CN107195521A - Silica nanometer chamber array electrode as ion channel application - Google Patents

Silica nanometer chamber array electrode as ion channel application Download PDF

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Publication number
CN107195521A
CN107195521A CN201710272486.8A CN201710272486A CN107195521A CN 107195521 A CN107195521 A CN 107195521A CN 201710272486 A CN201710272486 A CN 201710272486A CN 107195521 A CN107195521 A CN 107195521A
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China
Prior art keywords
ion
array electrode
sio
ion channel
electrode
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CN201710272486.8A
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Inventor
卢小泉
姬玲霞
何静
王晶
陈海咏
姚敏
汪天胜
魏红娟
陕多亮
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Northwest Normal University
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Northwest Normal University
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Priority to CN201710272486.8A priority Critical patent/CN107195521A/en
Publication of CN107195521A publication Critical patent/CN107195521A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/26Electron or ion microscopes; Electron or ion diffraction tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/02Details
    • H01J37/04Arrangements of electrodes and associated parts for generating or controlling the discharge, e.g. electron-optical arrangement, ion-optical arrangement

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)

Abstract

The invention discloses application of the silica nanometer chamber array electrode as ion channel, the silica nanometer chamber array electrode by ITO electro-conductive glass and duct perpendicular to ITO conductive glass surfaces SiO2Nano-cavity array is constituted.The present invention utilizes SiO2Nano-cavity array electrode Biomimetic membrane ion channel, under different pH condition, mesoporous SiO2Transfer of the difference regulation and control ion of surface charge property in confinement environment.With SiO2Nano-cavity array electrode is used as ion channel, the dynamic process of ion-transfer can preferably be studied, help preferably to recognize liquid/liquid interface ion-transfer mechanism, potassium ion and sodium ion film transfer mechanism in understanding life process have great importance to disclosing life secret.

Description

Silica nanometer chamber array electrode as ion channel application
Technical field
The present invention relates to application of the silica nanometer chamber array electrode as ion channel.
Background technology
In recent years, liquid/liquid interface microelectrode achieves very big development, and it has increase propagated flux, and reduction does not compensate molten The characteristic of liquid resistance, the glass-micropipe such as drawn, the micro- hole formed on polymer film with laser drill, micropore.
Famous Electroanalytical Chemistry man Bard etc. combines PSTM (Scanning Tunnel Microscope, STM) and ultramicroelectrode grown up a kind of new electrochemistry onthe technology of site test-scan-type electrochemical show Micro mirror (Scanning Electrochemical Microscopy, SECM).It has high chemosensitivity and spatial discrimination Rate, can not only study the homogeneous reaction dynamics in solution layer between probe and substrate, can also probe into probe, in substrate Electrochemical kinetics, differentiate the electrochemical nonuniformity of electrode surface microcell, and micro Process is carried out to material.SECM researchs liquid/ The advantage of liquid interface process:
1st, the iR between liquid/liquid interface can be overcome to drop
2nd, electro transfer can be distinguished(ET)And ion-transfer(IT)
3rd, charging current is smaller
4th, electrochemical window is relatively wider than journey.
The content of the invention
The purpose of the present invention is by the use of silica nanometer chamber array electrode as ion channel, available for detection liquid liquid The ion-transfer at interface.
In order to solve the above-mentioned technical problem, the invention provides following technical scheme:
Silica nanometer chamber array electrode as ion channel application.
Preferably, the silica nanometer chamber array electrode by ITO electro-conductive glass and duct perpendicular to the conductive glass of ITO The silica nanometer chamber array composition on glass surface.
Preferably, silica nanometer chamber array electrode as ion channel detection liquid/liquid interface ion-transfer in Using.
Preferably, the ion channel is the ion channel of potassium ion and/or sodium ion.The ion channel is to be controlled by pH The ion channel of system.
Compared with existing liquid/liquid interface microelectrode, the mesoporous silicon dioxide nano chamber array electrode in the present invention is a kind of New liquid/liquid interface electrode, in addition to having the advantages that existing liquid/liquid interface microelectrode, its preparation method is simple, cheap, Liquid volume required in experiment is smaller, and the biocompatibility of material more preferably, and can utilize the charge characteristic on its surface Electric charge transfer is regulated and controled, the charge transfer process on the more preferable Biomimetic membrane of energy.
The present invention utilizes SiO2Nano-cavity array electrode Biomimetic membrane ion channel, it is mesoporous under different pH condition SiO2Transfer of the difference regulation and control ion of surface charge property in confinement environment.With SiO2Nano-cavity array electrode as from Subchannel, can preferably study the dynamic process of ion-transfer, help preferably to recognize liquid/liquid interface ion-transfer machine Potassium ion and sodium ion film transfer mechanism in reason, understanding life process, have great importance to disclosing life secret.
Brief description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and constitutes a part for specification, the reality with the present invention Applying example is used to explain the present invention together, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is 0.5 M KCl in SiO2The K of liquid/liquid interface in nano-cavity array electrode+Transfer cycle voltammogram.
Fig. 2 is 0.5 M NaCl in SiO2The Na of liquid/liquid interface in nano-cavity array electrode+Transfer cycle voltammogram.
Fig. 3 is ionic strength to K+The SECM feedback profiles of transfer, the ionic strength change of aqueous phase solution respectively from 0.1~ 0.5 M, pH are 6.0,18- crown-s 6- ethers in organic phase(DB18C6)Concentration be 1 mM, sweep speed be 50 mV/s.
Fig. 4 is ionic strength to Na+The SECM feedback profiles of transfer, the ionic strength of aqueous phase solution changes respectively from 0.1 ~0.5 M, pH are 6.0, and DB18C6 concentration is 1 mM in organic phase, and it is 50 mV/s to sweep speed.
Fig. 5 is pH to K+The SECM feedback profiles of transfer, aqueous phase solution pH is 6.0,5.0,3.5 respectively from top to bottom, 3.0,2.0, the concentration that ionic strength is DB18C6 in 0.5M, organic phase is 1 mM, and it is 50 mV/s to sweep speed.
Fig. 6 is pH to Na+The SECM feedback profiles of transfer, aqueous phase solution pH is 6.0,5.0,3.5 respectively from top to bottom, 3.0,1.9, the concentration that ionic strength is DB18C6 in 0.5M, organic phase is 1 mM, and it is 50 mV/s to sweep speed.
Embodiment
The preferred embodiments of the present invention are illustrated below in conjunction with accompanying drawing, it will be appreciated that preferred reality described herein Apply example to be merely to illustrate and explain the present invention, be not intended to limit the present invention.
Embodiment 1
The water used in experimentation is redistilled water(Abbreviation secondary water), experiment reagent used is that analysis is pure.It is real Test and carried out at room temperature (20 ± 2) DEG C.
(1), instrument and reagent used in the present embodiment
A, micron tube preparation
It is raw material with capillary glass tube (o.d.=2.0 mm, i.d.=1.16 mm, L=10 cm), is drawn using microelectrode Instrument processed is drawn.Suitable control draws the parameter of instrument, pulls out the glass tube that the mouth of pipe relatively flat and needle type radius is a few to tens of microns.Pin The radius of point and the thickness of tube wall are estimated with light microscope, and aqueous phase solution is injected from glass tube afterbody using microsyringe.
B, the electrode of micro-pipe support preparation
Potassium chloride or sodium chloride liquid are injected from micron tube tail end with microsyringe, before the experiments, electron microscope is used The needle point of probe is observed, checks whether the inside has bubble.
C, cyclic voltammetry(CV)Detection
The experiment uses three-electrode system, and tetraphenylarsonium chloride boron silver is covered with surface(AgTPBCl)Filamentary silver as reference electrode, Pt the electrode of micro-pipe support is working electrode as to electrode, reference electrode and inserts oil phase to electrode.In electrochemistry work Make to complete experiment on the CHI 900 of station.
D, scan-type electrochemical microscope(SECM)Detection
The experiment uses three-electrode system, and surface is covered with AgTPBCl silver wire electrode as reference electrode, and Pt as to electricity Pole, the electrode of micro-pipe support is working electrode, reference electrode and inserts oil phase to electrode.In electrochemical workstation CHI 900 It is upper to complete experiment.
e、SiO2The preparation of nano-cavity array electrode
The SiO with vertical duct in order is prepared on ITO electro-conductive glass using Stober-solution growth methods2Nano-cavity Array electrode:By ITO electro-conductive glass saturation NaOH soaked overnights, then water, acetone, water, ethanol, each ultrasound of water are used successively 15min is cleaned, nitrogen drying.Place into precursor liquid(0.16g cetyl trimethylammonium bromides( CTAB)+70mL H2O+ The μ L tetraethyl orthosilicates of+10 μ L ammoniacal liquor of 30mL ethanol+80(TEOS))In, in 60 DEG C react 24h, rinsing, drying after 100 DEG C overnight.Finally SiO is removed with 0.1M ethanol solution hydrochloride2Template CTAB in nano-cavity array hole.
F, liquid/liquid interface ion-transfer
By the SiO prepared2Nano-cavity array electrode is fixed on electrolytic cell;Aqueous phase is first added, is characterized with cyclic voltammetry, directly SiO is injected to aqueous phase2In nano-cavity array duct, then the aqueous phase in electrolytic cell is discarded, by SiO2Nano-cavity array electrode gently blows It is dry, organic phase is added afterwards, makes SiO2The upper end of nano-cavity array just at two immiscible water-oil interfaces at, construct from Subchannel;With three-electrode system, AgTPBCl filamentary silver is covered with as reference electrode using surface, Pt as to electrode, micro-pipe The electrode of support is working electrode.The scanning of cyclic voltammetry curve and feedback profile is completed on electrochemical workstation CHI900, Potential scan scope is 1.4V to 0.4V.
Fig. 1, Fig. 2 are respectively 0.5M KCl and 0.3M NaCl in SiO2The ion of liquid/liquid interface in nano-cavity array electrode Shift CV figures.It can be seen that ion enters organic phase from aqueous phase in the way of linearly spreading, current-responsive be it is negative, There is current peak appearance, aqueous phase is returned in the way of spherical diffusion from organic phase again afterwards, electric current is just, to be shown as flat rubber belting electric current. The asymmetry of diffusion causes the asymmetric of CV figures.
Fig. 3, Fig. 4 are SiO2Feedback profile of the ionic strength of liquid/liquid interface to ion-transfer in nano-cavity array electrode Figure.The overall diffusion rate of ion in the channel changes with the change of limited diffusion zone.It can be seen that working as ion Intensity from 0.1 M increase to 0.5 M when, ion-transfer is more and more obvious.
Fig. 5, Fig. 6 are pH to sodium ion and the feedback profile figure of the ion-transfer of potassium ion.It can be seen that duct Surface charge properties influenceed very big by pH.PH is bigger, and the silicone hydroxyl deprotonation degree of channel surfaces is bigger, i.e., surface is negative Charge density is bigger, and the electrostatic attractions of ion and channel surfaces effect is bigger, on the contrary, when pH is smaller, the silicon of channel surfaces Hydroxyl deprotonation degree is smaller, i.e., the negative charge density on surface is just smaller, so, the electrostatic attraction of ion and channel surfaces is made With just it is smaller.The result that progressive curve is obtained is consistent with theory.Therefore, we can by change the pH of solution reach regulation from The purpose of son transfer.
Finally it should be noted that:The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic. Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., should be included in the present invention's Within protection domain.

Claims (5)

1. silica nanometer chamber array electrode is used as the application of ion channel.
2. application according to claim 1, it is characterised in that:The silica nanometer chamber array electrode is conductive by ITO Glass and duct are constituted perpendicular to the silica nanometer chamber array of ITO conductive glass surfaces.
3. application according to claim 1, it is characterised in that:The silica nanometer chamber array electrode is logical as ion Application of the road in detection liquid/liquid interface ion-transfer.
4. application according to claim 1, it is characterised in that:The ion channel be potassium ion and/or sodium ion from Subchannel.
5. application according to claim 4, it is characterised in that:The ion channel is the ion channel controlled by pH.
CN201710272486.8A 2017-04-24 2017-04-24 Silica nanometer chamber array electrode as ion channel application Pending CN107195521A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109580452A (en) * 2018-11-30 2019-04-05 西北师范大学 It is a kind of to study the infiltrative method of amino functional silica nanometer channel selecting with scan-type electrochemical microscope
CN109876157A (en) * 2019-02-27 2019-06-14 浙江大学 Ion specificity filter membrane/mesoporous silicon composite material, nano-sensor and products thereof and application
CN111137897A (en) * 2020-01-14 2020-05-12 苏州大学 Preparation method of silicon dioxide nanorod array

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103267875A (en) * 2013-04-28 2013-08-28 西北师范大学 Method for building ion channel on liquid/liquid interfaces and method for detecting effect of size of ion channel on ion transferring
CN104777212A (en) * 2015-03-20 2015-07-15 西北师范大学 Method using SECM to detect ion transfer behaviors in proton-response ion channel

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103267875A (en) * 2013-04-28 2013-08-28 西北师范大学 Method for building ion channel on liquid/liquid interfaces and method for detecting effect of size of ion channel on ion transferring
CN104777212A (en) * 2015-03-20 2015-07-15 西北师范大学 Method using SECM to detect ion transfer behaviors in proton-response ion channel

Non-Patent Citations (2)

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Title
姬玲霞 等: "介孔SiO2纳米腔阵列电极用于研究液/液界面离子转移", 《第十三届全国电分析化学学术会议 会议论文摘要集》 *
王巧红: "垂直介孔二氧化硅通道的电化学研究及应用", 《浙江大学硕士学位论文》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109580452A (en) * 2018-11-30 2019-04-05 西北师范大学 It is a kind of to study the infiltrative method of amino functional silica nanometer channel selecting with scan-type electrochemical microscope
CN109876157A (en) * 2019-02-27 2019-06-14 浙江大学 Ion specificity filter membrane/mesoporous silicon composite material, nano-sensor and products thereof and application
CN109876157B (en) * 2019-02-27 2020-12-15 浙江大学 Composite material of ion-specific filter membrane/mesoporous silicon, nano sensor, product of nano sensor and application of nano sensor
CN111137897A (en) * 2020-01-14 2020-05-12 苏州大学 Preparation method of silicon dioxide nanorod array
CN111137897B (en) * 2020-01-14 2023-08-15 苏州大学 Preparation method of silicon dioxide nanorod array

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Application publication date: 20170922