CN107727720A - HKUST‑1（Cu‑MOFs）Application in glucose sensor electrode is prepared - Google Patents

HKUST‑1（Cu‑MOFs）Application in glucose sensor electrode is prepared Download PDF

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Publication number
CN107727720A
CN107727720A CN201711230592.6A CN201711230592A CN107727720A CN 107727720 A CN107727720 A CN 107727720A CN 201711230592 A CN201711230592 A CN 201711230592A CN 107727720 A CN107727720 A CN 107727720A
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electrode
hkust
glucose
graphite
concentration
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张万庆
吴亮
陈娜
白秀芝
张裕平
宗路宽
陈军
张毅军
赵文机
杨靖华
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Henan Institute of Science and Technology
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Henan Institute of Science and Technology
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Abstract

The invention provides applications of the HKUST 1 (Cu MOFs) in glucose sensor electrode is prepared.The HKUST 1 (Cu MOFs) and graphite for weighing different ratio respectively are placed in beaker, then add 10ml ultra-pure water, and being put into Ultrasound Instrument makes its dispersed, obtains the graphite suspensions of HKUST 1/；Pipette the graphite suspensions of 10 μ L HKUST 1/ to be vertically added drop-wise on processed good glass-carbon electrode, irradiate 30min under infrared lamp, make the graphite of HKUST 1/ uniform curing on electrode in a short time；Electrode is taken out, 2.5 μ LNafion solution is pipetted and is in kind added dropwise on electrode, makes that the graphite carbon modified electrodes of HKUST 1/ are more stable, and standing is dried, the graphite working electrodes of HKUST 1/ are made.Application of the electrode in concentration of glucose in detecting blood plasma, it is characterised in that its concentration is 1 × 10‑4‑1.5×10‑3In the range of M, peak current shows good linear relationship with concentration, and detection is limited to 2.3 × 10‑5M。

Description

Applications of the HKUST-1 (Cu-MOFs) in glucose sensor electrode is prepared
Technical field
The present invention relates to new material technology, and in particular to HKUST-1 (Cu-MOFs) is preparing glucose sensor electrode In application.
Background technology
Metal organic frame (metal-organicframeworks, MOFs) material is that one kind has recurrent network structure A kind of class zeolitic material, be made up of organic ligand with metal ion self assembly.The specific surface area of MOFs materials is larger, tool There are higher pore volume, an aperture, structure and vdiverse in function.At present, applied to hydrogen storage, drug carrier, catalytic reaction biology Sensor, gas absorption and separate etc..In recent years, HKUST-1 materials were a kind of as the MOF materials of novel stabilising, drew The extensive concern of researcher is played, metal organic framework compound HKUST-1 is also known as MOF-199, Williams in 1999 Group reports the structure of the permeability coordination polymer on Science magazines first, and it is by phenyl ring organic linker and containing Cu Carboxylate metal complex cluster group, there is micropore and very big specific surface area, include wheel-oar type secondary structure unit [Cu2 (O2CR) 4] (R is an aromatic ring), these secondary structure units are crossed-over forming tridimensional network.HKUST-1 is right CH4And CO2Absorption and CH4And CO2Good performance is shown in terms of mixed gas separation, it is containing of being reported earliest There are one of square coordination structure Cu MOFs materials.
The HKUST-1 of existing literature report mainly has 2 kinds of synthetic methods：Normal temperature differential pressure synthetic method and solvent (water) thermal synthesis Method.HKUST-1 is prepared herein by more commonly used normal temperature differential pressure synthetic method, the process is simply easily controllable, product dispersiveness It is good.
Blood glucose is the main life process characteristic compounds of human body, and blood-sugar content only has the horizontal ability for keeping certain normal Maintain the needs of each organ and tissue in vivo.The measure of blood-sugar content is with analyzing to the health of the mankind and disease being examined Disconnected, treatment and control have extremely important meaning.Thus preparing new and effective glucose sensor has important science Research Significance and actual application value.And electrochemical glucose sensor is the glucose biological sensor developed earliest, grape Sugared electrochemical sensor can be divided into enzyme-free glucose electrochemical sensor and enzyme based electrochemical according to being whether there is in structure using enzyme Sensor.Enzyme base glucose sensor make use of the features such as selectivity of enzyme is high, reaction speed is fast, but the biology enzyme used is stable Property is poor, is easily influenceed by the condition such as temperature, humidity and pH value in environment, these shortcomings significantly limit it in clinic Deng the application in field；Comparatively, enzyme-free glucose electrochemical sensor is become for electrochemical glucose sensor research New study hotspot, it not only solves dependence of traditional enzyme base glucose sensor to enzymatic activity, and with higher steady Qualitative, good reappearance and the advantages that be easy to miniaturization.
Most of enzyme-free glucose electrochemical sensor is in electric current caused by electrode surface direct oxidation by glucose Detected.And the catalytic activity of electrode material can also be influenceed by the structure and pattern of detected material, suitable electricity is selected Pole material also turns into a new direction of research.The research for developing into material science of nanoscale science and technology provides with application Good opportunity, the electrode material of nanostructured are urged due to its unique structure and pattern with the electricity different from other materials Change property, can not only improve electrochemical reaction speed, reduce detection current potential, selectivity and the sensitivity of analysis can also be improved Deng, therefore electrochemical sensing field can be applied to as electrode material.
Platinum and gold is used to be used as electrode material earliest in enzyme-free glucose electrochemical sensor, but both materials are urged in electricity Many deficiencies be present in terms of changing oxidizing glucose, such as during glucose is detected, platinum and golden two kinds of noble metal electrodes are easily inhaled Attached intermediate product causes electrode poisoning, reduces detection sensitivity, and the detection to glucose is selectively relatively low.
The content of the invention
In order to solve deficiency of the prior art, the invention provides HKUST-1 (Cu-MOFs) to prepare glucose sensing Application in device electrode.
The technical scheme is that：HKUST-1 (Cu-MOFs) is provided in glucose sensor electrode is prepared Using.
Above-mentioned application, is specifically included：The HKUST-1 (Cu-MOFs) and graphite for weighing different ratio respectively are placed in beaker In, then addition 10ml ultra-pure water, and being put into Ultrasound Instrument makes its dispersed, obtains HKUST-1/ graphite suspensions；Move Take 10 μ L HKUST-1/ graphite suspensions to be vertically added drop-wise on processed good glass-carbon electrode, irradiate 30min under infrared lamp, Make HKUST-1/ graphite uniform curing on electrode in a short time；Electrode is taken out, pipettes 2.5 μ LNafion solution with same sample prescription Method is added dropwise on electrode, makes that HKUST-1/ graphite carbon modified electrodes are more stable, and standing is dried, and HKUST-1/ graphite work electricity is made Pole.
Nafion solution described in above-mentioned application is to use volume ratio as 5:1 water and aqueous isopropanol are by 5% Nafion Solution is diluted to 1%.
Above-mentioned application, the glass-carbon electrode are also needed by pretreatment：A diameter of 3mm glass-carbon electrodes are used into particle diameter successively For 0.3 and 0.05 micron of alumina powder on chamois leather grinding and polishing 3min, make mirror-smooth clean, afterwards using ultra-pure water Rinse, remove the alumina powder remained on glass-carbon electrode, then put the electrodes into successively containing acetone, 1:1 nitric acid, ultra-pure water In beaker, and the ultrasonic 10min in Ultrasound Instrument respectively, naturally dry is standby after taking-up.
It is dense another object of the present invention is to additionally provide HKUST-1/ graphite working electrodes glucose in blood plasma is detected Application in degree, it is characterised in that its concentration is 1 × 10-4-1.5×10-3In the range of M, peak current shows good with concentration Good linear relationship, Ip (μ A)=27.6382+34330.08c (M/L) (R2=0.99178), detection is limited to 2.3 × 10-5M。
Measure uses three-electrode system in above-mentioned application：Working electrode is from the glass-carbon electrode modified, auxiliary electricity Extremely platinum electrode, reference electrode is used as from saturated calomel electrode (Ag/AgCl).Three electrodes are connected to electrochemical workstation On, from 0.1M sodium hydroxide as electrolyte, then weigh a certain amount of glucose, be configured to using ultra-pure water dissolving dense Spend for 2 × 10-3M mother liquor, it is 2 × 10 to be made afterwards using 0.1M sodium hydroxide and glucose mother liquid containing concentration-4M Portugals The electrolyte of grape sugar, electrification is carried out in the range of 50mV/s 0~0.8V of sweep speed and scanning voltage using cyclic voltammetry Learn behavior determination.
The application, electrode is prepared as electrode material using HKUST-1 (MOF-199) and graphite, electrification is carried out to glucose Detection is learned, it is applied in the assay of glucose.
Brief description of the drawings
Fig. 1 is HKUST-1 XRD diffraction patterns.
Fig. 2 a. are that the impedance diagram of Different electrodes (is HKUST-1 (Cu-MOFs)/graphite electrode, naked electricity successively from left to right Pole, pure HKUST-1 (Cu-MOFs) electrode, graphite electrode).
Fig. 2 b. are HKUST-1 (Cu-MOFs)/graphite electrode impedance diagrams.
Fig. 3 be Different electrodes detection glucose cyclic voltammogram (be successively from up to down HKUST-1 (Cu-MOFs)/ Graphite electrode, graphite electrode, pure HKUST-1 (Cu-MOFs) electrode, bare electrode).
Fig. 4 a. are that (oxidation peak is followed successively by 1 from up to down for the cyclic voltammogram of different ratio:3、1:2、1:1、1:7、1:4、 1:5、1:6)。
Fig. 4 b. are that the peak position electric current line chart of different ratio (is followed successively by 1 from left to right:7、1:6、1:5、1:4、1:3、1: 2、1:1)。
Fig. 5 a. be different scanning rates cyclic voltammogram (be 400,350,300,250,200 successively from up to down, 150,100,80,50mV/s).
Fig. 5 b. are the peak position Line Charts of different scanning rates.
Fig. 6 are that the cyclic voltammogram of different electrolytes (is KOH, NaOH, Na2CO3, Na2HPO4 successively from up to down 12H2)。
Fig. 7 a. be different NaOH concentrations cyclic voltammogram (be followed successively by from up to down 0.1M, 0.15M, 0.08M, 0.08M, 0.1M 0.15M)。
Fig. 7 b. be different NaOH concentrations peak position electric current line chart (be followed successively by from left to right 0.01M, 0.05M, 0.05M0.01M)。
Fig. 8 a. are that the cyclic voltammogram of different concentration of glucose (is followed successively by 1.5 × 10-3M, 1.2 × 10- from up to down 3M、1×10-3M、8×10-4M、6×10-4M、4×10-4M、2×10-4M、1×10-4M)。
Fig. 8 b. are the peak position electric current Line Charts of different concentration of glucose.
Fig. 9 a are .i-t curve maps.
Fig. 9 b. are i-c Line Charts.
Figure 10 are stability cyclic voltammetric i-t figures.
Figure 11 are anti-interference measure i-t curve maps.
Figure 12 a. are glucose concentration determination i-t curve maps in glucose injection.
Figure 12 b. are the i-c Line Charts of standard sample.
Figure 13 a. are glucose concentration determination i-t curve maps in blood sample 1.
Figure 13 b. are the Plays sample i-c Line Charts of blood sample 1.
Figure 14 a. are glucose concentration determination i-t curve maps in blood sample 2.
Figure 14 b. are the Plays sample i-c Line Charts of blood sample 2.
Embodiment
The present invention is elaborated below in conjunction with the accompanying drawings.
Embodiment
Laboratory apparatus and reagent
HKUST-1 (Cu-MOFs) preparation
Reference literature (preparation, sign and the hydrogen adsorption performance study [D] of the strong .HKUST-1 nanostructureds of Du Hai:Nanjing University, 2011) it is prepared for HKUST-1 (Cu-MOFs).Weigh 0.21g1,3,5- trimesic acids (H3BTC, 1.0mM) it is dissolved in In 10ml absolute ethyl alcohols, solution (A) is prepared, weighs 0.3g copper acetates, monohydrate (Cu (OAc)2·H2O, 1.5mM) it is molten Solution obtains solution (B) in the mixed liquor of 10ml ultra-pure waters and 1ml glacial acetic acid.Under high velocity agitation, solution A is poured into B solution In, 30min is persistently stirred, 5min is centrifuged under 6000rpm rotating speeds afterwards collects.Repeated the above steps washing using absolute ethyl alcohol Product five times, acetone washed product 5 times (to remove unreacted material) under similarity condition is reused afterwards, finally at 80 DEG C Electric drying oven with forced convection in dry 4h, dry 4h in 60 DEG C of vacuum drying chambers.It is sealed standby.
The preparation of working electrode
Pretreatment of glassy carbon electrode
By a diameter of 3mm glass-carbon electrodes successively using 0.3 and 0.05 micron of alumina powder on chamois leather grinding and polishing 3min, make mirror-smooth clean, afterwards using ultrapure water, remove the alumina powder remained on glass-carbon electrode, then successively Put the electrodes into containing acetone, 1:1 nitric acid, ultra-pure water beaker in, the ultrasonic 10min in Ultrasound Instrument respectively is natural after taking-up Dry standby.Whether detecting electrode is handled totally, bare electrode can be connected into electrochemical workstation and be swept with linear scan cyclic voltammetric Retouch, otherwise appearance is not handled clean handled again scan image.
It is prepared by modified electrode
The HKUST-1 (Cu-MOFs) and graphite for weighing different ratio respectively are placed in beaker, then add the ultrapure of 10ml Water, and being put into Ultrasound Instrument makes its dispersed, obtains HKUST-1/ graphite suspensions.10 μ L HKUST-1/ graphite are pipetted to hang Supernatant liquid is vertically added drop-wise on processed good glass-carbon electrode, irradiates 30min under infrared lamp, makes HKUST-1/ graphite in the short time It is interior uniform curing on electrode.Electrode is taken out, 2.5 μ LNafion solution is pipetted and (uses V/V=5:1 water will with aqueous isopropanol 5% Nafion solution is diluted to 1%, you can with) be in kind added dropwise on electrode, make HKUST-1/ graphite carbon modified electrodes More stable, standing is dried, and HKUST-1/ graphite working electrodes are made.
Electrochemical determination method
All experiment measure are completed on electrochemical workstation, using three-electrode system：Working electrode is selected and modified Glass-carbon electrode, auxiliary electrode is platinum electrode, and reference electrode is used as from saturated calomel electrode (Ag/AgCl).By three electrodes Be connected on electrochemical workstation, from 0.1M sodium hydroxide as electrolyte, then weigh a certain amount of glucose, use Ultra-pure water dissolving is configured to concentration as 2 × 10-3M mother liquor, made afterwards using 0.1M sodium hydroxide and glucose mother liquid It is 2 × 10 containing concentration-4The electrolyte of M glucose, using following in the range of 50mV/s 0~0.8V of sweep speed and scanning voltage Ring voltammetry carries out electrochemical behavior measure.
Plasma sample pre-processes
Blood sample comes from Hospital of Henan Science and Technology College, and blood is centrifuged into (6000rmp 5min) after acquisition, The upper strata weak yellow liquid after centrifugation, as blood plasma are taken, it is stand-by to be put into refrigerator.
As a result with discussion
HKUST-1 (Cu-MOFs) sign
XRD is characterized
HKUST-1 (Cu-MOFs) sample does X-ray diffraction (XRD) phenogram as shown in figure 1, being obtained with this experimental method The compound product that can determine to obtain be HKUST-1.
Electrochemical Characterization
Bare electrode, graphite electrode, pure HKUST-1 (Cu-MOFs) electrodes and HKUST-1 (Cu-MOFs)/graphite are selected respectively Electrode carries out electricity in the 0.1M potassium ferricyanides/potassium ferrocyanide electrolyte (the 5mM potassium ferricyanides/potassium ferrocyanide+0.1M KCl) Chemical property determines, and as shown below, Fig. 2 is the ac impedance spectroscopy of four kinds of electrodes, it can be seen that bare electrode and pure HKUST-1 (Cu-MOFs) electrode AC impedance is larger, and graphite, HKUST-1 (Cu-MOFs)/graphite electrode impedance, which have, substantially to be changed It is kind, and HKUST-1 (Cu-MOFs)/graphite electrode impedance improvement is more obvious, shows HKUST-1 (Cu-MOFs)/graphite enhancing The electric conductivity of electrode, therefore HKUST-1 (Cu-MOFs)/graphite electrode is selected as working electrode.
Detection of the Different electrodes to glucose
Bare electrode, graphite electrode, pure HKUST-1 (Cu-MOFs) electrodes and HKUST-1 (Cu-MOFs)/graphite are selected respectively Electrode is containing 2 × 10-4Under the conditions of the electrolyte of M glucose and 50mV/s sweep speed electrochemistry is carried out using cyclic voltammetry Detection.Fig. 3 is testing result, and as can be seen from the figure bare electrode and pure HKUST-1 (Cu-MOFs) electrode do not have obvious electric current Rise, graphite electrode have obvious electric current to raise, but exist without detection peak, HKUST-1 (Cu-MOFs)/graphite electrode measurement result Occurs obvious detection peak on the basis of graphite electrode measurement result.Therefore it may indicate that HKUST-1 (Cu-MOFs)/graphite Electrode pair glucose has good Detection results.
Condition optimizing
Measure of the modified electrode of different ratio to glucose
Investigate the influence that different ratio determines to glucose content.By the amount of table 1, it is respectively 1 to prepare proportioning:1、1:2、1: 3、1:4、1:5、1:6、1:7 HKUST-1 (Cu-MOFs)/graphite suspension, the working electrode of different ratio is prepared into, containing 2 ×10-4Cyclic voltammetric is used in the NaOH electrolyte of M glucose and in the range of 50mV/s sweep speed and 0~0.8V Method carries out electrochemical gaging.Fig. 4 is measurement result, it can be found that proportioning is 1 from figure:3 electrode detection peak shape is obvious, Peak position electric current is higher, at a distance of larger, measure effect is more good for oxidation peak and reduction peak, this experimental selection 1:3 proportioning system Standby working electrode.
Table 1.HKUST-1 (Cu-MOFs)-graphite different ratio weighs quality
Influence of the sweep speed to glucose assays
1:Influence of the sweep speed to glucose detection is investigated under 3 electrode conditions.Respectively 50,80,100,150, 200th, 250,300,350,400mV/s sweep speed carries out cyclic voltammetry test, and measurement result is illustrated in fig. 5 shown below, Fig. 5 a For the cyclic voltammogram of different scanning rates, Fig. 5 b are the peak position Line Chart under different scanning rates.It can be seen that with The rise of sweep speed, the peak position electric current of glucose oxidation peak also gradually rises, and there is good linear relationship：
Oxidation peak Ip (μ A)=9.3737+0.1895v (mV/s), R2=0.99569.
Because sweep speed has certain influence on appearance effect, sweep speed, which crosses conference, influences peak position electric current, peak shape, peak Current potential is negative moves, and this experimental selection 150mV/s is as optimum scanning speed.
Influence of the different electrolytes to glucose assays
In the constant situation (1 of optimal conditions:3 electrodes, sweep speed 150mV/s) under investigate different electrolytes to glucose The influence of measure.Choose NaOH, KOH, Na2CO3、Na2HPO4·12H2Tetra- kinds of reagents of O, 0.1M electrolyte is each configured to, then With 2 × 10-3It is 2 × 10 that M glucose mother liquid, which is configured to containing concentration,-4The electrolyte of M glucose, afterwards using cyclic voltammetry Electrochemical gaging is carried out to the electrolyte prepared respectively, as a result as shown in Figure 6.As can be seen from the figure Na2CO3Electrolyte and Na2HPO4·12H2O electrolyte measure peak position is relatively low, and NaOH electrolyte and KOH electrolyte measure peak position are more obvious, and both Peak position electric current is preferable without significant difference, measurement result.But because NaOH electrolyte hydrated radius is less than KOH electrolyte, and it is conductive Property it is good, therefore this experiment choose NaOH solution as electrolyte.
Influence of the NaoH concentration to glucose assays
In the situation (1 that optimal conditions are constant:3 electrodes, sweep speed 150mV/s) under investigate NaOH pairs of various concentrations The influence of glucose assays.Compound concentration is respectively 0.01M, 0.05M, 0.08M, 0.1M, 0.15M NaOH solution, then with 2 ×10-3M glucose mother liquid is configured to contain 2 × 10-4The electrolyte of M glucose, afterwards respectively using the various concentrations prepared Electrolyte carry out cyclic voltammetry electrochemical gaging, as a result as shown in Figure 7.This it appears that concentration is 0.1M from Fig. 7 b NaOH electrolyte oxidation peak position electric current highests, be 66.838 μ A, the oxidation peak current of other concentration reduces constantly drop with concentration It is low.This experiment chooses NaOH of the concentration for 0.1M as optium concentration electrolyte.
Influence of the concentration of glucose to measurement result
(1 under optimum determining condition:3 electrodes, sweep speed 150mV/s, 0.1MNaOH) investigate different concentration of glucose Influence to measurement result.Concentration is 2 × 10-3M glucose mother liquid and 0.1M NaOH electrolyte quotas go out concentration point Han 1 × 10-4M、2×10-4M、4×10-4M、6×10-4M、8×10-4M、1×10-3M、1.2×10-3M、1.5×10-3M Portugals The electrolyte of grape sugar, carries out electrochemical gaging using cyclic voltammetry afterwards, and measurement result is as shown in Figure 8.Can from figure Go out the rise with concentration of glucose, the peak position electric current rise of glucose oxidation peak, electric current be divided into for：30.993~76.933 μ A, and 1 × 10-4M-1.5×10-3Good linear relationship is showed in M concentration range.Linear equation is：
Ip (μ A)=27.6382+34330.08c (M/L), R2=0.99178.
Amperometric Determination
Under optimum determining condition (detection current potential+0.6V, electrolyte is 0.1M NaOH, and starting electrolyte is 17ml), The glucose 0.5mL for adding 2mM into electrolyte every 100s carries out Amperometric Determination, has obtained steady-state current-response time (i- T) curve, as a result as shown in Figure 9.I-c scheme as shown in 9b, test linear equation is：
Ip (μ A)=17.9848+5.58473c (mM/L) (R2=0.99475)
HKUST-1 (Cu-MOFs)/graphite electrode stability
The stability of HKUST-1 (Cu-MOFs)/graphite electrode is investigated by 13h cyclic voltammetry.Use preparation Good electrode carries out cyclic voltammetry under optimum determining condition, and every 1h detections once, measurement result is as shown in Figure 10, It is 6.61% that relative standard deviation, which can be drawn, and stability is preferable.
The anti-interference of HKUST-1 (Cu-MOFs)/graphite electrode
The oxidable interfering material such as carbohydrate, ascorbic acid, dopamine, uric acid can be with human plasma Glucose coexists, therefore anti-interference measure and a critically important factor of biology sensor detection, the inspection of anti-interference Survey result to obtain by Amperometric Determination method (i-t curve methods), under optimum determining condition, be continuously added into 0.1M NaOH 2mM interfering material (lactose, sucrose, dopamine, ascorbic acid, uric acid) and 2mM glucose.As a result as shown in figure 11, do It is smaller to disturb the current-responsive of material, can ignore, shows that HKUST-1/ graphite has good selectivity.
Medical glucose injection glucose concentration determination
The measure of concentration of glucose is (detection current potential+0.6V, electricity under optimum determining condition in medical glucose injection Solution liquid is 0.1M NaOH) by the way that 30 μ L medical glucose injection is added in 17mL0.1MNaOH electrolyte, glucose The rate of recovery is that standard glucose sample is added in the electrolyte containing actual sample by standard addition method, such as Figure 12 institutes Show, it is 0.2323M that concentration of glucose in glucose injection, which is calculated, in summary, and the rate of recovery of standard glucose sample is 100.4%.
Glucose concentration determination in actual sample
Amperometric Determination method (i-t curves will be passed through by biosensor application in detecting concentration of glucose in human plasma Method) measurement result is obtained, two blood samples are tested altogether.The measure of concentration of glucose is passed through under optimum determining condition in blood sample 1 50 μ L human plasma is added in 17mL0.1MNaOH electrolyte, the measure of concentration of glucose is in optimum determining in blood sample 2 Under the conditions of by the way that 0.1mL human plasma is added in 17mL0.1MNaOH electrolyte, the rate of recovery of glucose is to pass through standard Standard glucose sample is added in the electrolyte containing actual sample by addition method, such as Figure 13 (blood sample 1), 14 (blood sample 2) institutes Show, it is 4.364mM that concentration of glucose in blood sample 1, which is calculated, in summary, and the rate of recovery of standard glucose sample is 100.1%；Blood Concentration of glucose is 4.869mM in sample 2, and the rate of recovery of standard glucose sample is 99.4%
Detection performance of the HKUST-1/ graphite electrode materials to glucose is have studied herein, has investigated the electrode of different ratio Influence of the material to glucose detection, it is determined that optimum proportioning.Selection 1：The electrode material of 3 proportionings, and investigated other conditions Influence to glucose detection, it was therefore concluded that, under 0.1MNaOH electrolyte conditions, when sweep speed is 150mV/s, Detection of the HKUST-1/ graphite electrodes to glucose is 1 × 10-4M-1.5×10-3There is good linear pass in M concentration ranges System, detection are limited to 2.3 × 10-5.The combination electrode material has that cost is relatively low, prepares simple, and fast response time, stability is good, The features such as sensitivity, the detection available for glucose content in human body.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent thereof.

Claims (6)

  1. Applications of the 1.HKUST-1 (Cu-MOFs) in glucose sensor electrode is prepared.
  2. 2. application according to claim 1, it is characterised in that weigh respectively different ratio HKUST-1 (Cu-MOFs) and Graphite is placed in beaker, then adds 10ml ultra-pure water, and being put into Ultrasound Instrument makes its dispersed, obtains HKUST-1/ stones Black suspension；Pipette 10 μ L HKUST-1/ graphite suspensions to be vertically added drop-wise on processed good glass-carbon electrode, under infrared lamp 30min is irradiated, makes HKUST-1/ graphite uniform curing on electrode in a short time；Electrode is taken out, it is molten to pipette 2.5 μ LNafion Liquid is in kind added dropwise on electrode, makes that HKUST-1/ graphite carbon modified electrodes are more stable, and standing is dried, and HKUST-1/ stones are made Black working electrode.
  3. 3. application according to claim 2, it is characterised in that the Nafion solution is to use volume ratio as 5:1 water with 5% Nafion solution is diluted to 1% by aqueous isopropanol.
  4. 4. application according to claim 2, it is characterised in that the glass-carbon electrode is also needed by pretreatment：Will be a diameter of 3mm glass-carbon electrodes are successively 0.3 and 0.05 micron of the alumina powder grinding and polishing 3min on chamois leather using particle diameter, make minute surface Smooth pieces, afterwards using ultrapure water, the alumina powder remained on glass-carbon electrode is removed, then put the electrodes into contain successively There are acetone, 1:1 nitric acid, ultra-pure water beaker in, and the ultrasonic 10min in Ultrasound Instrument respectively, naturally dry is standby after taking-up.
  5. Application of the 5.HKUST-1/ graphite working electrodes in concentration of glucose in detecting blood plasma, it is characterised in that its concentration is 1 ×10-4-1.5×10-3In the range of M, peak current shows good linear relationship, Ip (μ A)=27.6382+ with concentration 34330.08c(M/L)(R2=0.99178), detection is limited to 2.3 × 10-5M。
  6. 6. application according to claim 5, it is characterised in that measure uses three-electrode system：Working electrode is selected and repaiied The glass-carbon electrode adornd, auxiliary electrode are platinum electrode, and reference electrode is used as from saturated calomel electrode (Ag/AgCl).By three Electrode is connected on electrochemical workstation, from 0.1M sodium hydroxide as electrolyte, then weigh a certain amount of glucose, Concentration is configured to as 2 × 10 using ultra-pure water dissolving-3M mother liquor, matched somebody with somebody afterwards using 0.1M sodium hydroxide and glucose mother liquid It is 2 × 10 to make containing concentration-4The electrolyte of M glucose, make in the range of 50mV/s 0~0.8V of sweep speed and scanning voltage Electrochemical behavior measure is carried out with cyclic voltammetry.
CN201711230592.6A 2017-11-29 2017-11-29 HKUST‑1（Cu‑MOFs）Application in glucose sensor electrode is prepared Pending CN107727720A (en)

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CN108982626A (en) * 2018-05-30 2018-12-11 海南师范大学 It is a kind of for detecting the nano electrochemical enzyme sensor and its preparation method and application of trichloroacetic acid or sodium nitrite
CN109406599A (en) * 2018-09-03 2019-03-01 海南师范大学 A kind of preparation and application of the novel Electrochemical enzyme biosensor based on MOFs composite material
CN109487370A (en) * 2018-11-08 2019-03-19 河南科技学院 MOF-235-500 DEG C of material of spinning and its preparation method and application
CN114878662A (en) * 2022-05-20 2022-08-09 中南大学 Application of Cu-HHB or Cu-BTC in pyocin detection

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108982626A (en) * 2018-05-30 2018-12-11 海南师范大学 It is a kind of for detecting the nano electrochemical enzyme sensor and its preparation method and application of trichloroacetic acid or sodium nitrite
CN109406599A (en) * 2018-09-03 2019-03-01 海南师范大学 A kind of preparation and application of the novel Electrochemical enzyme biosensor based on MOFs composite material
CN109487370A (en) * 2018-11-08 2019-03-19 河南科技学院 MOF-235-500 DEG C of material of spinning and its preparation method and application
CN114878662A (en) * 2022-05-20 2022-08-09 中南大学 Application of Cu-HHB or Cu-BTC in pyocin detection
CN114878662B (en) * 2022-05-20 2023-02-28 中南大学 Application of Cu-HHB or Cu-BTC in detection of pyocin

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