) at 110 ° C for 24 h. The reaction was carried out using DMSO (5 ml) as the solvent and Cs 2 CO 3 as the base. Iodobenzene, 3,5-dimethylthiophenol and Cs 2 CO 3 were in a molar ratio of 1: 1.2: 2 and the amount of catalyst was in all cases between 22 and 30mg. All reactions were carried out using degassed solvents and under a nitrogen atmosphere. To prepare the iodobenzene solution, 153 mg (0.75 mmol) of iodobenzene was dissolved in 5.0 mL of degassed DMSO under nitrogen in a Schlenk tube.
    [0116] Subsequently, a Schlenk flask was filled with 3,5-dimethylthiophenol (124 mg, 0.9 mmol) and Cs 2 CO 3 (488 mg, 1.50 mmol) and copper-based materials as catalyst (25 mg) and three Vacuum / N 2 cycles (10 min / 1 min) were carried out to remove oxygen from the reaction atmosphere and reduce the hypothetical amount of water adsorbed from the solids.
    [0117] Subsequently, the 1-iodobenzene solution was transferred under N 2 to the Schlenk flask containing the solid mixture and the resulting suspension was heated to 110 ° C and stirred for 24 hours. After this time, the solution was cooled to room temperature and filtered over a nylon filter (0.4 pm). The filtered reaction mixture was then injected into a gas chromatograph with flame ionization detector or GC-FID (Perkin-Elmer GC Clarus 580) with the same column, temperature program, injection temperature and detector temperature as described. in example 2.
    [0119] The results are shown in Table 3.
    [0121] Table 3. Results of the C-S coupling reaction at 24 hours using as catalysts: DS / GO, Cu / GO, CuO / GO and Cu 2 O / GO.
    [0125] TON ( Turnover number): % conversion / Amount of catalyst active sites
    [0127] In this catalytic reaction, very high conversions were observed close to 100% for Cu / GO and Cu 2 O / GO and close to 90% for DS / GO and CuO / GO, which indicates that all the materials studied have very good activity. catalytic.
    [0129] When the TON values were analyzed, it could be observed that, as in the oxidation and C-C coupling reactions, the most effective catalyst was DS / GO with a TON value of 3.6. Again, the catalytic versatility of these Cu-based materials was demonstrated and the slightly higher catalytic activity of DS / GO was confirmed [27].
    [0131] Example 5. Application of the double salt of copper supported on graphene oxide (Cu (OH) 3 NO 3 / GO (DS / GO)) as a catalyst in CN coupling reactions
    [0133] The versatility of copper-based compounds supported on graphene oxide was studied by evaluating their catalytic activity in different coupling reactions. The following 3 C-N coupling reactions were analyzed.
    [0135] 5.1 Reaction of iodobenzene (Ph-I) with methylamine (MeNH y )
    [0136] The reaction studied was the coupling of iodobenzene (Ph-I) and methylamine (MeNH 2 ) at 110 ° C for 24h. The reaction was carried out using a mixture of DMF / H 2 O as soven eu zan or a voumen na emy 2 3 as ase. Oo enzene, methylamine and Cs 2 CO 3 were in a molar ratio of 1: 1.2: 2 and the amount of catalyst was 25 mg. The reaction was carried out using degassed DMF / water and under a nitrogen atmosphere. To prepare the iodobenzene solution, 153 mg (0.75 mmol) of iodobenzene was dissolved in 5.0 mL of DMF degassed under nitrogen in a Schlenk tube. Subsequently, a Schlenk flask was filled with 65.2 µl (0.90 mmol) of methylamine (40% aqueous solution), Cs 2 CO 3 (488 mg, 1.50 mmol) and copper-based materials as catalyst. (25 mg), and three cycles of vacuum / N 2 were carried out to remove oxygen from the reaction atmosphere. The 1-iodobenzene solution was then transferred under N 2 to the Schlenk flask containing the solid mixture and the resulting suspension was heated to 110 ° C and stirred for 24 hours. After this time, the solution was cooled to room temperature and filtered over a nylon filter (0.4 µm). The filtered reaction mixture was then injected into a gas chromatograph with flame ionization detector or GC-FID (Perkin-Elmer GC Clarus 580) with the same column, temperature program, injection temperature and detector temperature as described. in example 2.
    [0138] 5.2 Reaction of iodobenzene (Ph-I) with benzylamine (BzNH )
    [0139] The reaction studied was the coupling of iodobenzene and benzylamine (BzNH 2 ) at 110 ° C for 24 h. The reaction was carried out using DMF (5 ml) as the solvent and Cs2CO3 as the base. lodobenzene, benzylamine and Cs 2 CO 3 were in a molar ratio of 1: 1.2: 2 and the amount of catalyst was 25 mg in all cases. The reaction was carried out using degassed DMSO under a nitrogen atmosphere. To prepare the iodobenzene solution, 153 mg (0.75 mmol) of iodobenzene was dissolved in 5.0 mL of degassed DMSO under nitrogen in a Schlenk tube. Subsequently, a Schlenk flask was filled with benzylamine (5.35 mg, 0.050 mmol), Cs 2 CO 3 (16.3 mg, 0.050 mmol) and copper-based materials as catalyst (25 mg) and three Vacuum / N 2 cycles to remove oxygen from the reaction atmosphere. Subsequently, the 1-iodobenzene solution was transferred under N 2 to the Schlenk flask containing the solid mixture and the resulting suspension was heated to 110 ° C and stirred for 24 hours. After this time, the solution was cooled to room temperature and filtered over a nylon filter (0.4 µm). The filtered reaction mixture was then injected into a gas chromatograph with flame ionization detector or GC-FID (Perkin-Elmer GC Clarus 580) with the same column, temperature program, injection temperature and detector temperature as described. in example 2.
    [0141] 5.3 Reaction of 4-iodoanisole (Ani-I) with benzylamine (BzNH y )
    [0142] The reaction studied was the coupling of 4-iodoanisole (Ani-I) and benzylamine (BzNH 2 ) at 110 ° C for 24 h. The reaction was carried out using a procedure and quantities moares n cos a os writes en e empo. . To react I or enzene with benzylamine.
    [0144] The results are shown in Table 4.
    [0146] Table 4. Results of the C-N coupling reactions at 24 hours using as catalysts: DS / GO, Cu / GO, CuO / GO and Cu 2 O / GO.
    [0148]
    [0150] TON ( Turnover number): % conversion / Amount of catalyst active sites
    [0152] In all cases, the conversions are close to 90% or more, indicating good catalytic activity of these materials for this reaction. Again, the double salt with graphene oxide (DS / GO) has the highest TON value of 4.01.
    [0154] The nanocomposites studied were tested in similar C-N coupling reactions, but replacing methylamine with benzylamine. The catalytic results show a slight decrease in conversion, at values between 80-90%. The decrease in activity is due to the lower reactivity of benzylamine compared to methylamine due to the steric and electronic effects of the amine. Furthermore, the diffusion of benzylamine in a heterogeneous system is more difficult and this also decreases the catalytic activity.
    [0156] Finally, the catalytic study was completed by testing the nanocomposites studied in the reaction of 4-iodoanisole with benzylamine, observing that the conversion of the iodophenyl derivative decreases to values between 60-70%. In this case, this decrease in catalytic activity is due to steric effects when comparing iodobenzene with 4-iodoanisole. Again, in all cases the highest TON values for DS / GO were observed, as happened with the other reactions studied.
    [0158] Example 6. Method of obtaining a double salt supported on fumed silica (Cu (OH) 3 NO 3 / fumed silica (DS / FS))
    [0159] e ev a ca o sness e nanocomposites e mece with struc tures that consist of silver (Ag) and copper (Cu), which are not the object of the invention, and a double salt of copper (Cu2 (OH) 3NO3, DS) using as support pyrogenic silica (fumed silica, FS) for all.
    [0161] 1. Synthesis of Cu2 (OH) 3NO3 / Fumed Silica (DS / FS)
    [0162] CuNO3-3H2O (1 M) in absolute EtOH was added to 0.1 g of fumed silica and the mixture was sonicated with ultrasound for 10 min.
    [0164] Subsequently, the mixed solution was microwave irradiated using a 1450 W microwave (Sharp R-742 (IN) W) for a total time of 2 minutes in steps of 5 seconds of heating and 30 seconds of cooling.
    [0165] After cooling to room temperature, the mixture was filtered and the obtained solid was washed with hot ethanol, at least 5 times, and finally dried under vacuum at room temperature for 48 hours.
    [0167] 2. Synthesis of Cu / FS
    [0168] For the synthesis of Cu / FS, a two-step method was used. The first stage corresponds to the synthesis of DS / FS described above.
    [0170] In the second stage, 0.1 to 0.2 g of DS / FS were dispersed in 6 mL of absolute EtOH for 15 minutes by sonication with ultrasound. An aqueous solution of ascorbic acid (1 M, 2 mL) was added dropwise to the DS / FS suspension with vigorous stirring at room temperature, to obtain Cu / FS. After 10 minutes of reaction, the final product was collected by centrifugation and washed with distilled water and ethanol several times, and then dried under vacuum at room temperature for 48 hours.
    [0172] 3. Synthesis of Ag / FS
    [0173] The Ag / FS nanocomposite was synthesized by a one-step hydrothermal method, through the reduction of Ag + using only EtOH as a reducing agent. In a typical experiment, 10 mL of AgNO3 (0.1 M) in absolute EtOH was added to 0.1 g of fumed silica and sonicated for 10 min. Subsequently, the mixed solution was added to a hydrothermal reactor and heated at 200 ° C for 1 hr. The resulting product, Ag / FS, was collected by filtration, washed with hot ethanol several times, and dried under vacuum at room temperature for 48 h.
    [0175] The particles of silver (Ag), copper double salt (Cu2 (OH) 3NO3 and copper (Cu) were synthesized by the same methods, but without fumed silica. In the synthesis of the copper double salt, after irradiation Microwave 100 ml CuNO3-3H2O (1 M) in EtOH A sou o, a souc n will be seen in a bale e er ev ro and fall so that the precipitate of Cu2 (OH) 3NO3 is formed.
    [0177] Example 7. Application of the double salt of copper supported on fumed silica (Cu2 (OH) 3NO3 / fumed silica (DS / FS)) as a microbicide
    [0178] The antibacterial activity test performed was based on ISO 20776-1: 2006 ( "Reference method for testing the in vitro activity of antimicrobial agents against fast-growing aerobic bacteria involved in infectious diseases") with slight modifications.
    [0180] E. coli , as Gram negative model bacteria, and Staphylococcus aureus, as Gram positive model bacteria were used. Both were incubated on plate count agar (PCA) plates at 37 ° C for 24h. Next, two to three colonies of bacteria were cultivated in Mueller-Hinton (MH) culture medium for 2-3 hours at 37 ° C until reaching an exponential growth value of optical density at 625 nm (OD 625nm) of 0.11, corresponding to 108 CFU / mL.
    [0182] Subsequently, the bacterial medium was exposed to different concentrations of the nanocomposite samples (from 32 to 0.75 mg / mL), reference particles (from 8 to 0.1875 mg / mL) and the corresponding blanks (without the bacteria) at 37 ° C for 24 h with constant shaking (1000 rpm), in 96-well plates.
    [0184] The turbidity of the bacterial growth was determined by measuring the OD 625nm using a spectrophotometer (BioTeK ELx808 absorbance reader), to determine the MIC.
    [0186] MIC refers to the lowest concentration of composite samples that inhibited growth within 24 h. After the determination of the MIC, each set of bacteria / nanocomposites was cultured on agar plates at 37 ° C for 24 h for the determination of the minimum bactericidal concentration (CMB).
    [0188] Minimum Bactericidal Concentration (MBC) refers to the lowest concentration of composite samples that kill 99% of bacteria in 24 h. All experiments were performed in triplicate, and the results are presented as mean ± standard deviation.
    [0190] The antibacterial activity is clearly observed by the decrease in OD 625nm as a function of the various concentrations of nanocomposites in the samples (Fig. 1), the first OD value close to zero being considered as MIC, which means that there is no growth. acerano. ara, uyg, os values e ueron, and mg m para . coli, and 24, 12 and 12 mg / mL of MIC for S. aureus, respectively.
    [0192] A clear difference was found between the antibacterial activity of the nanocomposites, being lower in all cases with E. coli than with S. aureus. This result is usually due to differences in the cell wall structure of gram negative and positive bacteria, since in the latter the presence of a thicker peptidoglycan layer (approximately 30 nm) confers greater resistance.
    [0194] To verify the viability of the bacteria after determining the MIC, the bacterial growth was evaluated as a function of the various concentrations of nanocomposites in the samples (Fig. 2), in order to determine the CMB. A visual inhibition is clearly observed with the compound Cu / FS, at concentrations 4, 6, 8 and 12 mg / mL for E. coli, where the growth of the colonies is clearly affected, compared to the high growth at low concentrations. With DS / FS, Cu / FS and Ag / FS, CMB values of 8, 16 and 3 mg / ml of CMB were determined for E. coli , and 24, 12 and 32 mg / ml for S. aureus , respectively.
    [0196] Table 5 shows the results of MIC and CMB for E. coli and S. aureus, with the following nanoparticles:
    [0198] or AgNO 3 (Ag + )
    [0199] • Ag derivatives or Ag metal Nanoparticles (Ag *)
    [0201] o Silver nanoparticles on silica (Ag / FS)
    [0203] o CuNO 3 (Cu 2+ )
    [0205] o Copper metal nanoparticles (Cu)
    [0206] • Derivatives of Cu or Nanoparticles double copper salt (DS)
    [0208] o Copper metal nanoparticles on silica (Cu / FS)
    [0209] o Copper double salt nanoparticles on silica (DS / FS) • Pure fumed silica (FS)
    [0211] The concentrations in mg / ml (mg nanoparticles in ml of culture) obtained for CMI or CMB can be referred to the effective mass of metal Cu or Ag or that of nanoparticles (silica support metal, X / FS) indicated in each of the three columns.
    [0213] Table 5. Results of the antimicrobial activity of the nanoparticles
    [0214] E. coli S. aureus
    [0215]
    [0218] In conclusion, the MIC and CMB values (expressed in mg / ml) for the double salt are of the same order as those obtained under the same conditions for metallic silver nanoparticles (which is the most widely used microbicide currently). Therefore, the double salt of copper (Cu2 (OH) 3NO3) using fumed silica as a support is a real alternative to using silver as a microbicide.
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    权利要求:
    Claims (5)
    [1]
    1. Method for obtaining nanocomposites of copper double salts characterized in that it comprises the following stages:
    a) add copper nitrate, a support and a solvent,
    b) sonicate the mixture obtained in step a) with ultrasound, and
    c) irradiate with microwaves.
    [2]
    2. Method for obtaining nanocomposites of copper double salts according to claim 1, wherein the support is selected from graphene oxide or fumed silica.
    [3]
    3. Method for obtaining nanocomposites based on double copper salts according to claim 1, where the solvent is ethanol.
    [4]
    4. Use of a nanocomposite of double salt of copper supported on graphene oxide as a catalyst for oxidation and / or coupling reactions.
    [5]
    5. Use of a nanocomposite of double salt of copper supported on fumed silica as a microbicide.
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    同族专利:
    公开号 | 公开日
    ES2802422B2|2021-06-18|
    WO2021005255A1|2021-01-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN101273723A|2008-05-16|2008-10-01|曲阜师范大学|Method for preparing nano copper oxide anti-bacteria agent|
    CN105032353A|2015-07-29|2015-11-11|昆明理工大学|Preparation method and application of modified activated carbon|
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