CN109142474A - A kind of carbon nanomaterial modified electrode that can detect Cu+ and pH simultaneously and preparation method - Google Patents
A kind of carbon nanomaterial modified electrode that can detect Cu+ and pH simultaneously and preparation method Download PDFInfo
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- CN109142474A CN109142474A CN201710502964.XA CN201710502964A CN109142474A CN 109142474 A CN109142474 A CN 109142474A CN 201710502964 A CN201710502964 A CN 201710502964A CN 109142474 A CN109142474 A CN 109142474A
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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
- G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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Abstract
The invention discloses a kind of carbon nanomaterial modified electrodes and preparation method thereof, with carbon nanomaterial, Cu+Recognition ligand, reference molecules, pH response molecule are raw material, in a solvent, under the conditions of 10-25 DEG C, by carbon nanomaterial, Cu+The carbon nanomaterial modified electrode is prepared on carbon nanomaterial in recognition ligand, reference molecules, pH response molecular modification.The invention also discloses the carbon nanomaterial modified electrodes to detect Cu simultaneously in vivo and in vitro+With the application in pH.The invention also discloses the carbon nanomaterial modified electrodes to detect Cu at the same time+With the application in pH, carbon nanomaterial modified electrode of the invention has the advantages that highly selective and highly sensitive；For measuring intracorporal metal ion (Cu+) and pH, it can be achieved that simultaneously, in situ, online Electrochemical Detection in real time.Carbon nanomaterial modified electrode of the invention, for furtheing elucidate Cu+And effect of the pH in physiology and pathology is of great significance.
Description
Technical field
The invention belongs to analysis technical field, being related to one kind in vivo and/or in vitro while can detect cuprous ion and pH
Novel Carbon Nanomaterials modified electrode.
Background technique
Copper metal ion (Cu+And Cu2+) be the indispensable microelement of human health, they control biological metabolism,
It plays an important role in the growth course of growth and immune system.If the too high levels of copper ion in organism, will be right
Biosystem generates toxic action, even results in neurological disease, such as: Alzheimer's disease, Huntingdon disease, and copper is excessive
Caused oxidative stress process is considered as an important factor for leading to Alzheimer's disease.State there are two types of copper ions in organism,
The Cu of oxidisability2+With the Cu of reproducibility+.It is most of that antioxidant such as ascorbic acid, glutathione can restore Cu in vivo2+At
Cu+.And micro Cu+Reducing molecular oxygen be can trigger into superoxide anion and hydrogen peroxide.Therefore, abnormal Cu+Concentration may
Mean the excess generation of active oxygen.At the same time, excessive active oxygen will lead to pH reduction, and the slight fluctuation of pH will lead to
The exception of biochemistry, ionic conduction and electroneurographic signal transmitting behavior.More importantly the acidification of brain environment can aggravate oxygen
Change stress generation.Therefore, develop while detecting Cu+New method with pH is for substantially understanding Cu+With pH in cerebral disease
Effect has a very important significance.
Traditional metal ion analysis detection method mainly has atomic absorption spectrography (AAS) (AAS), inductively coupled plasma body
Mass spectrum (ICP-MS), the chromatography of ions (IC), fluorescence analysis etc..But it is these method expensive equipments, complicated for operation, it can not carry out
It is live in real time, quickly to detect.Therefore, a kind of simple and quick, selectivity height is explored, and can be realized Cu in organism+Side
Method has important research significance and application value.Electrochemical method is highly sensitive and highly selective, it can be achieved that original position, reality because of it
When, quickly detection the advantages of, be concerned.
With Cu2+Unlike, Cu+Electrochemical analysis have more difficulty, on the one hand derived from itself property it is unstable, it is another
Aspect is because there is no effective electrochemical probe to carry out selection type identification to it.In addition to this, Cu+It is also wanted with detection while pH
Seeking the electrochemical behavior of the two cannot interfere with each other.In the prior art, there is no effective electrochemical method so far, it can be achieved that
Simultaneously and accurately to Cu+It is detected with pH.
Summary of the invention
In order to overcome the drawbacks described above of the prior art, the present invention uses basic structure of the sulfide compound as organic ligand
Unit synthesizes a series of for Cu+With highly selective recognition ligand, the Cu+Recognition ligand, reference molecules, pH response point
Son effectively highly selective, highly sensitive can be used for examining simultaneously in conjunction with being prepared on the carbon nanomaterial haveing excellent performance
Survey Cu+With the Ratio-type carbon nanomaterial modified electrode of pH.Present invention combination carbon fiber microelectrodes with micro pipette tips technology, can be achieved at the same time biology
In vivo Cu+With the electrochemical analysis of pH.
The present invention provides a kind of preparation methods of carbon nanomaterial modified electrode, comprising the following steps: in a solvent,
Under the conditions of 10-25 DEG C, by carbon nanomaterial, Cu+Recognition ligand, reference molecules, pH response molecule are mixed in a certain ratio, by Cu+
The carbon nanomaterial modification electricity is prepared on carbon nanomaterial in recognition ligand, reference molecules, pH response molecular modification
Pole.
In the present invention, the carbon nanomaterial be selected from one of graphene, single-walled carbon nanotube, multi-walled carbon nanotube or
A variety of, the carbon fiber diameter is less than 10 μm.
In the present invention, the Cu+Shown in recognition ligand such as formula (I), the Cu+Recognition ligand can be selected from one of formula (I)
Or it is a variety of:
Wherein, R can be selected from following group:
In the present invention, the reference molecules are selected from 2,2- and join nitrogen-two (3- ethyl-benzothiazole -6- sulfonic acid) di-ammonium salts
(ABTS), ferrocene；It preferably, is ABTS.
In the present invention, it is luxuriant and rich with fragrance that the pH response molecule is selected from 1,2- naphthoquinones, 1,3- naphthoquinones, 1,4-naphthoquinone, 1,2- anthraquinone, 1,2-
Quinone, 1,3- phenanthrenequione, 2,3- phenanthrenequione, 2,4- phenanthrenequione, Nai Er are blue, Nai Er is red or celeste blue etc.；It preferably, is 1,2- naphthoquinones, Isosorbide-5-Nitrae-
Naphthoquinones, 1,2- anthraquinone.
In the present invention, the Cu+The molar ratio that recognition ligand, reference molecules, pH respond molecule is 1:1-10:1-50；It is excellent
Selection of land is 1:10:2.
In the present invention, the solvent is selected from water, methylene chloride, methanol, ethyl acetate and n,N-Dimethylformamide, diformazan
Base sulfoxide；It preferably, is methanol.
In the present invention, it is preferable that the temperature of the modification is room temperature.
In the present invention, the time of the modification is 12-24 hours；Preferably, the time is 24 hours.
In the present invention, it is preferable that the carbon nanomaterial need to be activated first, successively by carbon nanomaterial before modification
It is immersed in acetone, 3M nitric acid, ultrasound 3 minutes respectively in 10M potassium hydroxide and ultrapure water carry out cleaning activation.In nitrogen protection
Under be heated in tube furnace 600 DEG C and maintain 5 hours, used after being then down to room temperature about 2 hours.
The present invention also provides the carbon nanomaterial modified electrodes to measure Cu in vitro+, pH or measure Cu simultaneously+And pH
In application.
The present invention also provides the carbon nanomaterial modified electrodes, and Cu is measured in biological living+, pH or measure simultaneously
Cu+With the application in pH, wherein the biology includes mouse, rat etc..
The present invention also provides a kind of Cu+The preparation method of recognition ligand, using sulfide compound as organic ligand
Basic structural unit synthesizes a series of for Cu+With highly selective recognition ligand, comprising the following steps: in organic solvent
In, by R-COOH, thioether, carbodiimides and N-hydroxy-succinamide ester carry out amidation process, obtain the Cu+Identification
Ligand.
Wherein, the temperature of the amidation process is 20-50 DEG C；It preferably, is 20-40 DEG C.
Wherein, the time of the amidation process is 12-36 hours；Preferably, it is 36 hours.
Wherein, the organic solvent is selected from ethyl alcohol, methanol, n,N-Dimethylformamide, dimethyl sulfoxide, methylene chloride；It is excellent
Selection of land is ethyl alcohol.
Wherein, the molar ratio of the R-COOH, thioether, carbodiimides and N-hydroxy-succinamide ester is 1-2:1-2:
1.5-3.0:1.5-3.0；It preferably, is 1:1:1.5:1.5.
In the specific embodiment of the present invention, implement Cu+The preparation method of recognition ligand, comprising the following steps:
Under 30-50 DEG C of nitrogen protection, in ethanol by R-COOH (10-15mmol) and thioether (10-15mmol), in carbodiimides
Lower stirring 36 hours of (10-15mmol) and N-hydroxy-succinamide ester (10-15mmol), reaction solution is cooled to room temperature,
It is extracted using 100mL ethyl acetate.Organic phase post separation, (petroleum ether: ethyl acetate=1:5-1:10) obtain colorless oil
Amidated products (50-80% yield).
The present invention also provides the carbon nanomaterial modified electrodes that method as described above is prepared, and carbon nanomaterial is existed
It is maintained 5 hours using being heated to 600 DEG C under preceding nitrogen protection in tube furnace, is used after being then down to room temperature about 2 hours.
The beneficial effects of the present invention are the present invention is with carbon nanomaterial, Cu+Recognition ligand, reference molecules, pH response point
A kind of new carbon nanomaterial modified electrode, each probe molecule (Cu is prepared in son+Recognition ligand, reference molecules, pH response point
Son) it can effectively be integrated on carbon nanomaterial.Carbon nanomaterial modified electrode of the invention can detect Cu simultaneously+And pH, electrification
Cu can obviously be distinguished over by learning signal+With the reference molecules of pH response signal, preparation method has simple, at low cost, green reliable
The advantages of, the carbon nanomaterial modified electrode of preparation has the advantages that highly selective and highly sensitive.Carbon nanometer material of the invention
Material modified electrode is used to measure the metal ion (Cu in biological living+) and when pH, it can be achieved that simultaneously, it is in situ, online in real time
Electrochemical Detection.The present invention is by preparing highly selective and highly sensitive carbon nanomaterial modified electrode, for further explaining
Bright Cu+And effect of the pH in physiology and pathology has extremely important meaning；It is parsing metal ion in physiological and pathological activity
Effect improve reliable method, provide efficient, feasible analysis method to parse the pathogenesis of related disease.
Detailed description of the invention
Fig. 1 is that the electrode of carbon nanomaterial distribution modification prepared by the embodiment of the present invention 1 is linear in artificial cerebrospinal fluid
Scan volt-ampere curve: a is naked carbon nanomaterial, and b is the electrode that pH responds the modification of molecule 1.2- anthraquinone molecular, and c is reference molecules
The electrode of ABTS modification, d are that pH responds molecule 1,2- anthraquinone, Cu+Recognition ligand NS4 and reference molecules ABTS co-modified electricity
Pole.
Fig. 2 is linear scan volt of the carbon nanomaterial modified electrode of the preparation of the embodiment of the present invention 1 in artificial cerebrospinal fluid
Pacify curve, a is to contain 5 μM of Cu+With the linear sweep voltammetry curve in artificial cerebrospinal fluid, b is 20 μM of EDTA of subsequent addition
Linear sweep voltammetry curve afterwards.
Fig. 3 is the carbon nanomaterial modified electrode of the preparation of the embodiment of the present invention 1 in different Cu+Linear scan in concentration is bent
Line.
Fig. 4 is line of the carbon nanomaterial modified electrode of the preparation of the embodiment of the present invention 1 in the artificial cerebrospinal fluid of different pH
Property scanning curve.
Fig. 5 is linear scan curve of the carbon nanomaterial modified electrode of the preparation of the embodiment of the present invention 1 in living body mouse brain.
Specific embodiment
In conjunction with following specific embodiments and attached drawing, the present invention is described in further detail.Implement process of the invention,
Condition, experimental method etc. are among the general principles and common general knowledge in the art, this hair in addition to what is specifically mentioned below
It is bright that there are no special restrictions to content.
Embodiment 1
Linear volt-ampere is carried out to carbon nanomaterial modified electrode prepared by embodiment 1 using CHI660 electrochemical workstation to sweep
It retouches, sweeps speed: 0.05V/s, as shown in Figure 1；Wherein, a is naked carbon nanomaterial (naked carbon fiber electrode) in artificial cerebrospinal fluid
Linear scan aoxidizes curve, and b is that pH responds linear scan of the electrode of molecule 1.2- anthraquinone molecular modification in artificial cerebrospinal fluid
Curve is aoxidized, c is that linear scan of the electrode of reference molecules ABTS modification in artificial cerebrospinal fluid aoxidizes curve, and d is pH response
Molecule 1,2- anthraquinone, Cu+(in Formulas I, R is recognition ligand) C and the co-modified electrode of reference molecules ABTS be artificial
Linear scan in cerebrospinal fluid aoxidizes curve.Wherein, naked carbon nanomaterial only charges background current (Fig. 1 a).PH responds molecule
It can see near -0.45V having significantly in linear scan oxidation curve graph (Fig. 1 b) of the electrode of 1.2- anthraquinone molecular modification
Oxidation peak, this illustrates that 1.2- anthraquinone molecular has good electro-chemical activity.The linear scan of the electrode of ABTS modification aoxidizes bent
It can see there is oxidation peak near 0.55V on line chart (Fig. 1 c), this illustrates that reference ABTS molecule has electro-chemical activity.1,2- anthracene
Quinone can be seen in linear scan oxidation curve graph (Fig. 1 d) of NS4 and the co-modified electrode of tri- molecule of ABTS while in -0.45V
There are two oxidation peaks at 0.55V, this explanation 1,2- anthraquinone molecular and ABTS can be modified on carbon nanomaterial simultaneously, and be had
There is good electro-chemical activity.By as shown in Figure 1, the electrochemical signals of pH response molecule and reference molecules are distinguished, and can avoid
Signal interference between the two.
Embodiment 2
Linear volt-ampere is carried out to carbon nanomaterial modified electrode prepared by embodiment 1 using CHI660 electrochemical workstation to sweep
Retouch, sweep speed: 0.05V/s, experimental result is as shown in Fig. 2, curve a is that 5 μM of Cu are added in artificial cerebrospinal fluid+Carbon nanomaterial afterwards
The linear scan curve of modified electrode, it is seen that near 0.3V, an oxidation peak occurs, and responds molecule and reference with pH
The oxidation peak signal good separation of molecule.Curve b is after 20 μM of alkaline EDTA are added on the basis of a, and carbon nanomaterial is repaired
The linear sweep voltammetry curve for adoring electrode, can be clearly seen that, after EDTA is added into artificial cerebrospinal fluid, Cu at 0.3V+'s
Oxidation peak disappears, it was demonstrated that EDTA complexing power is better than selective Cu+(in formula (I), R group is recognition ligand), it can incite somebody to action
Cu+It is discharged again from electrode surface, therefore the oxidation peak at 0.3V is caused to disappear.At the same time, add in mechanical brains ridge buffer
After the EDTA solution for entering alkalinity, pH value rises, and moves so that pH probe current potential is negative.These results prove the carbon of the embodiment 1 preparation
Nanometer material modified electrode effectively simultaneous selection can identify Cu+And pH.
Embodiment 3
Univalent copper ion is carried out to carbon nanomaterial modified electrode prepared by embodiment 1 using CHI660 electrochemical workstation
Cu+Titration experiments, then successively carry out linear voltammetric scan, sweep speed: 0.05V/s, experimental result is as shown in figure 3, the carbon
Nanometer material modified electrode is for Cu+There is good response.Cu of the identified ligand capture in electrode surface+There is one in 0.3V
Oxidation peak, and the peak current density of the oxidation peak is gradually increased with the increase of copper ion concentration, and extremely at 0.5 μM
It is presented in the range of 11.0 μM good linear.It measures simultaneously, pH probe molecule and reference molecules signal stabilization, and will not be to copper
The detection of ion generates interference.
Embodiment 4
It is examined using pH performance of the CHI660 electrochemical workstation to carbon nanomaterial modified electrode prepared by embodiment 1
It surveys.After changing pH value, successively carry out linear voltammetric scan, sweep speed: 0.05V/s, experimental result is as shown in figure 4, the present embodiment
In, have recorded the linear scan oxidation curve for the carbon nanomaterial modified electrode that under different pH concentration prepared by embodiment 1.Solution
PH value is respectively 6.0,6.1,6.2,6.3,6.4,6.5,6.6,6.7,6.8,6.9,7.0,7.1,7.2,7.3,7.4,7.5,
7.6,7.7,7.8,7.9,8.0.As shown in figure 4, the carbon nanomaterial modified electrode is presented to the good response of pH, pH
The oxidation peak of probe is gradually shuffled with the reduction of pH, and at the same time, reference spike potential remains unchanged.The carbon nanomaterial is repaired
Decorations electrode has extraordinary response to pH in the range of 6.0~8.0, can meet the requirement of pH variation detection in organism.
The pH value of 5 pathological model mouse of embodiment and the detection of cuprous ion concentration
The real-time detection of living body mouse:
It tests APPswe/PS1dE9 transgenosis AD mouse used and normal mice is purchased from Shanghai south animal model center.
A. the preparation before experiment made on the living
Anaesthetize mouse: then configuration 0.1g/ml Ethylurethanm first weighs mouse, according to 30mg/100g mouse injection anaesthetic to mouse
It is anaesthetized.Later, every 3 hours injection about 0.3ml.
Surgical instrument disinfection: it is stand-by to be impregnated disinfection in ethanol by 75% ethyl alcohol of configuration for surgical instrument.
B. living body operation of opening cranium
Firstly, mouse is fixed on three-dimensional brain position indicator, thermostat heating cushion is spread, control vital body temperature maintains 37 DEG C.
Then, the wound that length is about 1cm is marked vertically in brain center position using scalpel, fix wound with hemostatic clamp, clear up
Completely, expose skull.Hippocampus (AP=5.0mm, L=5.0mm, V=2.5mm) is determined finally, composing according to brain, corpus straitum (AP
=0mm, L=2.5mm, V=7.0mm) and cortex (AP=0.2mm, L=5.6mm, V=3.0mm) position, with marking pen mark
After note, cranium is carried out out using cranial drill, aperture is about 5mm, for placing working electrode.In front end, at working electrode 5mm
The hole that an aperture is 2mm is opened, for placing to electrode and reference electrode.
Experimental result as shown in figure 5, the carbon nanomaterial modified electrode in living body mouse brain to Cu+There is good sound
It answers, is very sensitive to pH detection.Curve a indicates that the linear scan in normal mice brain aoxidizes curve, and curve b is indicated in AD mouse brain
Linear scan aoxidizes curve.The Cu of identified ligand capture+There is an oxidation peak in 0.3V, has the oxidation peak of pH in -0.45V.
It measures simultaneously, pH probe molecule and reference molecules signal stabilization, and interference will not be generated to the detection of copper ion.Comparison curves a
With curve b it can be found that pH changes unobvious, and Cu in normal mice and pathology mouse model+It is normal in pathological model mouse
2.2 times of concentration in mouse brain.
Protection content of the invention is not limited to above embodiments.Without departing from the spirit and scope of the invention, originally
Field technical staff it is conceivable that variation and advantage be all included in the present invention, and with appended claims be protect
Protect range.
Claims (15)
1. a kind of preparation method of carbon nanomaterial modified electrode, comprising the following steps: in a solvent, under the conditions of 10-25 DEG C,
By carbon nanomaterial, Cu+Recognition ligand, reference molecules and pH respond molecular mixing, by Cu+Recognition ligand, reference molecules, pH are rung
It answers molecular modification on carbon nanomaterial, the carbon nanomaterial modified electrode is prepared.
2. the method as described in claim 1, which is characterized in that the carbon nanomaterial be selected from graphene, single-walled carbon nanotube,
One of multi-walled carbon nanotube is a variety of, and the carbon nanomaterial carbon fiber diameter is less than 10 μm.
3. the method as described in claim 1, which is characterized in that the Cu+Shown in recognition ligand such as formula (I), the Cu+Identification
Ligand is selected from one of formula (I) or a variety of:
Wherein, R is selected from following group:
4. the method as described in claim 1, which is characterized in that the reference molecules are that 2,2- joins (the 3- ethyl-benzo of nitrogen-two
Thiazole -6- sulfonic acid) di-ammonium salts or ferrocene.
5. the method as described in claim 1, which is characterized in that the pH response molecule is selected from 1,2- naphthoquinones, 1,3- naphthoquinones, 1,
4- naphthoquinones, 1,2- anthraquinone, 1,2- phenanthrenequione, 1,3- phenanthrenequione, 2,3- phenanthrenequione, 2,4- phenanthrenequione, Nai Er are blue, Nai Er is red or celeste blue.
6. the method as described in claim 1, which is characterized in that the Cu+Recognition ligand, reference molecules, pH respond rubbing for molecule
You are than being 1:1-10:1-50.
7. the method as described in claim 1, which is characterized in that the solvent is selected from water, methylene chloride, methanol, ethyl acetate
With N,N-dimethylformamide, dimethyl sulfoxide.
8. the method as described in claim 1, which is characterized in that the time of the modification is 12~24 hours.
9. a kind of carbon nanomaterial modified electrode that any one the method such as claim 1~8 is prepared.
10. carbon nanomaterial modified electrode as claimed in claim 9 measures Cu simultaneously in vitro+With the application in pH.
11. carbon nanomaterial modified electrode as claimed in claim 9 measures Cu in biological living+With the application of pH.
12. a kind of Cu+The preparation method of recognition ligand, which is characterized in that the described method includes: in organic solvent, by R-
COOH, thioether, carbodiimides and N-hydroxy-succinamide ester carry out amidation process, obtain the Cu+Recognition ligand.
13. method as claimed in claim 12, which is characterized in that the temperature of the amidation process is 20-50 DEG C；The acyl
The time of aminating reaction is 12-36 hours.
14. method as claimed in claim 12, which is characterized in that the organic solvent is selected from ethyl alcohol, methanol, N, N- dimethyl
Formamide, dimethyl sulfoxide, methylene chloride.
15. method as claimed in claim 12, which is characterized in that the R-COOH, thioether, carbodiimides and N- hydroxyl amber
The molar ratio of amber imide ester is 1-2:1-2:1.5-3.0:1.5-3.0.
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| CN113295667A (en) * | 2021-04-30 | 2021-08-24 | 华东师范大学 | Detect Cu simultaneously+And Cu2+Surface-enhanced Raman spectrum probe and preparation method and application thereof |
| CN113295667B (en) * | 2021-04-30 | 2022-12-06 | 华东师范大学 | Detect Cu simultaneously + And Cu 2+ Surface-enhanced Raman spectrum probe and preparation method and application thereof |
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