CN110208249A - A kind of Raman spectra detection process being total to load-type ion liquid base polyester plastid SERS substrate based on ternary - Google Patents
A kind of Raman spectra detection process being total to load-type ion liquid base polyester plastid SERS substrate based on ternary Download PDFInfo
- Publication number
- CN110208249A CN110208249A CN201910634547.XA CN201910634547A CN110208249A CN 110208249 A CN110208249 A CN 110208249A CN 201910634547 A CN201910634547 A CN 201910634547A CN 110208249 A CN110208249 A CN 110208249A
- Authority
- CN
- China
- Prior art keywords
- polysome
- raman
- plastid
- liposome
- polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Molecular Biology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Manufacturing & Machinery (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention relates to a kind of Raman spectra detection process that load-type ion liquid base polyester plastid SERS substrate is total to based on ternary.Polysome@Au is dissolved in deionized water, ultrasonic disperse obtains Polysome@Au aqueous solution, and anion Raman microprobe sample X solution is added into Polysome@Au aqueous solution, magnetic agitation, centrifuge washing is carried out to product after reaction, it is dry, obtain Polysome@X@Au；Polysome X Au is uniformly coated in glass slide, in being detected in Raman detector.Method of the invention has highly sensitive detectability to the Raman detection of anion probe, has anti-interference ability to cationic probe molecule, shows excellent charge selectivity.The foundation of ternary SERS detection pattern of the present invention, has not only expanded the application field of Raman detection, also has very important significance in terms of the research to Raman enhancing mechanism.
Description
Technical field
The present invention relates to functional motor ability plastid nanocomposite technical fields, and in particular to one kind is loaded altogether based on ternary
The Raman detection method of type ionic liquid base polyester plastid SERS substrate.
Background technique
Surface enhanced Raman spectroscopy (SERS) is got over application of its highly sensitive Single Molecule Detection performance in biosystem
Come more important.Wherein, the biocompatibility of substrate is the key factor for restricting SERS and applying in the field.In addition, in order to adapt to
Complicated biotic environment, the substrate with finer selection or Solid Phase Extraction function have the promotion of Raman detection performance very big
Impetus.Liposome has the double membrane structure similar with biomembrane, is a kind of good assembly of biocompatibility,
The Raman detection neck of biosystem is introduced in due to the good structure designability of liposome and biocompatibility in recent years
Domain.But the structure of conventional liposome is difficult to keep stable, surface to the respond of organic-inorganic component also relatively
It is weak, to limit liposome and its derivative in the practical application in Raman field.In order to overcome the unstability of liposome, often
Polymerized liposome is often prepared using the polymerization reaction between lipid monomer, this polyester plastid advantage is: not only can be effective
Full double layer film is kept, while tolerance is embodied to different solvents.
In addition, ionic liquid is with its outstanding ion exchangeable, designability and chemical stability of molecular structure etc.
Many excellent performances show wide application prospect in many fields.Studies have shown that the unique exchangeability of ionic liquid, a side
Load organic-inorganic anion to the face property of can choose.On the other hand, excellent pattern and knot are shown to metal nanoparticle
Structure stability promotes metallic to have good monodispersity.Excellent properties based on polyester plastid and ionic liquid, if
The two is combined, the Raman detection model for having both biocompatibility and ionic reaction can be constructed.It is this integrated
SERS detection architecture is different from conventional SERS spectra detection, has the advantages that following three.One, without to Raman microprobe molecule into
Row sulfydryl modification has broken the mode that traditional probe molecule must be in contact with metallic.Two, have benefited from lipid body surface
The isotropism of surface properties, the reactivity that each site is exposed is completely the same, keeps metal nanoparticle uniform and stable
Ground is grown in surface of liposome.Three, the superposition of field-effect, promotes being emerged for hot spot, makes probe between substrate surface metallic
The Raman signal of molecule is significantly enhanced, and shows good signal repeatability.
Based on the intrinsic ion exchangeable of ionic liquid, if successfully the two combined, this ionic liquid base polyester
The composite construction of plastid is expected to realize the Raman detection with excellent universality, charge selectivity and solid phase microextraction characteristic.
In addition isotropic design feature, the hot spot enhancing that electromagnetic coupling is formed, has been further amplified the Raman signal of test sample,
To realize Single Molecule Detection.
Summary of the invention
The present invention successfully constructs a kind of ' ionic liquid base polyester plastid-organic probes molecule-by way of total load
The SERS detection model of AuNPs ' ternary system.Studies have shown that Au nanoparticle the modification of surface of liposome do not influence yin from
The ion exchange process of sub- probe.It is this load altogether by way of, ultimately form integrated SERS detection architecture.
The technical solution adopted by the present invention is that: one kind being total to load-type ion liquid base polyester plastid SERS substrate based on ternary
Raman spectra detection process, the method is as follows:
1) polyester plastid-gold nanoparticle Polysome@Au is dissolved in deionized water, ultrasonic disperse obtains
Polysome@Au aqueous solution, sample X solution is added into Polysome@Au aqueous solution, and it is anti-to carry out ion exchange under magnetic agitation
It answers, centrifuge washing is carried out to product after reaction, it is dry, it obtains ternary and is total to load-type ion liquid base polyester plastid SERS substrate
Polysome@X@Au；
2) Polysome@X@Au is uniformly coated in glass slide, is air-dried 10 minutes；It is subsequently placed in Raman
It is detected on detector.
Further, the polyester plastid-gold nanoparticle Polysome@Au's the preparation method is as follows:
1) 2-methylimidazole, triethylamine and bromo -11- carbene are sequentially added into toluene, it is cold after 90 DEG C of reaction 48h
But it to room temperature, filters and removes solid, gained filtrate solvent evaporated is washed with n-hexane, again after solvent evaporated, with acetonitrile-second
Acetoacetic ester mixed solvent recrystallization, vacuum drying obtain liposome monomer；
2) the liposome monomer that step 1) obtains is dissolved in deionized water, ultrasonic disperse obtains clear transparent solutions, for from
Sub- liquid base liposome (Liposome)；
3) into the ionic liquid base liposome (Liposome) that step 2) obtains, K is added2S2O8, nitrogen protection, 100 DEG C
Lower reaction for 24 hours, obtains suspension, 8000rpm/min centrifugation washing, and freeze-drying obtains ionic liquid base polyester plastid Polysome；
4) the ionic liquid base polyester plastid Polysome for taking step 3) to obtain is scattered in deionized water, is added dropwise
HAuCl4, 12h is vibrated at room temperature, and after reaction, 8000rpm/min centrifugation washing removes extra HAuCl4, will be centrifuged
Products therefrom is scattered in deionized water again, and NaBH is added dropwise4Reducing agent reacts 2h, after reaction, 8000rpm/min centrifugation
Washing, freeze-drying, obtains polyester plastid-gold nanoparticle (Polysome@Au).
Further, the sample X is organic Raman microprobe molecule of anion characteristic.
Further, organic Raman microprobe molecule of the anion characteristic be methyl orange (MO), methyl blue (MB) or 4-
Acetylenylbenzene sodium formate (4-EBA).
Further, the condition detected in Raman detector are as follows: excitation wavelength 633nm, laser power are
1.7mW, and within the time for exposure of 10s, to 100-3200cm-1Wave-number range in record Raman spectrum.
The beneficial effects of the present invention are:
1, of the invention, firstly, the olefin group thermal-initiated polymerization using lipid monomer tail portion forms polyester plastid
(Polysome).Then the ion exchangeable and in-situ reducing for utilizing the ionic liquid base on polyester plastid head react, poly-
Surface of liposome forms the inorganic decorative layer (Polysome@Au) being made of Au nanoparticle (Au NPs).Then pass through ion
The organic probes molecule of anion characteristic is carried on the surface Polysome@Au, ultimately formed by the Two-step ion-exchanging of liquid base
The Raman detection system of ternary structural.
2, the repeatability of SERS signal and stability dependency are in the structure of metallic substrates and the uniformity of pattern.This hair
It is bright using polyester plastid as the integrated SERS assembly of vector construction.Have benefited from the special self-assembled structures of liposome, table
The exposed group in face has the isotropism of height, and the reactivity in each site is equivalent, therefore the Au NPs of growth in situ has
There are the monodispersity and topography uniformity of height.This unique structure becomes the acquisition of stable, duplicate SERS signal
It may.In addition, high aggregation and evenly dispersed Au NPs generate ' hot spot ' effect in the superposition of polyester liposome surface field-effect,
The more conventional SERS system of SERS substrate of this immobilized mode altogether is caused to show more excellent signal enhancing.It is noticeable
It is that the ion exchangeable of polyester liposome surface assigns SERS substrate also with charged selectivity and Solid Phase Extraction performance.In short,
As long as probe molecule has anion characteristic, it can be detected by enrichment, to make the novel SERS substrate in complicated analysis
Under testing conditions, highly selective, highly sensitive detection is realized to organic anion probe.
3, in the context of detection of Raman spectrum, since monodispersed Au modification nanoparticle can be formed in surface of liposome
" hot spot ", this makes the organic probes molecule selectively fixed can express the performance better than conventional SERS spectra.Phase of the present invention
1. conventional system, which needs organic probe molecule to be immobilized onto the metals such as Au, is had the following characteristics that for conventional SERS detection architecture
Surface is to construct SERS substrate.In order to realize this model, the pre- modification that sulfhydrylation is carried out to organic probes molecule is generally required,
Limit the building and expansion of SERS system.And the present invention utilizes the characteristic of ionic liquid for the first time, respectively by in-situ reducing and
It is immobilized altogether in biocompatibility substrate that ion exchange realizes enhancing substrate Au and probe molecule.With conventional method phase
Compare, novel forming types of the invention are not necessarily to modify probe molecule progress sulfydryl in advance.2. SERS signal repeatability and
Stability depends on the structure of metallic substrates, the uniformity of pattern.The present invention is using polyester plastid by way of total load
Substrate constructs assembled metal body.Due to the special assembly structure of liposome, make the exposed group on its surface that there is each of height
To the same sex, so that the Au nanoparticle of growth in situ has the monodispersity and topography uniformity of height.This uniqueness
Structure to stablize, the acquisition of duplicate SERS signal.3. since monodispersed Au nanoparticle is in polyester matter
Body surface face high aggregation and evenly dispersed, this makes SERS substrate that can form numerous hot spots, so that this immobilized mode altogether
The more conventional SERS substrate of SERS substrate shows more excellent spectral characteristic.4. the ion of ionic liquid base polyester plastid substrate
Exchangeability assigns SERS substrate also with universality, charge selectivity and Solid Phase Extraction performance.This makes the new substrates can be
Highly selective, highly sensitive and high duplication Raman is realized to the organic molecule of negative electrical charge under the conditions of complicated analysis detection
Detection.
4, the ternary Raman detection modality that the present invention constructs is detected in the application to representative anion Raman microprobe molecule
In show excellent universality, charge selectivity and solid phase microextraction.The ternary Raman detection modality that the present invention constructs,
There is highly sensitive detectability to the Raman detection of anion probe, there is anti-interference ability, performance to cationic probe molecule
Excellent charge selectivity out.Based on the ion-exchange reactions of ionic liquid base component, make substrate to target molecule detection process
In have the function of Solid Phase Extraction, be based on this, 10 are reduced to the minimal detectable concentration of methyl orange anion-12M。
Detailed description of the invention
Fig. 1 is Polysome@Au (A) and Polysome@MO@Au (B) stereoscan photograph (SEM) in embodiment 1.
Fig. 2 is Polysome@Au (A) and Polysome@MO@Au (B) transmission electron microscope photo (TEM) in embodiment 1.
Fig. 3 is the infrared of Polysome@Au (a), Polysome@MO (b) and Polysome@MO@Au (c) in embodiment 1
Spectrogram.
Fig. 4 is that the X- of Polysome@Au (a), Polysome@MO (b) and Polysome@MO@Au (c) in embodiment 1 are penetrated
Photoelectron spectra (XPS).
Fig. 5 be in embodiment 1 SERS substrate Polysome@Au to the Raman detection of methyl orange (MO).
Fig. 6 is the charge selective enumeration method of SERS substrate Polysome@Au in embodiment 1.
Fig. 7 is that SERS substrate Polysome@Au concentration limit (solid phase microextraction performance) detects in embodiment 1.
Fig. 8 is the Raman enhancing mechanism study of SERS substrate Polysome@Au in embodiment 2.
Fig. 9 be in embodiment 2 SERS substrate Polysome@Au to the Raman detection of 4- acetylenylbenzene sodium formate (4-EBA).
Figure 10 be in embodiment 2 SERS substrate Polysome@Au to the Raman detection of methyl blue (MB).
Specific embodiment
Technical solution for a better understanding of the present invention, spy are described in further detail with specific embodiment, but side
Case is without being limited thereto.
Embodiment 1
A kind of Raman spectrum detection for the methyl orange being total to load-type ion liquid base polyester plastid SERS substrate based on ternary
Method
(1) load-type ion liquid base polyester plastid SERS substrate is total to based on ternary
1, ionic liquid base liposome (Liposome)
Take 30.00mL toluene in 100mL round-bottomed flask, sequentially add thereto 2-methylimidazole (3.05mmoL,
0.25g), triethylamine (3.65mmoL, 0.51mL) and bromo -11- carbene (6.10mmoL, 1.33mL), in 90 DEG C of reaction 48h.
It is cooled to room temperature after reaction, filters and remove amine salt solid, gained filtrate solvent evaporated is repeatedly washed, again with n-hexane
After solvent evaporated, products therefrom is recrystallized with acetonitrile-ethyl acetate mixed solvent (volume ratio about 1:3), and vacuum drying obtains Huang
White powder, as liposome monomer.
Liposome monomer 100.0mg is taken to be dissolved in 100.0mL deionized water, ultrasonic disperse 1h obtains clear transparent solutions,
For ionic liquid base liposome (Liposome), concentration 1.00mgmL-1。
2, polyester plastid (Polysome)
Taking 100mL concentration is 1.00mgmL-1Ionic liquid base liposome (Liposome), be added 50.0mg
K2S2O8, react for 24 hours under 100 DEG C of nitrogen protections, obtain milky suspension, 8000rpm is centrifuged 10min, and solid product distills
Three times, freeze-drying obtains polyester plastid (Polysome) to water centrifuge washing.
3, the synthesis of polyester plastid-gold nanoparticle (Polysome@Au)
The polyester plastid (Polysome) for taking 0.1g, is scattered in the deionized water of 100mL, the HAuCl of 10mL is added dropwise4
(10μL HAuCl4It is scattered in 20mL deionized water), 12h is vibrated at room temperature, after reaction, is centrifuged with 8000rpm
10min removes extra HAuCl4, disperse centrifugation obtained solid product in 100mL deionized water again, 5mL be added dropwise
NaBH4(by 10mg NaBH4It is scattered in 5mL deionized water) reducing agent reaction 2h, obtain dark red solution, 8000rpm centrifugation
10min, three times, freeze-drying obtains Polysome Au for solid product centrifugation washing.
4, ternary is total to the preparation of load-type ion liquid base polyester plastid SERS substrate Polysome@X@Au
0.1g polyester plastid-gold nanoparticle Polysome@Au is dissolved in 100mL deionized water, ultrasonic disperse obtains
Polysome@Au aqueous solution, it is 1 × 10 that 10mL concentration is added into Polysome@Au aqueous solution-6The methyl orange (MO) of M is water-soluble
Liquid carries out ion-exchange reactions for 24 hours under magnetic agitation, carries out centrifuge washing to products therefrom after reaction, dry, obtains methyl
The anion modified ternary of orange is total to load-type ion liquid base polyester plastid SERS substrate (Polysome@MO@Au).
5, Polysome@MO@Au is uniformly coated in glass slide, is compacted, is air-dried 10 minutes.
The instrument model that the present embodiment Raman detection is selected is Renishaw inVia (UK), the excitation wavelength used for
633nm (based on absorbance of the sample in ultraviolet-visible spectrum)；Laser power is 1.7mW, and the amplification factor of object lens is 50
Times.Before data acquisition, normalized is carried out to the Raman peak intensity under 633nm excitation wavelength on silicon wafer, and in 10s
Time for exposure in, to 100-3200cm-1Wave-number range in record Raman spectrum.Stablize at least half an hour to Raman spectrometer
Afterwards, Raman Measurement is carried out to sample.
(2) coherent detection
The SEM that Fig. 1 is Polysome@Au (A) and Polysome@MO@Au (B) schemes.The A from Fig. 1 this it appears that through
Cross the spherical vesicles structure that the Polysome@Au obtained after gold nanoparticle growth in situ completely remains liposome, size
Uniformly, particle diameter distribution is in 150-220nm.Further, the ionic liquid group and anion of polyester plastid hydrophilic head are utilized
Between ion exchangeable, by methyl orange (MO) load with the surface Polysome@Au.By B in Fig. 1 the results show that being prepared
Polysome MO Au still maintain the spherical structure of Polysome Au, to illustrate ion-exchange reactions and have not been changed
The structural stability of SERS substrate Polysome@Au.
The TEM that Fig. 2 is Polysome@Au (A) and Polysome@MO@Au (B) schemes.Similarly, it is compared by contrast, from
A can be seen that Polysome@Au has the spherical vesicles structure of complete liposome in Fig. 2, uniform in size, tests and ties with SEM
Fruit is consistent.In addition, being characterized by high-resolution-ration transmission electric-lens, it can be seen that between the lattice of the nano particle of polyester liposome surface growth
Away from for 0.234nm, to confirm that this nanoparticle belongs to gold nanoparticle.Similarly, pass through it can be seen from B in Fig. 2
The spherical structure of ion exchangeable, Polysome@MO@Au still keeps stable, the stabilization on this polyester plastid material structure
Property for its further SERS detection in application lay the foundation.
Fig. 3 is the infrared absorption spectrum of Polysome@Au (a), Polysome@MO (b) and Polysome@MO@Au (c)
(FT-IR) figure.By curve a it is found that 1191cm-1It is attributed to the in-plane deformation vibration of the C-H on imidazole ring, 1372cm-1With
1456cm-1It is attributed to C-H in-plane bending vibration, 1522cm-1It is attributed to imidazole ring C-N stretching vibration absworption peak, 2862cm-1、
2934cm-1And 3068cm-1It is attributed to be C-H stretching vibration absworption peak on imidazole ring, to carry out really liposome structure
Recognize.Polysome and MO are after ion-exchange reactions, in 1126,1314 and 1371cm it can be seen from curve b-1Occur
The characteristic absorption peak of methyl orange, to illustrate that methyl orange is successfully supported on the surface Polysome.Further, it utilizes
The Polysome@MO@Au nanocomposite that ion-exchange reactions between Polysome@Au and MO is prepared, and to it
Infrared test is carried out, result is similar to Polysome@MO it can be seen from curve c, occurs methyl orange respectively in curve c
Characteristic absorption peak.On the one hand illustrate that the success of the two is compound, on the other hand, the results showed that, the load of gold nanoparticle is simultaneously
The further ion-exchange performance for not influencing ionic liquid group shows the excellent architectural characteristic of the material.
In order to further illustrate the ion exchangeable that this SERS base material is excellent, x-ray photoelectron spectroscopy has been done
(XPS) it analyzes, as a result as shown in Figure 4.It can be seen that 284.6,401.1 from the XPS map of Polysome@Au (a) in Fig. 4,
C 1s is respectively corresponded at 85.4eV, N 1s and Au 4f is consistent with element contained by Polysome Au.Polysome and MO ion are handed over
After changing, there is S 2p from the XPS spectrum figure of Polysome@MO (b) in Fig. 4, characteristic peak, thus illustrate MO anion at
Function is compound.Similarly, the Polysome@being further prepared using the ion-exchange reactions between Polysome@Au and MO
Equally there is the spy of S 2p from the XPS spectrum figure of Polysome@MO@Au (c) in Fig. 4 as can be seen that at 168eV in MO@Au
Peak is levied, to prove the successful load of MO Yu SERS substrate Polysome@Au.
To the Raman detection of methyl orange, test results are shown in figure 5.As seen from Figure 5 Raman shift 1140,
1396、1442cm-1The absorption peak at place belongs to methyl orange azo characteristic absorption.Polyester plastid Polysome and methyl orange molecule
It will also be seen that the characteristic absorption peak of azo, compares in the raman spectrum for the Polysome@MO that electrostatic interaction is formed
In the Raman spectrum graph discovery of methyl orange, the characteristic peak of Polysome Au is not reinforced simultaneously.As a comparison, the present invention utilizes Jenner
Rice corpuscles and Adsorption of Methyl Orange effect have been prepared Au NPs-MO sample and have carried out Raman test to it.As a result, it has been found that Au
The approximate baseline of the raman spectrum of NPs-MO, illustrates that simple gold nanoparticle does not adsorb methyl orange, can not measure first
The SERS of base orange enhances signal.This is because the gold nanoparticle surface obtained using reduction of sodium citrate with it is a certain amount of just
Electrostatic repulsion between charge, and same positively charged methyl orange probe molecule prevents the combination of the two, therefore is difficult to survey
Raman signal out.SERS detection further is carried out to SERS base material Polysome@Au, as a result, it has been found that base material exists
1200-1800cm-1Occurs the corresponding characteristic absorption peak of polyester plastid imidazoline ionic liquid base in Raman shift range.Specifically
Ground, 1344cm-1- the CH in hydrophilic head imidazole group2Deformation vibration peak, 1424cm-1C-N derived from imidazole group stretches
Contracting vibration peak, 1563cm-1Derived from the stretching vibration peak of imidazole ring.Finally, using polymerized liposome substrate ion exchangeable and
Gold nanoparticle and methyl orange probe molecule are successfully successfully supported on base by way of total load by the characteristics of secondary response
Polysome@MO@Au organic-inorganic hybrid material has been prepared in bottom surface.Raman detection is carried out to it as a result, it has been found that, methyl
Azo feature peak intensity in orange structure is greatly enhanced.This is because in Polysome@Au detection architecture, probe molecule
With gold nanoparticle not in contact with showing as simple physics enhances, but uniformly the dividing in surface of liposome due to gold nanoparticle
The superposition of cloth, field-effect forms it into hot spot, further enhances Raman signal.It is this to be gone to compensate conventional Jenner's grain of rice with hot spot
The benefit of the Chemical enhancement of son is exactly the assertive evidence Raman signal and detection sensitivity for increasing probe molecule, is made based on gold nano
The SERS detection architecture of particle shows as Nano silver grain and detects similar reinforcing effect, and this advantage has benefited from stable homogeneous
Polysome@Au nanostructure.
(3) the charge selectivity of SERS substrate Polysome@Au
Select anionic dye molecule: methyl orange (MO) is Raman target molecule (target level: 1.0 × 10-6M).Cation has
Machine probe crystal violet (CV) and rhodamine 6G (R6G) are disturbing molecule (interference concentration: 1.0 × 10-5M)。
Isometric Raman microprobe molecule is added into the Polysome@Au aqueous solution of 1mg/mL, is carried out under magnetic agitation
Ion-exchange reactions.Centrifuge washing (6000rpm/min, 5min, three times) is carried out to product after reaction, obtains phase after dry
Solid powder is answered, Raman detection is carried out to it.Accordingly result is shown in Fig. 6.
For Polysome@Au detection architecture, by the ion exchange of substrate surface, as long as molecule has anion special
Property, it can be detected by enrichment, to get rid of the constraint to substrate.It is quiet that this property enables plasma substrate to pass through
Electro ultrafiltration selectively captures anion analysis object from complicated chemical environment, and repels cationic analytes.Therefore, SERS
Active Polysome@Au selects substrate used also as charge.In order to verify substrate to the selectivity of anion, dye molecule is selected
MO is as target analytes.It is tested with positive charge rhodamine 6G (R6G) and crystal violet (CV) for disturbing molecule.Such as Fig. 6
It is shown, do not observe the representative Raman letter of R6G or CV in the two systems for mixing R6G or CV with Polysome@Au
Number, show that SERS blocks the response of cationic probe completely due to electrostatic repulsion (the pink region in Fig. 6).
It is interesting that in anion and the Raman analysis of cationic probe mixture (green area in Fig. 6), no matter R6G+MO,
The hybrid system of CV+MO or R6G+CV+MO and Polysome Au substrate, only MO distinguish SERS signal appear in 1142,
1395 and 1443cm-1Place shows that this mixed substrates have good anti-interference ability.Moreover, it is noted that R6G
Or 10 times of MO high of the concentration ratio of CV.That is, even if the concentration of the Cation Interferences factor is higher, Polysome@Au still can only
Selectively identify anion targeted molecular, thus prove it is a kind of efficiently, the substrate of charge selectivity is successfully established.
(4) minimal detectable concentration (solid phase microextraction performance) of the SERS substrate Polysome@Au to methyl orange Raman
It is 1.0 × 10 that 10mL concentration is separately added into the Polysome@Au aqueous solution of 1mg/mL-6M、1.0×10-8M、
1.0×10-10M and 1.0 × 10-12The methyl orange aqueous solution of M carries out ion-exchange reactions under magnetic agitation.After reaction
Centrifuge washing (6000rpm/min, 5min, three times) is carried out to product, corresponding solid powder is obtained after dry, Raman is carried out to it
Detection.Accordingly result is shown in Fig. 7.
In fact, the analytic process of this SERS detection platform is a kind of " two steps " inspection policies, i.e., " enrichment-detection ".
That is, structure feature assigns Polysome@Au solid phase microextraction (SPME) ability.In brief, the limited MO yin of concentration
Ion analysis object can selectively be captured from ambient enviroment by ion pairing, and further be enriched in Polysome Au
Plasma surface, to realize highly sensitive SERS enhancing under extremely low content.In order to test the sound of Polysome@Au
Sensitivity is answered, by the concentration of MO target analytes from 1.0 × 10-6It is diluted to 1.0 × 10-12M, corresponding SERS spectra such as Fig. 7 institute
Show.It is obvious that even if the concentration of MO drops to 1.0 × 10-12M can also be observed that its Raman trait peak.The feature SERS of MO
Signal remains to be detected, and detection limit is lower than conventional SERS analysis.Utilize the ternary " Polysome@probe@Au NPs "
The ionic liquid segment integrated in system establishes the hypersensitive SERS with charge selectivity and noiseproof feature and detects
Platform.
Embodiment 2
The Raman spectrum detection side of the 4-EBA or MB of load-type ion liquid base polyester plastid SERS substrate are total to based on ternary
Method
(1) load-type ion liquid base polyester plastid SERS substrate is total to based on ternary to detect the Raman spectrum of 4-EBA
1, ionic liquid base liposome (Liposome)
Take 30.00mL toluene in 100mL round-bottomed flask, sequentially add thereto 2-methylimidazole (3.05mmoL,
0.25g), triethylamine (3.65mmoL, 0.51mL) and bromo -11- carbene (6.10mmoL, 1.33mL), in 90 DEG C of reaction 48h.
It is cooled to room temperature after reaction, filters and remove amine salt solid, gained filtrate solvent evaporated is repeatedly washed, again with n-hexane
After solvent evaporated, products therefrom is recrystallized with acetonitrile-ethyl acetate mixed solvent (volume ratio about 1:3), and vacuum drying obtains Huang
White powder, as liposome monomer.
Liposome monomer 100.0mg is taken to be dissolved in 100.0mL deionized water, ultrasonic disperse 1h obtains clear transparent solutions,
For ionic liquid base liposome (Liposome), concentration 1.00mgmL-1。
2, polyester plastid (Polysome)
Taking 100mL concentration is 1.00mgmL-1Ionic liquid base liposome (Liposome), be added 50.0mg
K2S2O8, react for 24 hours under 100 DEG C of nitrogen protections, obtain milky suspension, 8000rpm is centrifuged 10min, and solid product distills
Three times, freeze-drying obtains polyester plastid (Polysome) to water centrifuge washing.
3, the synthesis of polyester plastid-gold nanoparticle (Polysome@Au)
The polyester plastid (Polysome) for taking 0.1g, is scattered in the deionized water of 100mL, the HAuCl of 10mL is added dropwise4
(10μL HAuCl4It is scattered in 20mL deionized water), 12h is vibrated at room temperature, after reaction, is centrifuged with 8000rpm
10min removes extra HAuCl4, disperse centrifugation obtained solid product in 100mL deionized water again, 5mL be added dropwise
NaBH4(by 10mg NaBH4It is scattered in 5mL deionized water) reducing agent reaction 2h, obtain dark red solution, 8000rpm centrifugation
10min, three times, freeze-drying obtains Polysome Au for solid product centrifugation washing.
4, ternary is total to the preparation of load-type ion liquid base polyester plastid SERS substrate Polysome@X@Au
0.1g polyester plastid-gold nanoparticle Polysome@Au is dissolved in 100mL deionized water, ultrasonic disperse obtains
Polysome@Au aqueous solution, it is 10 that 10mL concentration is added into Polysome@Au aqueous solution-6The 4- acetylenylbenzene sodium formate of M
(4-EBA) aqueous solution carries out ion-exchange reactions for 24 hours under magnetic agitation, carries out centrifuge washing to products therefrom after reaction,
It is dry, it obtains the anion modified ternary of 4-EBA and is total to load-type ion liquid base polyester plastid SERS substrate (Polysome@4-
EBA@Au)。
5, Polysome@4-EBA@Au is uniformly coated in glass slide, is compacted, is air-dried 10 minutes.
The instrument model that the present embodiment Raman detection is selected is Renishaw inVia (UK), the excitation wavelength used for
633nm (based on absorbance of the sample in ultraviolet-visible spectrum)；Laser power is 1.7mW, and the amplification factor of object lens is 50
Times.Before data acquisition, normalized is carried out to the Raman peak intensity under 633nm excitation wavelength on silicon wafer, and in 10s
Time for exposure in, to 100-3200cm-1Wave-number range in record Raman spectrum.Stablize at least half an hour to Raman spectrometer
Afterwards, Raman Measurement is carried out to sample.
(2) load-type ion liquid base polyester plastid SERS substrate is total to based on ternary to detect the Raman spectrum of MB
1, ionic liquid base liposome (Liposome)
Take 30.00mL toluene in 100mL round-bottomed flask, sequentially add thereto 2-methylimidazole (3.05mmoL,
0.25g), triethylamine (3.65mmoL, 0.51mL) and bromo -11- carbene (6.10mmoL, 1.33mL), in 90 DEG C of reaction 48h.
It is cooled to room temperature after reaction, filters and remove amine salt solid, gained filtrate solvent evaporated is repeatedly washed, again with n-hexane
After solvent evaporated, products therefrom is recrystallized with acetonitrile-ethyl acetate mixed solvent (volume ratio about 1:3), and vacuum drying obtains Huang
White powder, as liposome monomer.
Liposome monomer 100.0mg is taken to be dissolved in 100.0mL deionized water, ultrasonic disperse 1h obtains clear transparent solutions,
For ionic liquid base liposome (Liposome), concentration 1.00mgmL-1。
2, polyester plastid (Polysome)
Taking 100mL concentration is 1.00mgmL-1Ionic liquid base liposome (Liposome), be added 50.0mg
K2S2O8, react for 24 hours under 100 DEG C of nitrogen protections, obtain milky suspension, 8000rpm is centrifuged 10min, and solid product distills
Three times, freeze-drying obtains polyester plastid (Polysome) to water centrifuge washing.
3, the synthesis of polyester plastid-gold nanoparticle (Polysome@Au)
The polyester plastid (Polysome) for taking 0.1g, is scattered in the deionized water of 100mL, the HAuCl of 10mL is added dropwise4
(10μL HAuCl4It is scattered in 20mL deionized water), 12h is vibrated at room temperature, after reaction, is centrifuged with 8000rpm
10min removes extra HAuCl4, disperse centrifugation obtained solid product in 100mL deionized water again, 5mL be added dropwise
NaBH4(by 10mg NaBH4It is scattered in 5mL deionized water) reducing agent reaction 2h, obtain dark red solution, 8000rpm centrifugation
10min, three times, freeze-drying obtains Polysome Au for solid product centrifugation washing.
4, ternary is total to the preparation of load-type ion liquid base polyester plastid SERS substrate Polysome@X@Au
0.1g polyester plastid-gold nanoparticle Polysome@Au is dissolved in 100mL deionized water, ultrasonic disperse obtains
Polysome@Au aqueous solution, it is 10 that 10mL concentration is added into Polysome@Au aqueous solution-6Blue (MB) aqueous solution of the methyl of M,
Ion-exchange reactions is carried out for 24 hours under magnetic agitation, and centrifuge washing is carried out to products therefrom after reaction, it is dry, obtain methyl orchid
Anion modified ternary is total to load-type ion liquid base polyester plastid SERS substrate (Polysome@MB@Au).
5, Polysome@MB@Au is uniformly coated in glass slide, is compacted, is air-dried 10 minutes.
The instrument model that the present embodiment Raman detection is selected is Renishaw inVia (UK), the excitation wavelength used for
633nm (based on absorbance of the sample in ultraviolet-visible spectrum)；Laser power is 1.7mW, and the amplification factor of object lens is 50
Times.Before data acquisition, normalized is carried out to the Raman peak intensity under 633nm excitation wavelength on silicon wafer, and in 10s
Time for exposure in, to 100-3200cm-1Wave-number range in record Raman spectrum.Stablize at least half an hour to Raman spectrometer
Afterwards, Raman Measurement is carried out to sample.
(2) SERS substrate Polysome@Au enhances mechanism study to anion probe molecule Raman
It is 1.0 × 10 that 10mL concentration is added into the Polysome@Au aqueous solution of 1mg/mL-6The 4-EBA aqueous solution of M, magnetic
Power stirring is lower to carry out ion-exchange reactions.Centrifuge washing (6000rpm/min, 5min, three times) is carried out to product after reaction,
Corresponding solid powder is obtained after drying, and Raman detection is carried out to it.As a comparison, add into the solution of gold nanoparticles of 1mg/mL
Enter 4- acetylenylbenzene thiophenol (4-PAPT) aqueous solution that 10mL concentration is 1.0 × 10-6M, product is centrifuged after reaction
Washing, carries out Raman detection to it.Accordingly result is shown in Fig. 8.
Enhance mechanism to further study the SERS of this ternary " Polysome@probe molecule@Au NPs ", selection passes
Mode is as a comparison for the binary " Au-NPs- sulfydryl probe molecule " of system.Further, since 4- acetylenylbenzene sodium formate (4-EBA) and
The finger-print of 4- acetylenylbenzene thiophenol (PATP) has very strong resolvability, therefore their alkynyl compounds is used as target
Probe.As shown in A in Fig. 8, under the same conditions, Raman shift is in 2014 and 2202cm-1Place, the Characteristic Raman letter of alkynyl end
Number occur in both modes, illustrates that two kinds of systems have Raman enhancement effect to alkynyl.However, their peak strength is
Entirely different.In ternary system, 2014cm-1When alkynyl intensity be 8 times of binary system intensity, illustrate ternary SERS
Detection model has good SERS reinforcing effect.
The reason of SERS performance greatest differences of this ternary " Polysome@probe molecule@Au NPs " system, can return
Because in their substantially different enhancing mechanism.As shown in B in Fig. 8, in traditional binary system, target PATP molecule passes through
Mercapto is directly anchored on Au NPs.Single Au NPs is difficult to be designated as ideal SERS platform, because its is limited scattered
It penetrates section and Electromagnetic enhancement intensity is also inadequate, it is unsatisfactory so as to cause the SERS enhancing of binary system.It is well known that SERS
The enhancing of signal depends greatly on the arrangement of nanostructure.In the ternary system, since ionic liquid section has
The uniform sequential growth of good ion-exchange performance, plasma Au NPs results in the superposition of localized electromagnetic field, produces
It is covered on the strong and consistent hot spot of matrix surface.By electrostatic interaction, anion analysis object is further captured and is concentrated to
The plasma surface of enhancing.That is, in the hypersensitive SERS analysis to various anion analysis objects, enrichment effect and hot spot effect
Effective synergistic effect should be obtained, Finite-Difference Time-Domain Method (FDTD) simulation also demonstrates this point, the SERS letter of adsorbate
Number great amplification is obtained, the detection of molecular level can be reached to a certain extent.
(3) coherent detection
Fig. 9 be in embodiment 2 SERS substrate Polysome@Au to the Raman detection of 4- acetylenylbenzene sodium formate (4-EBA).
Figure 10 be in embodiment 2 SERS substrate Polysome@Au to the Raman detection of methyl blue (MB).
It is well known that the ion exchangeable confrontation anion of ionic liquid has universality.Therefore, this in order to probe into
Polysome@Au detection pattern to the universalities of different organic anions, the present invention to the organic probes molecule of different structure into
Row test.Firstly, since the presence of the positive ion imidazoline base ionic liquid constituents of Polysome@Au surface of liposome makes this
Kind SERS substrate shows apparent positive charge property, this unique surface nature, so that it not only has height to anion
The selectivity of degree has repulsive interaction for cation.It is similar with the Raman detection method to methyl orange anion, the present invention
Continue to probe into other organic anion Raman microprobes, be illustrated by taking methyl orchid and 4- acetylenylbenzene sodium formate as an example.
As a result as shown in Figure 9 and Figure 10.Compared with MO, MB and 4-EBA receive similar enhancing SERS signal.Specifically, exist
1180,1365 and 1617cm-1The Raman shift that place occurs represents SO in methyl orchid molecule2The midplane extrusion of component vibrates and C=N
The asymmetric stretching vibration (Figure 10) of component.Raman shift is in 2014 and 2202cm-1The characteristic peak at place is attributed to 4-EBA molecule
C ≡ C group (Fig. 9).Meanwhile other Raman systems are compared to, novel Raman substrate Polysome@Au shows greatly excellent
Gesture.To illustrate that this SERS substrate has good universality to other anion probes in Raman detection.
Claims (5)
1. a kind of Raman spectra detection process for being total to load-type ion liquid base polyester plastid SERS substrate based on ternary, feature
It is, the method is as follows:
1) polyester plastid-gold nanoparticle Polysome@Au is dissolved in deionized water, ultrasonic disperse obtains Polysome@Au
Sample X solution is added into Polysome@Au aqueous solution, carries out ion-exchange reactions under magnetic agitation, reaction terminates for aqueous solution
Centrifuge washing is carried out to product afterwards, it is dry, it obtains ternary and is total to load-type ion liquid base polyester plastid SERS substrate Polysome@X@
Au；
2) Polysome@X@Au is uniformly coated in glass slide, is air-dried 10 minutes；It is subsequently placed in Raman detection
It is detected on instrument.
2. Raman spectra detection process according to claim 1, which is characterized in that the polyester plastid-gold nanoparticle
Polysome@Au's the preparation method is as follows:
1) 2-methylimidazole, triethylamine and bromo -11- carbene are sequentially added into toluene, after 90 DEG C of reaction 48h, are cooled to
Room temperature filters and removes solid, and gained filtrate solvent evaporated is washed with n-hexane, again after solvent evaporated, with acetonitrile-acetic acid second
Ester mixed solvent recrystallization, vacuum drying obtain liposome monomer；
2) the liposome monomer that step 1) obtains is dissolved in deionized water, ultrasonic disperse obtains clear transparent solutions, is ionic liquid
Body base liposome (Liposome)；
3) into the ionic liquid base liposome (Liposome) that step 2) obtains, K is added2S2O8, nitrogen protection is anti-at 100 DEG C
Suspension, 8000rpm/min centrifugation washing should be obtained for 24 hours, freeze-drying obtains ionic liquid base polyester plastid Polysome；
4) the ionic liquid base polyester plastid Polysome for taking step 3) to obtain is scattered in deionized water, and HAuCl is added dropwise4, in room
Temperature is lower to vibrate 12h, and after reaction, 8000rpm/min centrifugation washing removes extra HAuCl4, products therefrom weight will be centrifuged
It is newly scattered in deionized water, NaBH is added dropwise4Reducing agent reacts 2h, after reaction, 8000rpm/min centrifugation washing, freezing
It is dry, obtain polyester plastid-gold nanoparticle (Polysome@Au).
3. Raman spectra detection process according to claim 1, which is characterized in that the sample X is anion characteristic
Organic Raman microprobe molecule.
4. Raman spectra detection process according to claim 3, which is characterized in that organic Raman of the anion characteristic
Probe molecule is methyl orange, methyl orchid or 4- acetylenylbenzene sodium formate.
5. Raman spectra detection process according to claim 1, which is characterized in that the item detected in Raman detector
Part are as follows: excitation wavelength 633nm, laser power 1.7mW, and within the time for exposure of 10s, to 100-3200cm-1Wave number
Raman spectrum is recorded in range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910634547.XA CN110208249A (en) | 2019-07-15 | 2019-07-15 | A kind of Raman spectra detection process being total to load-type ion liquid base polyester plastid SERS substrate based on ternary |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910634547.XA CN110208249A (en) | 2019-07-15 | 2019-07-15 | A kind of Raman spectra detection process being total to load-type ion liquid base polyester plastid SERS substrate based on ternary |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110208249A true CN110208249A (en) | 2019-09-06 |
Family
ID=67797457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910634547.XA Pending CN110208249A (en) | 2019-07-15 | 2019-07-15 | A kind of Raman spectra detection process being total to load-type ion liquid base polyester plastid SERS substrate based on ternary |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110208249A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110927141A (en) * | 2019-12-02 | 2020-03-27 | 辽宁大学 | Temperature-sensitive intelligent response SERS substrate and preparation method and application thereof |
| CN113433111A (en) * | 2021-06-25 | 2021-09-24 | 辽宁大学 | Liposome-based core-shell material for Raman spectrum detection and preparation method and application thereof |
| CN114184592A (en) * | 2021-11-24 | 2022-03-15 | 厦门大学 | Electronegative molecule SERS detection method based on electronegative SERS substrate |
| CN114264641A (en) * | 2020-09-16 | 2022-04-01 | 中国科学院过程工程研究所 | Method for detecting concentration of trace ionic liquid |
| CN118376804A (en) * | 2024-06-25 | 2024-07-23 | 华昕生物医药(山东)集团有限公司 | Liposome online extraction detection device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080268548A1 (en) * | 2006-04-03 | 2008-10-30 | Nano Chocolate Lab, Inc. | Enhancing Raman spectrographic sensitivity by using solvent extraction of vapor or particulate trace materials, improved surface scatter from nano-structures on nano-particles, and volumetric integration of the Raman scatter from the nano-particles' surfaces |
| CN105364066A (en) * | 2015-12-02 | 2016-03-02 | 首都师范大学 | Method for modifying surfaces of gold nanoparticles through ionic liquid |
| CN106053571A (en) * | 2016-05-25 | 2016-10-26 | 辽宁大学 | Preparation and application of ionic liquid based polymerization liposome-gold nano-particle compound |
| CN107884385A (en) * | 2017-11-15 | 2018-04-06 | 东华大学 | A kind of preparation of nucleocapsid enhancing raman spectrum substrate and method of testing |
| CN108279227A (en) * | 2018-02-05 | 2018-07-13 | 辽宁大学 | A kind of novel surface enhancing raman spectrum substrate material and its preparation method and application |
| CN109358033A (en) * | 2019-01-08 | 2019-02-19 | 中国科学院烟台海岸带研究所 | One seed nucleus-satellite type gold and silver composite Nano SERS substrate and preparation method thereof |
-
2019
- 2019-07-15 CN CN201910634547.XA patent/CN110208249A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080268548A1 (en) * | 2006-04-03 | 2008-10-30 | Nano Chocolate Lab, Inc. | Enhancing Raman spectrographic sensitivity by using solvent extraction of vapor or particulate trace materials, improved surface scatter from nano-structures on nano-particles, and volumetric integration of the Raman scatter from the nano-particles' surfaces |
| CN105364066A (en) * | 2015-12-02 | 2016-03-02 | 首都师范大学 | Method for modifying surfaces of gold nanoparticles through ionic liquid |
| CN106053571A (en) * | 2016-05-25 | 2016-10-26 | 辽宁大学 | Preparation and application of ionic liquid based polymerization liposome-gold nano-particle compound |
| CN107884385A (en) * | 2017-11-15 | 2018-04-06 | 东华大学 | A kind of preparation of nucleocapsid enhancing raman spectrum substrate and method of testing |
| CN108279227A (en) * | 2018-02-05 | 2018-07-13 | 辽宁大学 | A kind of novel surface enhancing raman spectrum substrate material and its preparation method and application |
| CN109358033A (en) * | 2019-01-08 | 2019-02-19 | 中国科学院烟台海岸带研究所 | One seed nucleus-satellite type gold and silver composite Nano SERS substrate and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| WILLIAM LUM ET AL.: "Novel Liposome-Based Surface-Enhanced Raman Spectroscopy(SERS) Substrate", 《J. PHYS. CHEM. LETT.》 * |
| 中国科学技术协会: "《化学学科发展报告》", 30 April 2009 * |
| 徐如人 等: "《简明精细化工辞典》", 31 July 2000 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110927141A (en) * | 2019-12-02 | 2020-03-27 | 辽宁大学 | Temperature-sensitive intelligent response SERS substrate and preparation method and application thereof |
| CN114264641A (en) * | 2020-09-16 | 2022-04-01 | 中国科学院过程工程研究所 | Method for detecting concentration of trace ionic liquid |
| CN113433111A (en) * | 2021-06-25 | 2021-09-24 | 辽宁大学 | Liposome-based core-shell material for Raman spectrum detection and preparation method and application thereof |
| CN114184592A (en) * | 2021-11-24 | 2022-03-15 | 厦门大学 | Electronegative molecule SERS detection method based on electronegative SERS substrate |
| CN114184592B (en) * | 2021-11-24 | 2023-12-05 | 厦门大学 | Electronegative molecule SERS detection method based on electronegative SERS substrate |
| CN118376804A (en) * | 2024-06-25 | 2024-07-23 | 华昕生物医药(山东)集团有限公司 | Liposome online extraction detection device |
| CN118376804B (en) * | 2024-06-25 | 2024-09-13 | 华昕生物医药(山东)集团有限公司 | Liposome online extraction detection device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110208249A (en) | A kind of Raman spectra detection process being total to load-type ion liquid base polyester plastid SERS substrate based on ternary | |
| Zhang et al. | Hydrophobic slippery surface-based surface-enhanced Raman spectroscopy platform for ultrasensitive detection in food safety applications | |
| Guerrini et al. | Molecularly-mediated assemblies of plasmonic nanoparticles for Surface-Enhanced Raman Spectroscopy applications | |
| Wang et al. | Monodispersed gold Nanorod‐embedded silica particles as novel Raman labels for biosensing | |
| Xi et al. | Promoting intra-and intermolecular interactions in surface-enhanced Raman scattering | |
| US8470442B2 (en) | Metal nanoparticles functionalized with rationally designed coatings and uses thereof | |
| Zhou et al. | Highly selective and repeatable surface-enhanced resonance Raman scattering detection for epinephrine in serum based on interface self-assembled 2D nanoparticles arrays | |
| Yoon et al. | Multifunctional colloids with optical, magnetic, and superhydrophobic properties derived from nucleophilic substitution-induced layer-by-layer assembly in organic media | |
| Yang et al. | Gold–silver nanocomposite-functionalized graphene based electrochemiluminescence immunosensor using graphene quantum dots coated porous PtPd nanochains as labels | |
| Yang et al. | One-step preparation method of flexible metafilms on the water–oil interface: self-assembly surface plasmon structures for surface-enhanced Raman scattering detection | |
| CN108254352A (en) | A kind of liquid-liquid interface detection method for Surface enhanced Raman spectroscopy | |
| Puente et al. | Silver-chitosan and gold-chitosan substrates for surface-enhanced Raman spectroscopy (SERS): Effect of nanoparticle morphology on SERS performance | |
| Xiao et al. | Fluorescent nanomaterials combined with molecular imprinting polymer: synthesis, analytical applications, and challenges | |
| JP6030073B2 (en) | Raman scattering nanoprobe | |
| Li et al. | Glucose assay based on a fluorescent multi-hydroxyl carbon dots reversible assembly with phenylboronic acid brush grafted magnetic nanoparticles | |
| KR20140027033A (en) | Inorganic-organic nanofiber composite substrates for fast and sensitive trace analysis based on surface enhanced raman scattering and the method thereof | |
| Jalaja et al. | Effective SERS detection using a flexible wiping substrate based on electrospun polystyrene nanofibers | |
| Liu et al. | Silica nanowire assemblies as three-dimensional, optically transparent platforms for constructing highly active SERS substrates | |
| KR20150000751A (en) | Stimuli-responsive Surface Enhanced Raman Scattering Substrates with High Sensitivity for Trace Analysis and the Method Thereof | |
| Lee et al. | Multifunctional hybrid polymer‐based porous materials | |
| Liu et al. | Increasing hotspots density for high-sensitivity SERS detection by assembling array of Ag nanocubes | |
| CN104975279B (en) | A kind of colloidal sol and method for preparing surface enhanced Raman substrate | |
| CN112938979A (en) | MXene composite material with SERS effect and preparation method and application thereof | |
| US20170261434A1 (en) | Sers substrate | |
| Lu et al. | Detection of squamous cell carcinoma antigen in cervical cancer by surface-enhanced Raman scattering-based immunoassay |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190906 |
|
| RJ01 | Rejection of invention patent application after publication |