CN105628682B - Utilize the method for matrine content in composite modified dose of load pyrolytic graphite electrode electrogenerated chemiluminescence behavior determination medicine - Google Patents
Utilize the method for matrine content in composite modified dose of load pyrolytic graphite electrode electrogenerated chemiluminescence behavior determination medicine Download PDFInfo
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- 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
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Abstract
The present invention relates to a kind of method using matrine content in composite modified dose of load pyrolytic graphite electrode electrogenerated chemiluminescence behavior determination medicine, it is to utilize Ludox, the film forming of TiO 2 sol, the bigger serface of nano oxidized zinc-silver and the good electric property of CNT, it is prepared for composite modified dose, bipyridyl ruthenium is fixed on by pyrolytic graphite electrode surface based on this composite, the new method for preparing high-performance electric chemistry luminescence sensor is established, and based on matrine to Ru (bpy)3 2+Sensitization realizes the measure to matrine bolt.Under optimum experimental condition, matrine is 1.0 × 10‑8~1.0 × 10‑5Linear with relative luminous intensity in the range of mol/L, detection is limited to 8.16 × 10‑10Mol/L, continuous parallel determination 1.0 × 10‑5 Mol/L kuh-seng aqueous slkali 10 times, the relative standard deviation of luminous intensity is 4.25%.The measure that this method is used for matrine bolt has higher selectivity and sensitivity, and realizes the reuse of bipyridyl ruthenium.
Description
Technical field
It is more particularly to a kind of negative using composite modified dose the present invention relates to a kind of method for determining matrine content in medicine
The method for carrying matrine content in pyrolytic graphite electrode electrogenerated chemiluminescence behavior determination medicine.
Background technology
Matrine is made of the root by legume kuh-seng, strain and fruit extract through organic solvents such as ethanol, is biology
Alkali.Matrine has heat-clearing, diuresis, desinsection, clearing damp and other effects, while also has a variety of works such as antiviral, antitumor, antiallergy
With all kinds of preparations have been widely used for clinic, therefore determine the content of matrine in medicine, have safely to clinical application important
Meaning.At present, the assay method about matrine mainly has high performance liquid chromatography（HPLC）, efficient liquid phase-mass spectrography
（HPLC-MS）, Reversed phase high performance liquid chromatography method（RP-HPLC）, ion pair chromatography, capillary electrophoresis, thin layer chromatography scanning, gas phase color
Spectrometry（GC）, gas chromatography-mass spectrography, Fluorimetric Quenching Method etc..But these methods are operated loaded down with trivial details or set using valuable instrument
Standby or sensitivity is not high, it is impossible to fully meets the requirement of clinical trace analysis.Therefore, it is new to establish simple, quick, sensitive analysis
Method has great importance.
In presently disclosed document, 2 papers are the immediate prior arts of the present invention below：
(1) early stages such as Li Lijun, Luo Ying, Li Yanqing are on " bipyridyl ruthenium system ElectrochemiluminescDetermination Determination matrine
In research ", using bare electrode（Gold electrode）It is 4.0 × 10 in bipyridyl ruthenium concentration for working electrode-4Mol/L matrine is surveyed
Determine in system, its range of linearity is 1.5 × 10-7~1.5×10-4Mol/L, detection are limited to 7.3 × 10-9mol/L.The technology is not
On the one hand foot part is that every time measure is required to the expensive bipyridyl ruthenium of addition, measurement cost is high, while easily causes environment dirt
Dye；On the other hand compared with modified electrode system, matrine measure operation is relative complex, and easily causes because operation causes measurement to miss
Difference.
（2）Luo Ying, Li Lijun, Li Yanqing are waited in " Ludox-decorated by nano-gold gold electrode ElectrochemiluminescDetermination Determination kuh-seng
In the research of alkali ", use using nanogold as enhanced sensitivity material, by bipyridyl ruthenium technique for fixing, realize the efficient of bipyridyl ruthenium
Utilize, but be easily cracked during Ludox film forming, need to add it is suitable help film polyvinyl alcohol andL- cysteine, and the film technique
It is relatively conventional, so lack innovation enough in terms of electrode modification technology, and in terms of the matrine detection limit also compared with this technology at
In inferior position.
The content of the invention
The technical problem to be solved in the present invention is：One kind is provided using composite modified dose of load pyrolytic graphite electrode electroluminescentization
The method for learning matrine content in luminescent behavior measure medicine, this method utilize Ludox（Silica sol）, titanium dioxide it is molten
Glue（TiO2sol）Film forming, nano oxidized zinc-silver（ZnO@Ag）Bigger serface and CNT（MWCNTs）Well
Electric property, be prepared for Silica sol/MWCNTs- ZnO@Ag/TiO2Composite modified dose of sol, and pass through sensing
Device modification technique is by bipyridyl ruthenium（Ru(bpy)3 2+）Pyrolytic graphite electrode surface is supported on, prepares that stability is good, high sensitivity
Be used for determine the Electrochemiluminescsensor sensor of matrine, realize simple, the quick measure to matrine, this method is used for
The measure of matrine bolt has higher selectivity and sensitivity, and realizes the reuse of bipyridyl ruthenium.
Solve above-mentioned technical problem technical scheme be：One kind utilizes composite modified dose of load pyrolytic graphite electrode electroluminescentization
The method for learning matrine content in luminescent behavior measure medicine, comprises the following steps：
Multi-walled carbon nanotube after purification is configured to 0.001mol/L ~ 1.0mol/L multi-walled carbon nanotube solution A,；
B, the preparation of nano titanic oxide sol：By TiCl4It is 3.5~4.5% to be passed through dose volume fraction in ethanol
TiCl4- EtOH solution, takes TiCl4- EtOH solution simultaneously adjusts pH=8.5~9.0 with ammoniacal liquor, filters, filter cake is washed with deionized
To neutrality, H is used2O2Dissolving, adds Ludox and water, and it is molten that the 3.5~4.5h that flowed back in 92~98 DEG C obtains nano titanium oxide
Glue；H2O2, Ludox, the dosage of water press TiCl4- EtOH solution: H2O2: Ludox: the volume ratio of water is 1: 1.4~1.6: 0.2
~0.3: 3.2~3.4 calculate；
C, the preparation of nano zine oxide-silver-colored core-shell quanta dots：
C-1, by 0.1g silver nitrates: 28~32mL alcohol meters, silver nitrate is added in the ethanol solution that quickly stirs, and
Disperse 5~15min at 38~43 DEG C, obtain silver nitrate solution；
C-2, by 1g polyvinylpyrrolidones: 48~53mL alcohol meters, by polyvinylpyrrolidone add ethanol in and in
58~63 DEG C of 5~15min of dissolving, obtain polyvinylpyrrolidonesolution solution；
C-3, silver nitrate solution is added dropwise in polyvinylpyrrolidonesolution solution, silver nitrate solution and polyvinyl pyrrole
The volume ratio of alkanone solution is 1: 1~1.1, and 1.8~2.2h of reaction obtains silver sol；
C-4, by 0.01g NaOH: 22~28mL alcohol meters, NaOH is added at 48~53 DEG C disperse 15 in ethanol~
25min, obtain NaOH solution；
C-5, by 0.1g acetic anhydride zinc: 20~25mL alcohol meters, by acetic anhydride zinc add ethanol in, at 58~63 DEG C
15~25min dissolvings are persistently stirred down, obtain acetic anhydride zinc solution；
C-6, to obtain mixed solution, acetic anhydride zinc solution and silver sol by acetic anhydride zinc solution and silver sol are well mixed
Volume ratio is 1: 1.9~2.2, and mixed solution is progressively changed into Dark grey from initial yellow, final to stablize in grey, is now added
The polyethylene glycol of mixed liquor volume fraction 3.0~3.6%, after stirring 5~15min under the conditions of 48~53 DEG C, in fast in 30s
Speed adds the NaOH solution that step C-4 is prepared, and the addition of NaOH solution is mixed liquor volume fraction 64~70%, 38
0.8~1.2h is reacted at~43 DEG C, obtains ZnO@Ag core-shell quanta dots；
D, the preparation of sensor：
After polishing, polish, clean, room temperature is dried stand-by for D-1, pyrolytic graphite electrode；
D-2, the ZnO@Ag cores by 0.001mol/L ~ 1.0mol/L multi-walled carbon nanotube solution and 0.0025 mol/L
Shell quantum dot is 1 by volume:19~21 25~35min of ultrasonic disperse, prepare MWCNTs-ZnO@Ag composites, then with
Ludox, nano titanic oxide sol press MWCNTs-ZnO@Ag composites：Ludox：Nano titanic oxide sol volume ratio
1:1:2 ultrasonic mixings uniformly obtain homogeneous, stable Silica sol/MWCNTs- ZnO@Ag/TiO2Sol is compound molten
Liquid, by bipyridyl ruthenium solution:Ludox:MWCNTs-ZnO@Ag composites:Nano titanic oxide sol volume ratio is 1:1:1:
2 to Silica sol/MWCNTs- ZnO@Ag/TiO2It is molten that 0.001mol/L bipyridyl rutheniums are added in sol composite solutions
Liquid, sonic oscillation make its mixing, then take 1 ~ 4 μ L to add Silica sol/MWCNTs- ZnO@Ag of bipyridyl ruthenium solution
/ TiO2Sol composite solutions, it is added dropwise in the pyrolytic graphite electrode surface that step D-1 is obtained, is dried at 23~28 DEG C, you can
Obtain Silica sol/MWCNTs-ZnO@Ag/TiO2 sol - Ru(bpy)3 2+The pyrolytic graphite electrode of modification；
E, matrine content in medicine is determined：Silica sol/MWCNTs-ZnO@the Ag being prepared using step D
/ TiO2 sol - Ru(bpy)3 2+The pyrolytic graphite electrode of modification, conventionally determine matrine content in medicine.
The present invention further technical scheme be：Step A concrete operations are：Part multi-walled carbon nanotube is taken to be placed in dense sulphur
Acid is 3 with concentrated nitric acid volume ratio:In 1 solution, in 60 DEG C of back flow reaction 12h, using 0.22 μm of filtering with microporous membrane, filter cake is used
Deionized water is washed to neutrality, and 1mol/L multi-walled carbon nanotube solution is configured to by solvent of dimethylformamide after drying.
The polyethylene glycol is PEG200 polyethylene glycol.
The concentration of multi-walled carbon nanotube solution described in multi-walled carbon nanotube solution and step D-2 that step A is prepared is
0.008mol/L~0.012mol/L。
Electrogenerated chemiluminescence（Electrochemiluminescence, ECL）Analytic approach has that the range of linearity is wide, sensitivity
High and instrument is simple, controllability is strong, is easy to the advantages that detection, has been widely used in drug test, analysis, and chemical modification is electric
Pole technology by changing electrode surface micro-structural because can improving electrochemiluminescence analysis characteristic, improving modified electrode surface to surveying
The sensitivity of selectivity and the instrument detection of earnest matter, so by chemically modified electrode technology and electrochemiluminescence analysis method phase
With reference to being advantageous to widen the depth of investigation and application of the electrogenerated chemiluminescence method in Pharmaceutical Analysis, measure.
Nano zine oxide（ZnO）Because having unique skin effect, bulk effect, quantum size effect and macroscopical tunnel effect
Should, show many specific functions in catalysis, magnetics, optics etc..And metal Ag nano-particles have plasma resonance
Effect, when being combined into the small ZnO@Ag core-shell quanta dots of ultra micro with ZnO, the transfer of interface electronics can be directly affected, makes ZnO@
Ag has the performances such as unique electricity, catalysis.Meanwhile utilize multi-walled carbon nanotube（MWCNTs）Good electric conductivity and special
Electrical properties, by MWCNTs with ZnO@Ag are compound prepares composite modified dose of MWCNTs-ZnO@Ag of high activity.And in film forming agent
Aspect, Ludox（Silica sol）The milky white of three-dimensional net structure is uniformly diffuseed to form in water for silica colloidal particles
The translucent colloidal solution of color, there is higher caking property, adsorptivity, chemical inertness and preferable biocompatibility, catalysis to live
Property and it is almost non-swelling in water the features such as, it has also become important electrode modification film forming agent, but because Ludox is in film forming procedure
Volume contraction is larger, and film is easily cracked, and need to add certain auxiliary film forming matter, such as polyvinyl alcohol（PVA）, polyvinylpyrrolidone
（PVP）, kayexalate（PSS）Deng to improve Ludox filming performance.Improve Silica sol filming performances to establish
New method, research and utilization nano titanic oxide sol of the present invention（TiO2sol）During film forming have be not easily cracked, stability it is good
The advantages that, with TiO2Sol replaces traditional PVA, PVP and PSS, and by ratio optimization, has prepared that stability is good, corrosion resistant
The pyrolytic graphite modified electrode of erosion.
The present invention utilizes Silica sol, TiO2Sol film formings, and combine ZnO@Ag electrocatalysis and multi-wall carbon nano-tube
Pipe（MWCNTs）Satisfactory electrical conductivity, by the synergy between different component, its chemistry and electrochemical properties can be improved, be used for
Fixed bipyridyl ruthenium is used for the measure to matrine to establish a kind of new, efficient electrochemical luminescence sensor.This method
Not only simple to operate, high sensitivity, and the fixation of bipyridyl ruthenium is realized, brought so as to solve luminescence reagent constantly consumption
The problems such as analysis cost is high, environmental pollution.
The device have the advantages that it is described below again：
（1）The present invention is overcomes Ludox film forming to be easily cracked, with TiO 2 sol（Silica sol）Repaiied instead of tradition
Adorn agent polyvinyl alcohol, polyvinylpyrrolidone, kayexalate etc., using Silica sol filming performances it is good the advantages of,
The pyrolytic graphite modified electrode of stable performance, high sensitivity has been prepared, has innovated electrode modification technology, has been advantageous to electroluminescent chemistry
The expansion of luminescence technology application.
（2）When the present invention is determined by fixed bipyridyl ruthenium, in the case where modifying electrode conditions the same terms, it may be reused
Sample measure is carried out, and if not modifying fixed bipyridyl ruthenium, measure will add bipyridyl ruthenium solution every time, bipyridyl ruthenium
Usage amount is more.Meanwhile the amount of the bipyridyl ruthenium of modified electrode of the present invention is seldom, general composite solution usage amount is 2 μ L or so,
Bipyridyl ruthenium concentration is 1.0 × 10-3Mol/L, without immobilized bipyridyl ruthenium, addition concentration is 1.0 × 10 every time in reaction solution-4~1.0 × 10-3Mol/L bipyridyl ruthenium solution is at least 100 μ L, it is seen that the present invention is real by bipyridyl ruthenium load technology
Now to the recycling of bipyridyl ruthenium, reduce environmental pollution, save testing cost；In addition, with it is non-it is immobilized compared with, immobilized bipyridyl
Ruthenium improves transducer sensitivity.
（3）It is single with multi-walled carbon nanotube and ZnO@composite modified dose of replacement of Ag core-shell quanta dots on enhanced sensitivity material
Multi-walled carbon nanotube and ZnO@Ag core-shell quanta dots, are prepared for nano-nano type composite nanometer material modified electrode.
（4）Gold electrode is replaced with pyrolytic graphite electrode, has widened the diversity of electrode selection, and it is negative using composite modified dose
Bipyridyl ruthenium modification technique is carried, realizes the sensitive determination to matrine, the range of linearity is 1.0 × 10-8~1.0×10-5mol/
L, detection are limited to 8.16 × 10-10Mol/L, show that this method has lower detection limit.
With reference to the accompanying drawings and examples to a kind of electroluminescent using composite modified dose of load pyrolytic graphite electrode of the present invention
The technical characteristic of the method for matrine content is further described in chemiluminescence behavior determination medicine.
Brief description of the drawings
Fig. 1：ZnO@Ag core-shell quanta dots transmission electron microscopes of the present invention（TEM）Figure.
Fig. 2：Matrine is to Ru (bpy)3 2+Electrogenerated chemiluminescence intensity sensitization curve map；Wherein a. Silica sol
/ MWCNTs-ZnO@Ag / TiO2 sol - Ru(bpy)3 2+Pyrolytic graphite electrode is modified 1.0 × 10-5 Mol/L matrines
Determined with 0.2mol/L PBS (pH 8.5) mixed solution；B. naked pyrolytic graphite electrode is 1.0 × 10-5 Mol/L kuh-sengs
Determined in alkali and 0.2mol/L PBS (pH 8.5) mixed solution；c. Silica sol / MWCNTs-ZnO@Ag / TiO2
sol - Ru(bpy)3 2+Modification pyrolytic graphite electrode determines in 0.2mol/L PBS (pH 8.5) solution.
Fig. 3：Influence curve figures of the cushioning liquid pH to electrochemical luminescence intensity.
Fig. 4：Influence curve figure of the dressing agent dosage to ECL intensity.
Fig. 5：Silica sol、TiO2Sol is with the influence curve figure for comparing ECL, wherein a. Ludox/water/second
Alcohol-Ru (bpy)3 2+(1.0×10-3 mol/L) ( 1:2:1:1, V/V) modification pyrolytic graphite electrode, b. Ludox/bis-
Titanium oxide sol/ethanol-Ru (bpy)3 2+(1.0×10-3 mol/L) ( 1:2:1:1, V/V) modification pyrolytic graphite electricity
Pole, c. water/TiO 2 sol/ethanol-Ru (bpy)3 2+(1.0×10-3 mol/L) ( 1:2:1:1, V/V) repair
Adorn pyrolytic graphite electrode.
Fig. 6：MWCNTs volumes are to system electrogenerated chemiluminescence intensity effect curve map.
Fig. 7：Ru(bpy)3 2+Influence curve figure of the concentration to ECL.
Fig. 8：The calibration curve of matrine.
Fig. 9：The reappearance schematic diagram that METHOD FOR CONTINUOUS DETERMINATION is 10 times.
Embodiment
Embodiment 1：One kind is using in composite modified dose of load pyrolytic graphite electrode electrogenerated chemiluminescence behavior determination medicine
The method of matrine content, comprises the following steps：
（1）The purifying of multi-walled carbon nanotube
It is 3 to take part multi-walled carbon nanotube to be placed in the concentrated sulfuric acid with concentrated nitric acid volume ratio:It is anti-in 60 DEG C of backflows in 1 solution
12h is answered, using 0.22 μm of filtering with microporous membrane, filter cake is washed with deionized to neutrality, with dimethylformamide after drying
（DMF）0.01mol/L multi-walled carbon nanotube solution is configured to for solvent.
（2）The preparation of nano titanic oxide sol
By 4mLTiCl4100mL ethanol solutions are passed through, take 20mL TiCl4- EtOH solution is simultaneously adjusted with 37mL 2.5% ammoniacal liquor
PH=8.8 are saved, are filtered, filter cake is washed with deionized to neutrality, with 30mL H2O2Dissolving, adds 5 mL Ludox and 65 mL
Water, flow back 4h in 95 DEG C.
（3）The preparation of ZnO@Ag core-shell quanta dots
The present invention prepares ZnO@Ag core-shell quanta dots in ethanol solution at relatively low temperature.First, in silver-colored seed
In preparation, using silver nitrate as presoma, PVP is used as stabilizer and reducing agent, that is, takes 0.169g silver nitrates to add quick stirring
50mL ethanol solutions in, and at 40 DEG C disperse 10min；Meanwhile 1g PVP are added in 50mL ethanol and in 60 DEG C of dissolvings
10min, is then added dropwise to PVP solution by silver nitrate solution, and reaction 2h obtains silver sol.Secondly, 0.04g NaOH are taken, and in
Disperse 20min at 50 DEG C in 100mL ethanol；Similarly, that 0.2195 g acetic anhydrides zinc is persistently stirred into 20min at 60 DEG C is molten
In 50mL ethanol.Finally, acetic anhydride zinc solution and silver sol are well mixed, mixed solution can be observed by initial yellow
Progressively it is changed into Dark grey, it is final to stablize in grey, 5.0 mL PEG 200 are now added, after 10min is stirred at 50 DEG C, in
The NaOH solution prepared early stage is rapidly added in 30s, 1h is reacted at 40 DEG C, both can obtain ZnO@Ag core-shell quanta dots（Such as
Fig. 1）.
（4）The preparation of sensor
Pyrolytic graphite electrode is polished with abrasive paper for metallograph respectively, A12O3 Powder is polished to minute surface, rinses out unnecessary polishing powder
It is cleaned by ultrasonic successively with water, absolute ethyl alcohol He Shui, water afterwards, room temperature is dried stand-by.
First by a certain amount of 0.01mol/L multi-walled carbon nanotube solution and ZnO@Ag core-shell quanta dots（0.0025 mol/L）
By volume 1:20 ultrasonic disperse 30min, formed MWCNTs-ZnO@Ag composites, then with Silica sol, TiO2Sol is pressed
Volume ratio 1:1:2 vibrations are mixed to get homogeneous, stable Silica sol/TiO2Sol/MWCNTs- ZnO@Ag are compound
Solution.A certain amount of 0.001mol/L bipyridyl ruthenium solution is added into the solution（Volume ratio, Silica sol/MWCNTs-
ZnO@Ag / TiO2 sol/ Ru(bpy)3 2+=1:1:2:1）, sonic oscillation makes its mixing.Then 2 μ L are taken with micropipette rifle
The composite solution of bipyridyl ruthenium solution is added, is added dropwise on pyrolytic graphite electrode surface, is dried at 25 DEG C, you can obtain
Silica sol / MWCNTs-ZnO@Ag / TiO2 sol - Ru(bpy)3 2+The pyrolytic graphite electrode of modification.Same method,
By changing dressing agent dosage, modified electrode of different nature is made respectively.
（5）Determine matrine content in medicine：Use step（4）Silica sol/MWCNTs-ZnO the@being prepared
Ag / TiO2 sol - Ru(bpy)3 2+The pyrolytic graphite electrode of modification, test on MPI-E type electrogenerated chemiluminescence work stations
Carry out, scanned using CV（0.2-1.25 V）, photomultiplier negative high voltage is 800 V, and sweep speed is 100 mV/S, supports electricity
Solution matter is 0.2 mol/L phosphate buffers（PBS, pH=8.5）, determined at 25 DEG C, solution ultrasonic degassing 5 before measure
Min, electrochemical luminescence signals are recorded, with matrine-Ru (bpy)3 2+The peak height of the luminous signal of systemIDraw peak height intensity with
The calibration curve of matrine, and carry out the quantitative analysis of matrine.
As one kind conversion of the present embodiment, step（4）In the preparation process of sensor, multi-walled carbon nanotube solution it is dense
Degree can suitably adjust change, can be 0.001mol/L, 0.1mol/L or 1.0mol/L, general multi-walled carbon nanotube solution
Concentration selection is 0.001mol/L ~ 1.0mol/L；Corresponding step（1）Multi-walled carbon nanotube purify during, preparation it is more
The concentration of wall carbon nano tube solution is according to step（4）It needs to be determined that.
Under optimum experimental condition, matrine is 1.0 × 10-8~1.0 × 10-5It is strong with relative luminous in the range of mol/L
Spend linear（r2=0.9938）, detection limit (S/N=3) is 8.16 × 10-10mol/L.Continuous parallel determination 1.0 × 10-5
Mol/L kuh-seng aqueous slkali 10 times, the relative standard deviation of luminous intensity（RSDs）For 4.25%.Rate of recovery examination is carried out to sample
Test, the rate of recovery is between 97.25~104.80%.This method is used for the measure of matrine bolt with higher selectivity and sensitive
Degree, and the range of linearity is wide low with detection limit, while this method is not only simple to operate, and the reuse of bipyridyl ruthenium is realized,
The problems such as analysis cost that is brought so as to solve luminescence reagent constantly to consume is high, environmental pollution.
Using the present invention, method carries out sample analysis as described in Example 1：Take 1 matrine bolt（Specification：50mg/ grains）,
Ultrasonic dissolution adds deionized water ultrasonic dissolution in 5mL 0.1mol/L hydrochloric acid, and constant volume is in 100mL after washing and filtering repeatedly
It is rear to be diluted according to required measurement concentration in brown volumetric flask, and standard items recovery analysis and sample measure are carried out in 25 DEG C,
Wherein the rate of recovery is 97.25% ~ 104.80%, and result of the test is as shown in table 1.
The sample of table 1 determine and recovery test (n=5)
The present invention is using pyrolytic graphite electrode as working electrode, by TiO2Sol is applied to chemically modified electrode, is prepared for
Silica sol / MWCNTs- ZnO@Ag / TiO2Sol compounds, bipyridyl ruthenium development is loaded based on the composite
Electrochemistry of solids luminescence sensor there is good ECL behaviors.TiO2Sol addition improves the stability of modified membrane, and
MWCNTs- ZnO@Ag add catalytic activity and the sensitivity for significantly improving sensor.It is real by the fixation to bipyridyl ruthenium
The recycling of bipyridyl ruthenium is showed, sensitivity is improved while reducing analysis cost.The sensor is used for electrochemical luminescence
Method measure matrine bolt has the characteristics that method high sensitivity, the range of linearity are wide low with detection limit.
The research process of the present invention is as follows：
1st, the electrochemical luminescence behavior of matrine
1.0 × 10 have been investigated with cyclic voltammetry-5 0.2 mol/L of the mol/L matrine in supporting electrolyte pH=8.5
Electrochemical luminescence behavior in phosphate buffer solution.When current potential is swept to 1.25 V from 0.2 V, do not have on electrochemical luminescence figure
It was observed that luminous signal, therefore matrine does not produce electrochemical luminescence on pyrolytic graphite electrode.
2nd, matrine is to Ru (bpy)3 2+Sensitization
Ru (bpy) has been investigated in experiment respectively3 2+Electrochemical luminescence and matrine are to Ru (bpy)3 2+Sensitization（Such as Fig. 2
It is shown）.Wherein, a is Ru (bpy) in modified electrode in Fig. 23 2+1.0 × 10-5 Electrochemical luminescence in mol/L kuh-seng aqueous slkalis
Behavior；B is matrine-Ru (bpy) in Fig. 23 2+Electrochemical luminescence behavior of the system on bare electrode surface；C is to repair in Fig. 3
Adorn Ru (bpy) in electrode3 2+Electrochemical luminescence behavior in blank solution.
Analyzed from a in Fig. 2 and c, at Ru (bpy)3 2+In blank test, due to Ru (bpy)3 2+Bury in oblivion luminescence mechanism,
Its electrochemical luminescence intensity level is weaker, but when 1.0 × 10-5 Mol/L matrine and Ru (bpy)3 2+Form matrine-Ru
(bpy)3 2+During system, there is stronger electrochemical luminescence on modified electrode and bare electrode, matrine is to Ru (bpy)3 2+Electricity
Chemiluminescence has obvious sensitization.Meanwhile compared with bare electrode, matrine-Ru (bpy)3 2+System is on modified electrode
Not only there is stronger luminous signal, and replication can be realized, be advantageous to save Ru (bpy)3 2+Dosage, reduce environmental pollution.
3rd, the influence of buffer system and pH value to ECL
Buffer system and pH value are to amine-Ru (bpy)3 2+System electrochemical luminescence has important influence.The present invention investigates
0.2 mol/L H3BO3-0.05 mol/L Na2B4O7·10H2O buffer systems（BBS）With 0.2 mol/L Na2HPO4-0.3
mol/L NaH2PO4Buffer system（PBS）To matrine-Ru (bpy)3 2+The influence of the ECL strength and stabilities of system（Such as Fig. 3
It is shown）.As a result show, in dressing agent（Silica sol、TiO2sol、 MWCNTs（1mol/L）-ZnO@Ag、Ru(bpy)3 2+
(1.0×10-3 Mol/L) volume ratio is 1:2:1:1）Under the conditions of dosage is 1 μ L, when phosphate buffer is as supporting electrolyte
Luminous intensity be relatively higher than borate buffer systems, and when pH 8.5 phosphate buffer is as supporting electrolyte, system
Luminous intensity it is relatively stable.Therefore, experimental selection pH 8.5 phosphate buffer.
4th, the selection of modification amount
Dressing agent pyrolytic graphite electrode surface overlay capacity to Ru (bpy)3 2+Electrogenerated chemiluminescence has a major impact, examination
Test the influence for having investigated modification amount to ECL between 1~4 μ L.Fig. 4 shows, in Silica sol, TiO2 sol、 MWCNTs
（1mol/L）-ZnO@Ag、Ru(bpy)3 2+(1.0×10-3 Mol/L) volume ratio is 1:2:1:Under the conditions of 1, matrine-Ru
(bpy)3 2+System electrogenerated chemiluminescence intensity level subtracts afterwards as the increase of working electrode surface overlay capacity first increases, and goes out in 2 μ L
Existing maximum.This is probably that electrode surface loads Ru (bpy) because when dressing agent dosage is few3 2+Amount it is relatively fewer, system
Electrochemical luminescence value is low；And increasing with dressing agent dosage, electrode surface film thickness also constantly increase, make electronics in film
Transmit resistance and become big.
5、Silica sol、TiO2Sol ratio optimizations
As film forming agent Silica sol, TiO2Sol, it is with the stability and matrine for comparing electrode in modification electricity
To Ru (bpy) on extremely3 2+Sensitization have a major impact.More directly to react Silica sol, TiO2Sol is to modified electrode
The influence of performance, test and MWCNTs-ZnO@Ag solution is replaced with ethanol, and to Silica sol and TiO2Sol blank sample is then
Replaced with water.By analyzing to modified electrode ECL strength and stabilities, different Silica sol, TiO have studied2Sol is matched
To modified electrode ECL performance impacts（Fig. 5）.A shows in Fig. 5, when without TiO2During sol, matrine-Ru (bpy)3 2+System repairing
It is stronger to adorn electrode surface electrochemical luminescence initial value, and with measure number increase, electrochemical luminescence intensity in after first rapid decline by
Walk moderate tone.This is probably because due to part Ru (bpy) when the 1st time determines3 2+Modified electrode surface is attached to, system has
Relatively strong ECL responses, and with the increase of measure number, exist during due to Silica sol film forming shrink it is big, be easily cracked
The shortcomings that, it is supported on Ru (bpy) in modified electrode film3 2+Meeting part dissolution, declines measure system at initial stage electrochemical luminescence intensity
Substantially, Ru (bpy) is worked as3 2+Electrochemical luminescence intensity tends towards stability during dissolution unobvious.Equally, because of Ru when initial stage determines
(bpy)3 2+Modified electrode surface is attached to, electrochemical luminescence intensity is relatively strong when b and c also show to determine for the 1st time, but
Unlike a, due to TiO2Sol films are comparatively dense, the electron transmission being unfavorable between electrode surface and solution, so as to influence
ECL intensity.So c, compared with a, due to not mixing Silica sol, modified electrode surface electronic transmission speed is obstructed, and makes system
ECL intensity is relatively poor, but it is preferable to survey timing stability；As Silica sol, TiO2When sol is compounded, it is not only advantageous to improve
ECL intensity, and modified electrode shows preferable stability, therefore Silica sol and TiO are selected in experiment2Sol volume ratios are
1:2。
6th, the selection of MWCNTs volumes
To probe into MWCNTs and ZnO@Ag to matrine-Ru (bpy)3 2+The synergy of system ECL intensity, has been investigated not
With the influence under MWCNTs volumes to system ECL（As shown in Figure 6）.Experiment is learnt, between 0~1.0mol/L, system ECL
Intensity is in first to increase to subtract afterwards with the increase of MWCNTs molar concentrations, and 1.0 × 10-2 Maximum is reached during mol/L.With this section 5
（Silica sol、TiO2Sol ratio optimizations）Compared to understanding, MWCNTs and ZnO@Ag have preferable electro-catalysis effect, but work as
When MWCNTs volumes are larger, there is stronger inhibitory action to system ECL intensity, consider, this experiment selects 1.0 × 10-2
Mol/L MWCNTs are the concentration of modified electrode.
7、Ru(bpy)3 2+The selection of concentration
Preparing Silica sol/MWCNTs-ZnO@Ag/TiO2 sol - Ru(bpy)3 2+During modified gold electrode,
As the Ru of dressing agent and luminescence reagent (bpy)3 2+, its concentration is to matrine-Ru (bpy) 3 2+The electricity of system on the working electrode (s
Chemiluminescence behavior is caused to have a significant impact.Research is by investigating 1.0 × 10-4mol/L~1.0×10-2Ru in the range of mol/L
(bpy)3 2+Influence of the concentration to measure system electrogenerated chemiluminescence behavior（As shown in Figure 7）.Experiment shows, Ru (bpy)3 2+Concentration
To matrine-Ru (bpy) 3 2+The electrochemical luminescence intensity of system has a significant impact, and system electrochemical luminescence peak value is with Ru
(bpy)3 2+Concentration increases and increased.To save Ru (bpy)3 2+, reduce environmental pollution, meanwhile, to realize optimum signal-noise ratio, therefore try
Test selection 1.0 × 10-3 mol/L Ru(bpy)3 2+Carry out the electrochemiluminescence analysis research of matrine.
8th, the optimum choice of instrument parameter
In ECL instrument parameters, photomultiplier negative high voltage is the major influence factors of its sensitivity and linear measurement range, is
Realize that detection signal is optimal, study Silica sol/MWCNTs-ZnO@Ag/TiO2 sol - Ru(bpy)3 2+Modification heat
Solution graphite electrode is put into containing 1.0 × 10-5 In the phosphate buffer solutions of pH 8.5 of mol/L matrines, negative high voltage has been investigated
From -600 V change to -900 V during to matrine-Ru (bpy) 3 2+The influence of system electrochemical luminescence signal to noise ratio, find
Signal to noise ratio increases first increases and then decreases with negative high voltage, and reaches optimum value in -800 V, therefore selects -800 V.
Meanwhile under the mV/s sweep speeds of 20 mV/s ~ 120, matrine-Ru (bpy) 3 2+The electrochemical luminescence peak of system
The high trend to be eased up afterwards with sweep speed increase in first increasing, this may be with Ru in system (bpy) 3 2+Oxidation rate and matrine
Ru (bpy) is reduced after betatopic 3 3+Speed it is relevant, take into account lowering apparatus loss, using 100 mV/s as optimal test rate.
9th, the range of linearity and detection line of ECL sensors
In optimal conditions, investigate various concentrations kuh-seng aqueous slkali Silica sol/MWCNTs-ZnO Ag/
TiO2 sol - Ru(bpy)3 2+The electrochemical luminescence intensity response curve modified on pyrolytic graphite electrode, matrine exist
1.0×10-8~1.0×10-5 In the range of mol/L and relative peak height is in good linear relation（R 2=0.9938,n=16）, its is linear
Regression equation is：I（Counts）= 26.60×107 C+ 1404.7, detection limit (S/N=3) it is 8.16 × 10-10 mol/L（Figure
8）.
10th, the reappearance and anti-interference of ECL sensors
It is loaded with Ru (bpy)3 2+Silica sol/MWCNTs-ZnO@Ag/TiO2 sol - Ru(bpy)3 2+Repair
Decorations pyrolytic graphite electrode has preferable reappearance.Under the selected optimum condition of experiment, with modified electrode to 1.0 × 10-5
Mol/L matrines METHOD FOR CONTINUOUS DETERMINATION 10 times, the RSD of its ECL intensity level is 4.25%（Fig. 9）, show that the sensor is sent out for electrochemistry
Light measurement matrine has good reappearance.
In addition, the molar concentration of fixed matrine standard items is 1.0 × 10-5 Mol/L, the common inorganic salts in part are investigated
Ion and other influences of class material to system ECL.As a result show, keep relative measurement error≤± 0.5%, 1000 times of Na+、K+、Zn2+、SO4 2-、Cl-、CO3 2-；50 times of starch, glucose；25 times of Fe2+、Mg2+、Fe3+、Ca2+、Cu2+；2 times of sugarcane
Sugar, maltose do not produce interference to the measure of matrine.
Claims (4)
1. one kind utilizes matrine content in composite modified dose of load pyrolytic graphite electrode electrogenerated chemiluminescence behavior determination medicine
Method, it is characterised in that：Comprise the following steps：
Multi-walled carbon nanotube after purification is configured to 0.001mol/L ~ 1.0mol/L multi-walled carbon nanotube solution A,；
B, the preparation of nano titanic oxide sol：By TiCl4It is passed through the TiCl that dose volume fraction in ethanol is 3.5~4.5%4-
EtOH solution, takes TiCl4- EtOH solution simultaneously adjusts pH=8.5~9.0 with ammoniacal liquor, filters, filter cake is washed with deionized into
Property, use H2O2Dissolving, adds Ludox and water, and the 3.5~4.5h that flowed back in 92~98 DEG C obtains nano titanic oxide sol；
H2O2, Ludox, the dosage of water press TiCl4- EtOH solution: H2O2: Ludox: the volume ratio of water be 1: 1.4~1.6: 0.2~
0.3: 3.2~3.4 calculate；
C, the preparation of nano zine oxide-silver-colored core-shell quanta dots：
C-1, by 0.1g silver nitrates: 28~32mL alcohol meters, silver nitrate is added in the ethanol solution that quickly stirs, and 38~
Disperse 5~15min at 43 DEG C, obtain silver nitrate solution；
C-2, by 1g polyvinylpyrrolidones: 48~53mL alcohol meters, polyvinylpyrrolidone is added in ethanol and in 58~
63 DEG C of 5~15min of dissolving, obtain polyvinylpyrrolidonesolution solution；
C-3, silver nitrate solution is added dropwise in polyvinylpyrrolidonesolution solution, silver nitrate solution and polyvinylpyrrolidone
The volume ratio of solution is 1: 1~1.1, and 1.8~2.2h of reaction obtains silver sol；
C-4, by 0.01g NaOH: 22~28mL alcohol meters, NaOH is added at 48~53 DEG C disperse 15 in ethanol~
25min, obtain NaOH solution；
C-5, by 0.1g acetic anhydride zinc: 20~25mL alcohol meters, by acetic anhydride zinc add ethanol in, held at 58~63 DEG C
Continuous stirring 15~25min dissolvings, obtain acetic anhydride zinc solution；
C-6, to obtain mixed solution, acetic anhydride zinc solution and silver sol volume by acetic anhydride zinc solution and silver sol are well mixed
It is final stable in grey than for 1: 1.9~2.2, mixed solution is progressively changed into Dark grey from initial yellow, now add mixing
The polyethylene glycol of liquor capacity fraction 3.0~3.6%, after stirring 5~15min under the conditions of 48~53 DEG C, in 30s rapidly plus
Enter the NaOH solution that step C-4 is prepared, the addition of NaOH solution is mixed liquor volume fraction 64~70%, 38~43
0.8~1.2h is reacted at DEG C, obtains ZnO@Ag core-shell quanta dots；
D, the preparation of sensor：
After polishing, polish, clean, room temperature is dried stand-by for D-1, pyrolytic graphite electrode；
D-2, the ZnO@Ag nucleocapsid amounts by 0.001mol/L ~ 1.0mol/L multi-walled carbon nanotube solution and 0.0025 mol/L
Son point is 1 by volume:19~21 25~35min of ultrasonic disperse, MWCNTs-ZnO@Ag composites are prepared, then it is molten with silicon
Glue, nano titanic oxide sol press MWCNTs-ZnO@Ag composites：Ludox：Nano titanic oxide sol volume ratio 1:1:2
Ultrasonic mixing uniformly obtains homogeneous, stable Silica sol/MWCNTs- ZnO@Ag/TiO2Sol composite solutions, are pressed
Bipyridyl ruthenium solution:Ludox:MWCNTs-ZnO@Ag composites:Nano titanic oxide sol volume ratio is 1:1:1:2 to this
Silica sol / MWCNTs- ZnO@Ag / TiO20.001mol/L bipyridyl ruthenium solution is added in sol composite solutions, is surpassed
Sound oscillation makes its mixing, then take 1 ~ 4 μ L add bipyridyl ruthenium solution Silica sol/MWCNTs- ZnO@Ag/
TiO2Sol composite solutions, it is added dropwise in the pyrolytic graphite electrode surface that step D-1 is obtained, is dried at 23~28 DEG C, you can
To Silica sol/MWCNTs-ZnO@Ag/TiO2 sol - Ru(bpy)3 2+The pyrolytic graphite electrode of modification；
E, matrine content in medicine is determined：Silica sol/MWCNTs-ZnO@the Ag being prepared using step D/
TiO2 sol - Ru(bpy)3 2+The pyrolytic graphite electrode of modification, conventionally determine matrine content in medicine.
2. according to claim 1 utilize composite modified dose of load pyrolytic graphite electrode electrogenerated chemiluminescence behavior determination medicine
The method of matrine content in thing, it is characterised in that：Step A concrete operations are：Part multi-walled carbon nanotube is taken to be placed in dense sulphur
Acid is 3 with concentrated nitric acid volume ratio:In 1 solution, in 60 DEG C of back flow reaction 12h, using 0.22 μm of filtering with microporous membrane, filter cake is used
Deionized water is washed to neutrality, and 1mol/L multi-walled carbon nanotube solution is configured to by solvent of dimethylformamide after drying.
3. according to claim 1 utilize composite modified dose of load pyrolytic graphite electrode electrogenerated chemiluminescence behavior determination medicine
The method of matrine content in thing, it is characterised in that：The polyethylene glycol is PEG200 polyethylene glycol.
4. according to claim 1 utilize composite modified dose of load pyrolytic graphite electrode electrogenerated chemiluminescence behavior determination medicine
The method of matrine content in thing, it is characterised in that：It is more described in the multi-walled carbon nanotube solution and step D-2 that step A is prepared
The concentration of wall carbon nano tube solution is 0.008mol/L ~ 0.012mol/L.
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