CN109975471A - A kind of preparation method of the information pattern paper base sensor of detection of heavy metal ion - Google Patents

A kind of preparation method of the information pattern paper base sensor of detection of heavy metal ion Download PDF

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Publication number
CN109975471A
CN109975471A CN201910144146.6A CN201910144146A CN109975471A CN 109975471 A CN109975471 A CN 109975471A CN 201910144146 A CN201910144146 A CN 201910144146A CN 109975471 A CN109975471 A CN 109975471A
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detection
heavy metal
paper base
metal ion
information pattern
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曹榕
田君飞
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Hainan Medical College
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Hainan Medical College
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/90Plate chromatography, e.g. thin layer or paper chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/90Plate chromatography, e.g. thin layer or paper chromatography
    • G01N30/92Construction of the plate
    • G01N30/93Application of the sorbent layer

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention mainly relates to a kind of preparation methods of the information pattern paper base sensor of detection of heavy metal ion, this method provides a kind of at low cost, simple process and the constructing plans without constructing information pattern paper base sensor of the hydrophobic boundary applied to detection of heavy metal ion, inventive sensor detects reaction bonded by that will modify paper base and sedimentation type, and paper fiber network structure is made full use of to realize that the information patternization of detection of heavy metal ion result exports.Compared with traditional paper base transducer production method, the present invention can pattern detection of heavy metal ion reagent direct information, under conditions of not establishing hydrophobic barrier, complete the detection to heavy metal ion, realize the information patternization output of testing result.

Description

A kind of preparation method of the information pattern paper base sensor of detection of heavy metal ion
Technical field
The invention belongs to detection of heavy metal ion fields, and the substrate of paper base sensor is mainly patterned by set information It for the paper base without hydrophobic boundary, is reacted in conjunction with the fibrillar meshwork structure and sedimentation type detection of heavy metal ion of paper, realizes that paper base passes The testing result information patternization of sensor exports, and in particular to a kind of information pattern paper base sensor of detection of heavy metal ion Preparation method.
Background technique
Heavy metal element generally refers to the metallic element that density is greater than 5g/cm3, and all heavy metal elements are more than a certain concentration All it is harmful to the human body.With the popularization in city and the rapid development of industry, the heavy metal pollution problem in all kinds of environment is Increasingly severe.Not only toxicity is big for heavy metal, but also cannot degrade, easily be bioaccumulation in the environment, seriously threatens human security. Therefore, detection of heavy metal ion is significant.Currently, common heavy metal detection method includes atomic spectroscopy, mass spectral analysis Method, electrochemical methods, Neutron activation analysiss and UV-VIS spectrophotometry etc..There is time-consuming consumption mostly in these methods The disadvantages of power, expensive equipment and special messenger operate, continuous monitoring and in terms of be restricted.Therefore, explore quickly, Easy, low cost detection of heavy metal ion method has a very important significance.
Since Whitesides team, Harvard University in 2007 proposes " paper substrate micro-fluidic " concept (A.W.Martinez,S.T.Phillips,M.J.Butte,G.M.Whitesides,Patterned paper as a platform for inexpensive,low-volume,portable bioassays,Angew.Chem.Int.Ed., 2007,46,1318-1320), Novel paper based sensor chip has obtained extensive concern.Paper base sensor chip has cost It is cheap, easy to carry, easy to operate and analysis quickly etc. advantages, have good development prospect.
The paper base sensor chip provided in Chinese patent application CN201410177093.5, by paper base by hydrophobic Barrier and hydrophilic region building microfluidic channel carry out immunoassay.
The paper substrate micro-fluidic chip that Chinese patent application CN201410673498.8 is provided passes through with figuratum photosensitive marking Chapter pad introduces hydrophobic material preparation.
The paper substrate micro-fluidic chip provided in Chinese patent application CN201510047078.3, by using wax as hydrophobic material Material wire mark goes out hydrophilic round reaction tank array for DNA colorimetric detection.
The paper base sensor that Chinese patent application CN201610966066.5 is provided, by wax printer prepare hydrophobic wall with It obtains the hydrophilic working region of chromatographic paper and carries out fibrin ferment detection.
Therefore paper base sensor chip mainly relies on photoetching process, impact system, batik print process and silk-screen printing The methods of method hydrophobically modified paper fiber surface or closing paper fiber network porous structure, construct hydrophobic boundary on hydrophilic paper base, Hydrophobe contrast is formed, to realize the sample detection of hydrophilic region.Moreover, detection zone is mostly circle well form, itself can not Additional detections information is provided, user-friendliness is to be improved.
For above-mentioned challenge, information pattern paper base sensor such as text paper base sensor, bar code paper base sensor etc. It has been devised.Testing result is exported by text, coding form, and user is available multiple in addition to detectable substance concentration Information, including the detection method of detection reagent, use used and anti-counterfeiting information etc..Li et al. people passes through wax hydrophobically modified paper Corresponding detection of heavy metal ion reagent is limited in Cu, Ni, Cr alpha type hydrophilic region, detection of heavy metal ion by substrate As a result directly with element chemistry sign format presentation, help people easily interpret result (M.Li, R.Cao, A.Nilghaz, L.Guan,X.Zhang,W.Shen,"Periodic-table-style"paper device for monitoring heavy metals in water,Anal.Chem.,2015,87,2555-2559).Songjaroen et al. passes through Fuji-Xerox's wax spray Printer constructs hydrophobic barrier on paper base, and Blood grouping reagent is limited in bar code hydrophilic region, and blood group result is direct Presented with bar code form, the cooperation smart machines such as mobile phone can be realized high-volume automatic detection (T.Songjaroen, W.Laiwattanapaisal,Simultaneous forward and reverse ABO blood group typing using a paper-based device and barcode-like interpretation,Anal.Chim.ACTA, 2016,921,67-76)。
It is not difficult to find that there is the information pattern paper base sensor of very big application potential that the hydrophobic boundary of building is relied on substantially Information pattern hydrophilic channel is defined, preparation process needs to be further simplified to reduce cost, reduces equipment and rely on, thus favorably In large-scale production, promote the commercialization conversion of paper base sensor chip.
Summary of the invention
It is an object of the invention to propose a kind of preparation of the information pattern paper base sensor of detection of heavy metal ion Method.This method for the first time gets up modification paper base with sedimentation type detection of heavy metal ion reaction bonded, and the fiber that paper is utilized is empty Between network, and sedimentation type detection product is combined to be not easy the characteristic mobile with prepare liquid sample, with the help of no hydrophobic barrier, at Function completes the information patternization output of detection signal.The present invention does not need to establish hydrophobic barrier, is conducive to simplify paper base sensor The preparation flow of chip, flexible and convenient operation.
The technical scheme adopted by the invention is that: a kind of system of the information pattern paper base sensor of detection of heavy metal ion Preparation Method, comprising: be introduced directly into detection reagent in substrate and be allowed to information pattern, introduce in the detection reagent to test sample Product complete detection, which is characterized in that the substrate that set information patterns paper base sensor is the paper base without hydrophobic boundary, passes through paper Fibrillar meshwork structure and sedimentation type detection of heavy metal ion reaction, realize that the testing result information patternization of the sensor is defeated Out, construction comprises the following steps:
(1) cellulosic pulp board is dispersed by cellulose slurries using fiber card breaker.
(2) adsorbent for heavy metal, the quality of adsorbent for heavy metal and fiber pulp are added in cellulose slurries Than being greater than 250g/m for the grammes per square metre of 2:100, presetting paper base2It is less than 0.5mm with thickness, then manufactures paper with pulp on type paper sheet forming equipment Standard paper base with fibrillar meshwork structure;
(3) modification is modified to standard paper base, obtains modification paper base;
(4) it is obtained by mode of printing directly by detection of heavy metal ion reagent information patterned deposition on modification paper base To information pattern paper base sensor;
(5) heavy metal ion sample to be detected is applied on the detection of heavy metal ion reagent of information pattern, is precipitated Type reaction product is with the output of information pattern result, and character type pattern is directly read as a result, code-shaped pattern cooperates smart machine Close friend reads.
In the method and process that the invention patent provides, step (2) fibrillar meshwork structure is that the natural fiber of paper is arranged Column.
In the method and process that the invention patent provides, step (3) the paper base modification mode is that weight is added in fiber pulp Metal ion adsorbent, including chitosan and its derivative, polyacrylamide and its polymer-modified.
The invention patent provide method and process in, step (4) mode of printing be printing, air brushing, printing, writing, Spraying.
In the method and process that the invention patent provides, step (4) the detection of heavy metal ion reagent is not needed by dredging Water boundaries confinement.
In the method and process that the invention patent provides, step (4) the detection of heavy metal ion reagent is a sedimentation type huge sum of money Belong to ion detection reagent, including compound ligand, nanoparticle, nucleic acid.
A kind of preparation side of the information pattern paper base sensor of detection of heavy metal ion made from the preparation method Method.
The invention has the following advantages that
1. the hydrophilic region of information pattern is limited without hydrophobic boundary, paper base sensor chip preparation process is simple.
2. adsorbent for heavy metal is conducive to the enrichment of heavy metal ion, detection sensitivity is improved.
3. substrate used in traditional information pattern paper base sensor be chromatographic paper, modification paper base grammes per square metre of the present invention and Thickness is above chromatographic paper, and more prepare liquid samples can be carried in unit area, advantageously reduces detection limit.
Detailed description of the invention
Fig. 1 is the building schematic diagram of the information pattern paper base sensor of detection of heavy metal ion of the present invention;
Fig. 2 is iron ion testing result figure;
Fig. 3 is copper ion testing result figure.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, technical matters step, condition and material is embodied, to this hair Technical solution in bright embodiment is clearly and completely described, it is clear that described embodiment is only present invention a part Embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not paying wound Every other embodiment obtained under the premise of the property made labour, shall fall within the protection scope of the present invention.
Fig. 1 shows the information pattern paper base for not constructing hydrophobic barrier preparation and being used for detection of heavy metal ion of the invention The method of sensor.
Embodiment 1
Step 1, is added chitosan in fiber pulp, and the ratio of chitosan and fiber pulp is 1:100.It is poly- with shell is added to The fiber pulp of sugar is manufactured paper with pulp paper base, so that its grammes per square metre is reached 250g/m2, and with a thickness of 0.45mm.
Precipitation of iron ions type detection reagent is dissolved in ethyl alcohol to bathophenanthroline, makes its concentration 4mg/mL by step 2.Pass through The ethanol solution to bathophenanthroline is deposited on the modes directly paper bases obtained by step 1 such as writing, obtains " iron " and " iron " text It is patterned to bathophenanthroline reagent.
Step 3 introduces sample to be tested on the resulting information pattern iron ion paper base sensor of step 2.If to Contain ferrous ion in sample, red " iron " and " iron " information pattern will be presented on paper base sensor, such as Fig. 2 institute Show, directly informs in user's sample to be tested and contain iron ion.
Embodiment 2
Step 1, is added chitosan in fiber pulp, and the ratio of chitosan and fiber pulp is 1:100.It is poly- with shell is added to The fiber pulp of sugar is manufactured paper with pulp paper base, so that its grammes per square metre is reached 260g/m2, and with a thickness of 0.46mm.
Copper ion sedimentation type detection reagent bathocuproine is dissolved in chloroform, makes its concentration 50mg/mL by step 2.Pass through book It the chloroformic solution for depositing bathocuproine on the modes directly paper base obtained by step 1 such as writes, obtains " copper " and " copper " character pattern The bathocuproine reagent of change.
Step 3, is first added reducing agent hydroxylamine hydrochloride in sample to be tested, then to the resulting information pattern copper of step 2 from Sample to be tested is introduced on sub- paper base sensor.If containing copper ion in sample to be tested, yellow will be presented on paper base sensor " copper " and " copper " information pattern contains copper ion as shown in figure 3, directly informing in user's sample to be tested.
Every technical staff's notice: of the invention although the present invention is described according to above-mentioned specific embodiment Invention thought be not limited in the invention, any repacking with inventive concept will all be included in this patent protection of the patent right In range.

Claims (7)

1. a kind of preparation method of the information pattern paper base sensor of detection of heavy metal ion, comprising: directly draw in substrate Enter detection reagent and be allowed to information pattern, sample to be tested is introduced in the detection reagent and completes detection, which is characterized in that setting The substrate of information pattern paper base sensor is the paper base without hydrophobic boundary, passes through fibrillar meshwork structure and sedimentation type a huge sum of money for paper Belong to ion detection reaction, realize the testing result information patternization output of the sensor, construction comprises the following steps:
(1) cellulosic pulp board is dispersed by cellulose slurries using fiber card breaker.
(2) it is added adsorbent for heavy metal in cellulose slurries, the mass ratio of adsorbent for heavy metal and fiber pulp is The grammes per square metre of 2:100, presetting paper base are greater than 250g/m2It is less than 0.5mm with thickness, then manufacturing paper with pulp on type paper sheet forming equipment has The standard paper base of fibrillar meshwork structure;
(3) modification is modified to standard paper base, obtains modification paper base;
(4) letter is obtained directly by detection of heavy metal ion reagent information patterned deposition on modification paper base by mode of printing Breath patterning paper base sensor;
(5) heavy metal ion sample to be detected is applied on the detection of heavy metal ion reagent of information pattern, sedimentation type is anti- Answer product with the output of information pattern result, character type pattern is directly read as a result, code-shaped pattern cooperation smart machine is friendly It reads.
2. a kind of preparation method of the information pattern paper base sensor of detection of heavy metal ion according to claim 1, It is characterized in that, the natural fiber that step (2) fibrillar meshwork structure is paper arranges.
3. the preparation side of the information pattern paper base sensor of the ion detection of heavy metal species one by one according to claim 1 Method, which is characterized in that step (3) the paper base modification mode is that adsorbent for heavy metal, including shell are added in fiber pulp Poly- carbohydrates and their derivative, polyacrylamide and its polymer-modified.
4. a kind of preparation method of the information pattern paper base sensor of detection of heavy metal ion according to claim 1, It is characterized in that, step (4) mode of printing is printing, air brushing, printing, writing, spraying.
5. a kind of preparation method of the information pattern paper base sensor of detection of heavy metal ion according to claim 1, It is characterized in that, step (4) the detection of heavy metal ion reagent is not needed through hydrophobic boundary confinement.
6. a kind of preparation method of the information pattern paper base sensor of detection of heavy metal ion according to claim 1, It is characterized in that, step (4) the detection of heavy metal ion reagent is sedimentation type detection of heavy metal ion reagent, including compound Ligand, nanoparticle, nucleic acid.
7. a kind of information pattern paper of detection of heavy metal ion as made from preparation method described in any one of claims 1-6 Based sensor.
CN201910144146.6A 2019-02-27 2019-02-27 A kind of preparation method of the information pattern paper base sensor of detection of heavy metal ion Pending CN109975471A (en)

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Application publication date: 20190705