CN107290329A - A kind of preparation method and application of sulfydryl beta cyclodextrin functionalization SERS paper substrates - Google Patents
A kind of preparation method and application of sulfydryl beta cyclodextrin functionalization SERS paper substrates Download PDFInfo
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- CN107290329A CN107290329A CN201710349050.4A CN201710349050A CN107290329A CN 107290329 A CN107290329 A CN 107290329A CN 201710349050 A CN201710349050 A CN 201710349050A CN 107290329 A CN107290329 A CN 107290329A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The present invention relates to medicine analysis field, specifically a kind of preparation method and application of sulfydryl beta cyclodextrin functionalization SERS paper substrates comprises the following steps:(1) preparation of sulfydryl beta cyclodextrin functionalization gold nanorods;(2) absorption deposition of the functionalization gold nanorods in its surface;(3) Performance of the functionalization SERS paper substrates described in;(4) the functionalization SERS paper substrates described in are used to detect the method for violated addition Sudan red dyes in Chinese medicine.Sulfydryl beta cyclodextrin functionalization gold nanorods step of the present invention, the maximal cover rate of guarantee fund's nanorod surfaces sulfydryl beta cyclodextrin, the hydrophobic cavity for improving sulfydryl beta cyclodextrin is conducive to capture the efficiency of lipophilic molecule, sensitivity and specific detection of the increase paper substrate to Sudan molecules.This method preparation process is simple, and detection time is short, can realize the rapid sensitive detection to violated addition Sudan red dyes in Chinese medicine.
Description
Technical field
It is a kind of sulfydryl beta-schardinger dextrin functionalization SERS paper substrates specifically the present invention relates to medicine analysis technical field
Preparation method and application.
Background technology
With the continuous expansion of Chinese Medicinal Materials Markets, the event of the violated addition dyestuff of Chinese medicine emerges in an endless stream at home.It is illegal
Retailer hides inspection of the drug administration department to dyestuff in commodity to speculate, it will usually using the lipid-soluble dye of strong coloring force,
Or the substandard products in Chinese medicine are dyed using two kinds or more of mixed dye.But most of dye molecules are to human body
In the presence of harm hidden danger.Such as Sudan molecules, it is the compound that a class has phenylazo naphthols structure, by metabolism in vivo
Aromatic amine compound is converted into, causes liver cell producer in human body to be mutated, so as to improve the incidence of cancer.Therefore,
In order to ensure the drug safety of the public, setting up a kind of detection method of the live rapid sensitive suitable for Sudan molecules has weight
The meaning wanted.
At present, be usually used in Sudan molecules detection method mainly have high performance liquid chromatography, Capillary Electrophoresis chromatography,
Immunization method etc., although these method efficient and sensibles, instrument is huge, cost is high, analytical cycle length, sample pre-treatments are multiple
It is miscellaneous, it is impossible to meet the demand of field quick detection.On the contrary, SERS is because it is quick, sensitive, can be achieved to sample
Product Non-Destructive Testing and the abundant molecular fingerprint feature of offer, it is of great interest in quick detection at the scene, with very
Good application prospect.
The key of SERS technologies is the preparation of substrate, in recent years, and filter paper is due to light, thin, low cost, being convenient for carrying
With sample, can be mass and the features such as bio-compatible, favored by more and more researchers, as constructing various receive
The support carrier of rice structure, the practical SERS substrates applied to Site Detection.However, for lipophilic molecule, its is hydrophobic
Affinity is weak between property and hydrophilic paper substrate, and lipophilic molecule can not cause effectively close to the avtive spot (" focus ") of paper substrate
Paper substrate has limitation to the detection sensitivity of lipophilic molecule.Therefore, in order to improve the parent between substrate and lipophilic molecule
And power, it will usually surface-hydrophobicized or functional modification is carried out to substrate.At present, method constructs sulfydryl using alumina formwork
Beta-cyclodextrin modified Silver nanorod substrate, also has method to be based on constructing sulfydryl beta-cyclodextrin modified gold nanosphere base on sheet glass
Bottom, is used equally for improving the detection sensitivity to lipophilic molecule Polychlorinated biphenyls (PCB) in water pollution.However, above method institute
The SERS substrate quality of use is hard, and preparation cost is higher, and sample pre-treatments are complicated, and silver nano-grain is easily oxidized, and is led
Causing the detection sensitivity of substrate quickly reduces, and is unfavorable for the preservation and carrying of substrate.Therefore, the practical of SERS substrates is limited
Application prospect.The present invention is functional molecular modification gold nanorods (GNR) with sulfydryl beta-schardinger dextrin (HS- β-CD), not merely with HS-
β-CD hydrophobic cavity capture lipid-soluble dye, improves substrate and the affinity of lipid-soluble dye, and compared to silver nanoparticle material
Material, GNR is difficult to be oxidized, the steady key of signal, convenient storage.In addition, the present invention uses filter paper for backing material, frivolous flexible, side
Portable belt, and with water imbibition and capillary force characteristic, sample collection process can be simplified, it is latent with good practical application
Power.
The content of the invention
It is an object of the invention to provide a kind of preparation of the SERS paper substrates suitable for field quick detection lipid-soluble dye
Method.
To achieve these goals, there is provided a kind of sulfydryl beta-schardinger dextrin functionalization SERS paper substrates for the first aspect of the present invention
Preparation method, comprise the following steps:
Step one (S1):The preparation of sulfydryl beta-schardinger dextrin functionalization gold nanorods
Gold nanorods solution is pre-processed:Appropriate gold nanorods stoste is taken, surfactant is removed after centrifugation, with isometric
Ultra-pure water cleans the gold nanorods of bottom, supernatant is removed after centrifugation, the isometric ultra-pure water of bottom disperses standby again;Prepare
Concentration is 100~0.1 μM of sulfydryl beta-schardinger dextrin;Pretreated gold nanorods solution is taken to be mixed with sulfydryl beta-schardinger dextrin solution
Close, make sulfydryl beta-schardinger dextrin ultimate density be 50~1 μM, after vibration, in water bath with thermostatic control stand, make sulfydryl beta-schardinger dextrin with
Gold nanorods fully carry out chemisorption, and incorporation time is 3~48h, and centrifugal rotational speed is 8000~10000rpm, during centrifugation
Between be 10~20min;
Step 2 (S2):Absorption deposition of the functionalization gold nanorods in its surface
The functionalization gold nanorods that step one is obtained are adsorbed in its surface by way of immersion:Take appropriate functionalization
Supernatant is removed after gold nanorods centrifugation, bottom is disperseed again with the ultra-pure water of 2~4 times of concentration amounts, filter paper is cut into 1 ×
1cm2Square, in the functionalization gold nanorods solution that 3 concentration amounts are soaked in respectively, be statically placed in water bath with thermostatic control, make filter
The full and uniform adsorption function gold nanorods of paper;The centrifugal rotational speed be 8000~10000rpm, centrifugation time be 10~
20min, soak time is 12~48 hours.
It is preferred that, preferably 5 μM of the ultimate density for the sulfydryl beta-schardinger dextrin that step one is used, gold nanorods are pasted with sulfydryl β-ring
The mixed proportion preferably 9 of essence:1, the preferred 24h of incorporation time, preferably 40 DEG C of temperature in water-bath, the preferred 9000rpm of centrifugal rotational speed, from
Heart time preferred 15min.
It is preferred that, preferably 3 times of the cycles of concentration for the gold nanorods that step 2 is used, preferably 40 DEG C of temperature in water-bath, centrifugation
The preferred 9000rpm of rotating speed, the preferred 15min of centrifugation time.
There is provided a kind of sulfydryl beta-schardinger dextrin functionalization prepared using above-mentioned preparation method for the second aspect of the present invention
SERS paper substrates.
There is provided a kind of sulfydryl beta-schardinger dextrin functionalization prepared using above-mentioned preparation method for the third aspect of the present invention
The investigation method of SERS paper substrate SERS performances, using Sudan IV as probe molecule, investigates sensitivity, the reappearance of paper substrate respectively
And stability.
Specifically include following steps:
Step A:Investigate the sensitivity of functionalization SERS paper substrates
Prepared the Sudan IV solution for standby of various concentrations, respectively by the Sudan IV of 50 μM -0.5 μM of concentration be added dropwise in
Paper substrate surface, is detected under Raman spectrometer, the spectrum of 20 different locis is gathered, by choosing 1097cm-1Characteristic peak
Intensity be used as paper substrate to characterize the sensitivity of the Sudan IV of various concentrations;
Step B:Investigate the reappearance of functionalization SERS paper substrates
Concentration is added dropwise in paper substrate surface for 50 μM of Sudan IV, the spectrum of 50 different locis is collected, chosen
The characteristic peak 1097cm of Sudan IV-1(ω (C-H/N-H)/υ (N-N)) and 1485cm-1(ρ (N-H)/υ (C=N)/ρ (C-H)ph)
Strength co-mputation average standard deviation value;
Step C:Investigate the stability of functionalization SERS paper substrates
Paper substrate is placed and preserves 90 days in atmosphere, respectively the 1st, 7,15,30,60,90 days when, by 50 μM of tonyred
IV is added dropwise on paper substrate, collects spectrum, by the characteristic peak 1097cm for observing Sudan IV-1SERS Strength Changes, comment
Estimate the bin stability of functionalization SERS paper substrates.
It is preferred that, SERS testing conditions are time of integration 5s in described step A, B, C, and optical maser wavelength is 633nm.
With being contrasted conventional without by the gold nanorods paper substrate of functional modification, functionalization gold nanorods paper substrate is to the Sudan
Red IV shows more preferable sensitivity (LOD=0.5 μM).Paper substrate is equal in the mean standard deviation obtained by 50 different loci detections
Less than 15%.Paper substrate stability is stored 90 days as shown in figure 9, placing it in air, and SERS sensitivitys are only down to 60%.
There is provided a kind of above-mentioned sulfydryl beta-schardinger dextrin functionalization SERS paper substrates medicinal material in the detection for the fourth aspect of the present invention
In it is violated addition Sudan red dyes in application.
The fifth aspect of the present invention is used to detect Chinese medicine there is provided a kind of above-mentioned sulfydryl beta-schardinger dextrin functionalization SERS paper substrates
The method of violated addition Sudan red dyes, comprises the following steps in material:
With the described functionalization SERS paper substrates of acetone, ether, the wetting of hexamethylene reagent, wiped with the paper substrate after wetting to be checked
The surface of sample, SERS spectra is obtained by Raman detection, and obtained SERS spectra is carried out into baseline correction, analyzes measuring samples
In whether with the addition of Sudan red dyes.
It is preferred that, the preferred hexamethylene of described wet reagent, SERS testing conditions are time of integration 5s, and optical maser wavelength is
633nm。
The test limit of Sudan IV reaches in the sulfydryl beta-schardinger dextrin functionalization SERS paper substrates detection authentic sample of the present invention
38.04ng/cm2。
Compared with background technology, the beneficial effect of technical scheme is:
1st, using sulfydryl beta-schardinger dextrin functionalization gold nanorods, be conducive to capturing Sudan molecules
The present invention make use of HS- β-CD to have unique outer hydrophilic interior hydrophobic sky using HS- β-CD as function chemoattractant molecule
Cavity configuration has preferable compatibility there is provided a good hydrophobic site with lipophilic molecule, can include fat-soluble point
Son, shortens lipophilic molecule and strengthens the distance between substrate, realizes and the sensitivity of lipophilic molecule is detected.In addition, will
HS- β-CD are modified in GNR surfaces, because S-Au chemical bonds are stronger than Br-Au, therefore, it can replace out the CTAB on GNR surfaces, shape
Cheng Wenjian functionalization GNR substrates, it is ensured that stability of the paper substrate in detection environment.Sulfydryl beta-schardinger dextrin functionalization of the present invention
Gold nanorods step, it is ensured that GNR surfaces HS- β-CD maximal cover rate, is conducive to improving HS- β-CD hydrophobic cavity capture
The efficiency of lipophilic molecule, sensitivity and specific detection of the increase paper substrate to lipophilic molecule.
2nd, reappearance and stability are good
Paper substrate prepared by the present invention is more in its surface excess due to functionalization gold nanorods, and absorption profiles homogeneity
Preferably, thus carry out Raman detection when, show preferable reappearance.In addition, gold nanorods are difficult to be oxidized, so functionalization
The bin stability of paper substrate is also showed well.Therefore, functionalization SERS paper substrates can meet the requirement of practical substrate.
3rd, paper substrate provides 3D configurations, and prepares with operating process simply, and testing cost is low
Paper substrate surface constitutes 3D configurations by intersecting the cellulose stacked in the present invention, is conducive to producing more focus,
Improve the SERS enhancing performances of substrate.In addition, using the water imbibition and capillary force characteristic of paper substrate, can after being soaked by reagent
The simple extraction to the dye molecule on authentic sample surface is realized, the pretreatment process to sample is simplified, detection speed is fast.And
And the preparation method of paper substrate is simple, testing cost is low, meets the demand of field quick detection.
4th, the inventive method preparation process is simple, and detection time is short, can realize to violated addition tonyred in Chinese medicine
The rapid sensitive detection of dyestuff.
Brief description of the drawings
Streams of the Fig. 1 for the preparation of functionalization SERS paper substrates and applied to violated addition Sudan red dyes in detection Chinese medicine
Cheng Tu;
Fig. 2 is sulfydryl beta-schardinger dextrin and change of the gold nanorods with incorporation time of various concentrations in embodiment 1, and SERS is strong
The variation tendency of degree;
Fig. 3 is the SERS sensitivitys of the functionalization gold nanorods of different cycles of concentration in embodiment 1;
Fig. 4 is that the functionalization gold nanorods of 3 times of concentrations in embodiment 1 are sensitive in the SERS of the different sedimentation times in paper substrate surface
Property;
Fig. 5 detects spectrum for functionalization gold nanorods paper substrate in embodiment 1 to the sensitivity of the Sudan IV of various concentrations
And the comparison diagram with gold nanorods paper substrate sensitivity;
Fig. 6 is functionalization gold nanorods paper substrate in embodiment 1 in 50 spectrum obtained by different loci collection;
Fig. 7 is functionalization gold nanorods paper substrate detection 50 spectrum of gained in embodiment 1 in 1097cm-1It is strong at characteristic peak
Degree figure and its RSD values;
Fig. 8 is functionalization gold nanorods paper substrate detection 50 spectrum of gained in embodiment 1 in 1485cm-1It is strong at characteristic peak
Degree figure and its RSD values;
Fig. 9 is functionalization gold nanorods paper substrate in embodiment 1 with the change of holding time, detection Sudan IV characteristic peak
1097cm-1Peak intensity change;
Figure 10 is that the functionalization gold nanorods paper substrate wiping dragon's blood dummy of different reagent wettings in embodiment 2 is gathered
The blank background arrived;
Figure 11 is that the functionalization gold nanorods paper substrate wiping dragon's blood color card of different reagent wettings in embodiment 2 is gathered
The SERS spectra arrived;
Figure 12 gathers for the dragon's blood that functionalization gold nanorods paper substrate detection in embodiment 2 is dyed with various concentrations Sudan IV
The SERS spectra arrived and they in 1097cm-1Strength Changes at characteristic peak.
Embodiment
The embodiment provided with reference to embodiment the present invention elaborates.
Embodiment 1
The Raman spectrometer that the present embodiment 1 is used is LabRAM HR800 copolymerization micro-Raman spectroscopies (Horiba J
Y), the He-Ne lasers that optical maser wavelength is 632.8mn are equipped with, from × 50LMPLFLN object lens, numerical aperture (NA) is 0.5,
Laser power is~1mW.The enhancing substrate used is gold nanorods colloidal sol, and preparation method is:1. the preparation of gold nanorods:It will contain
The beaker for having 10mL cetyl trimethylammonium bromides (CTAB, 0.1M) is placed in water-bath (28 DEG C of constant temperature), adds 103 μ L
It is hydrated gold chloride (HAuCl4, 25mM) mix, the sodium borohydride solution (NaBH newly configured is rapidly added under agitation4,0.01M)
600 μ L, persistently stir 2min, and 28 DEG C of standing 1h, as seed liquor is standby.10mL CTAB (0.1M) triangular flask will be filled again
(28 DEG C of constant temperature) is placed in water-bath, 120 μ L silver nitrates (AgNO are successively added3, 0.08M), 100 μ L nitric acid (HNO3, 2M),
206 μ L hydration gold chlorides (HAuCl4·3H2O, 25mM), vitamin A (AA, 0.1M) after stirring and evenly mixing, adds 120 μ L seeds
Liquid, standing 24h after the stirring several seconds at 28 DEG C, to grow into gold nanorods standby.
Fig. 1 be the present embodiment to the preparation flow figure of the Different Optimization condition of functionalization gold nanorods paper substrate, specifically include
Three step below:
Step one (S1):The preparation condition optimization of sulfydryl beta-schardinger dextrin functionalization gold nanorods
Gold nanorods solution is pre-processed:Appropriate gold nanorods stoste is taken, surfactant is removed after centrifugation, with isometric
Ultra-pure water cleans the gold nanorods of bottom, supernatant is removed after centrifugation, the isometric ultra-pure water of bottom disperses standby again;Prepare
Concentration is 100~0.1 μM of sulfydryl beta-schardinger dextrin;Take pretreated gold nanorods solution respectively with the sulfydryl β of various concentrations-
Cyclodextrin is mixed in proper proportions, and the ultimate density for making sulfydryl beta-schardinger dextrin is 50~1 μM, after vibration, in water bath with thermostatic control
Stand, sulfydryl beta-schardinger dextrin is fully carried out chemisorption with gold nanorods, incorporation time is 3~48h, and centrifugal rotational speed is
8000~10000rpm, centrifugation time is 10~20min.
Step 2 (S2):Functionalization gold nanorods optimize in the absorption deposition of its surface
The functionalization gold nanorods that step one is obtained are adsorbed in its surface by way of immersion:Take appropriate functionalization
Supernatant is removed after gold nanorods centrifugation, bottom is disperseed again with the ultra-pure water of 2-4 times of concentration amount, filter paper is cut into 1 ×
1cm2Square, in the functionalization gold nanorods solution that 3 concentration amounts are soaked in respectively, be statically placed in water bath with thermostatic control, make filter
The full and uniform adsorption function gold nanorods of paper;The centrifugal rotational speed is 8000-10000rpm, and centrifugation time is 10-20min,
Soak time is 12-48 hours.
Step 3 (S3):The SERS Performances of functionalization gold nanorods paper substrate
The SERS performances for the functionalization gold nanorods paper substrate that step 2 is obtained are investigated, using Sudan IV as probe molecule,
Sensitivity, reappearance and the stability of paper substrate are investigated respectively.The Sudan IV solution for standby of various concentrations has been prepared, has been primarily looked at
The sensitivity of paper substrate, the Sudan IV of various concentrations (50 μM -0.5 μM) is added dropwise in paper substrate surface, in Raman spectrometer respectively
It is lower to be detected, the spectrum of 20 different locis is gathered, by choosing 1097cm-1The intensity of characteristic peak is dense to difference as paper substrate
The sensitivity of the Sudan IV of degree is characterized.Secondly the reappearance of paper substrate is investigated, concentration is added dropwise in paper for 50 μM of Sudan IV
Primary surface, collects the spectrum of 50 different locis, chooses the characteristic peak 1097cm of Sudan IV-1(ω(C-H/N-H)/υ
) and 1485cm (N-N)-1(ρ (N-H)/υ (C=N)/ρ (C-H)ph) Strength co-mputation mean standard deviation (RSD) value.Finally examine
Examine the stability of paper substrate, paper substrate placed and preserves 90 days in atmosphere, respectively the 1st, 7,15,30,60,90 days when, by 50 μM
Sudan IV be added dropwise on paper substrate, spectrum is collected, by the characteristic peak 1097cm for observing Sudan IV-1SERS intensity
Change, the bin stability of evaluation function SERS paper substrates.Above-mentioned SERS testing conditions are time of integration 5s, and optical maser wavelength is
633nm。
SERS effect analyses are carried out according to step one to step 3 (S1~S3) methods described.
Various concentrations sulfydryl beta-schardinger dextrin is obtained through step one with the SERS corresponding to gold nanorods mixing different time to believe
Number Strength Changes, as shown in Fig. 2 when the ultimate density of sulfydryl beta-schardinger dextrin is 5 μM, and gold nanorods and sulfydryl beta-schardinger dextrin
Mixed proportion 9:When 1, its SERS intensity with gold nanorods in any incorporation time than other concentration is higher, and in mixing
Time reaches highest when being 24h, therefore selection optimal conditions are 5 μM of concentration and 24h incorporation times.
The SERS signal response of the functionalization gold nanorods of different cycles of concentration is obtained through step 2, as shown in Figure 3.Filter paper
The SERS signal response of paper substrate in functionalization gold nanorods solution obtained by different soak times, as shown in Figure 4.Paper substrate
SERS signal strengthens with the increase of functionalization gold nanorods cycles of concentration, but 3 times with the gaps of 4 times of concentration amounts less, examine
Consider the concentration glue that cost benefit selection optimal conditions are 3 times.In addition, the SERS signal of paper substrate is as filter paper is in functionalization gold nano
The increase of soak time in rod solution and gradually strengthen, but 24h and 48h intensity difference away from little, it is considered to Saving in time costs select
Optimal conditions are 24h soak time.
The SERS performances of functionalization gold nanorods paper substrate are explored through step 3.Using Sudan IV as probe molecule, respectively
Detection sensitivity of the paper substrate to Sudan IV is investigated, as shown in figure 5, having investigated the SERS reappearances of paper substrate different loci, such as
Shown in Fig. 6,7,8, investigated paper substrate in atmosphere with period of storage extension SERS stability, as shown in Figure 9.With it is traditional
Do not contrasted by the gold nanorods paper substrate of functional modification, functionalization gold nanorods paper substrate is shown preferably to Sudan IV
Sensitivity (LOD is 0.5 μM).Paper substrate is respectively less than 15%, reappearance in the mean standard deviation obtained by 50 different loci detections
It is good.Place it in air and store 90 days, SERS sensitivitys are only down to 60%, and stability is good.
Embodiment 2
Functionalization paper substrate obtained by above-mentioned optimization preparation is applied to dye by various concentrations Sudan IV by the present embodiment 2
Dragon's blood Chinese medicine carry out analysis detection.
Step 4:Functionalization gold nanorods paper substrate is applied to the detection of the tonyred of the violated addition of dragon's blood Chinese medicine
The functionalization gold nanorods paper substrate that step 2 is obtained is applied to the detection of Sudan red dyes in dragon's blood, compound concentration
For 10-3Mol/L Sudan IV solution is as mother liquor, and other concentration are then obtained by being diluted to mother liquor.Measure 20 μ L's
The Sudan IV of corresponding solubility carries out simulation dyeing to dragon's blood, prepares the dragon's blood sample of dyeing.Functionalization paper substrate is treated as rag,
The paper substrate soaked respectively with three kinds of different reagents (ether, hexamethylene, acetone) gently wipes dragon's blood sample surface, simply extracts blood
The Sudan IV dyestuff on surface is exhausted, SERS spectra is obtained by Raman detection, baseline correction is carried out to obtained SERS spectra, point
Analyse detection sensitivity of the functionalization paper substrate to Sudan IV in dragon's blood sample.SERS testing conditions are time of integration 5s, laser wave
A length of 633nm.
Through step 4, the influence that different wetting reagent is detected to authentic sample is investigated, as shown in figure 9, three kinds of reagents point
Not Wei ether, hexamethylene, acetone, wetting paper substrate after wipe respectively blank dragon's blood and dyeing dragon's blood after detect SERS spectra, such as
Figure 10, shown in 11, it is found that ether and acetone wipe blank dragon's blood as wet reagent respectively and dyeing dragon's blood Surface testing is obtained
Spectrum between indifference, illustrate that ether and acetone can not realize effective extraction to dye molecule in dragon's blood.On the contrary, with ring
Almost there is not any impurity interference in the SERS spectra that blank dragon's blood surface wipes are obtained in the paper substrate of hexane reagent wetting
Peak, and the SERS signal peak enriched after dyeing dragon's blood is wiped, and contrasted with Sudan IV collection of illustrative plates, characteristic peak is basic
Unanimously, it is a kind of suitable wetting agent to illustrate hexamethylene, can at utmost reduce the matrix interference of authentic sample, and maximum journey
Degree improves the extraction to Sudan IV molecule in authentic sample.In addition, passing through the dragon's blood sample dyed to various concentrations Sudan IV
This progress SERS detections, as shown in figure 12, the test limit of Sudan IV reaches in functionalization gold nanorods paper substrate detection authentic sample
To 38.04ng/cm2.Therefore, the mercapto-cyclodextrin functionalization gold nanorods paper substrate set up herein is violated suitable for Chinese medicine to be added
Plus the sensitivity detection of Sudan red dyes.
The preferred embodiment to the invention is illustrated above, but the invention be not limited to it is described
Embodiment, those skilled in the art can also make a variety of equivalent on the premise of without prejudice to the invention spirit
Modification or replacement, these equivalent modifications or replacement are all contained in the application claim limited range.
Claims (9)
1. a kind of preparation method of sulfydryl beta-schardinger dextrin functionalization SERS paper substrates, it is characterised in that comprise the following steps:
Step one:The preparation of sulfydryl beta-schardinger dextrin functionalization gold nanorods
Gold nanorods solution is pre-processed:Appropriate gold nanorods stoste is taken, surfactant is removed after centrifugation, with isometric ultrapure
Water cleans the gold nanorods of bottom, supernatant is removed after centrifugation, the isometric ultra-pure water of bottom disperses standby again;Compound concentration
For 100~0.1 μM of sulfydryl beta-schardinger dextrin;Take pretreated gold nanorods solution to be mixed with sulfydryl beta-schardinger dextrin solution, make
The ultimate density of sulfydryl beta-schardinger dextrin is 50~1 μM, after vibration, is stood in water bath with thermostatic control, makes sulfydryl beta-schardinger dextrin and Jenner
Rice rod fully carries out chemisorption, and incorporation time is 3~48h, and centrifugal rotational speed is 8000~10000rpm, and centrifugation time is
10~20min;
Step 2:Absorption deposition of the functionalization gold nanorods in its surface
The functionalization gold nanorods that step one is obtained are adsorbed in its surface by way of immersion:Take appropriate functionalization Jenner
Supernatant is removed after rice rod centrifugation, bottom is disperseed again with the ultra-pure water of 2~4 times of concentration amounts, and filter paper is cut into 1 × 1cm2's
In square, the functionalization gold nanorods solution that 3 concentration amounts are soaked in respectively, it is statically placed in water bath with thermostatic control, makes filter paper abundant
Uniform adsorption functionalization gold nanorods;The centrifugal rotational speed is 8000~10000rpm, and centrifugation time is 10~20min, immersion
Time is 12~48 hours.
2. the sulfydryl beta-schardinger dextrin functionalization SERS paper substrates that a kind of preparation method as claimed in claim 1 is prepared.
3. a kind of investigation method of sulfydryl beta-schardinger dextrin functionalization SERS paper substrate SERS performances as claimed in claim 2, it is special
Levy and be, comprise the following steps:
Step A:Investigate the sensitivity of functionalization SERS paper substrates
The Sudan IV solution for standby of various concentrations has been prepared, the Sudan IV of 50 μM -0.5 μM of concentration has been added dropwise in paper substrate respectively
Surface, is detected under Raman spectrometer, the spectrum of 20 different locis is gathered, by choosing 1097cm-1Characteristic peak it is strong
Spend and the sensitivity of the Sudan IV of various concentrations is characterized as paper substrate;
Step B:Investigate the reappearance of functionalization SERS paper substrates
Concentration is added dropwise in paper substrate surface for 50 μM of Sudan IV, the spectrum of 50 different locis is collected, the Sudan is chosen
Red IV characteristic peak 1097cm-1(ω (C-H/N-H)/υ (N-N)) and 1485cm-1(ρ (N-H)/υ (C=N)/ρ (C-H)ph) it is strong
Degree calculates average standard deviation value;
Step C:Investigate the stability of functionalization SERS paper substrates
Paper substrate is placed and preserves 90 days in atmosphere, respectively the 1st, 7,15,30,60,90 days when, 50 μM of Sudan IV is dripped
It is added on paper substrate, collects spectrum, by the characteristic peak 1097cm for observing Sudan IV-1SERS Strength Changes, assess work(
The bin stability of SERS paper substrates can be changed.
4. a kind of sulfydryl beta-schardinger dextrin functionalization SERS paper substrates as claimed in claim 2 violated addition Soviet Union in medicinal material in the detection
Application in red red.
5. one kind is used to detect violated in Chinese medicine using sulfydryl beta-schardinger dextrin functionalization SERS paper substrates as claimed in claim 2
The method for adding Sudan red dyes, it is characterised in that comprise the following steps:
With the described functionalization SERS paper substrates of acetone, ether, the wetting of hexamethylene reagent, measuring samples are wiped with the paper substrate after wetting
Surface, SERS spectra is obtained by Raman detection, by obtained SERS spectra carry out baseline correction, analysis measuring samples in be
It is no to the addition of Sudan red dyes.
6. a kind of preparation method of sulfydryl beta-schardinger dextrin functionalization SERS paper substrates according to claim 1, it is characterised in that
The ultimate density for the sulfydryl beta-schardinger dextrin that step one is used is 5 μM, and the mixed proportion of gold nanorods and sulfydryl beta-schardinger dextrin is 9:
1, incorporation time is that temperature is 40 DEG C in 24h, water-bath, and centrifugal rotational speed is 9000rpm, and centrifugation time is 15min.
7. a kind of preparation method of sulfydryl beta-schardinger dextrin functionalization SERS paper substrates according to claim 1, it is characterised in that
The cycles of concentration for the gold nanorods that step 2 is used is 3 times, and temperature is 40 DEG C in water-bath, and centrifugal rotational speed is 9000rpm, during centrifugation
Between be 15min.
8. the investigation method of sulfydryl beta-schardinger dextrin functionalization SERS paper substrate SERS performances according to claim 3, its feature
It is, it is 5s the times of integration that step A, B, C SERS testing conditions, which are, and optical maser wavelength is 633nm.
9. sulfydryl beta-schardinger dextrin functionalization SERS paper substrates according to claim 5 are used to detect violated addition Soviet Union in Chinese medicine
The method of red red, it is characterised in that wet reagent is hexamethylene, and it is 5s, laser wave the time of integration that SERS testing conditions, which are,
A length of 633nm.
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