CN102436886B - Method for preparing gold-coated magnetic composite nanoparticles - Google Patents

Method for preparing gold-coated magnetic composite nanoparticles Download PDF

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CN102436886B
CN102436886B CN201110417960.4A CN201110417960A CN102436886B CN 102436886 B CN102436886 B CN 102436886B CN 201110417960 A CN201110417960 A CN 201110417960A CN 102436886 B CN102436886 B CN 102436886B
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magnetic
gold
concentration
aggregation
aqueous solution
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CN102436886A (en
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杨文胜
金秀梅
梁经纶
庄家骐
杨春凤
薛峥
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Jilin University
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Abstract

The invention discloses a method for preparing gold-coated magnetic composite nanoparticles, and belongs to the technical field of multifunctional composite nanoparticles. The method comprises the following steps of: dissolving hydrophobic magnetic nanoparticles in cyclohexane to serve as an oil phase; dissolving a gold-philic surfactant in de-ionized water to serve as a water phase; ultrasonically mixing; then protecting a volatile solvent with nitrogen to obtain magnetic aggregate aqueous solution of which the surface is modified by the gold-philic surfactant; secondly, adding chloroauric acid, a reducing agent and a stabilizing agent into the magnetic aggregate aqueous solution; and reacting to obtain gold shell-covered magnetic aggregate composite nanoparticles. In the method, a gold shell is directly grown on the surface of a magnetic aggregate; and the nanoparticles have the advantages of continuous adjustable gold shell, adjustable adsorption spectrum, adjustable magnetic content, simple preparation method and the like.

Description

A kind of method of preparing gold bag magnetic composite nanoparticle
Technical field
The invention belongs to the technical field of multi-functional composite nanoparticle, particularly a kind of preparation method of easy gold-coating magnetic nano particle.
Background technology
The structure of gold bag magnetic composite nanoparticle comprises magnetic aggregation kernel and golden shell.Gold bag magnetic nucleocapsid structure composite nanoparticle has a very wide range of applications in a lot of fields.As everyone knows, the application of magnetic nano-particle is very extensive, as cell separation, medicament transport, bio-separation, enzyme or protein labeling, biology sensor etc.But the shortcomings such as oxidizable, easy gathering that exposed magnetic nano-particle has, easy decomposition, have limited their range of application greatly.On the surface of magnetic nano-particle, preparing containment vessel is the main method that overcomes these defects.In numerous protective materials, Au receives much concern owing to possessing good chemical stability, biocompatibility, superior optical property.Gold bag magnetic nucleocapsid structure composite nanoparticle has the superior function of gold and magnetic material simultaneously, and is widely used at numerous areas such as cell detection, radiography, thermotherapies.
The method of preparing at present gold bag magnetic nucleocapsid structure composite nanoparticle mainly contains following two kinds.Method one is the synthetic gold bag of three-step approach magnetic nanometer, and key step comprises: 1. certain close golden part in magnetic particle finishing; 2. the less golden nanometer particle of size in aggregate surface absorption; 3. the gold of magnetic aggregate surface of take is growth site, the golden shell of growing.As (J.Phys.Chem.C 2010,114,19607-19613).The method is the main method that preparation gold wraps magnetic nuclear shell structure nano compound particle at present, and its shortcoming is that golden shell is discontinuous, spectrum can regulate and control narrow range.Method two: 1. on the surface of magnetic particle by multi step modification, connect can with Au 3+form the compound of chelate; 2. add after reducing agent, golden shell Direct precipitation is on the surface of magnetic particle.As the people's such as Yongdong Jin work (NATURE COMMUNICATIONS|1: 41|DOI:10.1038/ncomms1042).The advantage of the method is that golden shell is continuous; Shortcoming is that preparation process is complicated, magnetic content is low, spectrum can regulate and control narrow range.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency that overcomes background technology, prepare a kind of gold bag magnetic composite nanoparticle, this particle has nucleocapsid structure, comprise magnetic aggregation kernel and golden shell, and it is adjustable continuously to have golden shell, the advantages such as absorption spectrum, magnetic content is adjustable, and preparation method is simple.
A method of preparing gold bag magnetic composite nanoparticle, step has miniemulsion method to prepare the magnetic aggregation that finishing has close gold surface activating agent, and at the magnetic aggregate surface golden shell of growing;
Described miniemulsion legal system has the magnetic aggregation of close gold surface activating agent for finishing, be hydrophobicity magnetic nano-particle is dissolved in cyclohexane as oil phase, and the concentration of magnetic nano-particle in cyclohexane is 0.065~0.33g/mL; Close gold surface activating agent is dissolved in deionized water as water, and the concentration of close gold surface activating agent in deionized water is 0.004~0.008g/mL; Oil phase and water, by 1: 25~10 the ultrasonic 8~20min that mixes of volume ratio, are obtained to the emulsion oil droplets that contains magnetic particle; Under nitrogen protection, 50~70 ℃ add thermal agitation 7~10h, and volatilization cyclohexane, forms the magnetic aggregation aqueous solution that finishing has close gold surface activating agent;
The described superficial growth at magnetic aggregation gold shell is that in the magnetic aggregation aqueous solution that is 0.005~0.015g/mL to concentration, to add concentration be the gold chloride (HAuCl of 9~25mM 4), reducing agent and stabilizer, reaction 10~25min, obtains the coated magnetic aggregation composite nanoparticle of golden shell; Wherein, the magnetic aggregation aqueous solution, gold chloride volume ratio are 1: 0.95~2, and the concentration of the addition of reducing agent in system is 4~13.6mM, and the concentration of the addition of stabilizer in system is 0.0167~0.0667mg/mL.
In the superficial growth gold shell step of magnetic aggregation, the magnetic aggregation aqueous solution can be prepared as follows: have the magnetic aggregation aqueous solution of close gold surface activating agent to carry out centrifugal treating finishing, remove surfactant free in supernatant liquid and liquid, again add deionized water to be mixed with the magnetic aggregation aqueous solution that concentration is 0.005~0.015g/mL.
Described close gold surface activating agent refers to that water-soluble better water-wet side is with electron rich group, as amino, and sulfydryl, the surfactant of polyoxyethylene groups etc.Concrete, such as Tween 20 (polysorbas20), Tween 40 (polysorbate40), Tween 60 (polysorbate60), Tween 80 (Tween 80), N-(2-hydroxyalkyl) shitosan, 3-sulfydryl-1-propane sulfonic acid sodium etc.The amount of parent's gold surface activating agent, directly affect golden shell continuously, compactness extent.
Described hydrophobicity magnetic nano-particle can be Fe 3o 4nano particle, γ-Fe 2o 3nano particle, CoFe 2o 4nano particle or MnFe 2o 4nano particle, the mass concentration in cyclohexane is 0.065~0.33g/ml, and the size of magnetic aggregation mainly changes along with the concentration of hydrophobicity magnetic nano-particle in cyclohexane is different, and the magnetic aggregate size of gained of the present invention is generally 50~100nm.
Gold thickness of the shell can be by changing aggregation and gold chloride (HAuCl 4) amount regulate and control.In reaction system, the mass concentration of magnetic aggregation is 0.8~10mg/mL, and the concentration of gold chloride is 3~9mM, and the golden shell of 1~10nm can be prepared in the surface of corresponding magnetic aggregation.
Described reducing agent refers at normal temperatures can be by Au 3+be reduced into the reducing agent of Au, as ascorbic acid (Ascorbic acid), azanol (Hydroxylamine), methyl alcohol (Methanol) etc., concentration is generally 10mM.The addition of reducing agent changes with the amount of gold chloride and the kind of reducing agent.
Described stabilizer can be Tween 20, Tween 40, Tween 60, Tween 80, N-(2-hydroxyalkyl) shitosan, 3-sulfydryl-1-propane sulfonic acid sodium.The initial concentration of stabilizer does not affect product form, but need to guarantee that in reaction system, stabilizer concentration is 0.0167~0.0667mg/mL.
The concentration of the stabilizer in magnetic aggregation solution, the final gold of impact wraps the stability of magnetic core-shell structure nanometer particle, so directly affects the form of product.Preferably, magnetic aggregation is being carried out to, after centrifugal treating, remove supernatant liquid, then add stabilizer in system, making its concentration in system is 0.025~0.03mg/mL.
As mentioned above, the present invention is the surperficial direct growth gold shell at magnetic aggregation, has following advantage: 1. gold shell is adjustable continuously; 2. absorption spectrum is adjustable; 3. magnetic content is adjustable; 4. preparation method is simple.
Accompanying drawing explanation
Fig. 1 is the Fe that the finishing of embodiment 4 preparations has Tween 20 3o 4the transmission electron microscope picture of magnetic aggregation.
Fig. 2 is the Fe that the finishing of embodiment 5 preparations has Tween 20 3o 4the transmission electron microscope picture of magnetic aggregation.
Fig. 3 is the transmission electron microscope picture of the gold bag magnetic core-shell structure nanometer particle that makes of embodiment 9, and the magnetic content of this particle is 55emu/g, the about 1nm of shell thickness.
Fig. 4 is the transmission electron microscope picture of the gold bag magnetic core-shell structure nanometer particle that makes of embodiment 10, and the magnetic content of this particle is 30emu/g, the about 2.4nm of shell thickness.
Embodiment
Embodiment 1: the preparation of hydrophobic magnetic nano particle (1)
To 50mL, pass through the Fe that adds 0.023mol in the water of letting nitrogen in and deoxidizing 3+fe with 0.0115mol 2+obtain mixed solution.Get 200mL water letting nitrogen in and deoxidizing in the reaction bulb of 500mL, the concentrated ammonia liquor that the mass percent concentration that adds successively 10mL is 25% and 5.4g oleic acid are poured wherein above-mentioned molysite mixed solution into rapidly under vigorous stirring, at 50 ℃, react 1h.After completion of the reaction, with hydrochloric acid, reaction solution is adjusted to acidity, isolates the solid of black with the permanent magnet of 0.1T from reaction solution, gained solid cleans and obtains hydrophobic Fe 3~5 times with high purity water 3o 4nano particle.
By Fe 3+and Fe 2+replace to respectively Co 3+and Co 2+, can obtain hydrophobic Co 3o 4nano particle.
Embodiment 2: the preparation of hydrophobic magnetic nano particle (2)
To 50mL, pass through the Fe that adds 0.023mol in the water of letting nitrogen in and deoxidizing 3+fe with 0.0115mol 2+obtain mixed solution.Get 200mL water letting nitrogen in and deoxidizing in the reaction bulb of 500mL, the concentrated ammonia liquor that the mass percent concentration that adds successively 10mL is 25% and 2.76g myristic acid are poured wherein above-mentioned mixed solution into rapidly under vigorous stirring, at 80 ℃, react 1h.Then in reaction solution, pass into oxygen 1.5h.After completion of the reaction, with hydrochloric acid just reaction solution be adjusted to acidity, with the permanent magnet of 0.1T, from reaction solution, isolate red solid, gained solid cleans and to obtain hydrophobic γ-Fe 3~5 times with high purity water 2o 3nano particle.
Embodiment 3: the preparation of hydrophobic magnetic nano particle (3)
To 50mL, pass through the Fe that adds 0.023mol in the water of letting nitrogen in and deoxidizing 3+with 0.0115mol Co 2+obtain mixed solution.Get 200mL water letting nitrogen in and deoxidizing in the reaction bulb of 500mL, the concentrated ammonia liquor that the mass percent concentration that adds successively 10mL is 25% and 0.665g 10 hendecenoic acid are poured wherein above-mentioned mixed solution into rapidly under vigorous stirring, at 90 ℃, react 1h.After completion of the reaction, with hydrochloric acid, reaction solution is adjusted to acidity, isolates the solid of black with the permanent magnet of 0.1T from reaction solution, gained solid cleans and obtains CoFe 3~5 times with high purity water 2o 4dewatering nano particle.
By Co 2+replace to Mn 2+, can obtain hydrophobic MnFe 2o 4nano particle.
Embodiment 4: finishing has the preparation (1) of the magnetic aggregation of close gold surface activating agent
By the hydrophobic Fe in embodiment 1 3o 4magnetic nano-particle 0.3g is dispersed in the cyclohexane of 1.5mL and forms oil phase; Compound concentration is that the Tween 20 solution 30mL of 0.005g/ml are as water.Mixing water oil phase, ultrasonic 10min forms miniemulsion.In temperature, be 60 ℃, under nitrogen protection, stir 9h and carry out solvent flashing, by the centrifugal 5min separation of 8000rpm, obtain having high Fe 3o 4the magnetic aggregation of magnetic nuclear volume, average grain diameter is 85nm.What Fig. 1 showed is the transmission electron microscope picture of this aggregation.
Can be by hydrophobic Fe 3o 4magnetic nano-particle replaces with hydrophobic Co 3o 4nano particle.
Embodiment 5: finishing has the preparation (2) of the magnetic aggregation of close gold surface activating agent
By the hydrophobic Fe in embodiment 1 3o 4magnetic nano-particle 0.1g is dispersed in the cyclohexane of 1.5mL and forms oil phase; Compound concentration is that the Tween 20 solution 30mL of 0.005g/mL are as water.Mixing water oil phase, ultrasonic 10min forms miniemulsion.In temperature, be 65 ℃, under nitrogen protection, stir 8h and carry out solvent flashing, by the centrifugal 5min separation of 8000rpm, obtain having high Fe 3o 4the magnetic aggregation of magnetic nuclear volume, average grain diameter is 50nm.What Fig. 2 showed is the transmission electron microscope picture of this aggregation.
Embodiment 6: finishing has the preparation (3) of the magnetic aggregation of close gold surface activating agent
By the hydrophobic γ-Fe in embodiment 2 2o 3nano particle 0.24g is dispersed in the cyclohexane of 1.5mL and forms oil phase; Compound concentration is that the Tween 20 solution 30mL of 0.005g/mL are as water.Mixing water oil phase, ultrasonic 10min forms miniemulsion.In temperature, be 60 ℃, under nitrogen protection, stir 9h and carry out solvent flashing, by the centrifugal 5min separation of 8000rpm, obtain having high γ-Fe 2o 3the magnetic aggregation of magnetic nuclear volume, average grain diameter is 65nm.
Embodiment 7: finishing has the preparation (4) of the magnetic aggregation of close gold surface activating agent
By the hydrophobic Fe in embodiment 1 3o 4magnetic nano-particle 0.1g is dispersed in the cyclohexane of 1.5mL and forms oil phase; Compound concentration is that the Tween 40 solution 30mL of 0.005g/mL are as water.Mixing water oil phase, ultrasonic 10min forms miniemulsion.In temperature, be 60 ℃, under nitrogen protection, stir 9h and carry out solvent flashing, by the centrifugal 5min separation of 8000rpm, obtain having high Fe 3o 4the magnetic aggregation of magnetic nuclear volume, average grain diameter is 50nm.
Embodiment 8: finishing has the preparation (5) of the magnetic aggregation of surfactant
By the hydrophobic CoFe in embodiment 3 2o 4nano particle 0.48g is dispersed in the cyclohexane of 1.5mL and forms oil phase; Compound concentration is that the Tween 20 solution 30mL of 0.005g/ml are as water.Mixing water oil phase, ultrasonic 10min forms miniemulsion.In temperature, be 60 ℃, under nitrogen protection, stir 9h and carry out solvent flashing, by the centrifugal 5min separation of 8000rpm, obtain having high CoFe 2o 4the magnetic aggregation of magnetic nuclear volume, average grain diameter is 90nm.
Can be by hydrophobic CoFe 2o 4nano particle replaces to hydrophobic MnFe 2o 4nano particle.
Embodiment 9: the growth (1) of magnetic aggregate surface gold shell
To the high Fe that has in embodiment 5 3o 4the magnetic aggregation of magnetic nuclear volume carries out centrifugal treating, is again dispersed in water, and the concentration that makes aggregation is 0.01g/mL.Get the above-mentioned aggregation solution of 1mL and join the gold chloride (HAuCl that 2mL concentration is 9.56mM 4) in solution, then add the Tween 20 of 0.15mg as stabilizer in system, adding in a moment 3mL concentration is ascorbic acid (Ascorbic acid) solution of 10mM, after reaction 15min, obtains gold bag magnetic composite nanoparticle.What Fig. 3 showed is the transmission electron microscope picture of this product.
Embodiment 10: the growth (2) of magnetic aggregate surface gold shell
To the high Fe that has in embodiment 5 3o 4the magnetic aggregation of magnetic nuclear volume carries out centrifugal treating, is again dispersed in water, and the concentration that makes aggregation is 0.01g/mL.Get the above-mentioned aggregation solution of 1mL and join the gold chloride (HAuCl that 2mL concentration is 11.95mM 4) in solution, then add the Tween 20 of 0.15mg as stabilizer in system, adding in a moment 3mL concentration is ascorbic acid (Ascorbic acid) solution of 10mM, after reaction 15min, obtains gold bag magnetic composite nanoparticle.What Fig. 4 showed is the transmission electron microscope picture of this product.
Embodiment 11: the growth (3) of magnetic aggregate surface gold shell
To the high Fe that has in embodiment 5 3o 4the magnetic aggregation of magnetic nuclear volume carries out centrifugal treating, is again dispersed in water, and the concentration that makes aggregation is 0.01g/mL.Get the above-mentioned aggregation solution of 1mL and join the gold chloride (HAuCl that 2mL concentration is 11.95mM 4) in solution, then add the Tween 20 of 0.16mg as stabilizer in system, adding in a moment 3mL concentration is the hydroxylamine hydrochloride (NH of 13.1mM 2oHHCl) solution, after reaction 15min, obtains gold bag magnetic composite nanoparticle.
Embodiment 12: the growth (4) of magnetic aggregate surface gold shell
To the high Fe that has in embodiment 5 3o 4the magnetic aggregation of magnetic nuclear volume carries out centrifugal treating, is again dispersed in water, and the concentration that makes aggregation is 0.01g/mL.Get the above-mentioned aggregation solution of 1mL and join the gold chloride (HAuCl that 2mL concentration is 11.95mM 4) in solution, then add the Tween 20 of 0.16mg as stabilizer in system, adding in a moment 3mL concentration is the methyl alcohol (CH of 25mM 3oH) solution, after reaction 15min, obtains gold bag magnetic composite nanoparticle.
Embodiment 13: the growth (5) of magnetic aggregate surface gold shell
To the high γ-Fe that has in embodiment 6 2o 3the magnetic aggregation of magnetic nuclear volume carries out centrifugal treating, is again dispersed in water, and the concentration that makes aggregation is 0.01g/mL.Get the above-mentioned aggregation solution of 1mL and join the gold chloride (HAuCl that 2mL concentration is 11.95mM 4) in solution, then add the Tween 20 of 0.15mg as stabilizer in system, adding in a moment 3mL concentration is ascorbic acid (Ascorbic acid) solution of 10mM, after reaction 16min, obtains gold bag magnetic composite nanoparticle.
Embodiment 14: the growth (6) of magnetic aggregate surface gold shell
To the high γ-Fe that has in embodiment 6 2o 3the magnetic aggregation of magnetic nuclear volume carries out centrifugal treating, is again dispersed in water, and the concentration that makes aggregation is 0.01g/mL.Get the above-mentioned aggregation solution of 1mL and join the gold chloride (HAuCl that 2mL concentration is 11.95mM 4) in solution, then add the Tween 20 of 0.15mg as stabilizer in system, adding in a moment 3mL concentration is the hydroxylamine hydrochloride (NH of 13.1mM 2oHHCl) solution, after reaction 15min, obtains gold bag magnetic composite nanoparticle.
Embodiment 15: the growth (7) of magnetic aggregate surface gold shell
To the high Fe that has in embodiment 7 3o 4the magnetic aggregation of magnetic nuclear volume carries out centrifugal treating, is again dispersed in water, and the concentration that makes aggregation is 0.01g/mL.Get the above-mentioned aggregation solution of 1mL and join the gold chloride (HAuCl that 2mL concentration is 11.95mM 4) in solution, then add the Tween 40 of 0.18mg as stabilizer in system, adding in a moment 3mL concentration is ascorbic acid (Ascorbic acid) solution of 10mM, after reaction 18min, obtains gold bag magnetic composite nanoparticle.
Embodiment 16: the growth (8) of magnetic aggregate surface gold shell
To the high CoFe that has in embodiment 8 2o 4the magnetic aggregation of magnetic nuclear volume carries out centrifugal treating, is again dispersed in water, and the concentration that makes aggregation is that 0.006g/mL. gets the above-mentioned aggregation solution of 1mL and joins the gold chloride (HAuCl that 2mL concentration is 11.95mM 4) in solution, then add the Tween 20 of 0.15mg as stabilizer in system, adding in a moment 3mL concentration is ascorbic acid (Ascorbic acid) solution of 10mM, after reaction 15min, obtains gold bag magnetic composite nanoparticle.

Claims (4)

1. a method of preparing gold bag magnetic composite nanoparticle, step has miniemulsion method to prepare the magnetic aggregation that finishing has close gold surface activating agent, and at the magnetic aggregate surface golden shell of growing;
Described miniemulsion legal system has the magnetic aggregation of close gold surface activating agent for finishing, be hydrophobicity magnetic nano-particle is dissolved in cyclohexane as oil phase, and the concentration of magnetic nano-particle in cyclohexane is 0.065~0.33g/mL; Close gold surface activating agent is dissolved in deionized water as water, and the concentration of close gold surface activating agent in deionized water is 0.004~0.008g/mL; Oil phase and water, by 1: 25~10 the ultrasonic 8~20min that mixes of volume ratio, are obtained to the emulsion oil droplets that contains magnetic particle; Under nitrogen protection, 50~70 ℃ add thermal agitation 7~10h, and volatilization cyclohexane, forms the magnetic aggregation aqueous solution that finishing has close gold surface activating agent;
The described gold of the superficial growth at magnetic aggregation shell, that in the magnetic aggregation aqueous solution that is 0.005~0.015g/mL to concentration, to add concentration be gold chloride, reducing agent and the stabilizer of 9~25mM, reaction 10~25min, obtains the coated magnetic aggregation composite nanoparticle of golden shell; Wherein, the magnetic aggregation aqueous solution, gold chloride volume ratio are 1: 0.95~2, and the concentration of the addition of reducing agent in system is 4~13.6mM, and the concentration of the addition of stabilizer in system is 0.0167~0.0667mg/mL; Described reducing agent is ascorbic acid, azanol or methyl alcohol; Described stabilizer is Tween20, Tween40, Tween60, Tween80, N-(2-hydroxyalkyl) shitosan or 3-sulfydryl-1-propane sulfonic acid sodium.
2. the method for preparing gold bag magnetic composite nanoparticle according to claim 1, it is characterized in that, in the superficial growth gold shell step of magnetic aggregation, the magnetic aggregation aqueous solution is prepared as follows: have the magnetic aggregation aqueous solution of close gold surface activating agent to carry out centrifugal treating finishing, remove surfactant free in supernatant liquid and liquid, again add deionized water to be mixed with the magnetic aggregation aqueous solution that concentration is 0.005~0.015g/mL.
3. the method for preparing gold bag magnetic composite nanoparticle according to claim 2, it is characterized in that, described close gold surface activating agent is Tween20, Tween40, Tween60, Tween80, N-(2-hydroxyalkyl) shitosan or 3-sulfydryl-1-propane sulfonic acid sodium.
4. the method for preparing gold bag magnetic composite nanoparticle according to claim 1 and 2, is characterized in that, the addition of described stabilizer, and the concentration in system is 0.025~0.03mg/mL.
CN201110417960.4A 2011-12-14 2011-12-14 Method for preparing gold-coated magnetic composite nanoparticles Expired - Fee Related CN102436886B (en)

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CN103551146B (en) * 2013-09-10 2015-05-13 杭州师范大学 Precious metal-titanium dioxide nanocomposite particle preparation method
CN105727949B (en) * 2016-01-29 2018-12-11 浙江理工大学 One step of one kind prepares noble metal/SiO2The method of nano-complex particle
US10016745B2 (en) 2016-06-15 2018-07-10 Savannah River Nuclear Solutions, Llc Multifunctional nanomaterials and methods of photothermal heating and catalysis using the same
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