CN106916587B - oil-soluble carbon quantum dot, polymer OCDs @ PMMA, and preparation method and application thereof - Google Patents
oil-soluble carbon quantum dot, polymer OCDs @ PMMA, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to oil-soluble carbon quantum dots (OCDs), OCDs @ PMMA, a preparation method and application thereof. The particle size of the oil-soluble carbon quantum dot is as follows: 1-10nm, and the unsaturated carbon bond on the surface of the material is: 20 to 50 percent. The oil-soluble carbon quantum dot synthesized by the method has good dispersibility and luminescence property, can be used as an anti-aging probe of PMMA, and the composite material obtained by in-situ polymerization of the oil-soluble carbon quantum dot and the PMMA has excellent optical transparency (the transmittance is up to more than 85 percent), and improves the anti-ultraviolet light aging property of the PMMA by more than 10 times, so that the application of the carbon quantum dot in all-solid-state illumination in the prior art is solved, and the problem that the PMMA cannot be widely applied due to poor aging property is solved.
Description
Technical Field
The invention relates to oil-soluble carbon quantum dots (OCDs), OCDs @ PMMA, a preparation method and application thereof.
Background
The polymer composite material can make up for some physical or chemical defects of the polymer and can be widely applied in actual life. Its conventional synthetic route is to add high concentrations of filler modifiers to exploit its potential properties. Recently, it has been reported that the prepared polymers can be made more advantageous in terms of oxidation resistance, thermal stability and electrical conductivity than the original polymers by adding lower concentrations of fillers, for example, by using novel nanostructured fillers, especially carbon nanomaterials, such as fullerenes, carbon nanotubes, graphene and nanodiamonds, during polymerization. Aging phenomena are prevalent in various polymers and are recognized as a detrimental factor in practical applications. Therefore, many studies for slowing down the aging of polymers have been conducted. For example, Claus et al synthesized a compound containing 9 PDMs and fullerene units. There have also been many studies with significant success, but achieving uniform distribution of carbon nanotubes in a polymer matrix remains an urgent task for preparing all polymer composites. In particular for optical polymers, non-uniform agglomeration can result in the composite having poor optical transmission. Therefore, it is becoming necessary to develop polymer composite materials or new methods capable of reducing non-uniform agglomeration. Carbon quantum dots, an emerging carbon-based material with ultra-small dimensions, have been rapidly developed. Most reports on carbon quantum dots are essentially surface-modified or doped lipophilic groups. Carbon quantum dots with desired size, morphology and physicochemical properties are synthesized by top-down or bottom-up methods. However, general reports have been made only around their synthesis and their use in other applications, especially for slowing down polymer aging, has not been further developed.
Disclosure of Invention
An object of the present invention is to provide oil-soluble carbon quantum dots (OCDs) that can be synthesized using a simple one-step process and that contain a large number of unsaturated carbon bonds to reduce agglomeration.
The second purpose of the invention is to provide the polymer OCDs @ PMMA which is synthesized by physical bonding and covalent bonding and has transparent fluorescence.
The invention also aims to provide a preparation method of the polymer OCDs @ PMMA.
the fourth purpose of the invention is to provide the application of the polymer as an effective nanoscale additive in enhancing the ultraviolet aging resistance of PMMA composite materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
An oil-soluble carbon quantum dot is characterized in that the particle size of the oil-soluble carbon quantum dot is as follows: 1-10nm, and the content of unsaturated carbon bonds on the surface is as follows: 20 to 50 percent.
The polymer OCDs @ PMMA is prepared by in-situ polymerization of polymethyl methacrylate and the oil-soluble carbon quantum dots, and is characterized in that the mass ratio of the polymethyl methacrylate (PMMA) to the oil-soluble carbon quantum dots (OCDs) is as follows: 20:1-60: 1; the polymer is a random copolymer, and carbon points on a macromolecular chain and structural units of methacrylic acid value are arranged in a random manner.
A method for preparing the polymer OCDs @ PMMA is characterized by comprising the following specific steps:
(a) Dissolving methyl methacrylate and dodecylamine, octadecylamine or other long-chain surfactants containing amino groups in toluene or other nonpolar solvents, and carrying out hydrothermal reaction under a sealed condition, wherein the hydrothermal reaction temperature range is 140-260 ℃ and the reaction time is 2-10 hours; washing with water and ethanol, performing centrifugal separation, taking an organic layer, and performing dialysis separation with methanol to obtain oil-soluble carbon quantum dots; the molar ratio of the methyl methacrylate to the dodecylamine, the octadecylamine or other long-chain surfactants containing amino groups is 4:1-2: 3.
(b) Polymerizing the oil-soluble carbon quantum dots obtained in the step (a) and methyl methacrylate under the action of an initiator BPO or AIBN at room temperature, wherein the reaction conditions are as follows: in the prepolymerization process, the temperature range is 60-100 ℃, the reaction time is 30-200 minutes, slurry with certain viscosity is obtained, the slurry is cooled by ice water, and polymerization is suspended for later use. In the polymerization process, the slurry is moved into the environment of 40-60 ℃, and after polymerization for several days, the slurry is subjected to heat treatment at the high temperature of 100-120 ℃ to ensure that the residual monomers are fully polymerized. Finally obtaining polymer OCDs @ PMMA; the mass ratio of the Methyl Methacrylate (MMA) to the oil-soluble carbon quantum dots is as follows: 20:1-60:1.
Replacing the step (a) with:
(a) Taking ammonium bicarbonate and sodium citrate as raw materials and deionized water as a solvent, fully dissolving and uniformly stirring, carrying out hydrothermal reaction at the temperature of 160-260 ℃ for 2-10 hours, dialyzing for 24 hours, and evaporating the residual water to obtain dry carbon quantum dots; the mol ratio of the ammonium bicarbonate to the sodium citrate is as follows: 20:1-40:1.
(b) Dissolving the carbon quantum dots obtained in the step (a) and dodecylamine, octadecylamine or other long-chain surfactants containing amino groups in toluene or other nonpolar solvents according to the mass ratio of 1:2-1:20, carrying out hydrothermal treatment at the temperature of 140 ℃ and 200 ℃ for 1-6 hours, removing the upper layer solution, carrying out centrifugal washing by using distilled water, and removing the toluene to obtain the oil-soluble carbon quantum dots.
Compared with other oil-soluble or water-soluble carbon quantum dots, the oil-soluble carbon quantum dots (OOCDs) prepared by the method have smaller sizes and contain a large amount of unsaturated carbon bonds on the surfaces, so that the oil-soluble or water-soluble carbon quantum dots have better dispersibility and luminescence property.
compared with the prior art, the invention has the following obvious beneficial effects:
the carbon quantum dots prepared by the method contain rich unsaturated carbon bonds, have small size, high luminous intensity and good dispersibility and luminous performance, can be used as an anti-aging probe of PMMA, and the composite material obtained by in-situ polymerization of the oil-soluble carbon quantum dots and the PMMA has excellent optical transparency (the transmittance is up to more than 85 percent), and improves the ultraviolet light aging resistance of the PMMA by more than 10 times, so that the application of the carbon quantum dots in all-solid-state illumination in the prior art is solved, and the problem that the PMMA cannot be widely applied due to poor aging resistance is solved. The optimal excitation peak and emission peak of OCDs @ PMMA are distributed stably in an aging test, and stable and good optical performance is shown. The OCDs as an effective nano-scale additive can greatly enhance the ultraviolet aging resistance of PMMA. In addition, a single exponential function representing the emission intensity of OCDs is determined by the aging time, and compared with other methods, OCDs can be used as a highly sensitive fluorescent probe for detecting PMMA in the first aging stage.
drawings
FIG. 1 is a schematic diagram of in-situ polymerization of oil-soluble carbon quantum dots OOCDs and Methyl Methacrylate (MMA).
Fig. 2 is a diagram of oil-soluble carbon quantum dots OOCDs prepared in scheme one, wherein the inset is a particle size distribution diagram of the carbon quantum dots.
FIG. 3 is the excitation and emission spectra of OCDs with the inset being a photograph of the luminescence of OOCDs under UV light.
FIG. 4 shows XPS spectra of OOCDs for carbon quantum dots.
FIG. 5 composite photographs of neat PMMA, TOCDs @ PMMA and OOCDs @ PMMA and photographs of their luminescence under UV light.
FIG. 6 is a composite photograph of carbon quantum dots and PMMA and their excitation and emission spectra.
FIG. 7 transmittance of neat PMMA (a), TOCDs @ PMMA (b), and OOCDs @ PMMA (c) composites at different aging periods.
FIG. 8 is a photograph of OOCDs @ PMMA composite at various aging periods (24,48,72 hours).
FIG. 9 is an excitation and emission spectra of OOCDs @ PMMA composite at various aging periods (0,24,48,72 hours).
FIG. 10 shows excitation and emission spectra of TOCDs @ PMMA composites at different aging periods (0,24,48,72 hours).
Detailed Description
The invention provides a method for preparing a polymer with excellent aging resistance, OOCDs @ PMMA is prepared by adopting a one-step method, TOCDs @ PMMA is prepared by adopting a two-step method, and the stability and the aging process of PMMA compounded with carbon-free quantum dots under ultraviolet irradiation are compared. PMMA polymers with different degrees of ultraviolet light aging resistance are prepared by adjusting the reaction temperature, the reaction time and the amount of added dodecylamine (DDA).
Example 1
Synthesis of OOCDs
As shown below, Methyl Methacrylate (MMA) was used as a single precursor to synthesize oil-soluble carbon quantum dots (OOCDs) in one step: 5.30ml of Methyl Methacrylate (MMA) and 2.97ml of dodecylamine (DDA), and 2ml of NH 3. H2O were each added to 20ml of toluene, sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, and then reacted at 180 ℃ for 2 hours, respectively. Oil-soluble nanoparticles and oil-soluble residues are present from the appearance of the final reaction.
The product was purified to remove dodecylamine (DDA) and Methyl Methacrylate (MMA) residues. Thus, each product was washed with 20ml of water and 20ml of ethanol, the resulting emulsion was centrifuged at 10000r/min using a centrifuge, and the lower solution was separated and removed, and the process was repeated 2 times. An additional 20ml of pure water was added for washing 2 times, and the resulting organic product was further dialyzed in a dialysis tube for 24 hours and finally stored in the absence of light for later use.
Preparation of OOCDs @ PMMA
1ml of the OOCDs prepared were dried in a vacuum oven for 4 hours at room temperature, and then 10ml of Methyl Methacrylate (MMA) and 0.03g of Benzoyl Peroxide (BPO) were added to initiate polymerization. The reaction is carried out for 60 minutes under the condition of water bath at 85 ℃, and then the mixture is poured into a plastic box with the radius of 14mm and the height of 13mm for further reaction for 48 hours at 60 ℃, and finally the mixture is polished into round blocks.
Example 2
Synthesis of OOCDs
As shown below, Methyl Methacrylate (MMA) was used as a single precursor to synthesize oil-soluble carbon quantum dots (OOCDs) in one step: 5.30ml of Methyl Methacrylate (MMA) and 5.94ml of dodecylamine (DDA), and 2ml of NH 3. H2O were each added to 20ml of toluene, sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, and then each reacted at 200 ℃ for 4 hours. Oil-soluble nanoparticles and oil-soluble residues are present from the appearance of the final reaction.
The product was purified to remove dodecylamine (DDA) and Methyl Methacrylate (MMA) residues. Thus, each product was washed with 20ml of water and 20ml of ethanol, the resulting emulsion was centrifuged at 10000r/min using a centrifuge, and the lower solution was separated and removed, and the process was repeated 2 times. An additional 20ml of pure water was added for washing 2 times, and the resulting organic product was further dialyzed in a dialysis tube for 24 hours and finally stored in the absence of light for later use.
Preparation of OOCDs @ PMMA
1ml of the OOCDs prepared were dried in a vacuum oven for 4 hours at room temperature, and then 12ml of Methyl Methacrylate (MMA) and 0.03g of Benzoyl Peroxide (BPO) were added to initiate polymerization. The reaction is carried out for 90 minutes under the condition of water bath at 70 ℃, and then the mixture is poured into a plastic box with the radius of 14mm and the height of 13mm for further reaction for 48 hours at 60 ℃, and finally the mixture is polished into round blocks.
Example 3
Synthesis of OOCDs
As shown below, Methyl Methacrylate (MMA) was used as a single precursor to synthesize oil-soluble carbon quantum dots (OOCDs) in one step: 5.30ml of Methyl Methacrylate (MMA) and 11.88ml of dodecylamine (DDA), and 4ml of NH 3. H2O were each introduced into 20ml of toluene, sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, and then reacted at 220 ℃ for 6 hours, respectively. Oil-soluble nanoparticles and oil-soluble residues are present from the appearance of the final reaction.
The product was purified to remove dodecylamine (DDA) and Methyl Methacrylate (MMA) residues. Thus, each product was washed with 20ml of water and 20ml of ethanol, the resulting emulsion was centrifuged at 10000r/min using a centrifuge, and the lower solution was separated and removed, and the process was repeated 2 times. An additional 20ml of pure water was added for washing 2 times, and the resulting organic product was further dialyzed in a dialysis tube for 24 hours and finally stored in the absence of light for later use.
Preparation of OOCDs @ PMMA
1ml of the OOCDs prepared were dried in a vacuum oven for 4 hours at room temperature, and then 14ml of Methyl Methacrylate (MMA) and 0.06g of Benzoyl Peroxide (BPO) were added to initiate polymerization. The reaction is carried out for 60 minutes under the condition of water bath at 90 ℃, and then the mixture is poured into a plastic box with the radius of 14mm and the height of 13mm for further reaction for 48 hours at 60 ℃, and finally the mixture is polished into round blocks.
Example 4
Synthesis of OOCDs
As shown below, Methyl Methacrylate (MMA) was used as a single precursor to synthesize oil-soluble carbon quantum dots (OOCDs) in one step: 5.30ml of Methyl Methacrylate (MMA) and 17.82ml of dodecylamine (DDA), and 4ml of NH 3. H2O were each introduced into 20ml of toluene, sealed in a 100ml stainless steel autoclave with a polytetrafluoroethylene liner, and then reacted at 240 ℃ for 8 hours, respectively. Oil-soluble nanoparticles and oil-soluble residues are present from the appearance of the final reaction.
The product was purified to remove dodecylamine (DDA) and Methyl Methacrylate (MMA) residues. Thus, each product was washed with 20ml of water and 20ml of ethanol, the resulting emulsion was centrifuged at 10000r/min using a centrifuge, and the lower solution was separated and removed, and the process was repeated 2 times. An additional 20ml of pure water was added for washing 2 times, and the resulting organic product was further dialyzed in a dialysis tube for 24 hours and finally stored in the absence of light for later use.
Preparation of OOCDs @ PMMA
1ml of the OOCDs prepared were dried in a vacuum oven for 4 hours at room temperature, and then 16ml of Methyl Methacrylate (MMA) and 0.03g of Benzoyl Peroxide (BPO) were added to initiate polymerization. The reaction is carried out for 120 minutes under the condition of water bath at 65 ℃, and then the mixture is poured into a plastic box with the radius of 14mm and the height of 13mm for further reaction for 48 hours at 60 ℃, and finally the mixture is polished into round blocks.
Example 5
Synthesis of TOCDs
0.2g of ammonium bicarbonate, 1.5g of ammonia water and 10ml of high purity water were added to a 100ml stainless steel autoclave with a polytetrafluoroethylene liner at normal temperature and pressure, mixed and subjected to hydrothermal reaction at 180 ℃ for 4 hours. After dialysis for 24 hours with a dialysis tube, the remaining water was evaporated to obtain dry carbon quantum dots. Then 5ml of oil soluble carbon quantum dots were dispersed in 15ml of distilled water and adjusted to pH 5 with oxalic acid. To this solution were added 20ml of toluene and 0.1g of dodecylamine (DDA), and the mixed suspension was transferred to a 100ml autoclave with a polytetrafluoroethylene liner, heated at 160 ℃ for 4 hours, and then the upper solution was removed and centrifuged three times with distilled water. And finally, evaporating the residual toluene to obtain the dried oil-soluble carbon quantum dots prepared in the two steps.
preparation of TOCDs @ PMMA
1ml of the prepared TOCDs were put into a vacuum oven to dry for 4 hours at room temperature, and then 10ml of Methyl Methacrylate (MMA) and 0.03g of Benzoyl Peroxide (BPO) were added to initiate polymerization. The reaction is carried out for 60 minutes under the condition of water bath at 85 ℃, and then the mixture is poured into a plastic box with the radius of 14mm and the height of 13mm for further reaction for 48 hours at 60 ℃, and finally the mixture is polished into round blocks.
Example 6
Synthesis of TOCDs
0.4g of ammonium bicarbonate, 1.5g of ammonia water and 100ml of high purity water were added to a 100ml stainless steel autoclave with a polytetrafluoroethylene liner at normal temperature and pressure, mixed and subjected to hydrothermal reaction at 200 ℃ for 6 hours. After dialysis for 24 hours with a dialysis tube, the remaining water was evaporated to obtain dry carbon quantum dots. Then 5ml of oil soluble carbon quantum dots were dispersed in 15ml of distilled water and adjusted to PH 6 with oxalic acid. To this solution were added 20ml of toluene and 0.1g of dodecylamine (DDA), and the mixed suspension was transferred to a 100ml autoclave with a polytetrafluoroethylene liner, heated at 180 ℃ for 4 hours, and then the upper solution was removed and centrifuged three times with distilled water. And finally, evaporating the residual toluene to obtain the dried oil-soluble carbon quantum dots prepared in the two steps.
Preparation of TOCDs @ PMMA
1ml of the prepared TOCDs were put into a vacuum oven to dry for 4 hours at room temperature, and then 12ml of Methyl Methacrylate (MMA) and 0.03g of Benzoyl Peroxide (BPO) were added to initiate polymerization. The reaction is carried out for 90 minutes under the condition of water bath at 70 ℃, and then the mixture is poured into a plastic box with the radius of 14mm and the height of 13mm for further reaction for 48 hours at 60 ℃, and finally the mixture is polished into round blocks.
Example 7
Synthesis of TOCDs
0.6g of ammonium bicarbonate, 1.5g of ammonia water and 10ml of high purity water were added to a 100ml stainless steel autoclave with a polytetrafluoroethylene liner at normal temperature and pressure, mixed and subjected to hydrothermal reaction at 220 ℃ for 8 hours. After dialysis for 24 hours with a dialysis tube, the remaining water was evaporated to obtain dry carbon quantum dots. Then 5ml of oil soluble carbon quantum dots were dispersed in 15ml of distilled water and adjusted to PH 6 with oxalic acid. To this solution were added 20ml of toluene and 0.1g of dodecylamine (DDA), and the mixed suspension was transferred to a 100ml autoclave with a polytetrafluoroethylene liner, heated at 200 ℃ for 4 hours, and then the upper solution was removed and centrifuged three times with distilled water. And finally, evaporating the residual toluene to obtain the dried oil-soluble carbon quantum dots prepared in the two steps.
Preparation of TOCDs @ PMMA
1ml of the prepared TOCDs were put into a vacuum oven to dry for 4 hours at room temperature, followed by addition of 14ml of Methyl Methacrylate (MMA) and 0.06g of Benzoyl Peroxide (BPO) to initiate polymerization. The reaction is carried out for 40 minutes under the condition of water bath at 90 ℃, and then the mixture is poured into a plastic box with the radius of 14mm and the height of 13mm for further reaction for 48 hours at 60 ℃, and finally the mixture is polished into round blocks.
Example 8
Synthesis of TOCDs
0.8g of ammonium bicarbonate, 1.5g of ammonia water and 10ml of high purity water were added to a 100ml stainless steel autoclave with a polytetrafluoroethylene liner at normal temperature and pressure, mixed and subjected to hydrothermal reaction at 240 ℃ for 4 hours. After dialysis for 24 hours with a dialysis tube, the remaining water was evaporated to obtain dry carbon quantum dots. Then 5ml of oil soluble carbon quantum dots were dispersed in 15ml of distilled water and adjusted to PH 7 with oxalic acid. To this solution were added 20ml of toluene and 0.1g of dodecylamine (DDA), and the mixed suspension was transferred to a 100ml autoclave with a polytetrafluoroethylene liner, heated at 220 ℃ for 4 hours, and then the upper solution was removed and centrifuged three times with distilled water. And finally, evaporating the residual toluene to obtain the dried oil-soluble carbon quantum dots prepared in the two steps.
Preparation of TOCDs @ PMMA
1ml of the prepared TOCDs were put into a vacuum oven to dry for 4 hours at room temperature, followed by the addition of 16ml of Methyl Methacrylate (MMA) and 0.08g of Benzoyl Peroxide (BPO) to initiate polymerization. The reaction is carried out for 120 minutes under the condition of water bath at 65 ℃, and then the mixture is poured into a plastic box with the radius of 14mm and the height of 13mm for further reaction for 48 hours at 60 ℃, and finally the mixture is polished into round blocks.
The advantages of the product of the invention are illustrated in conjunction with the attached drawings:
The carbon quantum dots prepared by the method disclosed by the invention have rich unsaturated carbon bonds on the surface (shown in figures 1 and 4), are small in size (1-10nm), good in dispersity (shown in figure 2), and good in light emitting performance (shown in figure 3), can be used as an anti-aging probe of PMMA (polymethyl methacrylate), and the composite material obtained by in-situ polymerization of the oil-soluble carbon quantum dots and PMMA has excellent optical transparency (the transmittance is up to more than 85 percent, and is shown in figures 5 and 7), and the ultraviolet light aging resistance of PMMA is improved by more than 10 times, so that the application of the carbon quantum dots in all-solid-state illumination in the prior art is solved, and the problem that PMMA cannot be widely applied due to poor aging resistance is also solved. The optimal excitation peak and emission peak distribution of OCDs @ PMMA in the aging test is stable, and stable and good optical performance is shown (shown in figure 6, figure 7, figure 8, figure 9 and figure 10). The OCDs as an effective nano-scale additive can greatly enhance the ultraviolet aging resistance of PMMA. In addition, a single exponential function representing the emission intensity of OCDs is determined by the aging time, and compared with other methods, OCDs can be used as a highly sensitive fluorescent probe for detecting PMMA in the first aging stage.
Claims (1)
1. The preparation method of the polymer composite material of the polymethyl methacrylate and the oil-soluble carbon quantum dots is characterized in that the polymer composite material of the polymethyl methacrylate and the oil-soluble carbon quantum dots is prepared by in-situ polymerization of the methyl methacrylate and the oil-soluble carbon quantum dots, and the mass ratio of the methyl methacrylate to the oil-soluble carbon quantum dots is as follows: 20:1-60: 1; the polymer is a random copolymer, and carbon points on a macromolecular chain and structural units of methyl methacrylate are arranged randomly; the particle size of the oil-soluble carbon quantum dots is as follows: 1-10nm, and the content of unsaturated carbon bonds on the surface is as follows: 20% -50%;
The preparation method of the polymer composite material of the polymethyl methacrylate and the oil-soluble carbon quantum dots comprises the following specific steps:
(a) Dissolving methyl methacrylate and any one amino-containing long-chain surfactant of dodecylamine and octadecylamine in a toluene nonpolar solvent, and carrying out hydrothermal reaction under a sealed condition, wherein the hydrothermal reaction temperature range is 140-260 ℃, and the reaction time is 2-10 hours; washing with water and ethanol, performing centrifugal separation, taking an organic layer, and performing dialysis separation with methanol to obtain oil-soluble carbon quantum dots; the mol ratio of the methyl methacrylate to any one of the lauryl amine and the octadecyl amine containing the amino long-chain surfactant is 4:1-2: 3;
(b) Polymerizing the oil-soluble carbon quantum dots obtained in the step (a) and methyl methacrylate under the action of an initiator BPO or AIBN at room temperature, wherein the reaction conditions are as follows: in the prepolymerization process, the temperature range is 60-100 ℃, the reaction time is 30-200 minutes, slurry with certain viscosity is obtained, the slurry is cooled by ice water, polymerization is suspended for standby, in the polymerization process, the slurry is moved into the environment of 40-60 ℃, and after polymerization for several days, heat treatment is carried out at the high temperature of 100-120 ℃, so that residual monomers are fully polymerized, and finally the polymer composite material of the polymethyl methacrylate and the oil-soluble carbon quantum dots is obtained;
The mass ratio of the methyl methacrylate to the oil-soluble carbon quantum dots is as follows: 20:1-60:1.
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