CN107064103B - A kind of silver of containing the internal standard molecule/gold nano cavity dendrite and its preparation method and application - Google Patents
A kind of silver of containing the internal standard molecule/gold nano cavity dendrite and its preparation method and application Download PDFInfo
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- 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
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The present invention relates to the silver of a kind of containing the internal standard molecule/gold nano cavity dendrite and its preparation method and application, and preparation step is as follows: then alternately ultrasonic cleaning 3-5 times of copper simple substance ethyl alcohol and pure water is placed on spare in beaker with nitrogen stream drying；Be added excessive silver nitrate solution be stirred to react, aging；To reaction product eccentric cleaning, ultrasonic disperse is in PVP solution；Nitrogenous, sulphur atom internal standard molecule is added, oscillating reactions obtains micro-nano structure silver dendrite；It is dispersed in PVP solution again after centrifuge washing, aqueous slkali is added and adjusts pH；It is finally added in growth solution, reaction obtains silver/gold nano cavity dendritic materials of containing the internal standard molecule.The present invention prepares error caused by material structure, instrument or operation etc. when containing the internal standard nano silver/gold nano cavity dendrite corrects SERS detection by internal standard method, and then improves the reproducibility of signal, realizes relative quantification detection.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to the silver of containing the internal standard molecule/gold nano cavity dendrite
And its preparation method and application.
Background technique
Suitable for quick, accurate, real-time, selective enumeration method technology SERS base material and related detecting method, standard
It is one of research hotspot and the research emphasis in the current field, and SERS research field most probable realizes breakthrough and reality in recent years
Existing practical developing direction.For the current situation of SERS technology, constructed to meet different demands different
SERS substrate is always one of the research contents that the field SERS is paid close attention to the most, is had to the research and application range of expanding SERS
Very important effect.
It is known that reliable and stable and with certain universality quantitative detection ability is to assess a kind of determination method
Whether Cheng Shu primary condition.And currently, a large amount of SERS substrate researchs concentrate in the accurate control of hotspot architecture, to realize
The Controllable assembly of nanoscale to improve sensitivity, but often ignores the stability of substrate, reproducibility and detection signal
Anti-interference, so that in practical applications, SERS detection, which can not still provide, accurately and reliably analyzes data, it can only so as to cause it
Qualitative detection for primary dcreening operation.SERS detection is only extended to quantitative detection field, just the determination method can be made to have
More extensive practical prospect.Therefore, around the feasibility problems aspect of SERS quantitative detection, in recent years, scientific research personnel does
A large amount of exploration, containing the internal standard molecule nano noble metal structures unit are suggested as the strategy solved the problems, such as, wherein using interior
The reproducibility that ensure that testing result is normalized in the SERS signal of mark molecule, and combines hierarchical structure preparation process to control and use
Current one of research emphasis and hot spot are likely to become in SERS detection.
For the construction technology of further investigated nano-noble metal hierarchical structure and its for SERS quantitative detection research can
Row, we design and have constructed a kind of silver/gold nano cavity dendrite (hollow nanostructured of containing the internal standard
Silver/gold dendrites with internal standards, HNSGDs), inquire into this hierarchical structure material
Preparation process and detailed structure and performance characterization have been carried out to it, and ground with this SERS technology for quantitative detecting analysis
Study carefully.
Summary of the invention
The purpose of the present invention is constructing containing the internal standard molecule nano noble metal structures unit, consider SERS substrate stability,
The anti-interference of reproducibility and detection signal, material structure, instrument or operation etc. cause when correcting SERS detection by internal standard method
Error, and then improve signal reproducibility, realize substance relative quantification detection.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical schemes:
A kind of silver of containing the internal standard molecule/gold nano cavity dendrite preparation method, it is characterised in that: the following steps are included:
(1) cut the copper simple substance that quality is 20-25mg, and be alternately cleaned by ultrasonic with ethyl alcohol and pure water 3-5 times (every time 5~
10min), it is then placed on nitrogen stream drying spare in beaker；
(2) excessive silver nitrate solution is added into beaker to be stirred to react, after complete reaction, places aging 25-
35min；
(3) after carrying out eccentric cleaning to reaction product obtained in step (2), then by its ultrasonic disperse in PVP solution；
(4) nitrogenous, sulphur atom internal standard molecule is added, carries out oscillating reactions at room temperature, obtains micro-nano structure silver
Dendrite；
(5) after carrying out centrifuge washing to micro-nano structure silver dendrite, it is dispersed in again in PVP solution；Add alkali soluble
Liquid, adjusting its pH is 8-11, obtains mix products；
(6) mix products are added in growth solution, are reacted in the case where vibrating air-proof condition, obtains containing the internal standard molecule
Silver/gold nano cavity dendritic materials.
Further scheme, the copper simple substance in the step (1) are copper wire, copper foil, copper sheet or copper mesh.
Further scheme, the internal standard molecule in the step (4) are 4- mercaptopyridine (4-mercaptopyridine, 4-
Mpy) or 2- thionaphthol (2-naphthalenethiol, 2-NT), additional amount are 80-100 μ L；The concentration of the internal standard molecule
For 0.008-0.012mmol/L.
Further scheme, aqueous slkali is in strong base solution, strong base-weak acid salt, weakly alkaline solution in the step (5)
It is a kind of；Wherein strong base solution includes sodium hydroxide, potassium hydroxide, barium hydroxide；Strong base-weak acid salt includes that phosphate, carbonate are slow
Fliud flushing；Weakly alkaline solution is ammonium hydroxide.
Further scheme, the process for preparation of growth solution in the step (6) are as follows: at room temperature, water-soluble in CTAB
HAuCl is sequentially added in liquid4, ultrapure water, after mixing be added ascorbic acid (AA) aqueous solution, after shaking up, mixed liquor is rapidly by light
Yellow becomes colorless, to obtain growth solution.
Second goal of the invention of the invention is to provide a kind of silver/gold of containing the internal standard molecule prepared by above-mentioned preparation method
Lar nanometric cavities dendritic materials.
Silver/gold nano cavity dendritic materials that third goal of the invention of the invention is to provide a kind of containing the internal standard molecule are answered
With silver/gold nano cavity dendritic materials of the containing the internal standard molecule are used for the SERS substrate of the SERS quantitative detection of drugs.
Further scheme, the drugs include amphetamine, cocaine, m orphine, codeine, hydrochloric acid opium poppy alkali, bar ratio
Appropriate class, hemp, tetrahydrocannabinol, narcotine, caffeine, ketalar, Sauteralgyl, methadone, Clozapine, diphenoxylate,
Caffeine totokaine, is stabilized, oxazepans, surazepam, librium, Xanax, triazole storehouse, Lorazepam or sweet smell
Fluorine Lamine.
When detection, first prepare it is a piece of first through fresh chloroazotic acid impregnate at least 2h after clean, then with the concentrated sulfuric acid dioxygen water lotion leaching
The organic matter for steeping 1h removal surface, it is spare with the silicon wafer being dried with nitrogen after then being cleaned with a large amount of ultrapure water；By containing the internal standard point
It after silver/gold nano cavity dendritic materials suspension of son carries out eccentric cleaning, then is dripped on silicon wafer, obtains SERS after dry
Substrate；Body fluid after last modulus personification body drug abuse, is added drop-wise in SERS substrate, carries out SERS detection using Raman spectrometer,
It whether can be detected in humoral sample containing Poison.
The silver of containing the internal standard molecule prepared by the present invention/gold nano cavity dendritic materials, the principles of science are as follows:
One, fine copper simple substance and AgNO are utilized3Relationship in solution both between silver ion in potential difference, in copper foil and solution
The moment of contact generates Galvanic displacement reaction (galvanic displacement), and the dissolution of surface of bottom material atom, which falls off, dishes out
While a large amount of electronics, silver ion receives electronics in solution, thus rapidly in one layer of silver-colored simple substance layer of surface of bottom material generation, and
The presence of uneven phase, causes silver-colored simple substance to be grown to pine-tree structure on copper, silver-colored heterojunction structure surface and interface.
Two, the structure of containing the internal standard molecule is constructed, then needs the insertion before metal shell replaces growth that there is SERS signal
Molecular layer.But general Molecular Adsorption can all change the one of metal surface in micro-nano structure metal surface to varying degrees
A little physicochemical properties, wherein binding molecule layer will lead to original metal surface in growth-promoting media metal ion source it is affine
Property decreases.If the binding ability of binding molecule and metal surface be not it is very strong, carry out displacement growth on its surface
Or extensional mode grows metal layer, the molecular layer of absorption may peel off first, that is, be difficult to be embedded in, therefore it is required that insertion molecule
It is sufficiently large with the binding force of metal surface.But if insertion molecule and metal show binding force it is sufficiently large and in growth-promoting media
When metal ion source binding force is weak, in the case where binding molecule layer densification assembling, metal ion may be difficult to cross absorption point
Sublayer is grown in metal surface.Therefore, when being screened to internal standard molecule, be considered as its have with metal surface it is stronger
The influence that binding force and have stronger SERS signal while grow subsequent deposition metal ion.In general, more often
And the interior target molecule that can be used as that can be able to satisfy this condition has 4- mercaptopyridine (4-mercaptopyridine, 4-
Mpy), 2- thionaphthol (2-naphthalenethiol, 2-NT) etc..For different determinand systems, need to select different interior
Mark molecule also requires its peak position and the spectrogram peak position of determinand molecule not to weigh while internal standard molecule requires SERS signal clear
It is folded.
Three, upper one layer of internal standard molecule is reasonably modified on micro-nano silver dendrite surface, to be modified with the S sediment of internal standard molecule
It is template to prepare silver/gold nano cavity dendrite of containing the internal standard and for the research of SERS quantitative detecting analysis.Containing the internal standard molecule
Why system can be used for quantitative detection, be because usually, internal standard molecule and testing molecule all divide in homogeneous system
Cloth is and general it is believed that the internal standard molecule and testing molecule acquired in identical environment in same physicochemical environment
The relative signal intensity that Raman signal obtains after being corrected by internal standard method is the distribution that can quantify to react determinand molecule, i.e.,
The quantitative detection to determinand is realized indirectly.
The beneficial effects of the present invention are:
(1) preparation process of the present invention is simple and easy, and experiment condition is mild, reflects micro-nano structure first with Galvanic displacement
Silver-colored pine-tree structure, then the internal standard molecule in its surface modification, then as template, through the reduction of gold chloride in being modified with
The silver-colored dendrite surface layer for marking molecule grows golden shell layer, and internal standard molecule and testing molecule had both been made all to be distributed in same physicochemical environment
In, while internal standard molecule will not occupy the adsorption site of substrate, entire containing the internal standard silver/gold nano cavity pine-tree structure can be made again
For SERS substrate.
(2) silver/gold nano cavity dendritic materials of the containing the internal standard molecule prepared by the present invention are that its dendrite end is distributed as
Diameter dimension the nanometer branch stick array of the containing the internal standard molecule of 80~160nm magnitude and the silver with lar nanometric cavities structure and gold it is multiple
Zoarium system, and internal standard molecule is mainly distributed on inside the shell in total.
(3) material structure, instrument or behaviour when containing the internal standard nano-noble metal structure is expected to correct SERS detection by internal standard method
Error caused by work etc., and then the reproducibility of signal is improved, it realizes relative quantification detection, is shaken in the present invention by detecting drugs
Head ball has proven to.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is scanning electron microscope (SEM) picture of product different resolution prepared by embodiment 1, and wherein A, B are steps
Suddenly the micro-nano structure silver dendrite sample that (4) generate, C, D are silver/gold nano cavity dendrite samples of step (7) containing the internal standard.
Fig. 2 is Flied emission transmission scanning electron microscope (TEM) picture of different resolution prepared by embodiment 1: A, B is
Step (4) micro-nano structure silver dendrite sample, C, D are silver/gold nano cavity dendrite samples of step (7) containing the internal standard.
Fig. 3 is the XPS map of synthetic sample: (a), (b) and (c) is respectively pure micro-nano structure silver dendrite sample, repairs in figure A
It is decorated with the micro-nano structure silver dendrite sample of internal standard molecule 2-NT and silver/gold nano cavity dendrite sample of final product containing the internal standard molecule
The XPS map of product；(a) in figure B, (b) and it is respectively then and the high-resolution of scheming the corresponding S2p peak position of blocked areas in A (c)
XPS map.
Fig. 4 is the head-shaking pill for detecting various concentration for SERS substrate with the silver of containing the internal standard molecule/gold nano cavity dendrite
The serial SERS spectrogram of MDMA: (a) 0.5ppm；(b)1ppm；(c)5ppm；(d)10ppm；(e)20ppm；(f)50ppm.
Fig. 5 is the intensity of various concentration head-shaking pill MDMA and the linear fit datagram of concentration: wherein A, B are respectively MDMA
Molecule 715cm-1And 1249cm-1Locate spectral strength and log concentration carries out data fitting, C, D are respectively the 715cm of MDMA molecule-1And 1249cm-1With the 1067cm of internal standard molecule 2-NT-1The ratio for locating spectral strength carries out data fitting to log concentration.
Specific embodiment
The invention will be further described with reference to embodiments, but the present invention is not limited to following embodiments.
Embodiment 1
(1) copper simple substance that quality is 20mg is cut, and replaces ultrasonic cleaning 3 times, each 10min with ethyl alcohol and pure water, so
It is placed on afterwards with nitrogen stream drying spare in beaker；
(2) under normal temperature condition, the AgNO of 50mmol/L is newly prepared with brown volumetric flask3It is rapid to then take out 15mL for solution
Addition is contained in the small beaker for the copper foil that aforementioned processing is crossed；After placing aging 30min, cleaned with ethyl alcohol and ultrapure water, and lead to
It crosses and product is collected by centrifugation；Sample is finally distributed to in the 0.01%wt PVP aqueous solution of 15mL simultaneously ultrasonic disperse again, it is spare.
(3) liquid is stored with the 2- thionaphthol ethyl alcohol that brown volumetric flask compound concentration is 1mmol/L, be then diluted with water to
0.01mmol/L is spare；2- thionaphthol solution and 8.9mL ultrapure water that 100 μ L concentration are 0.01mmol/L are added to step
(2) in the 1mL PVP dispersion liquid in, and 120min is reacted at room temperature under conditions of persistent oscillation, obtains micro-nano structure silver dendrite；
Scanning electron microscope (SEM) figure of its different resolution is as shown in figure 1 shown in A, B；Micro-nano silver branch is apparent that from figure A
Crystalline substance is made of two-dimentional pine-tree structure, and for dendrite trunk structure up to a few micrometers, secondary skeletal structures are about 1~3 μm.It can be with from B figure
Find out the tertiary structure or microcosmic substructure of micro-nano silver dendrite, i.e. end is distributed, and shows nanoscale branch stick array, branch stick diameter
Scale is 50~80nm magnitude.Flied emission transmission scanning electron microscope (TEM) figure such as A, B institute in Fig. 2 of its different resolution
Show；It can be seen that dendrite trunk structure, secondary skeletal structures and end nanoscale branch stick array are all fine and close without cavity.
(4) product is cleaned with ultrapure water twice and by the way that sediment is collected by centrifugation, is then re-dispersed into
In 10mL0.01%wt PVP aqueous solution；Then, the NaOH aqueous solution that 100 μ L concentration are 0.1mol/L is added, mixes and adjusts it
PH is 8, obtains mix products；
(5) following growth solution is prepared: under room temperature, in the tool of a 0.1mol/L CTAB aqueous solution equipped with 5mL
It fills in conical flask, sequentially adds the 5mmol/LHAuCl of 1.5mL4, 3.5mL ultrapure water, the 0.1mol/L of 60 μ L is added after mixing
AA aqueous solution, after shaking up, mixed liquor is become colorless by faint yellow rapidly, shows that the gold ion of trivalent is reduced to monovalence；
(6) the micro-nano silver dendrite suspension for being modified with 2- thionaphthol molecule prepared by step (4) is rapidly added growth-promoting media
In, it is put into constant temperature oscillator under tool plug air-proof condition and reacts 60min, final product is containing the internal standard silver/gold nano cavity branch
It is brilliant.Shown in C, the D of scanning electron microscope (SEM) figure of its different resolution as shown in figure 1；From the point of view of microstructure, show
Apparent multi-level structure, figure C and D is the HNSGDs sample of different enlargement ratios respectively, it can be seen from the figure that its three-level knot
Structure, that is, end nanometer branch stick diameter dimension is 80~160nm magnitude.The Flied emission transmission scan electron microscopic of its different resolution
Mirror (TEM) figure is as shown in C, D in Fig. 2, it can be seen that apparent cavity structure is shown inside HNSGDs.In polyhedron pattern
Silver can be spread from inside to outside in nano-core-shell structure material, in diffusion process, on the one hand due to having strong knot with silver surface
The presence of the internal standard molecule of resultant force, on the other hand, reactant need to diffuse into nucleocapsid knot by the shell with fine duct
It can just react inside structure, therefore, control be passed through using the micro-nano silver dendrite with nanostructure as template according to this principle
The ratio of system addition reducing agent, gold chloride and silver, it is multiple to prepare silver and gold with fine duct shell and lar nanometric cavities structure
The dendrite of zoarium system.
Be the XPS map of sample as shown in Figure 3: (a), (b) and (c) is respectively pure micro-nano structure silver dendrite, modification in figure A
There are the micro-nano structure silver dendrite of internal standard molecule 2-NT and silver/gold nano cavity dendrite sample of final product containing the internal standard molecule
XPS map；(a) in figure B, (b) and it is respectively then and the high-resolution XPS figure of the corresponding S2p peak position of blocked areas in figure A (c)
Spectrum.
In comparison diagram B (a) and (b) as can be seen that (b) in be located at 162eV place occur the peak S2p be attributed to SH- with silver table
Face combines the Ag-S key formed, shows that a large amount of 2-NT molecular modification has arrived micro-nano structure silver dendrite surface.By comparing in figure B
(b) and (c) is then it can be found that after being subsequently generated lar nanometric cavities structure silver and golden compound system dendrite, the peak S2p of sample surfaces
Position disappears, and shows that silver/gold nano cavity dendrite sample surfaces of containing the internal standard do not have 2NT molecule.In addition, by comparison diagram A
(a), (b) and (c) as can be seen that with pure micro-nano structure silver dendrite sample and compared with being modified with internal standard molecule 2-NT molecule, most
There is a large amount of Au element in the silver of final product containing the internal standard/gold nano cavity dendrite sample surfaces, show silver/Jenner of containing the internal standard
Rice cavity dendrite sample surfaces are the compound system of Au and Ag element.
Embodiment 2
(1) copper simple substance that quality is 25mg is cut, and replaces ultrasonic cleaning 5 times, each 5min with ethyl alcohol and pure water, then
It is placed on nitrogen stream drying spare in beaker；
(2) under normal temperature condition, the AgNO of 50mmol/L is newly prepared with brown volumetric flask3It is rapid to then take out 15mL for solution
Addition is contained in the small beaker for the copper foil that aforementioned processing is crossed；After placing aging 25min, cleaned with ethyl alcohol and ultrapure water, and lead to
It crosses and product is collected by centrifugation；Sample is finally distributed to in 15mL0.01%wt PVP aqueous solution simultaneously ultrasonic disperse again, it is spare.
(3) liquid is stored with the 4- mercaptopyridine water that brown volumetric flask compound concentration is 1mmol/L, be then diluted to
0.01mmol/L is spare；4- mercaptopyridine solution and 8.9mL ultrapure water that 100 μ L concentration are 0.01mmol/L are added to step
(2) in the 1mL PVP dispersion liquid in, and 120min is reacted at room temperature under conditions of persistent oscillation, obtains micro-nano structure silver dendrite；
(4) product is cleaned with ultrapure water twice and by the way that sediment is collected by centrifugation, is then re-dispersed into
In 10mL0.01%wt PVP aqueous solution；Then, the NaOH aqueous solution that 100 μ L concentration are 0.1mol/L is added, mixes and adjusts it
PH is 10, obtains mix products；
(5) it prepares following growth solution: under room temperature, being bored in a tool plug equipped with 5mL 0.1M CTAB aqueous solution
In shape bottle, the 5mmol/LHAuCl of 1.5mL is sequentially added4, 3.5mL ultrapure water, the 0.1mol/L AA water of 60 μ L is added after mixing
Solution, after shaking up, mixed liquor is become colorless by faint yellow rapidly, shows that the gold ion of trivalent is reduced to monovalence；
(6) the micro-nano silver dendrite suspension for being decorated with 4- mercaptopyridine molecule prepared by step (4) is rapidly added growth-promoting media
In, it is put into constant temperature oscillator under tool plug air-proof condition and reacts 60min；Final product is containing the internal standard silver/gold nano cavity branch
It is brilliant.
Embodiment 3
(1) the containing the internal standard molecule silver for preparing embodiment 1/gold nano cavity dendrite substrate suspension is abandoned by centrifugation
Clear liquid adds water sonic oscillation and is dispersed to original volume again；
It (2) is respectively that 50ppm, 20ppm, 10ppm, 5ppm, 1ppm and 0.5ppm volume are with concentration by 20 μ L suspension
The head-shaking pill aqueous solution of 20 μ L mixes, shaken well；
(3) it takes 10 μ L mixing drops on silicon wafer, Raman signal acquisition is carried out after natural drying.Fig. 4 is various concentration
Head-shaking pill representative series SERS spectrogram in HNSGDs substrate, as shown in figure 4, wherein (a) indicate 20 μ L suspension with it is dense
The head-shaking pill aqueous solution that degree is the 20 μ L of 0.5ppm mixes SERS spectrogram detected；(b) indicate that 20 μ L suspension are with concentration
The head-shaking pill aqueous solution of the 20 μ L of 1ppm mixes SERS spectrogram detected；(c) 20 μ L suspension are indicated and concentration is 5ppm's
The head-shaking pill aqueous solution of 20 μ L mixes SERS spectrogram detected；(d) 20 μ L suspension and the 20 μ L's that concentration is 10ppm are indicated
Head-shaking pill aqueous solution mixes SERS spectrogram detected；(e) indicate 20 μ L suspension and concentration for the head-shaking pill of the 20 μ L of 20ppm
Aqueous solution mixes SERS spectrogram detected；(f) indicate 20 μ L suspension and concentration for the head-shaking pill aqueous solution of the 20 μ L of 50ppm
Mix SERS spectrogram detected.
Then with the 715cm of head-shaking pill molecule-1And 1249cm-1With the 1067cm of internal standard molecule 2-NT-1Locate spectral strength
Ratio carries out data fitting to log concentration, equation of linear regression is obtained, as shown in figure 5, A, B are respectively MDMA molecule in Fig. 5
715cm-1And 1249cm-1Locate spectral strength and log concentration carries out data fitting, C, D are respectively the 715cm of MDMA molecule-1、
1249cm-1With the 1067cm of internal standard molecule 2-NT-1The ratio for locating spectral strength carries out data fitting to log concentration.From Fig. 5
When A and B comparison be can be seen that with the SERS signal absolute intensity of MDMA to testing concentration progress data fitting, between the two
Not shown apparent linear response out, that is, the signal fluctuation shown again when substrate surface carries out SERS detection are bigger.
If by the 715cm of determinand MDMA-1、1249cm-1With the 1067cm of internal standard molecule 2-NT-1Locate the ratio of spectral strength to concentration
Logarithm carries out data fitting, we are then it can be found that obtained relative intensity value can be linear well with testing concentration presentation
Relationship, that is to say, that the presence of internal standard molecule can be used for the correction to determinand signal strength in HNSGDs, that is, show one
The HNSGDs that we design under fixed condition can be used for the SERS quantitative detecting analysis of MDMA.Obtained relative intensity value can with to
It surveys object concentration and good linear relationship is presented, to realize the quantitative detection of head-shaking pill molecule.
It is present pre-ferred embodiments above, is imposed any restrictions to technical scope of the invention.Therefore it is all
Any subtle modifications, equivalent variations and modifications made to the above embodiment according to the technical essence of the invention, belong to this hair
It is bright protect in the range of.
Claims (7)
1. a kind of silver nanoparticle cavity dendrite preparation method of containing the internal standard molecule, it is characterised in that: the following steps are included:
(1) copper simple substance that quality is 20-25mg is cut, and is alternately cleaned by ultrasonic 3-5 times with ethyl alcohol and pure water, nitrogen stream is then used
Drying is placed on spare in beaker；
(2) excessive silver nitrate solution is added into beaker to be stirred to react, after complete reaction, places aging 25-
35min；
(3) after carrying out eccentric cleaning to reaction product obtained in step (2), then by its ultrasonic disperse in PVP solution；
(4) nitrogenous, sulphur atom internal standard molecule is added, carries out oscillating reactions at room temperature, obtains micro-nano structure silver dendrite；
Internal standard molecule is 4- mercaptopyridine or 2- thionaphthol；
(5) after carrying out centrifuge washing to micro-nano structure silver dendrite, it is dispersed in again in PVP solution；Aqueous slkali is added, is adjusted
Saving its pH is 8-11, obtains mix products；
(6) mix products are added in growth solution, are reacted in the case where vibrating air-proof condition, in the silver-colored branch for being modified with internal standard molecule
Brilliant surface layer grows golden shell layer, obtains the silver nanoparticle cavity dendritic materials of containing the internal standard molecule；The process for preparation of the growth solution are as follows:
At room temperature, HAuCl is sequentially added in CTAB aqueous solution4, ultrapure water, aqueous ascorbic acid is added after mixing, shakes
After even, mixed liquor is become colorless by faint yellow rapidly, to obtain growth solution.
2. the preparation method according to claim 1, it is characterised in that: the copper simple substance in the step (1) is copper wire, copper
Foil, copper sheet or copper mesh.
3. the preparation method according to claim 1, it is characterised in that: the addition of the internal standard molecule in the step (4)
Amount is 80-100 μ L；The concentration of the internal standard molecule is 0.008-0.012 mmol/L.
4. the preparation method according to claim 1, it is characterised in that: it is molten to be selected from highly basic for aqueous slkali in the step (5)
One of liquid, strong base-weak acid salt, weakly alkaline solution；Wherein strong base solution includes sodium hydroxide, potassium hydroxide, barium hydroxide；
Strong base-weak acid salt includes phosphate, carbonate buffer solution；Weakly alkaline solution is ammonium hydroxide.
5. a kind of silver nanoparticle cavity dendritic materials of containing the internal standard molecule prepared by preparation method as described in claim 1.
6. a kind of application of the silver nanoparticle cavity dendritic materials of containing the internal standard molecule as claimed in claim 5, it is characterised in that: institute
State the SERS substrate of the silver nanoparticle cavity dendritic materials of containing the internal standard molecule for the SERS quantitative detection of drugs.
7. application according to claim 6, it is characterised in that: the drugs include amphetamine, cocaine, m orphine,
Codeine, hydrochloric acid opium poppy alkali, barbiturates, hemp, tetrahydrocannabinol, narcotine, caffeine, ketalar, Sauteralgyl, beauty
Husky ketone, diphenoxylate, caffeine, totokaine, is stabilized, oxazepans, surazepam, librium, A Pu azoles Clozapine
Storehouse, triazole storehouse, Lorazepam or fenfluramine.
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