CN116333551B - Micro-fluidic chip surface treating agent, preparation method and application thereof - Google Patents

Micro-fluidic chip surface treating agent, preparation method and application thereof Download PDF

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CN116333551B
CN116333551B CN202211635972.9A CN202211635972A CN116333551B CN 116333551 B CN116333551 B CN 116333551B CN 202211635972 A CN202211635972 A CN 202211635972A CN 116333551 B CN116333551 B CN 116333551B
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microfluidic chip
parts
chip surface
treating agent
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CN116333551A (en
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林志铿
陈志坚
刘峰
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Xiamen Wiz Biotech Co ltd
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    • C09D139/06Homopolymers or copolymers of N-vinyl-pyrrolidones
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Abstract

The application relates to a microfluidic chip surface treating agent, a preparation method and application thereof, and relates to the field of detection and analysis technology, wherein the microfluidic chip surface treating agent comprises the following raw materials in parts by weight: 1-10 parts of polyethylene glycol monomethyl ether; 0.1-0.5 part of coupling agent; 1-15 parts of 1, 2-propylene glycol; 1-15 parts of dimethylbenzene; 50-80 parts of deionized water; 1-25 parts of polyvinylpyrrolidone; 0.1-0.5 part of an antioxidant; 1-5 parts of a surfactant. The micro-fluidic chip surface treatment agent prepared by the application can form a hydrophilic coating with good hydrophilicity and stability on the surface of a polymer substrate, effectively improves the hydrophilic performance of the surface of the polymer substrate, and has stable and reliable hydrophilic performance and long aging time.

Description

Micro-fluidic chip surface treating agent, preparation method and application thereof
Technical Field
The application relates to the field of detection and analysis technology, in particular to a microfluidic chip surface treating agent, a preparation method and application thereof.
Background
Microfluidic chip technology is a scientific technology characterized by the manipulation of fluids in the micrometer scale space. The current mainstream microfluidic chip refers to integrating or basically integrating basic operation units such as sample preparation, reaction, separation, detection, cell culture, sorting, cracking and the like in the fields of chemistry, biology and the like onto a chip with a size of a few square centimeters or less, and forming a network by micro channels, so that controllable fluid penetrates through the whole system to realize various functions of different laboratories such as routine chemistry, biology, materials, optics and the like.
The material of the microfluidic chip determines the performance of the chip, and the materials commonly used at present for manufacturing the microfluidic chip comprise quartz, glass, polymers and the like. Among them, quartz is fragile, expensive, and the surface chemistry is complex; the glass microfluidic chip has a lengthy manufacturing process, is difficult to manufacture a channel with a large aspect ratio, and has a complex chip sealing process, so that the traditional inorganic materials such as quartz and glass are unfavorable for mass production of the microfluidic chip, and have been gradually replaced by polymer materials. The polymer material has the advantages of low cost, easy processing and the like, has good light transmittance and dielectric property, can be widely applied to the field of microfluidic chip base materials, and comprises office dimethyl siloxane, polystyrene, polymethyl methacrylate and the like which are most used at present. Because most of the polymer materials are hydrophobic materials, the surface hydrophilicity of the polymer materials is poor, so that liquid samples in the microfluidic chip are difficult to infiltrate, spread and flow in the micro-channels, and the surface is easy to adsorb hydrophobic macromolecules in the samples, so that the detection accuracy and sensitivity are reduced, and therefore, the polymer materials are required to be subjected to surface modification to improve the surface hydrophilicity of the polymer materials.
The method for modifying the surface of the polymer substrate of the microfluidic chip commonly used in the prior art mainly uses a wet chemical treatment method, and forms a layer of hydrophilic coating on the surface of the hydrophobic material by a chemical grafting or polymerization initiation method on the surface of the material to realize hydrophilic modification, but the method is extremely easy to destroy the bulk structure of the material, has complex process, can generate a large amount of industrial three wastes, and increases the cost of three wastes treatment, thus being not suitable for large-scale industrialized popularization.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a microfluidic chip surface treating agent, a preparation method and application thereof, so as to reduce the generation of industrial three wastes in the surface modification process of a polymer substrate and reduce the production and treatment cost.
In a first aspect, the application provides a microfluidic chip surface treating agent, which adopts the following technical scheme:
The micro-fluidic chip surface treating agent comprises the following raw materials in parts by weight:
1-10 parts of polyethylene glycol monomethyl ether;
0.1 to 0.5 part of coupling agent;
1-15 parts of 1, 2-propylene glycol;
1-15 parts of dimethylbenzene;
50-80 parts of deionized water;
1-25 parts of polyvinylpyrrolidone;
0.1 to 0.5 part of antioxidant;
1-5 parts of a surfactant.
By adopting the technical scheme, the organic functional groups in the coupling agent molecules can perform coupling reaction with the surface of the polymer substrate, and are stably grafted and attached to the surface of the polymer substrate, and the hydrophilic functional groups in the coupling agent molecules enable the coupling agent molecules to have good reactivity with water and other inorganic interfaces, so that a layer of stably attached amphiphilic bonding layer is formed on the surface of the polymer substrate. Polyvinylpyrrolidone is a nonionic water-soluble high molecular compound, is extremely soluble in water, has good adsorptivity, adhesiveness and film forming property, and has hydrophilic groups, so that the polyvinylpyrrolidone is extremely easy to combine with water to form hydrophilic gel; polyethylene glycol monomethyl ether has good water solubility and wettability; after being mixed with deionized water and 1, 2-propylene glycol, polyethylene glycol monomethyl ether can form an ether/water/alcohol mixed solution with good hydrophilicity and wettability, and the mixed solution and polyvinylpyrrolidone form a hydrophilic coating with good and long-acting hydrophilic effect; and then a layer of stable hydrophilic modified coating can be formed on the surface of the base material through the grafting bonding action of the coupling agent, and the hydrophilic coating can be stably bonded on the surface of the activated base material, so that the hydrophilic modification of the surface of the polymer base material is realized, and the stability of the hydrophilic modified coating on the surface of the base material is further improved through the grafting bonding of the coupling agent and the surface of the polymer base material.
The microfluidic chip surface treating agent provided by the application improves the wettability by forming a stable hydrophilic coating on the surface of a microfluidic chip substrate. The surface treatment agent disclosed by the application has less destructiveness on the surface structure of the substrate in the hydrophilic modification process, and is environment-friendly and reliable, and no industrial three wastes are generated. In addition, the hydrophilic coating formed after the surface treatment agent is treated can not adsorb active molecules in a detection sample, and can effectively reduce the influence on the detection accuracy and sensitivity.
Optionally, the average molecular weight of the polyethylene glycol monomethyl ether is 500-2000.
By adopting the technical scheme, the polyethylene glycol monomethyl ether with low molecular weight has lower viscosity, better wettability and better consistency of the mixed solution, and the prepared treating agent has better film forming performance.
Optionally, the average molecular weight of the polyvinylpyrrolidone is 10000-20000.
By adopting the technical scheme, the average molecular weight of polyvinylpyrrolidone is limited in the range, so that the polyvinylpyrrolidone has better wettability and film forming property, and better adhesion property with the surface of the substrate, and a more stable hydrophilic coating is obtained.
Optionally, the coupling agent is a silane coupling agent.
Optionally, the surfactant comprises one or more of sodium dodecyl sulfonate, polyethylene glycol, sodium lauryl sulfate and dioctyl sodium sulfosuccinate.
By adopting the technical scheme, the surfactant can further improve the wettability of the surface of the polymer substrate and promote the adhesion stability of the hydrophilic coating on the surface of the polymer.
Optionally, the antioxidant comprises one or more of dibutyl hydroxytoluene, phosphite, triphenyl phosphite, dilauryl thiodipropionate.
By adopting the technical scheme, the antioxidant can improve the oxidation resistance of the treating agent, so that the formed hydrophilic coating can maintain long-term stability and long-term hydrophilic effect.
In a second aspect, the application provides a preparation method of a microfluidic chip surface treating agent, which adopts the following technical scheme:
the preparation method of the microfluidic chip surface treating agent comprises the following steps:
s1, uniformly mixing polyethylene glycol monomethyl ether, 1, 2-propylene glycol and dimethylbenzene to prepare a component A;
s2, dissolving polyvinylpyrrolidone in deionized water, then adding a silane coupling agent, an antioxidant and a surfactant, and uniformly mixing to obtain a component B;
And S3, mixing the component A and the component B to obtain the micro-fluidic chip surface treating agent.
In a third aspect, the present application provides an application of a microfluidic chip surface treatment agent in a surface modification treatment of a microfluidic chip substrate, comprising the following steps: and (3) carrying out plasma treatment on the surface of the microfluidic chip substrate, and then dipping the surface of the microfluidic chip substrate with a microfluidic chip surface treating agent, and curing the surface treating agent to form a hydrophilic coating.
The surface of the substrate is subjected to plasma treatment to generate more activating groups which are beneficial to graft modification of active ingredients in the surface treatment agent, and meanwhile, the bonding effect and stability of the hydrophilic coating on the surface of the substrate can be enhanced. The plasma treatment gas is preferably oxygen; the polymeric substrate includes Polydimethylsiloxane (PDMS), polystyrene (PS), and polymethyl methacrylate (PMMA). After the surface of the base material is immersed with the surface treating agent, standing for 3-10 min, then blowing off the residual treating agent on the surface of the base material, and naturally curing the coating.
In summary, the present application includes at least one of the following beneficial technical effects:
1. According to the technical scheme, the hydrophilic coating with good hydrophilicity and wettability can be formed on the surface of the micro-fluidic chip polymer substrate through the synergistic effect of polyvinylpyrrolidone and polyethylene glycol monomethyl ether, active components in the hydrophilic coating are grafted and modified on the surface of the substrate through the effects of the coupling agent and the surfactant, and the hydrophilic coating can stably exist on the surface of the substrate and has a long-acting hydrophilic effect by combining the bonding effect of the components of the treatment agent.
2. The microfluidic chip surface treating agent provided by the application improves the wettability by forming a stable hydrophilic coating on the surface of a microfluidic chip substrate. The surface treatment agent disclosed by the application has less destructiveness on the surface structure of the substrate in the hydrophilic modification process, and is environment-friendly and reliable, and no industrial three wastes are generated.
3. Before modifying the surface of the substrate of the microfluidic chip by using the treating agent, plasma treatment is carried out, so that more active groups are generated on the surface of the substrate by the plasma treatment, and the grafting modification of the treating agent components on the surface of the substrate and the adhesion of the hydrophilic coating are facilitated.
Drawings
Fig. 1 is a photograph showing the surface wetting effect of a polymer substrate without being subjected to hydrophilic modification treatment;
fig. 2 is a photograph showing the surface wetting effect of the polymer substrate subjected to the hydrophilic modification treatment in example 1.
Fig. 3 is a photograph showing the surface wetting effect after the aging test of the polymer substrate subjected to the hydrophilic modification treatment in example 1.
Detailed Description
The present application will be described in further detail with reference to specific examples. In the following examples, no specific details are set forth, and the examples were conducted under conventional conditions or conditions recommended by the manufacturer; the raw materials used in the following examples were all commercially available from ordinary sources except for the specific descriptions.
Example 1
The micro-fluidic chip surface treating agent comprises the following components in proportion as shown in table 1:
s1, mixing polyethylene glycol monomethyl ether with average molecular weight of 800, 1, 2-propylene glycol and dimethylbenzene according to a proportion, and uniformly stirring to obtain a component A;
S2, dissolving polyvinylpyrrolidone with average molecular weight of 10000 in deionized water according to a proportion, then adding a silane coupling agent KH-570, polyethylene glycol and dibutyl hydroxy toluene, and uniformly stirring and mixing to obtain a component B;
And S3, uniformly mixing the component A and the component B to obtain the micro-fluidic chip surface treating agent.
Examples 2 to 4
The micro-fluidic chip surface treatment agents provided in examples 2 to 4 are mainly different from example 1 in the component ratio, and the rest are the same as example 1.
Comparative example 1
The comparative example differs from example 1 in that polyethylene glycol monomethyl ether was not added to the raw material, and the remainder remained the same as in example 1. The composition ratios are referred to in Table 1.
Comparative example 2
This comparative example differs from example 1 in that no polyvinylpyrrolidone was added to the raw material, and the remainder remained the same as in example 1. The composition ratios are referred to in Table 1.
Comparative example 3
This comparative example differs from example 1 in that 1, 2-propanediol was not added to the starting material, and the remainder was maintained as in example 1. The composition ratios are referred to in Table 1.
Comparative examples 4 to 6
Comparative examples 4 to 6 are different from example 1 in the raw material component ratios, and the specific component ratios are shown in Table 1, and the production method is the same as that of example 1.
Table 1: examples 1 to 4 component proportions (unit: g)
The microfluidic chip surface treatment agents prepared in examples 1 to 4 and comparative examples 1 to 6 were applied to the hydrophilic modification treatment of the microfluidic chip polymer substrate surface, and the hydrophilic properties of the substrate surface after the hydrophilic modification treatment were detected, specifically:
Taking a micro-fluidic chip substrate made of PS material, performing oxygen plasma treatment for 15s, soaking the substrate to prepare a micro-fluidic chip surface treating agent after the plasma treatment, standing for 5min, blowing off residual liquid on the surface of the substrate, standing for 2h at normal temperature, drying and solidifying, and finishing the hydrophilic modification treatment of the surface of the micro-fluidic chip.
Control group: the same batch of PS substrates was taken and subjected to oxygen plasma treatment for 15s.
Ageing test: and (3) placing the substrate subjected to hydrophilic modification treatment in a baking oven at 45 ℃ for ageing test, baking at constant temperature for 30 days, taking out, and detecting the water drop angle and wettability of the surface of the substrate.
The method for detecting the hydrophilia of the surface of the substrate comprises the following steps:
And (3) using distilled water as detection liquid by adopting a water drop angle tester to test the water drop angle and wettability of the surface of the substrate.
The results of the performance measurements for examples 1 to 4 and comparative examples 1 to 6 are shown in Table 2 below.
Table 2: results of the measurements of examples 1 to 4 and comparative examples 1 to 6
As can be seen from the data in table 2 and fig. 1 to 3, the surface hydrophilicity of the polymer substrate treated by the surface treating agent provided in the technical scheme of the present application is greatly improved, and the polymer substrate has good wettability. Compared with the control group, the control group only carries out plasma treatment on the polymer substrate, and the hydrophilia of the surface of the polymer substrate is greatly improved after the plasma treatment, but after the aging test, the surface hydrophilia is basically restored to the level before the plasma treatment, while the hydrophilia of the polymer substrate surface treated by the microfluidic chip surface treating agent is basically consistent before and after the aging, and the aging is long and has good stability.
Examples 1 to 4, in which the composition ratios of the surface treatment agents were adjusted within the range defined by the technical scheme of the present application, it can be seen from the data in table 2 that the prepared surface treatment agents all have good surface modification effects, and the formed hydrophilic coating has good stability and long hydrophilic performance aging.
Comparative examples 4 to 6, in which some adjustments were made to the components of the surface treatment agent, and the amounts of polyethylene glycol monomethyl ether, polyvinylpyrrolidone and 1, 2-propanediol added were increased, respectively, it was found from the test data that, under the condition of excessive addition of polyethylene glycol monomethyl ether or polyvinylpyrrolidone, although the initial wettability of the formed hydrophilic coating was not greatly affected, the stability of the hydrophilic coating was deteriorated, and after the aging test, the wettability of the hydrophilic coating was significantly reduced. However, after the 1, 2-propanediol is added excessively, the initial wetting property of the hydrophilic coating is obviously reduced, and water drops cannot be well wetted on the surface of the hydrophilic coating. This is probably because the excessively added components are completely film-formed on the surface of the polymer substrate or react with the surface of the substrate in a grafting manner, so that the free molecular structure in the formed hydrophilic coating is increased, and the stability of the hydrophilic coating is damaged.
In comparative examples 1 to 3, polyethylene glycol monomethyl ether, polyvinylpyrrolidone and 1, 2-propanediol were removed from the raw materials, respectively, it can be seen that after a part of the raw materials were missing, the synergistic effect between the components was destroyed, so that the hydrophilic modification effect of the microfluidic chip surface treatment agent was significantly reduced, and the stability of the hydrophilic coating was also greatly reduced.
Example 5
The micro-fluidic chip surface treating agent is different from example 4 in that the average molecular weight of polyethylene glycol monomethyl ether is 2000, the average molecular weight of polyvinylpyrrolidone is 20000, and the rest is the same as in example 4.
Example 6
The micro-fluidic chip surface treatment agent is different from example 4 in that the average molecular weight of polyethylene glycol monomethyl ether is 800, the average molecular weight of polyvinylpyrrolidone is 12000, and the rest is the same as in example 4.
Example 7
The micro-fluidic chip surface treatment agent is different from example 4 in that the average molecular weight of polyethylene glycol monomethyl ether is 5000, the average molecular weight of polyvinylpyrrolidone is 30000, and the rest is the same as in example 4.
Example 8
The micro-fluidic chip surface treating agent is different from the example 4 in that the surfactant is sodium dodecyl sulfate and polyethylene glycol are mixed according to the mass ratio of 1:1, and the rest is the same as the example 4.
Example 9
The micro-fluidic chip surface treating agent is different from the example 4 in that the surfactant is sodium dodecyl sulfate, sodium laurylsulfate and polyethylene glycol which are mixed according to the mass ratio of 1:1, and the rest is the same as the example 4.
Example 10
A microfluidic chip surface treatment agent is different from example 4 in that an antioxidant is mixed with dibutyl hydroxy toluene and triphenyl phosphite according to a mass ratio of 1:1, and the rest is the same as example 4.
The microfluidic chip surface treatment agent obtained in examples 5 to 10 is applied to the hydrophilic modification treatment of the surface of the microfluidic chip polymer substrate, and the hydrophilic performance of the substrate surface after the hydrophilic modification treatment is detected, specifically:
Taking a micro-fluidic chip substrate made of PS material, performing oxygen plasma treatment for 15s, soaking the substrate to prepare a micro-fluidic chip surface treating agent after the plasma treatment, standing for 5min, blowing off residual liquid on the surface of the substrate, standing for 2h at normal temperature, drying and solidifying, and finishing the hydrophilic modification treatment of the surface of the micro-fluidic chip.
Ageing test: and (3) placing the substrate subjected to hydrophilic modification treatment in a baking oven at 45 ℃ for ageing test, baking at constant temperature for 30 days, taking out, and detecting the water drop angle and wettability of the surface of the substrate.
Example 11
The proportion and preparation method of the surface treating agent for the microfluidic chip in this embodiment are the same as those in embodiment 10, and the difference is that the process of applying the surface treating agent for the microfluidic chip to the hydrophilic modification treatment of the surface of the polymer substrate of the microfluidic chip is different, specifically: taking a micro-fluidic chip substrate made of PS material, directly soaking the prepared micro-fluidic chip surface treating agent, standing for 5min, blowing off residual liquid on the surface of the substrate, standing for 2h at normal temperature, drying and solidifying, and finishing the hydrophilic modification treatment of the surface of the micro-fluidic chip.
The results of the performance measurements for examples 5-11 are shown in Table 3 below.
Table 3: results of the measurements of examples 1 to 4 and comparative examples 1 to 6
Examples 5 to 10 further adjust the parameters of the raw material components of the surface treatment agent for the microfluidic chip, and it can be seen that the hydrophilic performance of the formed hydrophilic coating and the stability of the hydrophilic coating can be further improved by optimizing the proportion of the types of the raw materials.
In example 11, when the surface modification treatment of the polymer substrate is performed, the surface of the polymer is not subjected to the plasma treatment, and it can be seen that the initial hydrophilic performance of the formed hydrophilic coating is not significantly changed, but the stability of the hydrophilic coating is significantly reduced, probably because the reactive groups on the surface of the polymer substrate which is not subjected to the plasma treatment are less, the graft modification and adhesion of the hydrophilic coating on the surface of the polymer substrate are affected, the bonding property between the hydrophilic coating and the polymer substrate is deteriorated, and the stability of the hydrophilic coating is affected.
The above embodiments are not intended to limit the scope of the present application, so: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.

Claims (8)

1. The micro-fluidic chip surface treating agent is characterized by comprising the following raw materials in parts by weight:
1-10 parts of polyethylene glycol monomethyl ether;
0.1 to 0.5 part of coupling agent;
1-15 parts of 1, 2-propylene glycol;
1-15 parts of dimethylbenzene;
50-80 parts of deionized water;
1-25 parts of polyvinylpyrrolidone;
0.1 to 0.5 part of antioxidant;
1-5 parts of a surfactant;
the coupling agent is a silane coupling agent with hydrophilic functional groups.
2. The microfluidic chip surface treatment agent according to claim 1, wherein the surfactant comprises one or more of sodium dodecyl sulfate, polyethylene glycol, sodium lauryl sulfate, and sodium dioctyl sulfosuccinate.
3. The microfluidic chip surface treatment agent according to claim 1, wherein the antioxidant comprises one or more of dibutyl hydroxy toluene, phosphite, dilauryl thiodipropionate.
4. A microfluidic chip surface treatment agent according to claim 3, wherein the phosphite is triphenyl phosphite.
5. The microfluidic chip surface treatment agent according to claim 1, wherein the average molecular weight of the polyethylene glycol monomethyl ether is 500-2000.
6. The microfluidic chip surface treatment agent according to claim 1, wherein the polyvinylpyrrolidone has an average molecular weight of 10000-20000.
7. The method for preparing the microfluidic chip surface treating agent according to any one of claims 1 to 6, which is characterized by comprising the following steps:
S1, mixing polyethylene glycol monomethyl ether, 1, 2-propylene glycol and xylene to prepare a component A;
S2, dissolving polyvinylpyrrolidone in deionized water, then adding a silane coupling agent, an antioxidant and a surfactant, and mixing to obtain a component B;
And S3, mixing the component A and the component B to obtain the micro-fluidic chip surface treating agent.
8. The use of a microfluidic chip surface treatment agent according to any one of claims 1 to 6 in a surface modification treatment of a microfluidic chip substrate, characterized in that: and (3) carrying out plasma treatment on the surface of the polymer substrate of the microfluidic chip, and then dipping the surface subjected to the plasma treatment into a surface treating agent of the microfluidic chip, wherein the surface treating agent is solidified to form a hydrophilic coating.
CN202211635972.9A 2022-12-20 2022-12-20 Micro-fluidic chip surface treating agent, preparation method and application thereof Active CN116333551B (en)

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Publication number Priority date Publication date Assignee Title
JP2002302644A (en) * 2001-04-04 2002-10-18 Kansai Paint Co Ltd Aqueous coating composition
CN111253850A (en) * 2020-01-17 2020-06-09 重庆创芯生物科技有限公司 Medical hydrophilic coating composition and preparation method and application thereof
WO2020138155A1 (en) * 2018-12-28 2020-07-02 日本ペイント・サーフケミカルズ株式会社 Hydrophilizing agent, method for forming hydrophilic film, and hydrophilic film
CN112625534A (en) * 2020-12-16 2021-04-09 苏州凝智新材料发展有限公司 Precursor liquid of hydrophilic lubricating coating and application of precursor liquid in preparation of surface coating of medical instrument

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002302644A (en) * 2001-04-04 2002-10-18 Kansai Paint Co Ltd Aqueous coating composition
WO2020138155A1 (en) * 2018-12-28 2020-07-02 日本ペイント・サーフケミカルズ株式会社 Hydrophilizing agent, method for forming hydrophilic film, and hydrophilic film
CN111253850A (en) * 2020-01-17 2020-06-09 重庆创芯生物科技有限公司 Medical hydrophilic coating composition and preparation method and application thereof
CN112625534A (en) * 2020-12-16 2021-04-09 苏州凝智新材料发展有限公司 Precursor liquid of hydrophilic lubricating coating and application of precursor liquid in preparation of surface coating of medical instrument

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