CN107121424B - The rapid detection method of rose red b in a kind of beverage - Google Patents
The rapid detection method of rose red b in a kind of beverage Download PDFInfo
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- CN107121424B CN107121424B CN201710457287.4A CN201710457287A CN107121424B CN 107121424 B CN107121424 B CN 107121424B CN 201710457287 A CN201710457287 A CN 201710457287A CN 107121424 B CN107121424 B CN 107121424B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- 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
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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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention discloses a kind of rapid detection methods of rose red b in beverage.This method drink sample is after filtering with microporous membrane, pre-treatment is purified without Solid Phase Extraction etc., the surface enhanced Raman substrate for directlying adopt homemade three-electrode electro Chemical pond in filamentary silver Surface Creation porous nano silver carries out extraction and in-situ surface enhancing Raman detection to object rose red b；When 616,732,1007,1073,1196,1277,1357,1503,1647cm‑1Then contain rose red b in sample there are when obvious characteristic Raman peaks in place；Then with 1277cm‑1The Characteristic Raman peak at place obtains calibration curve equation according to the linear ratio relation of the response intensity of the raman spectral signal of rose red b and content as quantitative peak, to carry out rapid quantitative detection to the rose red b in sample.This method is easy to operate, rapidly and efficiently, favorable reproducibility, accuracy rate it is high.
Description
Technical field
The present invention relates to a kind of rapid detection methods, and in particular to a kind of based on rose-red in the beverage for making filamentary silver substrate by oneself
The Raman spectrum method for detecting surface reinforcement of B.
Background technique
To reduce cost, assigning the tempting appearance of food, stable color, certain manufacturers are illegal in food production
Using non-edible industrial pigment, they are mainly using the aromatic hydrocarbons such as benzene, toluene, naphthalene chemical products as raw material, by sulfonation, nitre
Change, halogenation, a series of organic reactions of azoization are bound up, and have certain toxicity mostly.For this purpose, the Ministry of Public Health printed in 2008
" the non-edible material from soybeans list (first) of possible illegal addition in food " notice has been sent out, 6 kinds of non-foods for forbidding addition are listed
With pigment, wherein the most common red non-food coloring of application is rose red b.
Rose red b also known as RB 200 and basic rhodamine are a kind of artificial synthesized alkali with fresh pink
Property fluorescent dye；It is made by meta-hydroxy diethyl-aniline and anhydride phthalic acid condensation, commonly used is its chloride.Because of it
Have the characteristics that high poison, high residue and carcinogenic, teratogenesis, mutagenesis, American-European, Japan and other countries and area just explicit order from 1993
Forbid rose red b in food processing process.
Currently, the measuring method of rose red b mainly has high performance liquid chromatography, High Performance Liquid Chromatography/Mass Spectrometry connection in food
Usage, spectrophotometry etc..But complicated operation, time-consuming for the above detection method pre-treatment, instrument cost is expensive, and institute
Has the shortcomings that biggish toxicity and corrosivity with solvent, mobile phase, it is difficult to popularize.Therefore, it explores quick, easy, high
The food colour detection method of effect establishes effective security monitoring system, has very urgent realistic meaning.
Raman spectrum belongs to molecular vibration spectrum as infrared spectroscopy, can reflect the feature structure of molecule.But
Raman scattering effect is a very weak process, to carry out raman study to adsorption species and almost be employed to certain
Enhancement effect.Since surface-enhanced Raman effects are by it is found that later, metal nanoparticle is just used as a kind of SERS substrate quilt
Extensive to study, the metal nanoparticle in suspension is one of most important material of SERS substrate, however receiving in solution
The problem of rice grain aggregation can bring poor repeatability.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of quick detection sides of rose red b in beverage
Method.Drink sample purifies pre-treatment without Solid Phase Extraction etc., directlys adopt homemade table after filtering with microporous membrane in this method
There is the surface enhanced Raman substrate of porous nano silver structure to carry out extraction and in-situ surface enhancing drawing to object rose red b in face
Graceful detection.This method is easy to operate, rapidly and efficiently, favorable reproducibility, accuracy rate it is high.
The technical scheme adopted by the invention is as follows: a kind of rapid detection method of rose red b in beverage, characterized in that packet
Include following steps:
(1) sample preparation: carbonated sample needs ultrasound to remove carbon dioxide, and the sample containing pulp need to shake up, micro-
Hole membrane filtration obtains prepare liquid, spare；
(2) preparation of surface enhanced Raman substrate: filamentary silver is successively immersed to organic solvent, ultrapure water, is carried out in acid solution
Surface treatment；Using surface treated filamentary silver as working electrode, carried out in -0.2V~0.2V potential range using electrochemical cell
Electrochemical reaction makes the uniform porous nano silver of filamentary silver Surface Creation to get the surface enhanced with uniform porous nano silver structure is arrived
Raman filamentary silver substrate；
(3) it tests: surface-enhanced Raman filamentary silver substrate being immersed and stands extraction in prepare liquid, is subsequently placed on carrier and carries out
Surface enhanced Raman spectroscopy test；
(4) qualitative: it is tested through Surface enhanced Raman spectroscopy, then the standard Raman spectroscopy data comparison with rose red b, when
616,732,1007,1073,1196,1277,1357,1503,1647cm-1Place there are when the obvious characteristic Raman peaks of rose red b,
Then contain rose red b in sample；
(5) quantitative: with 1277cm-1The Characteristic Raman peak at place is as quantitative peak, according to the raman spectral signal of rose red b
The linear ratio relation of response intensity and content obtains calibration curve equation, to quickly determine to the rose red b in sample
Amount detection.
The filamentary silver diameter of step (2) of the present invention is 0.3-1mm, length 1-8cm.
The organic solvent of step (2) of the present invention is one or more of acetone, n-hexane or ethyl alcohol, is preferably submerged initially in third
In ketone, then immerses in ethyl alcohol and be surface-treated.
The acid solution of step (2) of the present invention is 0.1M nitric acid or hydrochloric acid.
The electrochemical cell of step (2) of the present invention is three electrodes, and filamentary silver is working electrode, and saturated calomel electrode is reference electricity
Pole, titanium bucket electrode are auxiliary electrode.It is preferred that homemade three-electrode electro Chemical pond.
The present invention includes the electrochemistry preparation facilities in above-mentioned three-electrode electro Chemical pond, including iron stand, electrochemical cell and
The electrochemical workstation being connected with electrochemical cell, electrochemical cell include reference electrode, auxiliary electrode, working electrode, glass container；
It is characterized in that further including the fixation bracket for fixing electrode；It is provided on the iron stand for controlling working electrode
The elevating mechanism of depth in electrochemical cell；
Elevating mechanism includes gear, micromotor, controller, elevating lever, the height sensor being arranged on elevating lever, folder
Hold frame, operator control panel；It is uniformly arranged on elevating lever fluted；The control terminal of the controller is connected with micromotor, miniature
The shaft of motor is connected with gear, and the teeth of gear are meshed with the groove of elevating lever；Holding frame is mutually fixed with elevating lever；Operation
Screen is fixed on iron stand, and height sensor and operator control panel are connected with controller respectively；
The auxiliary electrode is barrel shape electrode made of titanium, the glass container of barrel shape electrode and electrochemical cell it is interior
Wall is combined closely；Extend leader (titanium system) in the top edge of barrel shape electrode, the handle and electrochemical workstation
Electrical connection.
Further, the controller includes STC11F60XE single-chip microcontroller.
Further, a conductive clip is accompanied at the top of working electrode, conductive clip passes through copper wire and electrochemical workstation phase
Even.
Further, the fixation bracket and holding frame use insulating materials.
Preferably, the filamentary silver that diameter is 0.3-1.0mm the preparation of step (2) surface enhanced Raman substrate: is cut into 1-
8cm successively immerses acetone, ethyl alcohol, ultrapure water, is surface-treated in 0.1M nitric acid, last ultrapure water cleaning, drying for standby；
Using above-mentioned three-electrode electro Chemical pond, filamentary silver is working electrode, and saturated calomel electrode is reference electrode, and titanium bucket electrode is auxiliary
Electrode, 0.1M hydrochloric acid are electrolyte, carry out 10-20 electrification in -0.2V~0.2V potential range with the speed of 5-100mV/s
Reaction is learned, the surface-enhanced Raman filamentary silver substrate with uniform porous nano silver structure is prepared, the filamentary silver prepared cleans, is dry
It is spare.
The extraction time of step (3) is 1-10 minutes, preferably 8 minutes.
Carrier is sheet glass or titanium sheet.
The instrument parameter condition is as follows: it is 785nm that Raman spectrometer, which emits optical maser wavelength, and fixed laser power is
100-200mW, 2000~300cm of scanning range-1, time of integration 2-10s is averaged for each spot scan 5 times.
The standard Raman spectroscopy of rose red b in the step (4) are as follows: theoretical calculation auxiliary criteria sample Raman tests more hands
Section acquires the standard Raman spectroscopy of rose red b.
The present invention uses electrochemical roughening method, and silver wire electrode is placed in electrolyte solution and applies certain electrochemistry
Signal makes silver wire electrode surface that redox reaction occur, and then makes silver wire electrode Surface Creation porous nano silver-colored, passes through nanometer
Particle is evenly distributed on filamentary silver, overcomes the problem of nanoparticle aggregate in solution can bring poor repeatability.This hair simultaneously
Bright auxiliary electrode is titanium cylinder wall-like structure, is fitted closely with glass container inner wall, and with leader and electrochemical workstation
Electrical connection, it is ensured that lateral, the radially uniform corrosion of surface of metal electrode overcomes traditional auxiliary electrode and is difficult to ensure surface
The uniformity that enhancing Raman metallic substrates are axially and radially reacted.The present invention automatically controls working electrode by elevating mechanism and enters
The depth of liquid, it is ensured that the accuracy of experiment reduces error.Working electrode of the present invention passes through a conductive clip and electrochemical workstation
Connection, adapts to the working electrode of various states, and instead of Conventional electrochemical react in working electrode liquid level above section,
Substantially increase the output capacity of textured metal electrode.
Beneficial effects of the present invention:
(1) drink sample of the present invention is after filtering with microporous membrane, without the purification such as Solid Phase Extraction, concentration pre-treatment, sample
Pre-treatment is simple, consumables cost is cheap；
(2) present invention uses homemade three-electrode electro Chemical pond, and lateral, radially uniform porous nano silver knot can be made
The surface-enhanced Raman filamentary silver substrate of structure；Due to porous nano silver be in filamentary silver Surface Creation, it is axial, radially uniform to protect
The repeatability for demonstrate,proving testing result overcomes the existing nanoparticle aggregate bring poor repeatability without using in suspension when carrier
The problem of；Using homemade uniform, the silver-colored structure of porous nano surface-enhanced Raman filamentary silver substrate can to object rose red b into
Row selective extraction and in-situ surface enhance Raman detection；
(3) theoretical calculation auxiliary criteria sample Raman tests the standard Raman spectroscopy data that more means obtain rose red b, with
Accurate qualitative and quantitative analysis is carried out to object in actual sample.
The method of the present invention is simple, quick, accurate, and surface enhanced Raman substrate is at low cost, and easy to carry, storage can be used for
The fast slowdown monitoring in scene.
Detailed description of the invention
Fig. 1 is cyclic voltammetry curve, wherein (A) I-E curve, (B) E-t curve, (C) Q-t curve and (D) I-t curve, sweep
Retouching speed is 25mV/s, and scanning circle number is 15 times；
Fig. 2 is the porous silver nanostructured SEM figure (illustration is partial size statistic histogram) of different scanning speed preparation, wherein
(A) 5mV/s, (B) 10mV/s, (C) 25mV/s, (D) 50mV/s, (E) 75mV/s, (F) 100mV/s, scanning range -0.2~
0.2V, recurring number 15 times；
Fig. 3 is the XRD diagram and EDS figure of filamentary silver substrate, wherein (A) is the XRD diagram of filamentary silver substrate, the EDS of (B) porous filamentary silver
Constituency shape appearance figure, the constituency (C) interior element EDS photoelectron spectroscopy figure；
Fig. 4 is that the molecular structure of rose red b optimizes figure；
Fig. 5 is the theoretical calculation Raman spectrum (a) of rose red b and the comparison of solid etalon product experiment Raman spectrum (b)；
Fig. 6 is filamentary silver substrate extraction 1.0 × 10-6SERS spectra figure of the M rose red b at extraction time 8 minutes；
Fig. 7 is filamentary silver substrate extraction 1.0 × 10-6Adsorption curve of the M rose red b in extraction time 0.5-12min；
Fig. 8 is that (concentration is respectively as follows: 1 × 10 to various concentration from top to down-5M、5×10-6M、2.5×10-6M、1×10-6M、5
×10-7M、2.5×10-7M、5×10-8M、2.5×10-8M、5×10-9M) the SERS map of rose red b standard solution；
Fig. 9 is SERS 1277cm-1The adsorption curve (5 × 10 of rose red b is monitored at characteristic peak-9-1×10-5M)；
Figure 10 is SERS 1277cm-1The calibration curve (5 × 10 of characteristic peak-8-2.5×10-6M)；
Figure 11 is the SERS map of rose red b in positive tomato mixed fruit and vegetable juice drink sample；
Figure 12 is the SERS map of rose red b in positive laughable sample.
Figure 13 is electrochemistry preparation facilities structural schematic diagram；
In figure: 1, iron stand, 11, glass container, 12, fixed bracket, 2, reference electrode, 3, auxiliary electrode, 31, handle,
4, working electrode, 41, conductive clip, 411, copper wire, 51, gear, 52, elevating lever, 53, holding frame, 54, operator control panel, 6, electrochemistry
Work station.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples, and embodiment is not construed as limiting the scope of the present invention.
As shown in figure 13, electrochemistry preparation facilities, including iron stand 1, electrochemical cell and the electrification being connected with electrochemical cell
Learn work station 6, electrochemical cell include reference electrode 2, auxiliary electrode 3, working electrode 4, glass container 11, for fixing electrode
Fixed bracket 12；The elevator for controlling depth of the working electrode in electrochemical cell is provided on the iron stand 1
Structure.
Wherein elevating mechanism includes gear 51, micromotor, controller, elevating lever 52, the height being arranged on elevating lever
Sensor, holding frame 53, operator control panel 54；It is uniformly arranged on elevating lever 52 fluted；The control terminal and micromotor of controller
It is connected, the shaft of micromotor is connected with gear 51, and the teeth of gear are meshed with the groove of elevating lever；Holding frame 53 and lifting
52 phase of bar is fixed, and operator control panel 54 is arranged on iron stand, and height sensor and operator control panel are connected with controller respectively.It manually controls
When working electrode enters the depth of liquid, while fixed, the length that working electrode immerses liquid is always too high or too low, makes
Experimental data inaccuracy；The depth that working electrode enters liquid is automatically controlled by elevating mechanism, it is ensured that the accuracy of experiment subtracts
Small error.
Fixed bracket and holding frame use insulating materials.Controller includes STC11F60XE single-chip microcontroller.
Auxiliary electrode 3 is barrel shape electrode made of titanium, and the inner wall of the glass container of barrel shape electrode and electrochemical cell is tight
Close combination；Extend leader 31 in the top edge of barrel shape electrode, handle 31 is electrically connected with electrochemical workstation 6.Auxiliary
Electrode is fitted closely with glass container inner wall, and is connect with leader with electrochemical workstation, it is ensured that surface of metal electrode
Homogeneous corrosion, it is ensured that the uniformity that surface-enhanced Raman metallic substrates are axially and radially reacted overcomes traditional auxiliary electrode
The problem of being difficult to ensure the uniformity that surface-enhanced Raman metallic substrates are axially and radially reacted.
A conductive clip 41 is accompanied at the top of working electrode 4, conductive clip 41 passes through copper wire 411 and 6 phase of electrochemical workstation
Even；Conductive clip can be accommodated and be higher by liquid level 2-3mm in practical operation.The present invention is adapted to a variety of work using conductive clip
Electrode, such as paper pellet electrode；Working electrode is connect by a conductive clip with electrochemical workstation, is reacted instead of Conventional electrochemical
The liquid level above section of middle working electrode, substantially increases the output capacity of textured metal electrode.
The course of work are as follows: the conductive clip 41 of working electrode 4 reacted is clamped, clamps copper wire with holding frame 53
411, the depth into liquid is needed by 54 input service electrode of operator control panel；Controller controls the rotation of micromotor, miniature
Motor control gear 51 rotates, and gear 51 controls the lifting of elevating lever 52, to control the depth that working electrode immerses liquid.It is high
The adjustable height for spending sensor detection elevating lever 52, when adjustable height is equal with the height of setting, controller controls micro electric
Machine stops operating.
1 instrument and reagent
Raman spectrometer: Ocean Optics QE65Pro Raman spectrometer；Sensibility reciprocal is the assay balance (Switzerland of 0.1mg
Mei Tele company)；Milli-Q water purifior (Millipore company, the U.S.)；JEOL JSM-6700F awkward silence at a meeting scanning electron microscopy
Mirror；X-ray energy dispersion spectrum (Britain Oxford Instruments)；Bruker D8X ray powder diffractometer (German cloth Shandong
Gram).
High-purity filamentary silver (diameter 0.3-1.0mm, 99.99%) is from Beijing non-ferrous metal and rare earth research on utilization institute；First
Alcohol: chromatographically pure (Merk company)；Ethyl alcohol: chromatographically pure (Merk company)；Acetone: chromatographically pure (Merk company)；N-hexane: chromatographically pure
(Merk company)；Hydrochloric acid, nitric acid: it analyzes pure (Sinopharm Chemical Reagent Co., Ltd.)；Rose red b standard items: 97.0%, moral
State Sigma.Tomato mixed fruit and vegetable juice beverage (list of ingredients: water, catsup, concentrated apple juice, strained tomatoes, concentrated orange juice).
2 instrument conditions
Laser Raman spectrometer determination condition: optical maser wavelength 785nm, laser maximum intensity 200mW, scanning range 2000~
300cm-1, time of integration 5s, integral 2 times.Each sample at least scans 5 times, to obtain accurate Raman spectrogram.
Porous silver nanostructured electron microscope pattern measurement: the acceleration voltage of 5.0KV.
3 sample preparations
20.0-40.0g sample is weighed, the sample containing pulp need to shake up, and filtering with microporous membrane is to be measured.
The preparation of 4 surface enhanced substrates
Diameter is that the filamentary silver of 0.3-1.0mm is cut into 1-8cm, successively immerse acetone, ethyl alcohol, ultrapure water, in 0.1M nitric acid
It is surface-treated within 4-8 minutes, last ultrapure water cleaning, drying for standby.Electrochemistry experiment uses homemade three-electrode electro Chemical
Pond, filamentary silver are working electrode, and saturated calomel electrode is reference electrode, and large area titanium bucket electrode is auxiliary electrode, and 0.1M hydrochloric acid is
Electrolyte with the speed of 5-100mV/s carries out 10-20 electrochemical reaction in -0.2V~0.2V potential range, and preparation has
The surface-enhanced Raman filamentary silver substrate of uniform porous nano silver structure, the filamentary silver cleaning prepared, drying for standby.
5 substrates characterization
Porous silver nanostructured pattern is using awkward silence at a meeting scanning electron microscope (SEM, JEOL JSM-6700F) with 5.0KV
Acceleration voltage characterized, silver nanostructured object phase and crystalline condition analysis use X-ray energy dispersion spectrum (EDS, Oxford
Instruments it) is carried out with x-ray powder diffraction instrument (XRD, Bruker D8).Surface topography utilizes atomic force microscope
(AFM, Multimode, Veeco Instruments) is characterized and is carried out granularmetric analysis.
The foundation of 6 standard Raman spectroscopy databases
Successive optimization is carried out to rose red b with Gaussian W03 program and carries out the theory of raman frequency to optimum structure
It calculates, obtains theory characteristic spectrogram；Rose red b solid etalon product are scanned using Raman spectrometer, obtain solid mark product
Feature spectrogram.
7 tests
Surface enhanced Raman substrate is immersed in prepare liquid after standing extraction 1-10 minutes, is placed in progress surface increasing in titanium sheet
Hale graceful spectrum test.
7 results and discussion
7.1 electrochemistry prepare porous silver layer nanostructure
Using cyclic voltammetry, with 25mV/s scanning speed in -0.2~0.2V range, the I-E that scan round 15 is enclosed is bent
Line, E-t curve, Q-t curve and I-t curve are respectively as shown in Figure 1A, B, C, D.By Figure 1A it is observed that from -0.2 to 0.2V
In scanning process, occur the anodic oxidation peak of silver, occurring the cathode of silver ion at -0.095 in flyback process at 0.185V
Reduction peak.During this continuous scanning, oxidation and reduction peak height are gradually increased, filamentary silver surface have occurred continuous dissolution and
It is precipitated.With the increase of circulating ring number, the redox current and the quantity of electric charge of working electrode are to be gradually increased (Fig. 1 C Q-t curve
With Fig. 1 DI-t curve), after circulating ring number reaches 12 circles, electric current and quantity of electric charge variation tend to be steady, it was demonstrated that filamentary silver surface
Solution modeling and reduction deposition process reach balance, and electrode surface area reaches maximum, and roughening treatment is completed.
The characterization of 7.2 porous silver layer nanostructures
Scanning speed is the important parameter for influencing polarization overpotential, and the height of overpotential absolute value directly determines interface electrification
The speed of electron transmission during.Therefore, the speed of scanning speed directly affects porous silver nanostructured size and property.
Here, investigated the influence under different scanning speed to silver nanostructured pattern, we have chosen scanning speed and are respectively
When 5mV/s, 10mV/s, 25mV/s, 50mV/s, 75mV/s, 100mV/s, porous silver nanostructured SEM result as shown in Fig. 2,
Scanning potential range is -0.2 to 0.2V, and the SEM that scanning circle number is 15 times schemes.With the increase of scanning speed, porous silver structure
In the average grain diameter of silver nano-grain be gradually reduced, according to the partial size statistic histogram in illustration, maximum average grain diameter is successively
For 254.2nm, 192.0nm, 127.8nm, 109.5nm, 107.1nm, 101.2nm.The reason of this phenomenon, can be attributed to,
Under relatively slow scanning speed (5mV/s), electron transmission speed is slower, it is ensured that nano particle grows into of major diameter
Grain, and with fast increase is swept, electron transmission speed is accelerated, and the quantity increase of nuclearing centre just can guarantee that electronics is handed in same time
The speed and the increased speeds match of current potential changed, so causing particle size smaller.But high electron transmission speed, even
It has been more than the speed of diffusion mass transfer, therefore the speed of silver ion reduction is less than the speed of its silver atoms oxidation, reduction is caused not filled
Point, porous silver nanostructured layer occurs uneven.As can be seen from Figure 2: when scanning speed is 25mV/s (Fig. 2 C), porous silver
Nanostructure granularity is best.
It can be seen that, diffraction maximum and the peak of Ag (JCPDS No.04-0783) match in the XRD spectrum of Fig. 3 A, it was demonstrated that
Porous nanometer structure is the composition for having silver-colored simple substance, meanwhile, it can clearly identify (111), (200), (220), (311) crystal face
Diffraction maximum, it was demonstrated that nanostructure has good crystallinity.EDS analysis result further confirm, porous nanometer structure by
Ag element composition.Result above surface, using electrochemistry preparation it is porous it is silver nanostructured be mainly made of silver-colored simple substance, be roughened
Process does not cause porous structure surface to generate silver oxide.
7.3 theoretical Raman spectrums calculate and the ownership of vibration mode
Successive optimization is carried out with 03 program of Gaussian to rose red b molecule and raman frequency is carried out to optimum structure
Theoretical calculation, molecular structure optimum results are as shown in figure 4, calculated result file and molecular configuration are observed by Gaussview 5
And analysis, the theoretical Raman spectrum of molecular structure match after calculating calibration of the output results with solid etalon product experiment Raman spectrum presentation height
It spends (Fig. 5, table 1).
Theoretical Raman spectrum (DFT) and solid etalon product experiment Raman spectrum (NRS) main peaks of 1 rose red b of table compare
The foundation of 7.4 qualitative-and-quantitative methods and actual sample detection
7.4.1 qualitative detection
Its characteristic peak may be selected as standard of perfection to the qualitative detection of rose red b, 616,732,1007,1073,
1196,1277,1357,1503,1647cm-1It is higher (Fig. 6) to locate peak intensity, so selected above nine peaks are qualitative peak.
7.4.2 quantitative detection
7.4.2.1 the SERS response of rose red b
The difference of nanostructure can significantly affect the SERS response of binding molecule, and therefore, we have investigated rose red b not
With the SERS response swept on the porous Ag prepared under the conditions of speed.Rose red b sweeps the porous Ag substrate of speed preparation in difference
On reinforcing effect it is different, trend is the increase with scanning speed, and reinforcing effect gradually increases, and is 25mV/s when sweeping speed
When, reinforcing effect reaches maximum value, then as sweeping continuing growing and gradually decreasing for speed.It is obtained when using 25mV/s herein
Filamentary silver substrate carries out methodological study.
7.4.2.2 optimization
Equilibration time is optimized in order to obtain best effect of extracting using standing direx process in this experiment.
In order to select optimum extraction time, we have investigated 1.0 × 10-6The SERS feature peak intensity of M rose red b and moving for extraction time
Force diagram.Porous Ag extraction silk is immersed 1.0 × 10-6In the rose red b extraction working solution of M, interval different time is continuous
SERS spectra on acquisition extraction silk, as shown in fig. 7, feature peak intensity no longer increases after rose red b extraction time is more than 8min
In balance, select optimum extraction time for 8min.
7.4.2.3 detection limit and linear
In optimum condition, a series of rose red b compound that porous Ag extraction silk immerses concentration is extracted
8min is taken, obtains the serial solution SERS spectra data of Fig. 8 after reaching balance, by result as it can be seen that working as the concentration of rose red b solution
It is down to 5 × 10-91007,1196,1277,1357,1647cm when M-1Equal peaks remain to the presence for being seen that there is SERS enhancing peak, this is dense
Spend the detection limit as method.Take 1277cm-1A series of peaks SERS at place do the equilibrium adsorption of peak intensity Yu rose red b concentration
Curve (Fig. 9) and linear relationship curve (Figure 10).
7.4.3 the comparison of actual sample SERS detection and HPLC-MS/MS method
Choose tomato mixed fruit and vegetable juice beverage addition rose red b, S naphthol yellow S, acid violet 6B, the representative sun of quinoline yellow production
Property sample carries out above-mentioned situ extracting SERS method after filtering with microporous membrane and is detected, as a result curve as shown in figure 11, and 616,
732,1007,1073,1196,1277,1357,1503,1647cm-1The drawing at the peak SERS and rose red b powder standard substance at place
Graceful peak is substantially coincident, can be confirmed that SERS of the invention detects the presence of rose red b in tomato mixed fruit and vegetable juice beverage,
Its content is 63.3 μ g/L, and the S naphthol yellow S of addition, acid violet 6B, quinoline yellow do not generate interference to object rose red b.In order to test
The accuracy for demonstrate,proving the above method uses liquid chromatography-tandem level four bars mass spectrum after carrying out Solid Phase Extraction pre-treatment to above-mentioned sample
Method detects wherein rose red b, and comparison result is shown in Table 2.
2 tomato of table mixes the testing result that fruit closes vegetable juice beverage sample
It can be seen from comparing result SERS detection method can under the premise of guaranteeing accuracy, save detection time,
It is easy to operate, compared to liquid chromatography-tandem mass avoid complicated time-consuming pre-treatment and organic phase flow pollution,
Testing cost is saved, SERS enhances substrate can low cost self-control and field quick detection easy to carry, suitable for batch sample.
Embodiment 1:
The rapid detection method of rose red b in laughable sample
1, sample to be tested: laughable (list of ingredients: water, fructose syrup, white granulated sugar, carbon dioxide, burnt sugar coloring, phosphoric acid, coffee
Cause, edible essence).
2, sample preparation: 30.0g sample addition rose red b, the representative positive sample of azorubine production are weighed, because containing two
Carbonoxide needs ultrasound to remove carbon dioxide, and filtering with microporous membrane is to be measured.
3, the preparation of surface enhanced substrate
Diameter is that the filamentary silver of 0.7mm is cut into 5cm, successively immerses acetone, ethyl alcohol, ultrapure water, carries out table in 0.1M nitric acid
Surface treatment, last ultrapure water cleaning, drying for standby.Electrochemistry experiment uses homemade three-electrode electro Chemical pond, and filamentary silver is work
Electrode, saturated calomel electrode are reference electrode, and large area titanium bucket electrode is auxiliary electrode, and 0.1M hydrochloric acid is electrolyte, in -0.2V
15 electrochemical reactions are carried out with the speed of 25mV/s in~0.2V potential range, preparing has uniform porous nano silver structure
Surface-enhanced Raman filamentary silver substrate, the filamentary silver cleaning prepared, drying for standby.
4, it tests: the surface-enhanced Raman filamentary silver substrate prepared being immersed and stands extraction 10 minutes in prepare liquid, then
It is placed in progress Surface enhanced Raman spectroscopy test on carrier；Laser Raman spectrometer determination condition: optical maser wavelength 785nm, laser
Maximum intensity 200mW, 2000~300cm of scanning range-1, time of integration 5s, integral 2 times.Each sample at least scans 5 times, with
Obtain accurate Raman spectrogram.
5, result: result curve as shown in figure 12,616,732,1007,1073,1196,1277,1357,1503,
1647cm-1The peak SERS at place and the Raman peaks of rose red b powder standard substance are substantially coincident, can be confirmed of the invention
SERS detects the presence of rose red b in laughable sample, and content is 332.6 μ g/L, and the azorubine of addition is not to object
Rose red b generates interference.In order to verify the accuracy of the above method, liquid is used after carrying out Solid Phase Extraction pre-treatment to above-mentioned sample
Phase chromatography-QQ-TOF mass spectrometry method detects wherein rose red b using Liquid Chromatography-Tandem Mass Spectrometry, comparison result
It is shown in Table 3.
The testing result of the laughable sample of table 3
Claims (5)
1. the rapid detection method of rose red b in a kind of beverage, characterized in that the following steps are included:
(1) sample preparation: first ultrasound removes carbon dioxide to carbonated sample, and the sample containing pulp first shakes up, then micro-
Hole membrane filtration obtains prepare liquid, spare；
(2) preparation of surface enhanced Raman substrate: taking diameter is that the filamentary silver of 0.3-1.0mm is cut into 1-8cm, successively immerses third
Ketone, ultrapure water, is surface-treated in 0.1M nitric acid, last ultrapure water cleaning, drying for standby ethyl alcohol；Using three electrode electrochemicals
Pond is learned, filamentary silver is working electrode, and saturated calomel electrode is reference electrode, and titanium bucket electrode is auxiliary electrode, and 0.1M hydrochloric acid is electrolysis
Liquid uses cyclic voltammetry to carry out 10-20 electrochemistry in -0.2V~0.2V potential range with the speed of 5-100mV/s anti-
It answers, prepares the surface-enhanced Raman filamentary silver substrate with uniform porous nano silver structure, filamentary silver cleaning, the drying prepared is standby
With；
(3) it tests: surface-enhanced Raman filamentary silver substrate being immersed and stands extraction in prepare liquid, is subsequently placed on carrier and carries out surface
Enhance Raman spectrum test；
(4) qualitative: it is tested through Surface enhanced Raman spectroscopy, then the standard Raman spectroscopy data comparison with rose red b, when 616,
732,1007,1073,1196,1277,1357,1503,1647cm-1Place is there are when the Characteristic Raman peak of obvious rose red b, then sample
Contain rose red b in product；
(5) quantitative: with 1277cm-1The Characteristic Raman peak at place is as quantitative peak, according to the response of the raman spectral signal of rose red b
The linear ratio relation of intensity and content obtains calibration curve equation, to carry out quantitative detection to the rose red b in sample；
It include the electrochemistry preparation facilities in above-mentioned three-electrode electro Chemical pond, it includes iron stand, electrochemical cell and and electrochemistry
The connected electrochemical workstation in pond, electrochemical cell include reference electrode, auxiliary electrode, working electrode, glass container, further include using
In the fixation bracket of fixed electrode；The depth for controlling working electrode in electrochemical cell is provided on the iron stand
Elevating mechanism；
The auxiliary electrode is barrel shape electrode made of titanium, and the inner wall of the glass container of barrel shape electrode and electrochemical cell is tight
Close combination；Extend leader in the top edge of barrel shape electrode, the handle is electrically connected with electrochemical workstation.
2. the rapid detection method of rose red b in a kind of beverage as described in claim 1, characterized in that the elevating mechanism
Including gear, micromotor, controller, elevating lever, the height sensor being arranged on elevating lever, holding frame, operator control panel；It is rising
It is uniformly arranged on drop bar fluted；The control terminal of the controller is connected with micromotor, the shaft and gear of micromotor
It is connected, the teeth of gear are meshed with the groove of elevating lever；Holding frame is mutually fixed with elevating lever；Operator control panel is fixed on iron stand
On, height sensor and operator control panel are connected with controller respectively.
3. the rapid detection method of rose red b in a kind of beverage as described in claim 1, characterized in that the step (3)
Extraction time is 1-10 minutes.
4. the rapid detection method of rose red b in a kind of beverage as described in claim 1, characterized in that the step (3)
Carrier is sheet glass or titanium sheet.
5. the rapid detection method of rose red b in a kind of beverage as described in any one of claim 1-4, characterized in that
Step (3) the instrument parameter condition are as follows: it is 785nm that Raman spectrometer, which emits optical maser wavelength, and fixed laser power is 100-
200mW, 2000~300cm of scanning range-1, time of integration 2-10s is averaged for each spot scan 5 times.
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| CN112853400B (en) * | 2021-01-05 | 2022-11-08 | 昆明理工大学 | Preparation method of nano-porous silver-based substrate with surface having Raman signal enhancing function |
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