CN109781695A - A kind of Raman enhancing nano material and its preparation method and application - Google Patents
A kind of Raman enhancing nano material and its preparation method and application Download PDFInfo
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- CN109781695A CN109781695A CN201811529831.2A CN201811529831A CN109781695A CN 109781695 A CN109781695 A CN 109781695A CN 201811529831 A CN201811529831 A CN 201811529831A CN 109781695 A CN109781695 A CN 109781695A
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Abstract
The invention discloses a kind of Raman enhancing nano materials and its preparation method and application, pass through the internal standard Raman signal molecule cresol-purple in the nanogold surface modification that crystal seed growth method synthesizes；Ag shell further is superscribed on its surface, synthesizes the Au- cresol-purple@Ag nano material that colloidal stability is good, Raman reinforcing effect is excellent；Then, which is further mixed with flocculation aid and certain density food synthetic pigment testing sample solution, the Raman signal of cresol-purple and food synthetic pigment in mixture is detected by Portable Raman spectrometer.Finally, realizing that the scene of synthetic dyestuff in sample, fast, accurate and quantitative are detected by internal standard method according to the relation curve of the two ratio of Raman peak intensity and pigment concentration to be measured at specific peak.Sensor building process and detection process in this method need not rely on large-scale instrument, expensive reagent and organic reagent, easy to operate, quick, high sensitivity.
Description
Technical field
The invention belongs to field of detection of food safety, and in particular to a kind of Raman enhancing nano material and preparation method thereof and
Using.
Background technique
As the improvement of people's living standards, the health and safety of food more seems important.Pigment is as a kind of common
Additive is widely used in the food industry.Addition pigment can substantially improve the Color Quality of food, and then solicit more
Customer, especially children.Pigment can be divided into two class of natural pigment and synthetic dyestuff according to source.Wherein natural pigment although
It is highly-safe, but coloring effect is poor, price is higher, in the food industry using less；Review synthetic dyestuff, tinting strength, tinting power is good,
Not fugitive color, at low cost, is widely used in the food industry.However, it is noted that synthetic dyestuff has certain poison
Property, leading to diarrhea property and carcinogenicity.These toxicity are mostly derived from arsenic, lead, copper, phenol, aniline, ether, chloride in synthetic dyestuff
And sulfate, they can cause different degrees of harm to human body.Numerous studies report, which shows to take for a long time, contains secondary colour
The food of element is easy to cause child behavior is too drastic, influences its intellectual development and interferes its internal normal physiological metabolism etc..Therefore,
Stringent regulation and limitation are all done to the additive amount of synthetic dyestuff in food in various countries.For example, " food additives use is defended in China
Raw standard " regulation, the research on maximum utilized quantity of sunset yellow, lemon yellow in the beverage is 0.1g/kg, and luring red research on maximum utilized quantity is 0.05g/
kg.Acid orange is violated addition pigment.Nevertheless, some businessmans abuse secondary colour to seek exorbitant profit, reduce cost privately
The phenomenon of element happens occasionally.For example, the food safety affairs such as known " tonyred egg ", " dyeing steamed bun " are exactly fine
Explanation.
Currently, the method for detection synthetic dyestuff mainly has high performance liquid chromatography, thin-layered chromatography, spectrophotometry etc..
Some need the instrument of Large expensive in them, and it is complicated for operation, need professional operator；Some sensitivity are inadequate
High, data processing method complexity, is not suitable for live, quick, the highly sensitive detection of synthetic dyestuff.Surface enhanced Raman spectroscopy skill
Art (surface enhanced Raman scattering, SERS) is as a kind of emerging Fingerprint formula detection technique, tool
Have that high sensitivity, specificity are good, detection is quick, easy to operate and the characteristics of can realize non-destructive testing, is in existing fast detecting method
Most possible one of the technology for realizing " foolproof " detection, examines field in food safety fastly and is increasingly taken seriously.In recent years, base
The detection method of a variety of synthetic dyestuffs is developed in SERS technology.For example, realizing the inspection of the light yellow O of beverage neutral and alkali using SERS method
It surveys.Although above method is successfully realized live, simple, quick, the highly sensitive detection of synthetic dyestuff, the Raman of synthesis increases
Strong material homogeneity is bad, and ignore SERS for it is quantitative when common problem --- enhance the inhomogeneities of substrate
And unknown chaff interferent can all have a huge impact the repeatability of SERS testing result in system, and then influence the standard of result
True property.
Summary of the invention
The purpose of the invention is to overcome the defect of above-mentioned SERS testing result of the existing technology, a kind of drawing is provided
Graceful enhancing nano material and its preparation method and application, the stability of above-mentioned Raman enhancing nano material is good, homogeneity is good, enhancing
Effect is good, when being detected using Surface enhanced Raman spectroscopy internal standard method, efficiently solves because of other materials interference, enhancing base in system
The problem of Raman results poor repeatability caused by the reasons such as bottom is inhomogenous.
To achieve the goals above, in the embodiment on basis, one aspect of the present invention provides a kind of Raman enhancing nanometer
Material, including kernel, the internal standard molecule modified on kernel and the shell in the core surface package for being modified with internal standard molecule,
The kernel is ball shaped nano gold, and the internal standard molecule is cresol-purple (CVa), and the shell is metallic silver shell.
In a preferred embodiment, the partial size of the nano material is 30~80nm.
Another aspect of the present invention provides the preparation method of above-mentioned nano material, includes the following steps:
S1, good, uniform particle diameter the ball shaped nano gold using crystal seed growth method synthesis colloidal stability；
S2, interior target Raman signal molecule CVa is served as in ball shaped nano gold surface modification, is being modified with receiving for CVa
Meter Jin
Ag shell is further wrapped up on surface, synthesizes Au-CVa@Ag nano material.
In a preferred embodiment, the crystal seed growth method synthesizing spherical nanogold of the step S1, comprising:
(1) by the HAuCl43H after dilution2O solution is vigorously stirred, and after being heated to boiling, rapidly joins sodium citrate-
Citric acid mixed solution, continues heating stirring, and synthesis obtains seed-solution, is cooled to room temperature spare；
(2) it after the seed-solution dilution for taking step (1) to synthesize, is vigorously mixed at room temperature for, by A liquid and B liquid using wriggling
Pump is slowly added in seed-solution；It is heated to boiling later, continues to stir, obtain the first step and increase solution, be cooled to room temperature；Its
In: A liquid is HAuCl4·3H2The dilute solution of O, it is that ascorbic acid and sodium citrate are mixed that the w/v of A liquid, which is 0.2%, B liquid, before diluting
The dilute solution of solution is closed, the w/v of B liquid is 1% before diluting；
(3) it after the first step for taking step (2) to synthesize increases solution dilution, is vigorously stirred at room temperature, A liquid and B liquid is used
Peristaltic pump is slowly added to the first step simultaneously respectively and increases in solution；It is heated to boiling later, continues to stir, synthesis obtains nanometer
Gold；It is cooled to room temperature spare；Wherein A liquid is HAuCl4·3H2The dilute solution of O, the w/v of A liquid is that 0.2%, B liquid is before diluting
The dilute solution of ascorbic acid and sodium citrate mixed solution, the w/v of B liquid is 1% before diluting.
In a preferred embodiment, in above-mentioned steps (2)-(3), the w/v be 0.2% HAuCl4·3H2O
The volume ratio for the sodium citrate solution that the ascorbic acid solution and w/v that solution, w/v are 1% are 1% is 8:2:1.
In a preferred embodiment, in above-mentioned steps (2)-(3), the parameter of the peristaltic pump is set as 2.5~
3.0。
In a preferred embodiment, it is synthesized to obtain Ag nanometers of Au-CVa@by the nanogold in the step S2
Material specifically includes:
CVa solution is added in the nanogold, after ambient temperature overnight stands or mildly vibrates, centrifugation is resuspended to ultrapure water
In, obtain Au-CVa solution；Under stirring, sodium citrate solution, ascorbic acid solution are sequentially added, then dropwise slowly
Silver nitrate solution is added, continues to stir after solution adds, 4 DEG C of products therefrom refrigerator save backup.
In a preferred embodiment, the concentration of the CVa solution is 1.0mM, the quality point of sodium citrate solution
Number is 0.1%~1%, and the concentration of ascorbic acid and silver nitrate is respectively 17.6mg/mL and 1.69mg/mL.
In a preferred embodiment, the volume of the CVa solution is 0.5~10 μ L, sodium citrate solution, anti-bad
The volume of hematic acid solution and silver nitrate solution is respectively 200 μ L, 50 μ L, 50~600 μ L.
In a preferred embodiment, it is synthesized to obtain Ag nanometers of Au-CVa@by the nanogold in the step S2
Material specifically includes:
CVa solution is added in the nanogold, after ambient temperature overnight stands or mildly vibrates, centrifugation is resuspended to ultrapure water
In, obtain Au-CVa solution；Under stirring, trisodium citrate, ascorbic acid, nitric acid are sequentially added in Au-CVa solution
Silver, sodium hydroxide, room temperature continues to stir after solution adds, and is finally centrifuged, is resuspended in isometric ultrapure water, and 4 DEG C of preservations are standby
With.
In a preferred embodiment, the concentration and volume of the CVa solution are respectively 1.0mM and 0.5~10 μ L,
The concentration and volume of silver nitrate solution are respectively 16.9mg/mL and 15~60 μ L, concentration and the volume difference of sodium hydroxide solution
For 4mg/mL and 50~150 μ L.
Another aspect of the present invention provides above-mentioned applications to nanostructures, is applied to Surface enhanced Raman spectroscopy internal standard
Food synthetic pigment is detected in method.
In a preferred embodiment, the food synthetic pigment is selected from Bengal rose red, chrysoidine, red moss
Red, rhodamine B and Rhodamine G.
In a preferred embodiment, the side of the Surface enhanced Raman spectroscopy internal standard method detection food synthetic pigment
Method, comprising:
A1, the pigment standard solution to be measured of Au-CVa@Ag nano material, flocculation aid and known concentration is placed in container
Mixed at room temperature obtains mixture, reacts 1~2min, Raman test is directly carried out using Portable Raman spectrometer, with conjunction to be measured
At a certain obvious characteristic peak peak intensity of pigment and CVa in 591cm-1The ratio for locating peak intensity is ordinate, the concentration of synthetic dyestuff to be measured
For abscissa, quantitative analysis standard working curve is drawn；
A2, by the pigment sample of unknown concentration to be measured and Au-CVa@Ag nano material, flocculation aid mixed at room temperature, reaction 1~
2min；By Portable Raman spectrometer, a certain obvious characteristic peak peak intensity of pigment to be measured in mixture and CVa are detected in 591cm-1
The ratio for locating peak intensity is substituted into the standard working curve that step A1 is obtained, to obtain the accurate of pigment to be measured in sample
Content.
In a preferred embodiment, the flocculation aid is the citric acid-sodium citrate solution containing 40mM KBr,
The concentration of the citric acid-sodium citrate solution is 0.1M, and pH is 3.0~4.0；Or it is 4.4% that the flocculation aid, which is w/v,
The mixed solution of the sodium hydroxide of formic acid solution and 0.1~0.5M.
In a preferred embodiment, when Raman is tested in the step A1 and A2, the group of mixture becomes 200~
300 μ LAu-CVa@Ag nanomaterial solutions, 50~100 μ L flocculation aids, 200 μ L pigment solutions to be measured.
In a preferred embodiment, when Raman is tested in the step A1 and A2, instrument test condition are as follows: laser
Wavelength is 785nm, and the time for exposure is 5~20s, and integral number of times is 3 times, is averaged, laser power 300mW.
Through the above technical solutions, the package of ball shaped nano Jin Weiyin shell provides template in nano material of the present invention, simultaneously
By internal standard molecule CVa, (raman spectra is relatively pure, only in 591cm-1There is obvious characteristic peak at place, several with the peak overlap of determinand
Rate very little, good discrimination) it modifies between nanogold and silver-colored shell, it can not only increase the Raman signal of CVa, but also have silver-colored shell
The influence of system environment when protectioning from the test of practical sample；And have the supporting role of nanogold in outmost silver-colored shell,
Not only stability greatly improves, but also can be used for directly enhancing the Raman signal of the substances such as synthetic dyestuff.
Meanwhile the present invention is slowly loaded method synthesis nanogold using crystal seed growth-peristaltic pump, products therefrom is not only dispersed
Well, uniform particle diameter is in regular spherical, and colloidal stability is good, and 4 DEG C can save half a year, this, increasing good for synthesising stability
The good Au-CVa@Ag nano material of potent fruit is had laid a good foundation；The present invention uses Surface enhanced Raman spectroscopy internal standard method
Food synthetic pigment is detected, has not only given full play to the fingerprint characteristic of Raman spectrum, but also enhance internal standard molecule CVa in substrate
Use, Raman results repeat caused by efficiently solving because of other materials interference, the enhancing reasons such as substrate is inhomogenous in system
Property difference problem, and then the quantitative accuracy of determinand has been effectively ensured；In addition, the entire building process of the method for the present invention and inspection
Survey process does not need large-scale instrument, expensive reagent and organic reagent, and only needing when detection will be to test sample and Au-CVa Ag
Nano material, flocculation aid 1~2min of mixed at room temperature can satisfy showing for base and food synthetic pigment from far-off regions completely
Field, simple, quick, safety, highly sensitive detection.
Detailed description of the invention
Fig. 1 is the TEM figure of nanogold prepared by the embodiment of the present invention 1.
Fig. 2 (a) is the UV-vis phenogram of the Ag-CVa@Ag nano material synthesis process of the embodiment of the present invention 1；Fig. 2 (b)
The feasibility Raman test chart of Bengal rose red is detected for 1 Surface enhanced Raman spectroscopy internal standard method of the embodiment of the present invention.
Fig. 3 is that the embodiment of the present invention 1 passes through Surface enhanced Raman spectroscopy internal standard method detection various concentration Bengal rose red
Raman test chart (3a) and corresponding working curve diagram (3b).
Fig. 4 is that the embodiment of the present invention 2 is surveyed by the feasibility Raman that Surface enhanced Raman spectroscopy internal standard method detects rhodamine B
Attempt (4a) and sensitivity experiment figure (4b).
Specific embodiment
In order to better understand the above technical scheme, being done below by specific embodiment to technical scheme detailed
Explanation, it should be understood that the specific features in the embodiment of the present application and embodiment be to technical scheme specifically
It is bright, rather than the restriction to technical scheme, in the absence of conflict, the skill in the embodiment of the present application and embodiment
Art feature can be combined with each other.It should be understood that term "and/or" used herein above includes listed by one of them or more
Any and all combinations of associated item out.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Below with reference to the drawings and specific embodiments, the present invention will be described in detail.Material used in embodiment can lead to
Commercially available channel is crossed to obtain.
Embodiment 1
The synthetic method of Au-CVa@Ag nano material of the embodiment of the present invention includes the following steps:
(1) synthesis of crystal seed: by 2.5mL HAuCl4·3H2O (0.2%w/v) solution is diluted to 50mL, and round bottom is added and burns
In bottle；It is vigorously stirred, after being heated to boiling, rapidly joining 2mL sodium citrate-citric acid mixed solution, (its w/v is respectively 1%
With 0.05%).Continue heating stirring 5min, is cooled to room temperature spare.
(2) first step increases: the seed-solution for taking 3mL step (1) to synthesize is diluted to 20mL, is added in round-bottomed flask, room
It is vigorously stirred under temperature, A liquid and B liquid are slowly added in flask simultaneously using peristaltic pump (peristaltic pump parameter is set as 2.5~
3.0)；It is heated to boiling under the conditions of oil bath later, continues to stir 30min, be finally cooled to room temperature.Wherein A liquid is 2mL
HAuCl4·3H2O (0.2%w/v) solution is diluted in 10mL ultrapure water, and B liquid is 0.5mL ascorbic acid and 0.25mL citric acid
Sodium (its w/v is 1%) mixed solution is diluted in 10mL ultrapure water.
(3) synthesis of nanogold: the first step for taking 4.5mL step (2) to synthesize increases solution and is diluted to 20mL, acute at room temperature
A liquid and B liquid are slowly added in flask (peristaltic pump parameter is set as 2.5~3.0) simultaneously respectively by strong stirring；Later in oil bath
In be heated to boiling, continue stir 30min, it is spare to be finally cooled to room temperature.Wherein A liquid is 1mLHAuCl4·3H2O (0.2%w/
V) solution is diluted in 10mL ultrapure water, and B liquid is that 0.25mL ascorbic acid and 0.125mL sodium citrate (its w/v is 1%) are mixed
Solution is closed to be diluted in 10mL ultrapure water.
(4) 3 μ L 1.0mM CVa solution, room temperature mistake the synthesis of Au-CVa@Ag nano material: are added in 6mL nanogold
After night stands or mildly vibrates, centrifugation is resuspended in 5mL ultrapure water；Then, 200 μ L, 1% lemon quickly is sequentially added under stirring
Lemon acid sodium solution, 50 μ L 17.6mg/mL ascorbic acid solutions, it is molten to be then slowly added to 200 μ L 1.69mg/mL silver nitrates dropwise
Liquid continues 20~30min of stirring after solution adds, and 4 DEG C of products therefrom refrigerator save backup.
The Au-CVa@Ag nano material prepared using the embodiment of the present invention, is examined by Surface enhanced Raman spectroscopy internal standard method
Bengal rose red is surveyed, is included the following steps:
S1: the synthesis of 300 μ L steps (4) detection of Bengal rose red standard solution: is sequentially added in 2mL glass tube
Au-CVa@Ag nano material, the mixed solution of 50 μ L formic acid solutions (w/v 4.4%) and sodium hydroxide (0.1M), 200 μ L are not
With the Bengal rose red standard solution (50,100,200,500,1000ppb) of concentration, mix after 2min in portable Raman
Raman test is carried out on spectrometer.Test condition are as follows: optical maser wavelength 785nm, time for exposure 10s, integral number of times are 3 times,
It is averaged, laser power 300mW.It records under various concentration, mixed solution is in 591cm-1With 1325cm-1The Raman peaks at place
Intensity.
Firstly, the nanogold of synthesis is carried out TEM characterization, the result is shown in Figure 1.There it can be seen that nanogold dispersibility is good
It is good, it is in regular spherical, uniform particle diameter, about 75nm.Secondly, having carried out UV- to the synthesis process of Au-CVa@Ag nano material
Vis characterization.As shown in Fig. 2 (a), in nanogold surface modification after CVa, maximum absorption band by 546nm slightly red shift to 547.6nm,
After further wrapping up silver-colored shell, occurs the absorption peak of silver and gold respectively at 419nm and 535nm, show that silver-colored shell is successfully wrapped in
Nanometer gold surface.Then, the mixed solution of Au@Ag and cresol-purple is tested respectively；Au@Ag, flocculation aid and Bengal rose red
Mixed solution；The Raman figure of the mixed solution of Au-CVa@Ag, flocculation aid and Bengal rose red.It can be seen that from Fig. 2 (b)
There is the raman spectra of CVa and Bengal rose red simultaneously in third group mixed solution, and the Raman peaks of the latter are apparent.The knot
Fruit shows that the Au-CVa@Ag nano material of synthesis can be used for the inner mark method ration of Bengal rose red.Then, we are to difference
Concentration Bengal rose red has carried out sensitivity experiment, as a result sees Fig. 3 (a).There it can be seen that working as the dense of Bengal rose red
When degree is down to 50ppb, raman spectra is still, it is apparent that show the detectable Bengal rose red down to 50ppb of this method.It is logical
It crosses with Bengal rose red characteristic peak 1325cm-1Locate peak intensity and CVa characteristic peak 591cm-1Place's peak intensity ratio is ordinate, Meng Jia
Drawing rose-red concentration is abscissa, obtains the standard working curve as shown in Fig. 3 (b).After fitting, curvilinear equation y=
1.5034×10-4X+0.0193, R2It is 0.984.The range of linearity for detecting Bengal rose red is 50~1000ppb.
S2: the detection of Bengal rose red in drink sample: supermarket is bought back to the beverage come first and carries out simple mistake
Filter processing；Then take 200 μ L prepare liquids that 300 μ L Au-CVa@Ag nano materials, 50 μ L formic acid solutions (w/v 4.4%)-are added
In the mixed solution of sodium hydroxide (0.1M), after mixed at room temperature 2min, Raman test is carried out, records the solution in 1325cm-1With
591cm-1The Raman peak intensity at place.The peak intensity ratio of the two is substituted into the working curve that step S1 is obtained, beverage can be calculated
The concentration of middle Bengal rose red.
Embodiment 2
The synthetic method of Au-CVa@Ag nano material of the embodiment of the present invention includes the following steps:
(1) synthesis of crystal seed: by 2.5mL HAuCl4·3H2O (0.2%w/v) solution is diluted to 50mL, and round bottom is added and burns
In bottle；It is vigorously stirred, after being heated to boiling, rapidly joining 2mL sodium citrate-citric acid mixed solution, (its w/v is respectively 1%
With 0.05%).Continue heating stirring 5min, is cooled to room temperature spare.
(2) first step increases: the seed-solution for taking 3mL step (1) to synthesize is diluted to 20mL, is added in round-bottomed flask, room
It is vigorously stirred under temperature, A liquid and B liquid are slowly added in flask simultaneously using peristaltic pump (peristaltic pump parameter is set as 2.5~
3.0)；It is heated to boiling under the conditions of oil bath later, continues to stir 30min, be finally cooled to room temperature.Wherein A liquid is 2mL
HAuCl4·3H2O (0.2%w/v) solution is diluted in 10mL ultrapure water, and B liquid is 0.5mL ascorbic acid and 0.25mL citric acid
Sodium (its w/v is 1%) mixed solution is diluted in 10mL ultrapure water.
(3) synthesis of nanogold: the first step for taking 4.5mL step (2) to synthesize increases solution and is diluted to 20mL, acute at room temperature
A liquid and B liquid are slowly added in flask (peristaltic pump parameter is set as 2.5~3.0) simultaneously respectively by strong stirring；Later in oil bath
In be heated to boiling, continue stir 30min, it is spare to be finally cooled to room temperature.Wherein A liquid is 2mLHAuCl4·3H2O (0.2%w/
V) solution is diluted in 10mL ultrapure water, and B liquid is that 0.5mL ascorbic acid and 0.25mL sodium citrate (its w/v is 1%) mix
Solution is diluted in 10mL ultrapure water.
(4) 6 μ L 1.0mM CVa solution, room temperature mistake the synthesis of Au-CVa@Ag nano material: are added in 10mL nanogold
After night stands or mildly vibrates, centrifugation is resuspended in 10mL deionized water；Then, room temperature is slowly stirred down, in the Au- of acquisition
Sequentially added in CVa solution 400 μ L citric acid three sodium solutions (1.41mg/mL), 180 μ L ascorbic acid solutions (17.6mg/mL),
45 μ L silver nitrate solutions (16.9mg/mL), 150 μ L sodium hydroxide solutions (4mg/mL), room temperature continues quick after solution adds
30min is stirred, is finally centrifuged, is resuspended in isometric ultrapure water, 4 DEG C save backup.
The Au-CVa@Ag nano material prepared using the embodiment of the present invention, is examined by Surface enhanced Raman spectroscopy internal standard method
Rhodamine B is surveyed, is comprised the following steps that
The detection of rhodamine B standard solution: sequentially added in a 2mL cuvette 200 μ L Au-CVa@Ag nano materials,
The rhodamine B standard of the citric acid-sodium citrate solution (0.1M, pH=3.0) of 100 μ L 40mM KBr, 200 μ L various concentrations
Solution (20,50,100,5000ppb) carries out Raman test after mixing 2min on Portable Raman spectrometer.Test condition
Are as follows: optical maser wavelength 785nm, time for exposure 10s, integral number of times are 3 times, are averaged, laser power 300mW.Record
Under various concentration, mixed solution is in 591cm-1With 1358cm-1Raman scattering intensity at (rhodamine B characteristic peak).
Firstly, the Au-CVa@Ag nano material based on the present embodiment synthesis, the feasibility for having carried out rhodamine B detection is real
It tests.As shown in Fig. 4 (a), the mixed solution of Au@Ag and rhodamine B is tested respectively；Au@Ag, flocculation aid and rhodamine B it is mixed
Close solution；The Raman figure of Au-CVa@Ag, flocculation aid and the mixed solution of rhodamine B.There it can be seen that the mixing of third group is molten
There is the raman spectra of CVa and rhodamine B simultaneously in liquid, and the Raman peaks of the latter are apparent.Should the result shows that, the Au- of synthesis
CVa@Ag nano material can be used for the inner mark method ration of rhodamine B.Then, difference is tested based on Au-CVa@Ag nano material
The Raman figure of concentration rhodamine B, is as a result shown in Fig. 4 (b).There it can be seen that with the increase of rhodamine B concentration,
1358cm-1The Raman peak intensity at place gradually increases, and when its concentration is 5000ppb, is declined instead.Should the result shows that, Au-
CVa@Ag nano material can be used for the internal standard method detection of rhodamine B, and when concentration up to 5000ppb, reach saturation, peak intensity is no longer
Increase.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of Raman enhances nano material, it is characterised in that: the internal standard molecule modified including kernel, on kernel and repairing
It is decorated with the shell of the core surface package of internal standard molecule, the kernel is ball shaped nano gold, and the internal standard molecule is cresol-purple, institute
Stating shell is metallic silver shell.
2. Raman according to claim 1 enhances nano material, which is characterized in that the partial size of the nano material is 30~
80nm。
3. the preparation method of nano material as described in claim any one of 1-2, which comprises the steps of:
S1, using crystal seed growth method synthesizing spherical nanogold；
S2, interior target Raman signal molecule cresol-purple is served as in ball shaped nano gold surface modification, is being modified with cresol-purple
Nanometer gold surface further wraps up Ag shell, synthesizes Au-CVa Ag nano material.
4. the preparation method of nano material according to claim 3, which is characterized in that the crystal seed growth method of the step S1 is closed
At spherical nanogold, comprising:
(1) by the HAuCl after dilution4·3H2O solution is vigorously stirred, and after being heated to boiling, rapidly joins sodium citrate-citric acid
Mixed solution, continues heating stirring, and synthesis obtains seed-solution, is cooled to room temperature spare；
(2) it after the seed-solution dilution for taking step (1) to synthesize, is vigorously mixed at room temperature for, A liquid and B liquid is delayed using peristaltic pump
It is slow to be added in seed-solution；It is heated to boiling later, continues to stir, obtain the first step and increase solution, be cooled to room temperature；Wherein A
Liquid is HAuCl4·3H2The dilute solution of O, it is that ascorbic acid and sodium citrate mixing are molten that the w/v of A liquid, which is 0.2%, B liquid, before diluting
The dilute solution of liquid, the w/v of B liquid is 1% before diluting；
(3) it after the first step for taking step (2) to synthesize increases solution dilution, is vigorously stirred at room temperature, by A liquid and B liquid using wriggling
Pump is slowly added to the first step simultaneously respectively and increases in solution；It is heated to boiling later, continues to stir, synthesis obtains nanogold；It is cold
But spare to room temperature；Wherein A liquid is HAuCl4·3H2The dilute solution of O, it is Vitamin C that the w/v of A liquid, which is 0.2%, B liquid, before diluting
The dilute solution of acid and sodium citrate mixed solution, the w/v of B liquid is 1% before diluting.
5. the preparation method of nano material according to claim 4, it is characterised in that: in above-mentioned steps (2)-(3), the w/
The HAuCl that v is 0.2%4·3H2The body for the sodium citrate solution that the ascorbic acid solution and w/v that O solution, w/v are 1% are 1%
Product is than being 8:2:1；
Preferably, the parameter of the peristaltic pump is set as 2.5~3.0.
6. the preparation method of nano material according to claim 3, which is characterized in that by the nanogold in the step S2
Synthesis obtains Au-CVa@Ag nano material, specifically includes:
CVa solution is added in the nanogold, after ambient temperature overnight stands or mildly vibrates, centrifugation is resuspended in ultrapure water, is obtained
To Au-CVa solution；Under stirring, sodium citrate solution, ascorbic acid solution are sequentially added, is then slowly added to dropwise
Silver nitrate solution continues to stir after solution adds, and 4 DEG C of products therefrom refrigerator save backup；
Preferably, the concentration of the CVa solution is 1.0mM, and the mass fraction of sodium citrate solution is 0.1%~1%, Vitamin C
The concentration of acid and silver nitrate is respectively 17.6mg/mL and 1.69mg/mL；
Preferably, the volume of the CVa solution is 0.5~10 μ L, and sodium citrate solution, ascorbic acid solution and silver nitrate are molten
The volume of liquid is respectively 200 μ L, 50 μ L, 50~600 μ L.
7. the preparation method of nano material according to claim 3, it is characterised in that: by the nanogold in the step S2
Synthesis obtains Au-CVa@Ag nano material, specifically includes:
CVa solution is added in the nanogold, after ambient temperature overnight stands or mildly vibrates, centrifugation is resuspended in ultrapure water, is obtained
To Au-CVa solution；Under stirring, trisodium citrate, ascorbic acid, silver nitrate, hydrogen are sequentially added in Au-CVa solution
Sodium oxide molybdena, room temperature continues to stir after solution adds, and is finally centrifuged, is resuspended in isometric ultrapure water, and 4 DEG C save backup；
Preferably, the concentration and volume of the CVa solution are respectively 1.0mM and 0.5~10 μ L, the concentration and body of silver nitrate solution
Product is respectively 16.9mg/mL and 15~60 μ L, and the concentration and volume of sodium hydroxide solution are respectively 4mg/mL and 50~150 μ L.
8. the applications to nanostructures as described in claim any one of 1-2, is applied to Surface enhanced Raman spectroscopy internal standard method
Middle detection food synthetic pigment.
9. applications to nanostructures according to claim 8, it is characterised in that: the Surface enhanced Raman spectroscopy internal standard method inspection
The method for surveying food synthetic pigment, comprising:
A1, the pigment standard solution to be measured of Au-CVa@Ag nano material, flocculation aid and known concentration is placed in room temperature in container
Mixing obtains mixture, reacts 1~2min, Raman test is directly carried out using Portable Raman spectrometer, with secondary colour to be measured
Plain a certain obvious characteristic peak peak intensity and CVa are in 591cm-1The ratio for locating peak intensity is ordinate, and the concentration of synthetic dyestuff to be measured is cross
Coordinate draws quantitative analysis standard working curve；
A2, by the pigment sample of unknown concentration to be measured and Au-CVa@Ag nano material, flocculation aid mixed at room temperature, reaction 1~
2min；By Portable Raman spectrometer, a certain obvious characteristic peak peak intensity of pigment to be measured in mixture and CVa are detected in 591cm-1
The ratio for locating peak intensity is substituted into the standard working curve that step A1 is obtained, to obtain the accurate of pigment to be measured in sample
Content.
10. applications to nanostructures according to claim 9, it is characterised in that: the flocculation aid is to contain 40mM KBr's
Citric acid-sodium citrate solution, the concentration of the citric acid-sodium citrate solution are 0.1M, and pH is 3.0~4.0；Or it is described
Flocculation aid is the mixed solution of the formic acid solution that w/v is 4.4% and the sodium hydroxide of 0.1~0.5M；
Preferably, when Raman is tested in the step A1 and A2, the group of mixture becomes 200~300 Ag nanometers of μ L Au-CVa
Material solution, 50~100 μ L flocculation aids, 200 μ L pigment solutions to be measured；
Preferably, when Raman is tested in the step A1 and A2, instrument test condition are as follows: optical maser wavelength 785nm, time for exposure
For 5~20s, integral number of times is 3 times, is averaged, laser power 300mW；
Preferably, the food synthetic pigment is selected from Bengal rose red, chrysoidine, erythrosine, rhodamine B and Rhodamine G.
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| CN113125407A (en) * | 2020-01-16 | 2021-07-16 | 武汉市农业科学院 | Cr (chromium)6+Ion rapid detection method |
| CN114113033A (en) * | 2021-11-05 | 2022-03-01 | 王翠娟 | Method for rapidly detecting bromadiolone in urine based on surface enhanced Raman spectroscopy |
| CN114778512A (en) * | 2022-03-25 | 2022-07-22 | 江南大学 | Raman detection method of hydrogen peroxide based on Au-Ag @ manganese dioxide nano material |
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| CN107328753A (en) * | 2017-07-14 | 2017-11-07 | 厦门稀土材料研究所 | The nanoparticle surface enhancing Raman spectrum quantitative analysis method of embedded internal standard molecule |
| CN108526483A (en) * | 2018-04-18 | 2018-09-14 | 厦门大学 | A kind of preparation method of the super round gold-silver alloy nanoparticles of size adjustable |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107328753A (en) * | 2017-07-14 | 2017-11-07 | 厦门稀土材料研究所 | The nanoparticle surface enhancing Raman spectrum quantitative analysis method of embedded internal standard molecule |
| CN108526483A (en) * | 2018-04-18 | 2018-09-14 | 厦门大学 | A kind of preparation method of the super round gold-silver alloy nanoparticles of size adjustable |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113125407A (en) * | 2020-01-16 | 2021-07-16 | 武汉市农业科学院 | Cr (chromium)6+Ion rapid detection method |
| CN113125407B (en) * | 2020-01-16 | 2024-05-03 | 武汉市农业科学院 | Cr (chromium)6+Ion rapid detection method |
| CN114113033A (en) * | 2021-11-05 | 2022-03-01 | 王翠娟 | Method for rapidly detecting bromadiolone in urine based on surface enhanced Raman spectroscopy |
| CN114778512A (en) * | 2022-03-25 | 2022-07-22 | 江南大学 | Raman detection method of hydrogen peroxide based on Au-Ag @ manganese dioxide nano material |
| CN115184335A (en) * | 2022-07-08 | 2022-10-14 | 西安交通大学 | Raman detection method based on in-situ formation of coating layer on surface of nano gold particle induced by coagulation agent |
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