CN101886283A - A preparation method and application of magnetically encoded nanowires - Google Patents

A preparation method and application of magnetically encoded nanowires Download PDF

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CN101886283A
CN101886283A CN 201010208253 CN201010208253A CN101886283A CN 101886283 A CN101886283 A CN 101886283A CN 201010208253 CN201010208253 CN 201010208253 CN 201010208253 A CN201010208253 A CN 201010208253A CN 101886283 A CN101886283 A CN 101886283A
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magnetic
magnetically encoded
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nanowires
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潘敏
杨昊
惠国华
吴莉莉
陈裕泉
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Zhejiang University ZJU
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Abstract

一种磁性编码纳米线的制备方法及其用途,通过制备时进行磁性编码,可作为标记物用于多元同步免疫检测,其特征在于:通过电化学沉积技术,在阳极氧化铝模板的纳米盲孔内,分层分别进行磁性/非磁性材料的电化学沉积,以不同的沉积顺序作为不同的编码,例如:磁性,磁性/非磁性,非磁性/磁性/非磁性,通过功能基团表面修饰,将磁性编码纳米线与不同待测抗原的相应抗体进行交联制备生物探针,以磁性检测技术为基础进行解码,实现多元免疫检测。与现有技术相比,本发明的优点是:此磁性编码纳米线作为标记物用于多元同步免疫检测,结构简单,成本较低,可用标记物较多,不同编码标记物的分析条件一致。

Figure 201010208253

A preparation method and application of a magnetically encoded nanowire, which can be used as a marker for multivariate simultaneous immunodetection through magnetic encoding during preparation, and is characterized in that: through electrochemical deposition technology, the nanometer blind hole of the anodized aluminum template Electrochemical deposition of magnetic/non-magnetic materials in layers, respectively, with different deposition sequences as different codes, such as: magnetic, magnetic/non-magnetic, non-magnetic/magnetic/non-magnetic, surface modification by functional groups, The magnetically encoded nanowires are cross-linked with the corresponding antibodies of different antigens to be tested to prepare biological probes, which are decoded based on magnetic detection technology to realize multiple immunoassays. Compared with the prior art, the present invention has the advantages that: the magnetically encoded nanowire is used as a marker for multiple simultaneous immunoassays, and has a simple structure, low cost, more available markers, and consistent analysis conditions for different encoded markers.

Figure 201010208253

Description

A kind of preparation method and its usage of magnetically encoded nano-wire
Technical field
The present invention relates to the marker that a kind of immunodetection is used, the preparation method of magnetically encoded nano-wire and application thereof.
Technical background
Detect the polycomponent in the biased sample in the immunoassay, adopt parallel single component analytical method usually, this method need be carried out a plurality of testing processes synchronously, the test set complexity, and reagent consumption is many, and workload is excessive.How in single flow process, to realize the synchronous detection of a plurality of indexs, become the research focus of immunoassay in recent years.
The polynary synchronous immunodetection that sees report at present mainly is divided into: spatial discrimination pattern and multi-tracer pattern.The spatial discrimination pattern need adopt comparatively complicated array apparatus, and difficulty of processing is bigger, and the technique for fixing of immunoreagent is had relatively high expectations, and requires each array point uniformity, and can not be inter-adhesive; Especially when using electrochemical mode to detect, the requirement of counter electrode array is more strict, and the distance that needs to keep enough is to avoid cross reaction; This method is also higher to the requirement of detector, needs to adopt expensive array detector, therefore, is subjected to certain restriction on use range.
In the multi-tracer pattern, when marking thing with enzyme, different markers has distinct optimum analysis condition usually, in same analysis system, unite simply and use multiple marker, can only in the optimum analysis condition of different markers, select a tendency towards compromise condition, caused the reduction of analytical effect thus, marker is many more, selects difficulty big more; And in such as optics or Electrochemical Detection mode, the resolution efficient of different markers is often limited, and the signal overlap problem is sometimes very outstanding, and therefore, the research temperature of this method greatly reduces in recent years.
Summary of the invention
The technology of preparing that the purpose of this invention is to provide a kind of magnetically encoded nano-wire, and provide a kind of brand-new marker for polynary synchronous immunodetection with this nano wire.
Magnetically encoded nano-wire of the present invention adopts electrochemical deposition technique, and in the nanometer blind hole on anodic oxidation aluminium formwork, the electrochemical deposition of magnetic/nonmagnetic substance is carried out in layering respectively.
Described magneticsubstance is a kind of in iron, the nickel; Described nonmagnetic substance is the copper metal.
The nanometer blind hole of described anodic oxidation aluminium formwork is evenly distributed, and is parallel to each other and perpendicular to template surface, and the regular hexagon that is high-sequential is arranged.Nanometer blind hole mean diameter is 50nm, and nanometer blind hole density is 10 6Individual/mm 2, the nanometer blind hole road degree of depth is 10 μ m.
Described magnetically encoded nano-wire diameter is 50nm, and the degree of depth is 750nm.
A kind of preparation method of magnetically encoded nano-wire is characterized in that adopting following steps:
A) preparation anodic oxidation aluminium formwork: aluminium foil is cut into suitable dimension, is placed in the 0.3M oxalic acid solution ice bath, voltage 40V anodic oxidation 1 hour through electrochemical etching, cleaning; Then the template after the oxidation was soaked 1 hour in phosphoric acid and chromic acid mixture, repeat the identical oxidation step in front again; Carry out the ladder step-down at last and handle, obtain porous anodic alumina template, the mol ratio of phosphoric acid and chromic acid is 3: 1 in the mixed solution;
B) preparation electrolytic solution: prepare electrolytic iron liquid respectively, nickel electrolyte, copper electrolyte is standby, wherein:
Electrolytic iron liquid is by FeSO 47H 2O 100g/L, (NH 4) 2SO 415g/L, MgSO 430g/L, xitix 1g/L, glycerol 2mg/L mixes, adjust pH to 3;
Nickel electrolyte is by NiSO 46H 2O 60g/L, boric acid 30g/L, MgSO 430g/L, Na 2SO 45g/L mixes adjust pH to 3;
Copper electrolyte is by CuSO 420g/L, MgSO 420g/L, C 6H 8O 7H 2O 15g/L mixes adjust pH to 3;
C) preparation magnetically encoded nano-wire: respectively with anodic oxidation aluminium formwork and stereotype as anode and negative electrode, adopt the 50Hz alternating-current, in corresponding electrolytic solution, carry out electrochemical deposition according to the metallic substance of making nano wire, remove the template aluminum substrate that is obtained behind the electrochemical deposition with saturated tin chloride then, template is immersed dissolving removal in the sodium hydroxide solution, with deionized water clean repeatedly, magnetic support is settled down to pH value of solution=7.0, after supersound process, obtain homodisperse relevant nanometer line solution.
Described ladder step-down was behind secondary oxidation, reduced once oxidation voltage every 10 minutes, and each step-down 2V is till voltage drops to 10V, with the blocking layer of attenuate and homogenizing anodic oxidation aluminium formwork; The metallic substance that is used to make nano wire is selected magneticsubstance iron or nickel for use, and nonmagnetic substance copper.
A kind of purposes of magnetically encoded nano-wire is characterized in that: the multi-tracer that this magnetically encoded nano-wire is used as immunodetection.
Compare with prior art, advantage of the present invention is: this magnetically encoded nano-wire thing that serves as a mark is used for polynary synchronous immunodetection, and is simple in structure, cost is lower, the serviceable indicia thing is more, the analysis condition unanimity of different coding marker.
Description of drawings
Fig. 1 is porous anodic alumina template FSEM figure
Fig. 2 is the TEM shape appearance figure of Fe nano wire
Embodiment
Embodiment 1:
The preparation anodic oxidation aluminium formwork
Aluminium foil is cut into suitable dimension, is placed in the 0.3M oxalic acid solution ice bath, voltage 40V anodic oxidation 1 hour through electrochemical etching, cleaning; Then the template after the oxidation was soaked 1 hour in phosphoric acid and chromic acid mixing solutions (mol ratio 10: 3), repeat the identical oxidation step in front again; Carry out the ladder step-down at last and handle, can obtain porous anodic alumina template.
Preparation electrolytic solution
Electrolytic iron liquid is by FeSO 47H 2O 100g/L, (NH 4) 2SO 415g/L, MgSO 430g/L, xitix 1g/L, glycerol 2mg/L mixes, adjust pH to 3;
Copper electrolyte is by CuSO 420g/L, MgSO 420g/L, C 6H 8O 7H 2O 15g/L mixes adjust pH to 3.
The preparation Fe nanowire
Respectively with anodic oxidation aluminium formwork and stereotype as two electrodes, adopt the 50Hz alternating-current, in electrolytic iron liquid, carry out electrochemical deposition, deposition voltage 15V, depositing time 5min makes Fe nanowire.
Preparation iron/copper nano-wire
Respectively with anodic oxidation aluminium formwork and stereotype as two electrodes, adopt the 50Hz alternating-current, at first in electrolytic iron liquid, carry out electrochemical deposition, deposition voltage 15V, depositing time 4min; Then, ultrasonic washing was carried out supersound process 5 minutes in copper electrolyte, carry out electrochemical deposition in copper electrolyte, deposition voltage 15V, and depositing time 1min obtains iron/copper nano-wire.
Preparation copper/iron/copper nano-wire
Respectively with anodic oxidation aluminium formwork and stereotype as two electrodes, adopt the 50Hz alternating-current, at first in copper electrolyte, carry out electrochemical deposition, deposition voltage 15V, depositing time 0.5min; Then, ultrasonic washing, supersound process is 5 minutes in electrolytic iron liquid, carries out electrochemical deposition in electrolytic iron liquid, deposition voltage 15V, depositing time 4min; After the ultrasonic washing, supersound process is 5 minutes in copper electrolyte, carries out electrochemical deposition in copper electrolyte, deposition voltage 15V, and depositing time 0.5min obtains copper/iron/copper nano-wire.
Remove the template aluminum substrate that is obtained after the different galvanic deposit with saturated tin chloride respectively, template immersed in the 1mol/L sodium hydroxide solution remove, with deionized water clean repeatedly, magnetic support is settled down to pH value of solution=7.0, obtain homodisperse iron, iron/copper, copper/iron/copper nano-wire solution through supersound process.
Embodiment 2:
The preparation anodic oxidation aluminium formwork
Aluminium foil is cut into suitable dimension, is placed in the 0.3M oxalic acid solution ice bath, voltage 40V anodic oxidation 1 hour through electrochemical etching, cleaning; Then the template after the oxidation was soaked 1 hour in phosphoric acid and chromic acid mixing solutions (mol ratio 10: 3), repeat the identical oxidation step in front again; Carry out the ladder step-down at last and handle, can obtain required anodic oxidation aluminium formwork.
Preparation electrolytic solution
Nickel electrolyte is by NiSO 46H 2O 60g/L, boric acid 30g/L, MgSO 430g/L, Na 2SO 45g/L mixes adjust pH to 3;
Copper electrolyte is by CuSO 420g/L, MgSO 420g/L, C 6H 8O 7H 2O 15g/L mixes adjust pH to 3.
Preparation nickel nano wire
Respectively with anodic oxidation aluminium formwork and stereotype as two electrodes, adopt the 50Hz alternating-current, in nickel electrolyte, carry out electrochemical deposition, deposition voltage 15V, depositing time 5min obtains the nickel nano wire.
Preparation nickel/copper nano-wire
Respectively with anodic oxidation aluminium formwork and stereotype as two electrodes, adopt the 50Hz alternating-current, at first in nickel electrolyte, carry out electrochemical deposition, deposition voltage 15V, depositing time 4min; Then, ultrasonic washing was carried out supersound process 5 minutes in copper electrolyte, carry out electrochemical deposition in copper electrolyte, deposition voltage 15V, and depositing time 1min obtains nickel/copper nano-wire.
Preparation copper/nickel/copper nano-wire
Respectively with anodic oxidation aluminium formwork and stereotype as two electrodes, adopt the 50Hz alternating-current, at first in copper electrolyte, carry out electrochemical deposition, deposition voltage 15V, depositing time 0.5min; Then, ultrasonic washing, supersound process is 5 minutes in nickel electrolyte, carries out electrochemical deposition in nickel electrolyte, deposition voltage 15V, depositing time 4min; At last, ultrasonic washing, supersound process is 5 minutes in copper electrolyte, carries out electrochemical deposition in copper electrolyte, deposition voltage 15V, depositing time 0.5min obtains copper/nickel/copper nano-wire.
Remove the template aluminum substrate that is obtained after the different galvanic deposit with saturated tin chloride respectively, template immersed in the 1mol/L sodium hydroxide solution remove, with deionized water clean repeatedly, magnetic support is settled down to pH value of solution=7.0, obtain homodisperse nickel, nickel/copper, copper/nickel/copper nano-wire solution through supersound process.

Claims (4)

1.一种磁性编码纳米线的制备方法,其特征在于采用以下步骤:1. A preparation method for magnetically encoded nanowires, characterized in that the following steps are adopted: A)制备阳极氧化铝模板:将铝箔裁剪成合适尺寸,经电化学抛光、清洗后置于0.3M草酸溶液中,冰浴,电压40V阳极氧化1小时;然后把氧化后的模板在磷酸和铬酸混合液中浸泡1小时,再重复前面相同的氧化步骤;最后进行阶梯降压处理,获得多孔阳极氧化铝模板,混合液中磷酸和铬酸的摩尔比为3∶1;A) Preparation of anodized aluminum template: Cut the aluminum foil into a suitable size, place it in 0.3M oxalic acid solution after electrochemical polishing and cleaning, put it in an ice bath, and anodize it at 40V for 1 hour; then put the oxidized template in phosphoric acid and chromium Immerse in the acid mixture for 1 hour, and then repeat the same oxidation steps above; finally, step-down treatment is carried out to obtain a porous anodized aluminum template, and the molar ratio of phosphoric acid and chromic acid in the mixture is 3:1; B)配制电解液:分别配制铁电解液,镍电解液,铜电解液备用,其中:B) Preparation of electrolyte: respectively prepare iron electrolyte, nickel electrolyte, and copper electrolyte for subsequent use, wherein: 铁电解液由FeSO4·7H2O 100g/L,(NH4)2SO4 15g/L,MgSO4 30g/L,抗坏血酸1g/L,丙三醇2mg/L混合而成,调pH值至3;The iron electrolyte is prepared by mixing FeSO 4 7H 2 O 100g/L, (NH 4 ) 2 SO 4 15g/L, MgSO 4 30g/L, ascorbic acid 1g/L, and glycerol 2mg/L. Adjust the pH value to 3; 镍电解液由NiSO4·6H2O 60g/L,硼酸30g/L,MgSO4 30g/L,Na2SO45g/L,混合而成,调pH值至3;The nickel electrolyte is mixed with NiSO 4 6H 2 O 60g/L, boric acid 30g/L, MgSO 4 30g/L, Na 2 SO 4 5g/L, and adjust the pH value to 3; 铜电解液由CuSO4 20g/L,MgSO4 20g/L,C6H8O7·H2O 15g/L混合而成,调pH值至3;Copper electrolyte is made by mixing CuSO 4 20g/L, MgSO 4 20g/L, C 6 H 8 O 7 ·H 2 O 15g/L, adjust the pH value to 3; C)制备磁性编码纳米线:分别以阳极氧化铝模板和铅板作为阳极和阴极,采用50Hz交流电,根据制作纳米线的金属材料在相应的电解液中进行电化学沉积,然后用饱和氯化锡去除电化学沉积后所获得的模板铝基体,将模板浸入氢氧化钠溶液中溶解去除,用去离子水反复清洗、磁座沉降至溶液pH=7.0,经超声处理后得到均匀分散的相应纳米线溶液。C) Preparation of magnetically encoded nanowires: use anodized aluminum template and lead plate as anode and cathode respectively, use 50Hz alternating current, perform electrochemical deposition in the corresponding electrolyte according to the metal material for making nanowires, and then use saturated tin chloride Remove the template aluminum matrix obtained after electrochemical deposition, dissolve and remove the template by immersing it in sodium hydroxide solution, wash it repeatedly with deionized water, and settle the magnetic base to the solution pH=7.0, and obtain uniformly dispersed corresponding nanowires after ultrasonic treatment solution. 2.根据权利要求1所述的磁性编码纳米线的制备方法,其特征在于:阶梯降压是在二次氧化后,每隔10分钟降低一次氧化电压,每次降压2V,直到电压降到10V为止,以减薄和均匀化阳极氧化铝模板的阻挡层。2. The preparation method of magnetically encoded nanowires according to claim 1, characterized in that: the step-down step is to reduce the oxidation voltage once every 10 minutes after the secondary oxidation, and step down the voltage by 2V each time until the voltage drops to 10V to thin and homogenize the barrier layer of the anodized aluminum template. 3.根据权利要求1所述的磁性编码纳米线的制备方法,其特征在于:用于制作纳米线的金属材料选用磁性材料铁或者镍,以及非磁性材料铜。3 . The method for preparing magnetically encoded nanowires according to claim 1 , wherein the metal materials used to make the nanowires are magnetic materials such as iron or nickel, and non-magnetic materials such as copper. 4 . 4.一种磁性编码纳米线的用途,其特征在于:该磁性编码纳米线作为免疫检测用的多标记物。4. The use of a magnetically encoded nanowire, characterized in that: the magnetically encoded nanowire is used as a multi-label for immunoassay.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102650066A (en) * 2012-05-17 2012-08-29 西安交通大学 Method for preparing aluminum oxide template by step decompression reaming
CN103111615A (en) * 2013-03-06 2013-05-22 中国科学院合肥物质科学研究院 Nano chain composed by metallic nickel particles connected by copper oxide fimls and preparation method thereof
CN104073857A (en) * 2014-06-18 2014-10-01 华南理工大学 Preparation method of nanoimprint nickel seal
CN104087997A (en) * 2014-06-16 2014-10-08 北京工业大学 Method for preparing regular small-aperture anodized aluminum template through mixed acid variable pressure two-stage oxidation
CN105858625A (en) * 2016-06-26 2016-08-17 彭晓领 Iron nitride nanowire and production method thereof
CN105862104A (en) * 2016-06-02 2016-08-17 哈尔滨工程大学 Preparation method of wear-resistant anti-friction composite aluminum oxide film
CN107604408A (en) * 2017-08-25 2018-01-19 洛阳师范学院 A kind of bismuth ferrite thin film and preparation method thereof
CN109764960A (en) * 2019-03-15 2019-05-17 南京大学 A low-temperature readout method for multi-channel superconducting nanowire single-photon detectors
CN110165840A (en) * 2018-02-13 2019-08-23 通用电气公司 Engine and formation with magnetic part and the method using the magnetic part
WO2024070341A1 (en) * 2022-09-30 2024-04-04 富士フイルム株式会社 Metal nanowire production method

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《中国博士学位论文全文数据库》 20081231 杨昊 基于磁性纳米线的免疫检测技术的研究 1-4 , 第9期 2 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102650066A (en) * 2012-05-17 2012-08-29 西安交通大学 Method for preparing aluminum oxide template by step decompression reaming
CN103111615A (en) * 2013-03-06 2013-05-22 中国科学院合肥物质科学研究院 Nano chain composed by metallic nickel particles connected by copper oxide fimls and preparation method thereof
CN103111615B (en) * 2013-03-06 2014-09-03 中国科学院合肥物质科学研究院 Nano chain composed by metallic nickel particles connected by copper oxide fimls and preparation method thereof
CN104087997A (en) * 2014-06-16 2014-10-08 北京工业大学 Method for preparing regular small-aperture anodized aluminum template through mixed acid variable pressure two-stage oxidation
CN104073857A (en) * 2014-06-18 2014-10-01 华南理工大学 Preparation method of nanoimprint nickel seal
CN105862104A (en) * 2016-06-02 2016-08-17 哈尔滨工程大学 Preparation method of wear-resistant anti-friction composite aluminum oxide film
CN105862104B (en) * 2016-06-02 2018-03-13 哈尔滨工程大学 A kind of preparation method of wear resistant friction reducing composite alumina film
CN105858625A (en) * 2016-06-26 2016-08-17 彭晓领 Iron nitride nanowire and production method thereof
CN105858625B (en) * 2016-06-26 2018-01-30 中国计量大学 One kind nitridation Fe nanowire and preparation method thereof
CN107604408A (en) * 2017-08-25 2018-01-19 洛阳师范学院 A kind of bismuth ferrite thin film and preparation method thereof
CN107604408B (en) * 2017-08-25 2019-11-08 洛阳师范学院 A kind of bismuth ferrite thin film and preparation method thereof
CN110165840A (en) * 2018-02-13 2019-08-23 通用电气公司 Engine and formation with magnetic part and the method using the magnetic part
CN110165840B (en) * 2018-02-13 2021-11-26 通用电气公司 Engine having magnetic component and method of forming and using the same
CN109764960A (en) * 2019-03-15 2019-05-17 南京大学 A low-temperature readout method for multi-channel superconducting nanowire single-photon detectors
WO2024070341A1 (en) * 2022-09-30 2024-04-04 富士フイルム株式会社 Metal nanowire production method

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