CN106807462A - A kind of acid etch modifies the preparation method of micro-fluidic paper chip - Google Patents

A kind of acid etch modifies the preparation method of micro-fluidic paper chip Download PDF

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CN106807462A
CN106807462A CN201710023453.XA CN201710023453A CN106807462A CN 106807462 A CN106807462 A CN 106807462A CN 201710023453 A CN201710023453 A CN 201710023453A CN 106807462 A CN106807462 A CN 106807462A
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acid
filter paper
paper
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CN106807462B (en
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马铭
何燕
陈波
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Hunan Normal University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • B01L3/502707Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2300/00Additional constructional details
    • B01L2300/12Specific details about materials
    • B01L2300/126Paper

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  • Health & Medical Sciences (AREA)
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  • Analytical Chemistry (AREA)
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Abstract

A kind of acid etch modifies the preparation method of micro-fluidic paper chip, comprises the following steps:(1)The preparation of super-hydrophobic filter paper;(2)The making of filter paper mask;(3)The local hydrophilic of super-hydrophobic filter paper is modified.Micro-fluidic paper chip prepared by the present invention, to water and the mixed solution with certain proportion water had be impregnated with effect, while acidproof and organic solvent, with good hydrophilic, hydrophobic property and stability higher, can be repeated several times and use, it is easy to accomplish large-scale industrial production, be particularly well-suited to the fields such as relevant clinical analysis, food safety and controlling and environmental monitoring, paper after use can be processed by the mode such as recovery or burning, and environmental pollution is small.

Description

A kind of acid etch modifies the preparation method of micro-fluidic paper chip
Technical field
The present invention relates to new material technology field, specifically a kind of acid etch modifies the preparation side of micro-fluidic paper chip Method.
Background technology
Paper chip(Microfluidic Paper-Based Analytical Devices)It is emerging development in recent years Microflow control technique on paper, because its have it is simple and quick, with low cost, liquid stream, analysis system miniaturization, detection are driven without external force The low reason for turning into traditional analysis of the replacement with silicon, glass and high polymer etc. as substrate the advantages of few with sample consumption of background Think object.Whitesides seminars proposed the concept based on micro-fluidic paper chip as chemical analysis device in 2007 first Make paper chip gradually by scientific research person cognition, its unique aspect be patterned by using hydrophobic agents restriction it is hydrophilic Property flow channel, sample from entrance is directed to defined location and a series of analysis detections are realized, it is this it is initiative envision make It has obtained relatively broad application and development at aspects such as clinical medicine detection, environmental analysis and food analyses.Current document Main use wax printing, inkjet printing, the photoetching of report, the mode such as laser ablation or corona treatment build close and distant aqua region system Standby paper chip, this kind of method shortcoming is the passage viscosity for building high, reappearance and stability is not good enough and pattern form is limited, together When need the O&M of instrument costly and professional, largely increased cost of manufacture, therefore can not It is applied to all patterns.Advanced technology has been developed at present, preferably having evaded needs specific apparatus and reagent and plasma The problems such as paper that the seepage and ultraviolet lighting of body gas cause turns to be yellow, but prepare micro-fluidic paper chip for acid etching processes and not yet have Report.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided a kind of method is relatively simple, cost compared with Low, environmentally friendly acid etch modifies the preparation method of micro-fluidic paper chip, with realize relevant clinical analysis, food safety and controlling with And the application in the field such as environmental monitoring.
The technical scheme that the present invention solves the use of its technical problem is that a kind of acid etch modifies the preparation of micro-fluidic paper chip Method, the base material filter paper for being used possesses the fibre structure of hydrophilicity, and it is modified with silylating reagent, with There is the filter paper of hydrophobic performance to surface, then allow the modified super-hydrophobic filter paper to carry out local acid etch modification, by hydrophobic paper table The long chain alkane cut-out in face, makes the hydrophilic radicals such as the formation of paper surface-OH ,-COOH ,-CO ,-COO, can just be obtained and possess certain figure The micro-fluidic paper chip of parent/hydrophobic channel of case.
Specifically include following steps:
(1)The preparation of super-hydrophobic filter paper:The super-hydrophobic filter paper that contact angle is 140 ~ 150 ° is prepared with silanization paper modification technique;
The preparation of the super-hydrophobic filter paper, the silanization paper modification technique for being used, referring to prior art Method for fabrication of paper-based microfluidic devices by alkylsilane self- assembling and UV/O3-patterning. Qiaohong He et al. Anal. Chem., 2013, 85 (3), pp 1327–1331;
(2)The making of filter paper mask:The channel configurations of different pattern are designed by mapping software on filter paper, by adding by hand Filter paper mask is obtained final product after work;
Paper matrix procedure of processing in 57-61 pages;Concrete operations according to《A kind of paper chip Simple Machining and Phen- Application in iron complex composition measuring》, Cai Longfei etc., Hanshan Normal College's journal, the 6th phase in 2014
(3)The local hydrophilic of super-hydrophobic filter paper is modified:By step(2)The filter paper mask made is soaked in acid etch agent, leaching Profit is completely rear to take out, and is covered in step(1)Clamped on the super-hydrophobic filter paper for preparing and with sheet glass, be placed in 60~90 DEG C of temperature Lower 15~25 min, etch acid etch agent and are impregnated with super-hydrophobic filter paper, after taking out cooling, are rinsed with ethanol, distilled water successively, room The lower natural air drying of temperature, obtains final product micro-fluidic paper chip.
In each step, filter paper used can be in quantitative analysis filter paper, qualitative analysis filter paper, chromatography qualitative analysis filter paper It is a kind of.
Described acid etch agent is preferably the acid solution of 0.5~1 mol/L(That is the solution of PH < 7), preferably hydrochloric acid, sulphur In acid, nitric acid, phosphoric acid, sulfurous acid, hydrofluoric acid, carbonic acid, hydrosulphuric acid, boric acid, oxalic acid, sulfinic acid, thionothiolic acid, acetic acid etc. at least It is a kind of.
It is to modify part of the method to super-hydrophobic filter paper by acid etch that the acid etching processes of the present invention modify micro-fluidic paper chip Hydrophilic modifying is carried out, parent/hydrophobic network channel is built in modifying process.
Micro-fluidic paper chip prepared by the present invention, the fiber of its otherwise smooth is recovered on filter paper fibre surface again after hydrophilic modifying Structure, shows strongly hydrophilic, shows with reference to its Static water contact angles sign, infrared and scanning electron microscope analysis result, alkane long Hydrocarbon is destroyed, and hydrophobic region switchs to hydrophily, and with porous and super hydrophilic characteristic, maximum Static water contact angles are 0 °;It is right What water and the mixed solution with certain proportion water had had is impregnated with effect, while acidproof and organic solvent, with good parent, Hydrophobicity and stability higher, can be repeated several times and use, it is easy to accomplish large-scale industrial production, be particularly well-suited to relevant clinic The fields such as analysis, food safety and controlling and environmental monitoring, the paper after use can be entered by the mode such as recovery or burning Row treatment, environmental pollution is small.
Brief description of the drawings
Fig. 1 is the flow chart that acid etching processes modify micro-fluidic paper chip;
Fig. 2 is the performance test figure in micro-fluidic paper chip different zones;A is former filter paper;B is non-etch areas;C is acid etch Region;
Fig. 3 is micro-fluidic paper chip stability test result figure, and a is the change of hydrophobic region contact angle in figure;B connects for etch areas Feeler changes.
Specific embodiment
Below by way of specific embodiment, the present invention will be further described.
Embodiment 1:
(1)The preparation of super-hydrophobic filter paper:It is super thin for 140 ° ~ 150 ° contact angle to be prepared by existing silanization paper modification technique Water filter paper;
Filter paper, the min of ultrasonic reaction 5, tweezers are infiltrated with octadecyl trichlorosilane alkane-hexane solution that volume fraction is 0.1% Rinsed three times with n-hexane, ethanol, distilled water successively after taking-up, natural air drying, super-hydrophobic filter is after thoroughly drying at room temperature Paper;
(2)The making of filter paper mask:The logical of different pattern is designed by mapping software on common chromatography qualitative analysis filter paper Road configuration, by obtaining final product filter paper mask after processing by hand;
(3)The local hydrophilic of super-hydrophobic filter paper is modified:By step(2)The filter paper mask made is soaked in the hydrochloric acid of 1 mol/L In solution, taken out after infiltration completely, be covered in step(1)Clamped on the super-hydrophobic filter paper for preparing and with sheet glass, be placed in 80 DEG C At a temperature of 20 min, etch hydrochloric acid solution and be impregnated with super-hydrophobic filter paper, after taking out cooling, rinsed with ethanol, distilled water successively, Natural air drying, obtains final product micro-fluidic paper chip at room temperature.Operating process is as shown in Figure 1.
Micro-fluidic paper chip performance test obtained by the present embodiment:Pigment is added in water as color mark, respectively not Non- etch areas and etch areas are added dropwise 2 microlitres of pigment aqueous solutions on the filter paper of modified, the filter paper of modified, modified mistake The non-etch areas Static water contact angles of filter paper are in the range of 140 ° ~ 150 °, and filter paper etch areas of modified and unmodified Filter paper on pigment aqueous solution all absorbed by filter paper, illustrate that super-hydrophobic filter paper recovers its by the hydrophilic region after partial modification former Some strongly hydrophilics.Result is as shown in Figure 2.
Micro-fluidic paper chip stability test:Paper chip after acid etch is positioned under the conditions of conventional chambers, is placed six months, The non-etch areas of paper chip and etch areas are determined when 5 days, 10 days, 30 days, 90 days, 180 days in different time Static water contact angles during section, measurement result are as shown in figure 3, micro-fluidic paper chip prepared by explanation acid etch modification possesses well Stability.The detection method of use is pressed《People's Republic of China's oil and gas industry standard<Surface and interfacial tension are tested Method>(SY/T5370-1999)》Operation.
Embodiment 2:
(1)The preparation of super-hydrophobic filter paper:It is super thin for 140 ° ~ 150 ° contact angle to be prepared by existing silanization paper modification technique Water filter paper;
Filter paper, the min of ultrasonic reaction 5, tweezers are infiltrated with octadecyl trichlorosilane alkane-hexane solution that volume fraction is 0.1% Rinsed three times with n-hexane, ethanol, distilled water successively after taking-up, natural air drying, super-hydrophobic filter is after thoroughly drying at room temperature Paper;
(2)The making of filter paper mask:The logical of different pattern is designed by mapping software on common chromatography qualitative analysis filter paper Road configuration, by obtaining final product filter paper mask after processing by hand;
(3)The local hydrophilic of super-hydrophobic filter paper is modified:By step(2)The filter paper mask made is soaked in the carbon of 0.5 mol/L In acid solution, taken out after infiltration completely, be covered in step(1)Clamped on the super-hydrophobic filter paper for preparing and with sheet glass, be placed in 60 25 min at a temperature of DEG C, etches carbon acid solution and is impregnated with super-hydrophobic filter paper, after taking out cooling, is floated with ethanol, distilled water successively Wash, at room temperature natural air drying, obtain final product micro-fluidic paper chip.
Micro-fluidic paper chip performance test obtained by the present embodiment:Pigment is added in water as color mark, respectively not Non- etch areas and etch areas are added dropwise 2 microlitres of pigment aqueous solutions on the filter paper of modified, the filter paper of modified, modified mistake The non-etch areas Static water contact angles of filter paper are in the range of 140 ° ~ 150 °, and filter paper etch areas of modified and unmodified Filter paper on pigment aqueous solution all absorbed by filter paper, illustrate that super-hydrophobic filter paper recovers its by the hydrophilic region after partial modification former Some strongly hydrophilics.
Micro-fluidic paper chip stability test:Paper chip after acid etch is positioned under the conditions of conventional chambers, is placed six months, The non-etch areas of paper chip and etch areas are determined when 5 days, 10 days, 30 days, 90 days, 180 days in different time Static water contact angles during section, non-etch areas are still hydrophobicity, and water contact angle is 140 ° ~ 150 °, and the region after etching is static Water contact angle is 0 °, illustrates that micro-fluidic paper chip prepared by acid etch modification possesses good stability.The detection side of use Method is pressed《People's Republic of China's oil and gas industry standard<Surface and interfacial tension method of testing>(SY/T5370-1999)》 Operation.
Embodiment 3:
(1)The preparation of super-hydrophobic filter paper:It is super thin for 140 ° ~ 150 ° contact angle to be prepared by existing silanization paper modification technique Water filter paper;
Filter paper, the min of ultrasonic reaction 5, tweezers are infiltrated with octadecyl trichlorosilane alkane-hexane solution that volume fraction is 0.1% Rinsed three times with n-hexane, ethanol, distilled water successively after taking-up, natural air drying, super-hydrophobic filter is after thoroughly drying at room temperature Paper;
(2)The making of filter paper mask:The logical of different pattern is designed by mapping software on common chromatography qualitative analysis filter paper Road configuration, by obtaining final product filter paper mask after processing by hand;
(3)The local hydrophilic of super-hydrophobic filter paper is modified:By step(2)The filter paper mask made is soaked in the grass of 0.8 mol/L In acid solution, taken out after infiltration completely, be covered in step(1)Clamped on the super-hydrophobic filter paper for preparing and with sheet glass, be placed in 90 15 min at a temperature of DEG C, etches oxalic acid solution and is impregnated with super-hydrophobic filter paper, after taking out cooling, is floated with ethanol, distilled water successively Wash, at room temperature natural air drying, obtain final product micro-fluidic paper chip.
Micro-fluidic paper chip performance test obtained by the present embodiment:Pigment is added in water as color mark, respectively not Non- etch areas and etch areas are added dropwise 2 microlitres of pigment aqueous solutions on the filter paper of modified, the filter paper of modified, modified mistake The non-etch areas Static water contact angles of filter paper are in the range of 140 ° ~ 150 °, and filter paper etch areas of modified and unmodified Filter paper on pigment aqueous solution all absorbed by filter paper, illustrate that super-hydrophobic filter paper recovers its by the hydrophilic region after partial modification former Some strongly hydrophilics.
Micro-fluidic paper chip stability test:Paper chip after acid etch is positioned under the conditions of conventional chambers, is placed six months, The non-etch areas of paper chip and etch areas are determined when 5 days, 10 days, 30 days, 90 days, 180 days in different time Static water contact angles during section, non-etch areas are still hydrophobicity, and water contact angle is 140 ° ~ 150 °, and the region after etching is static Water contact angle is 0 °, illustrates that micro-fluidic paper chip prepared by acid etch modification possesses good stability.The detection side of use Method is pressed《People's Republic of China's oil and gas industry standard<Surface and interfacial tension method of testing>(SY/T5370-1999)》 Operation.

Claims (4)

1. a kind of acid etch modifies the preparation method of micro-fluidic paper chip, it is characterised in that comprise the following steps:
(1)The preparation of super-hydrophobic filter paper:The super-hydrophobic filter paper that contact angle is 140 ~ 150 ° is prepared with silanization paper modification technique;
(2)The making of filter paper mask:The channel configurations of different pattern are designed by mapping software on filter paper, by adding by hand Filter paper mask is obtained final product after work;
(3)The local hydrophilic of super-hydrophobic filter paper is modified:By step(2)The filter paper mask made is soaked in acid etch agent, leaching Profit is completely rear to take out, and is covered in step(1)Clamped on the super-hydrophobic filter paper for preparing and with sheet glass, be placed in 60~90 DEG C of temperature Lower 15~25 min, etch acid etch agent and are impregnated with super-hydrophobic filter paper, after taking out cooling, are rinsed with ethanol, distilled water successively, room The lower natural air drying of temperature, obtains final product micro-fluidic paper chip.
2. acid etch according to claim 1 modifies the preparation method of micro-fluidic paper chip, it is characterised in that each step In, filter paper used is quantitative analysis filter paper, qualitative analysis filter paper, the one kind chromatographed in qualitative analysis filter paper.
3. acid etch according to claim 1 and 2 modifies the preparation method of micro-fluidic paper chip, it is characterised in that step (3)In, described acid etch agent is the acid solution of 0.5~1 mol/L.
4. acid etch according to claim 1 and 2 modifies the preparation method of micro-fluidic paper chip, it is characterised in that described Acid etch agent be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfurous acid, hydrofluoric acid, carbonic acid, hydrosulphuric acid, boric acid, oxalic acid, sulfinic acid, sulphur At least one in carboxylic acid, acetic acid.
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CN108745427A (en) * 2018-05-18 2018-11-06 陕西科技大学 The preparation method of hydrophily runner in a kind of paper base material
CN109046480A (en) * 2018-08-09 2018-12-21 广西大学 Controllable micro-fluidic paper chip of fluid transport and preparation method thereof and application method
CN111359683A (en) * 2019-12-03 2020-07-03 北京信息科技大学 Gradient micro-fluid channel for unpowered liquid drop transportation and preparation method thereof
CN112916065A (en) * 2021-05-11 2021-06-08 湖南师范大学 Microfluidic paper chip, preparation method thereof, microfluidic paper chip detection system and application
CN113856779A (en) * 2021-11-08 2021-12-31 哈尔滨工业大学 Method for manufacturing planar microfluidic chip based on ink-jet printing
CN114570445A (en) * 2022-03-03 2022-06-03 广州大学 Microfluidic chip for synthesizing manganese dioxide nanoflowers and application method thereof

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CN104677896A (en) * 2015-01-31 2015-06-03 太原理工大学 Preparation and application of paper-based microfluidic chip for colorimetric analysis
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CN108745427A (en) * 2018-05-18 2018-11-06 陕西科技大学 The preparation method of hydrophily runner in a kind of paper base material
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CN109046480B (en) * 2018-08-09 2021-10-08 广西大学 Microfluidic paper chip with controllable fluid transportation and preparation method and use method thereof
CN111359683A (en) * 2019-12-03 2020-07-03 北京信息科技大学 Gradient micro-fluid channel for unpowered liquid drop transportation and preparation method thereof
CN112916065A (en) * 2021-05-11 2021-06-08 湖南师范大学 Microfluidic paper chip, preparation method thereof, microfluidic paper chip detection system and application
CN113856779A (en) * 2021-11-08 2021-12-31 哈尔滨工业大学 Method for manufacturing planar microfluidic chip based on ink-jet printing
CN113856779B (en) * 2021-11-08 2022-10-14 哈尔滨工业大学 Method for manufacturing planar microfluidic chip based on ink-jet printing
CN114570445A (en) * 2022-03-03 2022-06-03 广州大学 Microfluidic chip for synthesizing manganese dioxide nanoflowers and application method thereof

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