CN108845014A - A kind of molecular engram amphiphilic chitosan derivatives LB film modified electrode and its construction method and application - Google Patents
A kind of molecular engram amphiphilic chitosan derivatives LB film modified electrode and its construction method and application Download PDFInfo
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- CN108845014A CN108845014A CN201810761158.9A CN201810761158A CN108845014A CN 108845014 A CN108845014 A CN 108845014A CN 201810761158 A CN201810761158 A CN 201810761158A CN 108845014 A CN108845014 A CN 108845014A
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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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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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
Abstract
The present invention discloses a kind of molecular engram amphiphilic chitosan derivatives LB film modified electrode and its construction method and application.This method passes through Langmuir technology first and combines to form cholesterol-chitosan carbonic ester/histamine mixed composition monomolecular film using the interaction force reconstruct of amphiphilic cholesterol-functional group between chitosan carbonic ester and histamine in air/water interface；Then mixed composition monomolecular film is transferred on ito glass electrode using LB technology；Histamine is eluted from mixed composition LB film followed by molecular imprinting method the molecular engram LB membrane electrode that Selective recognition histamine is made；Electrochemical method is finally combined to measure molecular engram LB membrane electrode high to the electrochemical response of histamine, histamine linear detection range is wide, detection limit is low, selectivity, repeatability and has good stability, and realizes and rapidly and sensitively detect the histamine of trace in beer and grape wine.This method is that surface molecule print technology opens up a kind of approach.
Description
Technical field
The invention belongs to functional polymer ultrathin membrane fields, and in particular to a kind of molecular engram amphiphilic chitosan derivatives LB
Film modified electrode and its construction method and application.
Background technique
Histamine (HA), 2- (4- imidazoles)-ethamine, the catalysis in human body by histidine through histidine decarboxylase (HDC) are de-
Carboxylic and generate, be that one of wide, bioactive substance that effect is strong is distributed in human tissue cell.Histamine by G-protein be coupled by
The mediation of body participates in the adjusting of internal different physiological roles such as cardiovascular circulation etc. and the pathologic process of disease such as tumour etc..By
Modern genetic engineering technology, people can from gene level inquire into histamine receptor structure and with the phase interaction of histamine
With.So far, as glimmering in being widely used in blood plasma, tissue detection in organism there are many kinds of the test methods of histamine content
Optical analysis, high performance liquid chromatography etc..But its own defect causes it to be difficult to reach people succinct for test analysis process
It is efficient to require, as needed to carry out sample complicated extraction process before fluorescence analysis test；The test specimens of high performance liquid chromatography
Time-consuming for product, dosage is big.Therefore, the research and development for the sensor that can directly test and rapidly, precisely obtain a result are extremely necessary.
Langmuir membrane technology is that orderly and intensive amphiphiles layer is prepared in empty air liquid interface（I.e.
Langmuir film）Technology.It forms the thickness of molecular level Langmuir film uniformly and accurately controls, the molecules align in film
High-sequential.Britt research group uses Langmuir monolayer surface blotting, with cation and nonionic lipid body in air
Langmuir single layer is formed with the interface of water.Liposome end group can be recombinated with the protein molecule recurring structure of addition, make it
Part recombination end-group structure can be complementary with protein molecule in shape and charge, to realize protein imprinted.The preparation of LB method
Molecular engram film, have and be evenly distributed, easy to operate, the advantages that film thickness is controllable.This method has mass transfer good and energy
The advantage combined with sensor platform.It yet there are no so far using the related work that the amphipathic compound of non-liposomal carries out trace
Report.Langmuir-Blodgett (LB) membrane technology is then to be transferred to the monomolecular film in above-mentioned empty air liquid interface admittedly
Body surface face and the technology for realizing continuous transfer assembling.In thin film technique, organized molecular structure and accurate in order to obtain
Thickness has considerable meaning using LB technology preparation monolayer assembly, and LB film is used for material science and nanometer
The research fields such as technology.
Chitosan is derivative of the natural polymer chitin through deacetylation, feature be mainly on strand C2 and
C3 and C6 contains a large amount of reactive amino and hydroxyl group, therefore can have covalently bonded by structurally-modified introduce
It closes, the functional groups of electrostatic interaction and coordination.Document report mainly passes through chitosan molecule chain C2 introducings and dredges
Water chain, the present invention is in C6 introducing Long carbon chains, the C2 reservation amino hydrophilic radical end of the chains.Pass through and has introduced long-chain hydrophobic base
The obtained amphiphilic chitosan derivatives of group, to prepare the Langmuir monolayer of chitosan derivatives and point of identification cholesterol
Sub- imprinted polymer（Tong Y, et al. Synthesis ofO,O′-dipalmitoyl chitosan and its
amphiphilic properties and capability of cholesterol absorption. Carbohydr.
Polym., 2005, 60(2): 229-233 ）.Research shows that amphiphilic chitosan derivatives, which can be used as absorption, identifies that perfluor is pungent
The raw material of the Langmuir film of alkyl sulfonate（Zhang Xinli on air-water interface chitosan derivatives amphipathic and its
With the research master thesis of histamine interaction, 2016,40-50）.
Amphiphile, amphiphilic molecule trace membrane material is based on introducing the hydrophobic end of the chain of cholesterol on chitosan molecule chain hydroxyl in the present invention,
Retain amphiphilic cholesterol-chitosan carbonic ester that amino water-wet side is formed in chitosan molecule chain.Microsphere group of the invention
Amine, histamine strand have amino and imidazole radicals functional group.Cholesterol-can be by means of hydrogen between chitosan carbonic ester and histamine
The interaction force of the diversified forms such as key, electrostatic interaction, Van der Waals force, to realize phase interaction of the chitosan derivatives with histamine
With.
The present invention passes through Langmuir technology first, utilizes the cholesterol-with reactive amino on amphiphilic and strand
Chitosan carbonic ester can be in the characteristic of air/water interface formation Langmuir film, in Langmuir rooved face amphiphilic cholesterol-
Chitosan carbonic ester experience occurs interaction reconstruct with histamine in water phase and combines to form cholesterol-chitosan carbonic ester/histamine
Mixed composition Langmuir film；Then mixed composition monomolecular film is transferred to by indium tin oxide (ITO) glass using LB technology
On electrode；Followed by molecular imprinting technology, the histamine as target molecule is eluted from mixed composition LB film to be made and histamine
The structure snd size of molecule match hole Selective recognition histamine molecular engram LB membrane electrode, so that amphiphilic shell can be realized
The interaction of polysaccharid derivative and histamine specificity.Finally combine electrochemical method, the molecular engram LB of research identification histamine
The electrochemical response and recognition performance of membrane electrode, and modified electrode of the invention is used for the inspection of beer and grape wine actual sample
It surveys, realizes the histamine for rapidly and sensitively detecting trace in beer and grape wine.ITO electrode has high conductivity, wide electrochemistry
Working window, stable electrochemistry physical characteristic and be chosen as electrode basement.
Summary of the invention
The purpose of the present invention is to provide a kind of molecular engram amphiphilic chitosan derivatives LB film modified electrode and its buildings
Methods and applications.Using having a large amount of reactive aminos on cholesterol-chitosan carbonate molecule chain, group amine molecule has this method
There are amino and imidazole radicals functional group, the two can pass through the interaction of hydrogen bond, electrostatic interaction and Van der Waals force diversified forms
Power realizes the interaction of chitosan derivatives and histamine.Furthermore utilize the amphipathic and histamine of cholesterol-chitosan carbonic ester
Water solubility, form mixed component monomolecular film in Langmuir slot air/water interface, group further will be mixed using LB technology
Part monomolecular film is transferred on ito glass electrode, and utilizes molecular imprinting technology, histamine is eluted from mixed composition LB film system
Match the molecular engram LB membrane electrode of the Selective recognition histamine in hole at the structure snd size with group amine molecule, so as to reality
The interaction of existing amphiphilic chitosan derivatives and histamine specificity.In conjunction with electrochemical method, molecular engram LB membrane electrode is utilized
The electrochemical response during absorption and Selective recognition to histamine probes into adsorption capacity and Selective recognition ability, and will
Modified electrode of the invention is used for the detection of beer and grape wine actual sample.
To achieve the goals above, the present invention uses following technical scheme：
A kind of construction method of molecular engram amphiphilic chitosan derivatives LB film modified electrode, includes the following steps：（1）Amphiphilic gallbladder
The preparation of sterol-chitosan carbonic ester and histamine solution
Cholesterol-chitosan carbonic ester is dissolved in chloroform, a series of cholesterol-chitosan carbonic ester of various concentrations is prepared
Solution, constant volume are spare in volumetric flask；Histamine is dissolved in the histamine solution of 1.0 mg/mL of compound concentration in ultrapure water, in low
It is saved under the conditions of temperature, it is spare；
（2）The formation of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film
After completing previous work according to the requirement of Langmuir slot operating method, ultrapure water is added into slot（Resistivity >=
18.25 Ω·m）As parfacies, the group amine aqueous solution that 100 μ L concentration are 0.2 mg/mL is added dropwise with microsyringe
（By step（1）The group amine aqueous solution of preparation dilutes）, microsyringe removing step is used after mixing（1）The gallbladder of preparation
Sterol-chitosan carbonic ester chloroformic solution, is slowly added dropwise to the parfacies water surface, spreads over it on water surface.It is complete to chloroform
Volatilization, pressure sensor is zeroed, and fixed sliding barrier speed is 50 cm2/ min starts to compress the sliding barrier of A and B, obtain orderly intensive
The cholesterol of arrangement-chitosan carbonic ester/histamine mixed composition Langmuir film（Monolayer）, record the surface of monolayer
The average monolayer area isothermal curve of pressure-and collapsing for mixed composition film are pressed with determination.Every group of experiment is at least in triplicate；
（3）The transfer of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film
According to the requirement of Langmuir slot operating method, pretreatment ITO electrode is put into Langmuir slot, according to step（2）It will
Histamine and cholesterol-chitosan carbonate solution are added dropwise into parfacies respectively, cholesterol to be formed-chitosan carbonic ester/histamine
After mixed monolayer film, Langmuir-Blodgett is utilized（LB）Technology is proposed mixed composition monomolecular film with the speed of 5 mm/s
The transfer for pulling film forming, is deposited on film in ITO substrate, forms cholesterol-chitosan carbonic ester/histamine mixed composition LB film and repairs
The ito glass electrode of decorations；
（4）The preparation of molecular engram amphiphilic chitosan derivatives LB film modified electrode
With a certain amount of milli-Q water by step（3）The cholesterol of formation-chitosan carbonic ester/histamine mixed LB film modification
Ito glass electrode surface certain time removes histamine template molecule and obtains molecular engram cholesterol-chitosan carbon of identification histamine
Acid esters LB film modified electrode.
（5）The experiment that molecular engram amphiphilic chitosan derivatives LB film modified electrode identifies histamine
Utilize electrochemistry three-electrode system, cyclic voltammetry potential range -0.4-0.8 V, 50 mV/s of scanning speed；With ethyl alcohol
With 0.2 M KCl and 1mM K3Fe(CN)6Test solution system of the water mixed solution as redox probe；Using circulation
Voltammetry probes into molecular engram amphiphilic chitosan derivatives LB film modified electrode（Abbreviation molecular engram LB film）Absorption to histamine
Performance, test molecule trace LB film modified electrode is in histamine respectively（3 ml 1µM）In the presence of or electrochemical response when not depositing,
The result shows that molecular engram LB film can identify a group amine molecule in the case where optimizing adsorption conditions, and non-molecule print made from same procedure
Mark amphiphilic chitosan derivatives LB film modified electrode（Referred to as non-molecular engram LB film, is not added template molecule histamine and is printed
The process of mark）To histamine almost without response, i.e. the sensitivity with higher in terms of detecting histamine target molecule.Linear scan
The peak current response (i) of volt-ampere curve and Histamine concentrations are in a linear relationship within the scope of 0.01-1.5 μM, detection limit (S/N=
3) 0.09 μM, same root molecular engram LB film modified electrode is 2.4% (n to the response peak current relative standard deviation of histamine
=6) 。
（6）The building of non-molecular engram amphiphilic chitosan derivatives LB film modified electrode and its electrification in histamine solution
Learn responsiveness
1. the formation of cholesterol-chitosan carbonic ester monofilm：Work early period is completed according to the requirement of Langmuir slot operating method
After work, ultrapure water is added into slot as parfacies, pipettes 100 μ L steps with microsyringe（1）Cholesterol-shell of preparation is poly-
The chloroformic solution of sugar charcoal acid esters is slowly added dropwise to the parfacies water surface, spreads over it on water surface.It volatilizees, will be pressed completely to chloroform
Force snesor zero, fixed sliding barrier speed is 50 cm2/ min starts to compress sliding barrier A and B, and the gallbladder for obtaining orderly dense arrangement is solid
Alcohol-chitosan carbonic ester Langmuir film, record monomolecular film surface press-be averaged monomolecular film area isothermal curve with
Langmuir film collapses pressure.Every isothermal curve is at least in triplicate to ensure reproducibility；2. cholesterol-chitosan carbonic ester
The transfer of Langmuir film：According to the requirement of Langmuir slot operating method, pretreatment ITO electrode is put into Langmuir slot,
1. cholesterol-chitosan carbonate solution is added dropwise in parfacies according to step, is compressed to cholesterol-chitosan carbon to sliding barrier A and B
In solid-state isothermal curve section, about half corresponds to stopping compression when surface is pressed to acid esters monofilm.Followed by Langmuir-
Blodgett（LB）Monomolecular film is lifted the transfer for completing film with the speed of 5 mm/s, film is made to be deposited on ITO substrate by technology
On, form the film modified ito glass electrode of 4 layers of cholesterol-chitosan carbonic ester LB；3. non-molecular engram amphiphilic chitosan derivative
The production of object LB film modified electrode：Cholesterol-chitosan carbonic ester LB the film 2. formed by step is eluted with a certain amount of ultrapure water
The ito glass electrode surface certain time of modification removes histamine template molecule and obtains the molecular engram cholesterol-of non-identifying histamine
Chitosan carbonic ester LB film modified electrode（Labeled as non-ITO A）；4. electrochemical response of the non-ITO A in histamine solution
Property：Using with step（5）Identical electrochemistry three-electrode system and redox probe test solution system, using cyclic voltammetric
Method is tested non-ITO A and is existed in histamine（1 μM of 3 ml of Histamine concentrations）Or electrochemical response when not depositing, exist as the result is shown
Cyclic voltammetry curve is almost consistent in the case where with or without histamine, it is meant that non-ITO A is to histamine almost without generation
Electrochemical response；
（7）The identification selection of molecular engram amphiphilic chitosan derivatives LB film modified electrode is tested
Using histidine and dopamine as the analogue in molecular engram LB film detection template molecular process.It is respectively configured 1
μM histamine solution, containing 5 μM of histidines and 1 μM of histamine solution, containing 5 μM of dopamines and 1 μM of histamine solution, contain
5 μM of histidine, dopamine and 1 μM of histamine solution totally 5 groups of solution, by same root molecular engram LB film modified electrode point
Above-mentioned solution Shi Bie not be adsorbed, surveys that its electrochemical response signal discovery peak point current difference is minimum, and reason is after 8-16 min
The hole that the electrode surface histamine trace leaves is only with histamine structure matching, and histidine and dopamine cannot be matching, therefore
Histidine and dopamine are noiseless to molecular engram LB film modified electrode identification histamine.
In the methods of the invention, step（2）With（3）Described in cholesterol-chitosan polycarbonate loadings be 25-300
μL（Concentration is 1.0 mg/mL）.
In the methods of the invention, step（3）Described in cholesterol-chitosan carbonic ester/histamine mixed composition LB film can
It is 1-30 layers, step（6）Described in cholesterol-chitosan carbonic ester LB film can be 1-30 layers.
In the methods of the invention, step（4）Described in for washing cholesterol-chitosan carbonic ester/histamine mixing LB
The mode of film modified ito glass electrode surface includes washing by soaking and elution, washing by soaking water 5-100 mL, wash time
8-20 min；Leaching quantity 5-20 mL, wash time 30-100 s.
In the methods of the invention, step（5）Described in molecular engram LB film modified electrode absorption histamine adsorption time
In 2-20 min；Step（5）Described in linear sweep voltammetry curve determination peak current response (i) and Histamine concentrations relationship,
Histamine concentrations are investigated at 0.01-500 μM.
In the methods of the invention, step（7）Described in analogue histidine and dopamine, their amount is in 0.5-
35 μM。
A kind of molecular engram amphiphilic chitosan derivatives LB film modified electrode made from above-mentioned construction method of the invention.
In the present invention, a kind of molecular engram amphiphilic chitosan derivatives LB made from above-mentioned construction method of the invention
Film modified electrode is applied as detection, the specific steps are：By introducing molecular engram amphiphilic shell in ito glass conductive circuit electrode surface
Polysaccharid derivative LB film assigns modified electrode to the Selective recognition of histamine, for standard sample-adding method to beer and grape wine reality
The average recovery rate of the detection of histamine in the sample of border, beer and wine sample is respectively 98.3-105.9%, 99.8-
105.2%, electrochemical response peak current relative standard deviation is less than 4.5% (n=3).
A kind of corresponding non-molecular engram amphiphilic chitosan derivatives LB film modified electrode of the present invention is by cholesterol-chitosan
Carbonic ester one pack system LB film modified electrode obtains after washing removes histamine step.
Molecular engram amphiphilic chitosan derivatives LB film modified electrode and its construction method provided by the invention and application,
Advantage is：
（1）As cholesterol-chitosan carbonic ester of molecular engram ultrathin membrane base-material in the present invention, by natural polymer chitin
Combine to be formed in the form of covalent with cholesterol after deacetylated, have biocompatibility and biodegradability, bioactivity,
The advantages that low immunogenicity；
（2）The present invention is using cholesterol-chitosan carbonic ester and histamine mixed component monolayer LB multilayer film as molecular engram
Ultrathin membrane precursor, due to LB thin film thickness, thickness is uniform and film thickness is controllable, prepares molecular engram film process template molecule thus and washes
De- faster more complete, template molecule elution efficiency directly affects the identification of molecular engram film, separating capacity；Due to molecular engram film
Identification process, target molecule can be rapidly introduced into the recognition site of molecular engram film in sample, and molecular engram film identifies target point
Subprocess is also more rapidly, it might even be possible to reach adsorption equilibrium in a few minutes.In short, due to the characteristic of LB film thickness, molecular engram
Film identity with higher, electrochemical response speed is fast, can be quickly detected blot signals by electrochemical method；
（3）The present invention has the characteristics that thin film thickness, film thickness are controllable, uniform fine and close using LB film, and molecular imprinting technology has
The characteristics of precordainment, identity and practicability and electrochemical method have many advantages, such as quickly, facilitate detection, in conjunction with these three
Method is in glass electrode surface-assembled histamine molecular engram LB film.
（4）The molecular engram amphiphilic cholesterol that the present invention uses-chitosan carbonic ester LB film immunoblot method, is current one
Novel, the exquisite surface molecule print technology of kind.This novel LB film surface molecular imprinting method is not only that environmental monitoring mentions
Theoretical foundation is provided for effective ways, and to study the molecularly imprinted polymer of other polymer surface functionalization.
The present invention for molecularly imprinted polymer ultrathin membrane sensing element structure design, modification conductive electrode building and
The specific detection of target molecule.
Detailed description of the invention
Fig. 1 is mixed for a kind of amphiphilic cholesterol-chitosan carbonic ester one pack system (a) prepared by the present invention and its with histamine
Average monomolecular film area (Area) isothermal of surface pressure (Surface pressure)-for being combined point (b) monomolecular film is bent
Line.
Fig. 2 is a kind of amphiphilic cholesterol-chitosan carbonic ester/histamine mixed component monomolecular film prepared by the present invention
Transfer curve.
Fig. 3 is a kind of molecular engram amphiphilic chitosan derivatives LB film modified electrode (I) constructed by the present invention and non-
The comparison diagram of the electrochemical response of molecular engram LB film modified electrode (II).
Fig. 4 is a kind of selectivity of molecular engram amphiphilic chitosan derivatives LB film modified electrode constructed by the present invention
Figure.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention will be described in detail
The present invention utilizes the design feature and interaction mechanism of amphipathic polymer and template molecule histamine, empty in Langmuir slot
Gas/parfacies interface forms amphiphilic chitosan derivatives/histamine mixed component monolayer；Mixed component is shifted by LB membrane technology
Monolayer constructs LB film and molecular engram LB film to the surface ITO.Compared with traditional molecular engram material, the present invention
The molecularly imprinted polymer LB film of building is a kind of novel molecular engram material, has good biocompatibility, can biology
The characteristics such as degradability, hypotoxicity and cell compatibility, analog cell membrane and as drug conveying carrier；It is printed with traditional molecule
Mark method compares, and the molecular engram method that the present invention uses is a kind of novel surface imprinted technology of exquisiteness, has both overcome conventional point
It is eluted from block molecular engram material not exclusively in sub- immunoblot method by the template molecule of trace, and it is ultra-thin to accelerate molecular engram
Membrane material by imprinted sites and target molecule in conjunction with.The surface imprinted technology of molecular engram ultrathin membrane will become molecular engram
The Disciplinary Frontiers of material development.
Embodiment 1
The synthesis of amphiphilic cholesterol-chitosan carbonic ester.Steps are as follows：First in the reaction vessel, 5.49 g cholesterol chlorine are taken
Formic acid esters is dissolved inN, NIn dimethylformamide, in 2.4 g 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide hydrochloride
Salt, which exists, and stirring is lower reacts 5 h（50℃）The cholesteryl chloroformate solution activated；Then add in another container
Enter 1.0 g chitosans and methanesulfonic acid, stirring is completely dissolved to chitosan, under nitrogen protection, above-mentioned steps is added dropwise and obtain
Activation cholesterol chloroformate solution, 60 h are reacted at 50 DEG C.Product mixed system is through precipitating, centrifugation, washing and freezing
It is dried to obtain cholesterol chitosan carbonic ester solid.The chemical structure of product is confirmed through infrared spectroscopy and nuclear-magnetism carbon spectrum.
Embodiment 2
（1）The preparation of amphiphilic cholesterol-chitosan carbonic ester and histamine solution
Cholesterol chitosan carbonic ester solid made from embodiment 1 is prepared into generating cholesterol -1.00 mg/mL of chitosan carbonic ester
Chloroformic solution, it is spare；Histamine is dissolved in the histamine solution of 1.0 mg/mL of compound concentration in ultrapure water, under cryogenic conditions
It saves, it is spare；
（2）The formation of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film
After completing previous work according to the requirement of Langmuir slot operating method, ultrapure water is added into slot（Resistivity >=
18.25 Ω·m）As parfacies, the group amine aqueous solution that 100 μ L concentration are 0.2 mg/mL is added dropwise with microsyringe
[the step of by embodiment 2（1）The group amine aqueous solution of preparation dilutes], 25 μ L are pipetted with microsyringe after mixing
The step of embodiment 2（1）Cholesterol-chitosan carbonic ester chloroformic solution is prepared, is slowly added dropwise to the parfacies water surface, makes its paving
Exhibition is on the water surface.It volatilizees completely to chloroform, the pressure sensor of Langmuir slot is zeroed, fixed sliding barrier speed is 50 cm2/
Min starts to compress A and the sliding barrier of B in Langmuir slot, obtains cholesterol-chitosan carbonic ester/histamine of orderly dense arrangement
Mixed composition Langmuir film（Monolayer）, record monolayer surface press-be averaged monolayer area isothermal curve and
Mixed composition film collapses pressure to determine the surface pressure of monolayer transfer.Step in the embodiment 2（2）Operation at least
In triplicate to ensure reproducibility.
Embodiment 3
The formation of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film.According to Langmuir slot operating method
Requirement complete previous work after, ultrapure water is added into slot（Resistivity >=18.25 Ω m）As parfacies, micro-sampling is used
Group amine aqueous solution [the step of by embodiment 2 that 100 μ L concentration are 0.2 mg/mL is added dropwise in device（1）The group amine aqueous solution of preparation
Dilute], the step of pipetting 50 embodiment 2 μ L with microsyringe after mixing（1）Cholesterol-chitosan of preparation
Carbonic ester chloroformic solution is slowly added dropwise to the parfacies water surface, spreads over it on water surface.It volatilizees completely to chloroform, pressure is passed
Sensor zero, fixed sliding barrier speed is 50 cm2/ min starts to compress the sliding barrier of A and B, obtains the cholesterol-of orderly dense arrangement
Chitosan carbonic ester/histamine mixed composition Langmuir film（Monolayer）, unimolecule is pressed-is averaged on the surface for recording monolayer
Level product isothermal curve and collapsing for mixed composition film are pressed to determine that the surface that monolayer shifts is pressed.The behaviour of the embodiment 3
Make at least in triplicate to ensure reproducibility.
Embodiment 4
The formation of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film.According to Langmuir slot operating method
Requirement complete previous work after, ultrapure water is added into slot（Resistivity >=18.25 Ω m）As parfacies, micro-sampling is used
Group amine aqueous solution [the step of by embodiment 2 that 100 μ L concentration are 0.2 mg/mL is added dropwise in device（1）The group amine aqueous solution of preparation
Dilute], the step of pipetting 75 embodiment 2 μ L with microsyringe after mixing（1）Cholesterol-chitosan of preparation
Carbonic ester chloroformic solution is slowly added dropwise to the parfacies water surface, spreads over it on water surface.It volatilizees completely to chloroform, pressure is passed
Sensor zero, fixed sliding barrier speed is 50 cm2/ min starts to compress the sliding barrier of A and B, obtains the cholesterol-of orderly dense arrangement
Chitosan carbonic ester/histamine mixed composition Langmuir film（Monolayer）, unimolecule is pressed-is averaged on the surface for recording monolayer
Level product isothermal curve and collapsing for mixed composition film are pressed to determine that the surface that monolayer shifts is pressed.The behaviour of the embodiment 4
Make at least in triplicate to ensure reproducibility.
Embodiment 5
The formation of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film.According to Langmuir slot operating method
Requirement complete previous work after, ultrapure water is added into slot（Resistivity >=18.25 Ω m）As parfacies, micro-sampling is used
Group amine aqueous solution [the step of by embodiment 2 that 100 μ L concentration are 0.2 mg/mL is added dropwise in device（1）The group amine aqueous solution of preparation
Dilute], the step of pipetting 100 embodiment 2 μ L with microsyringe after mixing（1）Cholesterol-chitosan of preparation
Carbonic ester chloroformic solution is slowly added dropwise to the parfacies water surface, spreads over it on water surface.It volatilizees completely to chloroform, pressure is passed
Sensor zero, fixed sliding barrier speed is 50 cm2/ min starts to compress the sliding barrier of A and B, obtains the cholesterol-of orderly dense arrangement
Chitosan carbonic ester/histamine mixed composition Langmuir film（Monolayer）, unimolecule is pressed-is averaged on the surface for recording monolayer
Level accumulates isothermal curve（As shown in figure 1 shown in b）It presses with collapsing for mixed composition film to determine that the surface that monolayer shifts is pressed.
Simultaneously in order to which compared with mixed component Langmuir film, production cholesterol-chitosan carbonic ester one-component Langmuir film is simultaneously
Press-be averaged monolayer area isothermal curve in the surface of record monolayer（As shown in figure 1 shown in a）.Every isothermal curve is at least
In triplicate to ensure reproducibility.
Embodiment 6
The formation of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film.According to Langmuir slot operating method
Requirement complete previous work after, ultrapure water is added into slot（Resistivity >=18.25 Ω m）As parfacies, micro-sampling is used
Group amine aqueous solution [the step of by embodiment 2 that 100 μ L concentration are 0.2 mg/mL is added dropwise in device（1）The group amine aqueous solution of preparation
Dilute], the step of pipetting 150 embodiment 2 μ L with microsyringe after mixing（1）Cholesterol-chitosan of preparation
Carbonic ester chloroformic solution is slowly added dropwise to the parfacies water surface, spreads over it on water surface.It volatilizees completely to chloroform, pressure is passed
Sensor zero, fixed sliding barrier speed is 50 cm2/ min starts to compress the sliding barrier of A and B, obtains the cholesterol-of orderly dense arrangement
Chitosan carbonic ester/histamine mixed composition Langmuir film（Monolayer）, unimolecule is pressed-is averaged on the surface for recording monolayer
Level product isothermal curve and collapsing for mixed composition film are pressed to determine that the surface that monolayer shifts is pressed.The behaviour of the embodiment 6
Make at least in triplicate to ensure reproducibility.
Embodiment 7
The formation of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film.According to Langmuir slot operating method
Requirement complete previous work after, ultrapure water is added into slot（Resistivity >=18.25 Ω m）As parfacies, micro-sampling is used
Group amine aqueous solution [the step of by embodiment 2 that 100 μ L concentration are 0.2 mg/mL is added dropwise in device（1）The group amine aqueous solution of preparation
Dilute], the step of pipetting 200 embodiment 2 μ L with microsyringe after mixing（1）Cholesterol-chitosan of preparation
Carbonic ester chloroformic solution is slowly added dropwise to the parfacies water surface, spreads over it on water surface.It volatilizees completely to chloroform, pressure is passed
Sensor zero, fixed sliding barrier speed is 50 cm2/ min starts to compress the sliding barrier of A and B, obtains the cholesterol-of orderly dense arrangement
Chitosan carbonic ester/histamine mixed composition Langmuir film（Monolayer）, unimolecule is pressed-is averaged on the surface for recording monolayer
Level product isothermal curve and collapsing for mixed composition film are pressed to determine that the surface that monolayer shifts is pressed.The behaviour of the embodiment 7
Make at least in triplicate to ensure reproducibility.
Embodiment 8
The formation of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film.According to Langmuir slot operating method
Requirement complete previous work after, ultrapure water is added into slot（Resistivity >=18.25 Ω m）As parfacies, micro-sampling is used
Group amine aqueous solution [the step of by embodiment 2 that 100 μ L concentration are 0.2 mg/mL is added dropwise in device（1）The group amine aqueous solution of preparation
Dilute], the step of pipetting 300 embodiment 2 μ L with microsyringe after mixing（1）Cholesterol-chitosan of preparation
Carbonic ester chloroformic solution is slowly added dropwise to the parfacies water surface, spreads over it on water surface.It volatilizees completely to chloroform, pressure is passed
Sensor zero, fixed sliding barrier speed is 50 cm2/ min starts to compress the sliding barrier of A and B, obtains the cholesterol-of orderly dense arrangement
Chitosan carbonic ester/histamine mixed composition Langmuir film（Monolayer）, unimolecule is pressed-is averaged on the surface for recording monolayer
Level product isothermal curve and collapsing for mixed composition film are pressed to determine that the surface that monolayer shifts is pressed.The behaviour of the embodiment 8
Make at least in triplicate to ensure reproducibility.
Embodiment 9
The transfer of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film.It is wanted according to Langmuir slot operating method
It asks, acetone, ethyl alcohol, 0.1 M sodium hydroxide and isopropanol mixture will be passed through（Volume ratio 1.5:1）It is ultrasonic respectively with deionized water
30 min and dry pretreated ito glass electrode [i.e. indium tin oxide (ITO) glass electrode is commercial product] is put into
It is the group amine aqueous solution of 0.2 mg/mL [by embodiment 2 with microsyringe 100 μ L concentration of dropwise addition in Langmuir slot
Step（1）The group amine aqueous solution of preparation dilutes], the step of 100 μ L embodiments 2 is pipetted with microsyringe after mixing
Suddenly（1）The cholesterol of preparation-chitosan carbonic ester chloroformic solution, is slowly added dropwise to the parfacies water surface, spreads over it on water surface.
It volatilizees completely to chloroform, pressure sensor is zeroed, fixed sliding barrier speed is 50 cm2/ min starts to compress the sliding barrier of A and B, when
The cholesterol chitosan carbonic ester of the sequence dense arrangement of formation/histamine mixed composition Langmuir film（Monolayer）Surface pressure
When for 41.00 mN/m, Langmuir-Blodgett is utilized（LB）Technology, with the speed of 5 mm/s by mixed composition monomolecular film
The transfer of film is completed in lifting, makes 4 tunic alternating deposits in ITO substrate, forms cholesterol-chitosan carbonic ester/histamine mixing
Component LB film modified ito glass electrode（Film transfer curve is shown in Fig. 2）, under equal conditions, construct 50 sheet modified electrodes.It is simultaneously
Compared with the ito glass electrode film modified with mixed component Langmuir, cholesterol-chitosan carbonic ester one-component LB is made
Film modified ito glass electrode.
Embodiment 10
The preparation of molecular engram amphiphilic chitosan derivatives LB film modified electrode.It is eluted with 10 mL ultrapure waters and is constructed by embodiment 8
Cholesterol-chitosan carbonic ester/histamine mixed LB film modification 1 min of ito glass electrode surface, remove histamine template molecule
Obtain molecular engram cholesterol-chitosan carbonic ester LB film modified electrode of identification histamine（Labeled as ITO A）, equal conditions
Under, 10 molecular engram LB film modified electrodes are constructed respectively.Under the same conditions simultaneously, it is eluted with 10 mL ultrapure waters by implementing
Film modified 1 min of ito glass electrode surface of cholesterol-chitosan carbonic ester one-component LB that example 8 makes, is prepared non-molecule
Trace LB film modified electrode（Labeled as non-ITO A）.
Embodiment 11
The preparation of molecular engram amphiphilic chitosan derivatives LB film modified electrode.It is embathed with 50 mL ultrapure waters and is constructed by embodiment 8
Cholesterol-chitosan carbonic ester/histamine mixed LB film modification 10 min of ito glass electrode surface, remove histamine template point
Son obtains molecular engram cholesterol-chitosan carbonic ester LB film modified electrode of identification histamine（Labeled as ITO B）.Equal conditions
Under, 10 molecular engram LB film modified electrodes are constructed respectively.
Embodiment 12
Absorption of the molecular engram LB film modified electrode ITO A constructed by embodiment 9 to histamine.Using three electrode body of electrochemistry
System, cyclic voltammetry potential range -0.4-0.8 V, 50 mV/s of scanning speed；With ethyl alcohol and 0.2 M KCl and 1mM K3Fe
(CN)6Test solution system of the water mixed solution as redox probe.Cyclic voltammetry is for measuring molecular engram LB
Film modified electrode is in histamine（3 ml 1µM）In the presence of or electrochemical response when not depositing, as the result is shown in optimization adsorption conditions
Under, to histamine quick response electrochemical signals, [shown in such as Fig. 3 (I), curve a is represented naked molecular engram LB film modified electrode in figure
ITO electrode, b represent ITO A, and c represents ITO A and is labeled as ITO A-HA in conjunction with a group amine molecule HA], and it is identical by embodiment 8
Non- molecular engram LB film modified electrode made from method（The process that template molecule histamine carries out trace is not added）It is several to histamine
Not having electrochemical response signal, [shown in such as Fig. 3 (II), curve a represents naked ITO electrode in figure, and b represents non-ITO A, c generation
Table non-ITO A is labeled as non-ITO A-HA in conjunction with a group amine molecule HA], i.e., molecular engram LB film modified electrode is in detection group
The sensitivity with higher of amine target molecule.The peak current response (i) of linear sweep voltammetry curve and Histamine concentrations are in 0.01-
In a linear relationship within the scope of 1.50 μM, 0.09 μM of detection limit (S/N=3), same root molecular engram LB film modified electrode is to group
The response peak current relative standard deviation of amine is 2.4% (n=6).
Embodiment 13
Absorption of the molecular engram LB film modified electrode ITO B constructed by embodiment 9 to histamine.Using three electrode body of electrochemistry
System, cyclic voltammetry potential range -0.4-0.8 V, 50 mV/s of scanning speed；With ethyl alcohol and 0.2 M KCl and 1mM K3Fe
(CN)6Test solution system of the water mixed solution as redox probe.Cyclic voltammetry is for measuring molecular engram LB
Film modified electrode is in histamine（3 ml 1µM）In the presence of or electrochemical response when not depositing, as the result is shown in optimization adsorption conditions
Under, molecular engram LB film modified electrode is overstepping one's bounds to histamine quick response electrochemical signals, and as made from 8 same procedure of embodiment
Sub- trace LB film modified electrode（The process that template molecule histamine carries out trace is not added）Histamine is rung almost without electrochemistry
Induction signal, i.e. molecular engram LB film modified electrode are in detection histamine target molecule sensitivity with higher.Linear sweep voltammetry
The peak current response (i) of curve and Histamine concentrations are in a linear relationship within the scope of 0.01-1.45 μM, detection limit (S/N=3)
0.10 μM, same root molecular engram LB film modified electrode is 2.5% (n=6) to the response peak current relative standard deviation of histamine
。
Embodiment 14
The identification selection of molecular engram LB film modified electrode.Using histidine and dopamine as molecular engram LB film detection template
Analogue in molecular process.1 μM of histamine solution (labeled as HA) is respectively configured, containing 5 μM of histidines and 1 μM
Histamine solution (being labeled as HA-HD) contains 5 μM of dopamines and 1 μM of histamine solution (being labeled as HA-DM), containing 5 μM
Histidine, dopamine and 1 μM of histamine solution totally 5 groups of solution (being labeled as HA-HD- DM), are printed by the molecule that embodiment 9 constructs
Mark LB film modified electrode A or B are inserted into above-mentioned solution respectively, its electrochemical response signal discovery peak point current value difference is surveyed after 8 min
Not minimum, reason is the hole and histamine molecular matching that electrode surface histamine trace leaves, as a group amine structure homologue
Histidine and dopamine cannot be matching, therefore histidine and dopamine are to molecular engram LB film modified electrode ITO A）Know
Other histamine is noiseless（As shown in Figure 4）.
Embodiment 15
Using the histamine in standard sample-adding method measurement beer actual sample.0.5,1.0 and 1.5 μ are separately added into test solution
M histamine solution, with the molecular engram LB film modified electrode constructed by embodiment 9（ITO A）Detect histamine average recovery rate difference
105.9,103.0 and 98.3%, standard deviation is respectively 3.5,2.6 and 2.7%, and realization rapidly and sensitively detects beer and Portugal
The histamine of trace in grape wine.
Embodiment 16
Using the histamine in standard sample-adding method measurement grape wine actual sample.0.5,1.0 and 1.5 are separately added into test solution
μM histamine solution, with the molecular engram LB film modified electrode constructed by embodiment 9（ITO B）Detect histamine average recovery rate difference
104.4,99.8 and 105.2%, standard deviation is respectively 1.9,3.5 and 4.3%, and realization rapidly and sensitively detects beer and Portugal
The histamine of trace in grape wine.
Above-mentioned specific embodiment is the further description to the present patent application, but the claims in the present invention are protected
Range be not limited to range described in embodiment, it is all using equivalent replacement or the technical solution of equivalent deformation,
Fall in the protection scope of the claims in the present invention.
Claims (10)
1. a kind of construction method of molecular engram amphiphilic chitosan derivatives LB film modified electrode, which is characterized in that including as follows
Step：
（1）The preparation of amphiphilic cholesterol-chitosan carbonic ester and histamine solution
Cholesterol-chitosan carbonic ester is dissolved in chloroform, a series of cholesterol-chitosan carbonic ester of various concentrations is prepared
Solution, constant volume are spare in volumetric flask；Histamine is dissolved in the histamine solution of 1.0 mg/mL of compound concentration in ultrapure water, in low
It is saved under the conditions of temperature, it is spare；
（2）The formation of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film
Ultrapure water is added into Langmuir slot as parfacies, 100 μ L are added dropwise by step with microsyringe（1）The group of preparation
The histamine solution that amine aqueous solution dilution is 0.2 mg/mL into concentration, uses microsyringe removing step after mixing（1）It prepares
Cholesterol-chitosan carbonic ester chloroformic solution, be slowly added dropwise to the parfacies water surface, spread over it on water surface；To chloroform
Volatilization completely, pressure sensor is zeroed, and fixed sliding barrier speed is 50 cm2/ min starts to compress sliding barrier, obtains orderly intensive
Single point is pressed-are averaged in the cholesterol of arrangement-chitosan carbonic ester/histamine mixed composition Langmuir film, record monomolecular film surface
Sub- membrane area isothermal curve and mixed composition film collapse pressure；Every isothermal curve is at least in triplicate to ensure reproducibility；
（3）The transfer of cholesterol-chitosan carbonic ester/histamine mixed composition Langmuir film
Pretreated ito glass electrode is put into Langmuir slot, ultrapure water is added into Langmuir slot as parfacies,
100 μ L are added dropwise by step with microsyringe（1）The group that concentration made of the group amine aqueous solution dilution of preparation is 0.2 mg/mL
Amine aqueous solution uses microsyringe removing step after mixing（1）The cholesterol of preparation-chitosan carbonic ester chloroform is molten
Liquid is slowly added dropwise to the parfacies water surface, spreads over it on water surface；It volatilizees completely to chloroform, pressure sensor is zeroed, it is fixed
Sliding barrier speed is 50 cm2/ min starts to compress sliding barrier, is compressed to step to sliding barrier（2）Middle cholesterol-chitosan carbonic ester/group
Amine mixed composition Langmuir film institute when monomolecular film area isothermal curve solid-state section half is pressed-is averaged on monomolecular film surface is right
Stop compression when the monomolecular film surface pressure answered, followed by Langmuir-Blodgett（LB）Technology, with the speed of 5 mm/s
Mixed composition monomolecular film is lifted to the transfer for completing film, is deposited on film in ITO substrate, forms cholesterol-chitosan carbonic acid
Ester/histamine mixed composition LB film modified ito glass electrode；
（4）The preparation of molecular engram amphiphilic chitosan derivatives LB film modified electrode
With a certain amount of milli-Q water by step（3）The cholesterol of formation-chitosan carbonic ester/histamine mixed LB film modification
Ito glass electrode surface certain time removes histamine template molecule and obtains molecular engram cholesterol-chitosan carbon of identification histamine
Acid esters LB film modified electrode；
（5）Recognition performance of the molecular engram amphiphilic chitosan derivatives LB film modified electrode to histamine
Using electrochemistry three-electrode system ,-0.4-0.8 V of cyclic voltammetry potential range, 50 mV/s of scanning speed；With second
Pure and mild 0.2 M KCl and 1mM K3Fe(CN)6Test solution system of the water mixed solution as redox probe；Using following
Ring voltammetry probes into molecular engram amphiphilic chitosan derivatives LB film modified electrode to the absorption property of histamine, difference test molecule
Trace LB film modified electrode is in the electrochemical response that 3 mL concentration are when 1 μM of histamine exists or do not deposit, the results showed that is optimizing
Under adsorption conditions, molecular engram LB film modified electrode can identify a group amine molecule, i.e., in terms of detecting histamine target molecule have compared with
High sensitivity, the peak current response (i) of linear sweep voltammetry curve and Histamine concentrations are within the scope of 0.01-1.50 μM
Linear relationship, 0.09 μM of detection limit (S/N=3), same root molecular engram LB film modified electrode is after adsorption-desorption 6 times circulations
Response peak current relative standard deviation to histamine is 2.4%.
2. a kind of construction method of molecular engram amphiphilic chitosan derivatives LB film modified electrode according to claim 1,
It is characterized in that, the building of non-molecular engram amphiphilic chitosan derivatives LB film modified electrode and its electrification in histamine solution
Learn responsiveness
1. the formation of cholesterol-chitosan carbonic ester monofilm：Ultrapure water is added into Langmuir slot as parfacies, use is micro
Sample injector pipettes 100 μ L steps（1）The cholesterol of preparation-chitosan carbonic ester chloroformic solution, is slowly added dropwise to the parfacies water surface
On, spread over it on water surface；It volatilizees completely to chloroform, pressure sensor is zeroed, fixed sliding barrier speed is 50 cm2/ min,
Start to compress sliding barrier, obtain cholesterol-chitosan carbonic ester Langmuir film of orderly dense arrangement, records monomolecular film surface
Pressure-averagely monomolecular film area isothermal curve and Langmuir film collapse pressure.Every isothermal curve is at least in triplicate with true
Protect reproducibility；
2. the transfer of cholesterol-chitosan carbonic ester Langmuir film：Pretreatment ito glass electrode is put into Langmuir slot
In, according to step, 1. it is poly- to be compressed to cholesterol-shell to sliding barrier by cholesterol-chitosan carbonate solution dropwise addition parfacies for method
Sugar charcoal acid esters Langmuir film is corresponding when monomolecular film area isothermal curve solid-state section half is pressed-is averaged on monomolecular film surface
Monomolecular film surface pressure when stop compression, followed by Langmuir-Blodgett（LB）Technology, will with the speed of 5 mm/s
The transfer of film is completed in monomolecular film lifting, is deposited on film in ITO substrate, and it is film modified to form cholesterol-chitosan carbonic ester LB
Ito glass electrode；
3. the production of non-molecular engram amphiphilic chitosan derivatives LB film modified electrode：It is eluted by step 2. with a certain amount of ultrapure water
The cholesterol of formation-chitosan carbonic ester LB film modified ito glass electrode surface certain time removes histamine template molecule and obtains
To molecular engram cholesterol-chitosan carbonic ester LB film modified electrode of non-identifying histamine（Labeled as non-ITO A）；
4. electrochemical response of the non-ITO A in histamine solution：Using with step（5）Identical electrochemistry three-electrode system
Solution system is tested with redox probe, uses cyclic voltammetry test non-ITO A in 3 ml concentration of concentration for 1 μM of group
Amine exists or electrochemical response when not depositing, and cyclic voltammetry curve is almost with or without histamine as the result is shown
Unanimously, it is meant that non-ITO A generates electrochemical response to histamine.
3. a kind of construction method of molecular engram amphiphilic chitosan derivatives LB film modified electrode according to claim 1,
It is characterized in that, the identification selection of molecular engram amphiphilic chitosan derivatives LB film modified electrode
Using histidine and dopamine as the analogue in molecular engram LB film detection template molecular process, specific steps
For：Be respectively configured 1 μM of histamine solution, containing 5 μM of histidines and 1 μM of histamine solution, containing 5 μM of dopamines and 1 μ
M histamine solution, the histidine containing 5 μM, dopamine and 1 μM of histamine solution totally 5 groups of solution, by same root molecular engram
LB film modified electrode identifies the above-mentioned solution of absorption respectively, and it is poor to survey its electrochemical response signal discovery peak point current after 8-16 min
Not minimum, reason is the hole and histamine structure matching that the electrode surface histamine trace leaves, and histidine and dopamine are not
Can be matching, therefore histidine and dopamine are to the identification histamine of molecular engram amphiphilic chitosan derivatives LB film modified electrode
It is noiseless.
4. a kind of construction method of molecular engram amphiphilic chitosan derivatives LB film modified electrode according to claim 1,
It is characterized in that, step（2）With（3）Described in cholesterol-chitosan carbonic acid ester concentration be 1.0 mg/mL, additional amount 25-
300 μL。
5. a kind of construction method of molecular engram amphiphilic chitosan derivatives LB film modified electrode according to claim 2,
It is characterized in that, step（3）Described in cholesterol-chitosan carbonic ester/histamine mixed composition LB film be 1-30 layers, it is described
Cholesterol-chitosan carbonic ester LB film is 1-30 layers.
6. a kind of construction method of molecular engram amphiphilic chitosan derivatives LB film modified electrode according to claim 1,
It is characterized in that, step（4）Described in for washing cholesterol-chitosan carbonic ester/histamine mixed LB film modification ito glass
The mode of electrode surface includes washing by soaking and elution, washing by soaking water 5-100 mL, wash time 8-20 min；Washing water
Measure 5-30 mL, wash time 30-100 s.
7. a kind of construction method of molecular engram amphiphilic chitosan derivatives LB film modified electrode according to claim 1,
It is characterized in that, step（5）Described in molecular engram LB film modified electrode absorption histamine adsorption time in 2-20 min.
8. a kind of construction method of molecular engram amphiphilic chitosan derivatives LB film modified electrode according to claim 1,
It is characterized in that, step（5）Described in linear sweep voltammetry curve determination peak current response (i) and Histamine concentrations relationship,
Histamine concentrations are investigated at 0.01-500 μM.
9. a kind of molecular engram amphiphilic chitosan derivatives LB made from any construction method of claim 1-8 is film modified
Electrode.
10. a kind of application of molecular engram amphiphilic chitosan derivatives LB film modified electrode as claimed in claim 9, feature exist
In by introducing molecular engram amphipathic chitose derivative LB film, imparting modified electrode pair in ito glass conductive circuit electrode surface
The Selective recognition of histamine, the detection for standard sample-adding method to histamine in beer and grape wine actual sample, beer and grape
The average recovery rate of histamine is respectively 98.3-105.9% in wine standardized sample, 99.8-105.2%, and glass conductive electrode is being inhaled
Electrochemical response peak current relative standard deviation is less than 4.5% after attached-circulation of desorption 3 times.
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