CN109283168A - A kind of highly sensitive SERS molecular detecting method based on both sexes nano particle - Google Patents

A kind of highly sensitive SERS molecular detecting method based on both sexes nano particle Download PDF

Info

Publication number
CN109283168A
CN109283168A CN201810916543.6A CN201810916543A CN109283168A CN 109283168 A CN109283168 A CN 109283168A CN 201810916543 A CN201810916543 A CN 201810916543A CN 109283168 A CN109283168 A CN 109283168A
Authority
CN
China
Prior art keywords
sexes
sio
hybrid particulates
highly sensitive
solution
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.)
Granted
Application number
CN201810916543.6A
Other languages
Chinese (zh)
Other versions
CN109283168B (en
Inventor
唐龙华
江涛
赵慧
刘旭
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN201810916543.6A priority Critical patent/CN109283168B/en
Publication of CN109283168A publication Critical patent/CN109283168A/en
Application granted granted Critical
Publication of CN109283168B publication Critical patent/CN109283168B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention discloses a kind of highly sensitive SERS molecular detecting method based on both sexes nano particle.Utilize both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates make it form the thin layer of self-assembling nanoparticles at amphiprotic solvent interface；Has Raman enhancing activity to the modification of both sexes particle surface further progress golden shell；Utilize both sexes granular absorption determinand molecule, water-oil phase mixed solvent is added and forms miniature vesica, generating Nano silver grain by illumination or heating again enhances hot spot to form phasmon, utilize the Magneto separate ability of both sexes particle, miniature vesica is separated with organic solvent, finally carries out raman spectroscopy measurement.The present invention is able to achieve the highly sensitive Raman detection of determinand, without complicated pretreatment, can have the promotion of an order of magnitude in Raman signal intensity, stability and reproducibility with higher have a wide range of application.

Description

A kind of highly sensitive SERS molecular detecting method based on both sexes nano particle
Technical field
The present invention is especially a kind of based on both sexes nano particle in relation to a kind of convenient and fast high sensitivity SERS detection method Highly sensitive SERS molecular detecting method significantly improves Raman signal intensity using both sexes nano particle and without complicated pre- place Reason.
Background technique
Surface enhanced Raman scattering (Surface-Enhanced Raman Scattering, abbreviation SERS) is that people will Laser Raman spectroscopy is applied to abnormal surface optical phenomena found in the exploration of Surface Science research.
India's scientist's Raman finds Raman scattering phenomenon in nineteen twenty-eight and obtains Nobel's physics after the two years Prize.But since the detection sensitivity of Raman spectrum is extremely low, it still can't be effective experimental tool.
1974, after smooth silver electrode surface is subject to roughening treatment by Southampton, Britain university Fleischmann etc., The Raman spectrum for being adsorbed on the high quality of monolayer Pyridine Molecules in silver electrode surface is obtained for the first time, and intensification factor reaches 104 ~106, being simply considered that rough surface causes can more polymolecular.The experiment that Northwestern Univ USA Van Duyne passes through system With the drawing of the Raman scattering signal and the pyridine in solution phase that calculate each Pyridine Molecules that discovery is adsorbed on roughened silver surfaces Graceful scattered signal is compared, and about 6 orders of magnitude are enhanced, it is indicated that this is a kind of surface enhanced effect relevant to rough surface, i.e. table Face enhances Raman (Surface-Enhanced Raman Scattering, abbreviation SERS).
SERS technology not only has the advantages that the most of of Raman spectrum, is capable of providing the structure letter of richer chemical molecular Breath, it can be achieved that in real time, in-situ investigation, and high sensitivity, data processing is simple, accuracy rate is high, is very strong trace Detection instrument.
The further breakthrough of the sensitivity of SERS, there are also certain difficulty for especially up to monomolecular detection, therefore lead to Simple processing is crossed to effectively improve sensitivity with very big meaning.
Summary of the invention
In order to solve the problems, such as to propose in background technique, it is different from the prior art, the present invention provides one kind to be based on both sexes The highly sensitive SERS molecular detecting method of nano particle can enhance Raman signal intensity when SERS is detected.
The present invention is mainly based upon both sexes nano particle and is self-assembly of miniature vesica in two-phase interface, while also using light Former or thermal reduction effectively enhancing SPR effect, and by externally-applied magnetic field separation and concentration, Raman signal can be obviously improved by this technology Intensity, greatly improve detection sensitivity and reliability, while easy to operate.
Specifically, technical solution of the present invention includes the following steps:
1) both sexes γ-Fe is synthesized2O3||SiO2Two-sided hybrid particulates (both sexes nano particle): it is prepared in a manner of spray burning γ-Fe2O3||SiO2Two-sided hybrid particulates simultaneously carry out in-situ modified, obtain both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates；
γ-Fe2O3||SiO2Two-sided hybrid particulates are the grain structure that two sides hemisphere corresponds to heterogeneity, wherein side half Ball is Fe2O3, other side hemisphere is SiO2.Both sexes γ-the Fe prepared2O3||SiO2Two-sided hybrid particulates have it is amphipathic, Refer to that there are different compatibilities in water phase and oily phase.
2) to both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates carry out golden shell modification: in both sexes γ-Fe2O3||SiO2It is two-sided The side hemisphere surface of hybrid particulates wraps up layer gold；
3) silver-colored reducing solution is configured: by AgNO3It is added to acquisition argentiferous reducing solution in PVP solution；
4) to test substance processing: test substance being mixed with silver-colored reducing solution, organic solvent is added, adds step 2) Both sexes γ-Fe after modification2O3||SiO2Two-sided hybrid particulates form miniature vesica after ultrasonic treatment, then will be to containing miniature The mixed solution of vesica carries out photo-reduction or is heat-treated, and silver-colored reducing solution reacts inside miniature vesica, generates Nano silver grain；
5) Magneto separate: externally-applied magnetic field traction separates miniature vesica with organic solvent, and enrichment obtains miniature vesica；
6) SERS spectrogram detects: carrying out detection with the resulting miniature vesica of step 5) and obtains Surface enhanced Raman scattering (SERS) spectrogram.
The present invention is distinguishingly to both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates carry out golden selective modification iron content wherein One side, and test substance is mixed with silver-colored reducing solution by step 4), then with the particle after modification in conjunction at Reason, so that test substance is enclosed in both sexes γ-Fe by self assembly2O3||SiO2The Fe of two-sided hybrid particulates2O3The inner ring one of formation In side.Both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates have been self-assembly of on water-organic solvent two-phase interface into miniature capsule Bubble, and form phasmon by light processing or heat treatment and silver-colored reducing solution generation Nano silver grain and enhance hot spot, it can increase The Raman scattering of strong test substance.
The reaction principle of this step self assembly is as follows: both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates are in SiO2Side tool Having hydrophobic group in organic solvent has better dispersibility, and Fe2O3There is a better dispersibility in side in water, therefore It has been self-assembly of on water-organic solvent two-phase interface into miniature vesica.
Test substance in the step 3) is mixed when not making any pretreatment with silver-colored reducing solution.
The test substance specifically uses 4- aminothiophenol (4-Aminothiophenol).
The organic solvent is toluene.
In the step 2), to both sexes γ-Fe2O3||SiO2The Fe of two-sided hybrid particulates2O3Side superscribe one layer 5~ The golden shell of 10nm thickness.
In the step 4), both sexes γ-Fe2O3||SiO2The self assembly on water-toluene two-phase interface of two-sided hybrid particulates Having been formed into partial size is micron-sized miniature vesica, and it is more than week can to stablize holding one for miniature vesica.
In the step 4), photo-reduction processing or heating reduction treatment are carried out to the mixed solution of formation, can be enhanced Raman signal intensity.
In the step 4), carrying out photo-reduction processing is to be placed in mixed solution under ultraviolet lamp to irradiate.
In the step 4), carrying out heating reduction treatment is to be placed in mixed solution under water-bath to heat.
The step 1), specifically:
Using closed reactor, both sexes γ-Fe has been synthesized by a step flame assistant spray thermal decomposition manner2O3|| SiO2Two-sided hybrid particulates:
S1, precursor solution, ferric nitrate and orthosilicic acid are prepared in ethanol by dissolving ferric nitrate and tetraethyl orthosilicate It is respectively 0.25mol/L and 0.25M mol/L that tetra-ethyl ester, which is dissolved in the concentration in precursor solution,；
S2, precursor solution is added in reactor with the rate of 5mL/min and is dispersed by oxygen, oxygen rates are 0.3m3/ h, oxygen pneumatic 0.15Mpa form fine spray droplet；
S3, hydrogen is added in reactor, to obtain higher total gas flow rate, and adjusts oxygen rates；Spray droplet It is lighted and is supported by hydrogen and oxygen, the thermal energy for generation of burning is used for γ-Fe2O3||SiO2The thermal decomposition of two-sided hybrid particulates and Crystal growth；When burning, hydrogen and oxygen rates are respectively 0.76m3/h、1m3/h；
S4, continue stage addition γ-methacryloxypropyl trimethyl silane after combustion as modifying agent progress original Position is modified, and hydrophobic group is grafted to SiO2Hemisphere surface complete it is in-situ modified, to obtain both sexes γ-Fe2O3|| SiO2Two-sided hybrid particulates；
S5, by means of vacuum pump, pass through glass fiber filter and collect both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates Final product.
The step 2), specifically:
Firstly, being dissolved in PVP containing both sexes γ-Fe2O3||SiO2In the aqueous solution of two-sided hybrid particulates, PVP in solution Concentration unit be equivalent to vinylpyrrolidone monomer 0.4mol/L；
Then, the chlorauric acid solution that concentration 0.073mol/L is added forms reaction mixture, so that both sexes γ-Fe2O3|| SiO2Two-sided hybrid particulates surface forms PVP-Au3+Colloidal film, Au3+With PVP (to be equivalent to vinylpyrrolidone monomer calculating Mole) molar ratio in the reactive mixture is 1:100；
It reacts finally, the ammonium hydroxide that the concentration that 0.5mL is added is 0.1mol/L stirs 12 hours at normal temperature, passes through after reaction Magnetic separation collects both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates are washed with water 3 times.
The step 4), specifically: test substance does not do any pretreatment, will contain 10-5The water of the test substance of mol/L Solution is mixed with silver-colored reducing solution, the both sexes γ-Fe after adding step 2 modification2O3||SiO2Two-sided hybrid particulates, add Toluene, ultrasonic treatment；Two different phases of toluene and water are separated into after ultrasound, and the interface between toluene and water is formed from group Both sexes γ-the Fe of dress2O3||SiO2The thin layer of two-sided hybrid particulates forms miniature vesica；Finally contain miniature capsule for resulting The mixed solution of bubble, which is placed under ultraviolet lamp, irradiates or is placed in heating water bath.
Complete procedure is as shown in Fig. 2, the invention firstly uses both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates (following letter Claim both sexes nano particle), so that it is formed the thin layer of self-assembling nanoparticles at amphiprotic solvent interface；To both sexes particle surface into one Step carries out golden shell modification and has Raman enhancing activity；Using both sexes granular absorption determinand molecule, it is molten that water-oil phase mixing is added Dosage form generates Nano silver grain at miniature vesica, then by illumination or heating to form phasmon enhancing hot spot；Utilize both sexes The Magneto separate ability of particle separates miniature vesica with organic solvent；Finally, carrying out raman spectroscopy measurement, determinand is realized Highly sensitive Raman detection.
Compared with the existing technology, beneficial effects of the present invention performance is as follows:
1), the both sexes γ-Fe that the present invention utilizes2O3||SiO2Two-sided hybrid particulates property is stablized, and can save, be convenient for for a long time Storage.
2), detection method of the invention can be to sample to be tested without complicated pretreatment, and operating procedure is simple, experiment week Phase is short, at low cost, and can reach the high sensitive precision of detection.
3) the case where, present invention utilizes the effect of externally-applied magnetic field separation and concentration, can satisfy minute quantity test substance.
4), the present invention can detecte sewage, human body fluid etc., and to meet the needs of practice examining difference, use scope is wide.
5), detection of the invention sensitivity with higher, stability, and there is good reproducibility.
Detailed description of the invention
Fig. 1 is Fe obtained by 1 step 2 of embodiment2O3Side superscribes the both sexes γ-Fe of golden shell2O3||SiO2Two-sided hydridization The structure chart of grain.
Fig. 2 is that embodiment 1 is based on both sexes γ-Fe2O3||SiO2The highly sensitive SERS Molecular Detection of two-sided hybrid particulates The principle process schematic of method.
Fig. 3 is Fe obtained by 1 step 2 of embodiment2O3Side superscribes the both sexes γ-Fe of golden shell2O3||SiO2Two-sided hydridization The transmission electron microscope photo of grain.
Fig. 4 is using embodiment 1 based on both sexes γ-Fe2O3||SiO2The highly sensitive SERS molecule of two-sided hybrid particulates Detection method carries out the Raman spectrogram that Raman signal detection obtains to 4- aminothiophenol.
Specific embodiment
Below according to drawings and examples, the present invention will be described in detail.
The embodiment of the present invention and comparative example are as follows:
Embodiment 1
Step 1: synthesis both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates
Using closed reactor, γ-Fe has been synthesized by a step flame assistant spray thermal decomposition manner2O3||SiO2It is double Face hybrid particulates:
S1, precursor solution, ferric nitrate and orthosilicic acid are prepared in ethanol by dissolving ferric nitrate and tetraethyl orthosilicate It is respectively 0.25mol/L and 0.25M mol/L that tetra-ethyl ester, which is dissolved in the concentration in precursor solution,；
S2, precursor solution is added in reactor with the rate of 5mL/min and is dispersed by oxygen, oxygen rates are 0.3m3/ h, oxygen pneumatic 0.15Mpa form fine spray droplet；
Reactor specifically uses by internal diameter the stainless steel tube that for 5cm and length is 100cm.
S3, hydrogen is added in reactor, to obtain higher total gas flow rate, and adjusts oxygen rates；Spray droplet It is lighted and is supported by hydrogen and oxygen, the thermal energy for generation of burning is used for γ-Fe2O3||SiO2The heat of two-sided hybrid nanomaterial point Solution and crystal growth；When burning, hydrogen and oxygen rates are respectively 0.76m3/h、1m3/h；
The burning of presoma and the formation of final oxide material are carried out in closed reaction chamber.
S4, continue stage addition γ-methacryloxypropyl trimethyl silane (KH570 silane coupling agent) after combustion It is in-situ modified as modifying agent progress, by the reaction of KH570 silane coupling agent, hydrophobic group is grafted to SiO2Half Ball surface completion is in-situ modified, to obtain both sexes γ-Fe2O3||SiO2Two-sided hybrid nanomaterial；
Due to the reactivity difference of surface hydroxyl, this unique duplex surface makes γ-Fe2O3||SiO2Two-sided hydridization Particle can be realized in-situ modified during gas phase flame.
S5, by means of vacuum pump, pass through glass fiber filter (ADVTECH/GA55, Toyo Roshi Kaisha Ltd, Japan) collect both sexes γ-Fe2O3||SiO2The final product of two-sided hybrid particulates.
Step 2: golden shell selectively package both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates
It carries out being coated with PVP-Au as follows3+Both sexes γ-the Fe of colloidal film2O3||SiO2The preparation of two-sided hybrid particulates.
Firstly, the PVP (polyvinylpyrrolidone, MW=30000) of 0.17g, which is dissolved in 5mL, contains 1mg both sexes γ- Fe2O3||SiO2In the aqueous solution of two-sided hybrid particulates, the concentration unit of PVP is to be equivalent to vinyl pyrrolidone list in solution Body 0.4mol/L；
Then, the chlorauric acid solution that the concentration 0.073mol/L of 0.27mL is added forms reaction mixture, so that both sexes γ- Fe2O3||SiO2Two-sided hybrid particulates surface forms PVP-Au3+Colloidal film, Au3+With PVP (to be equivalent to vinyl pyrrolidone Monomer calculates mole) molar ratio in the reactive mixture is 1:100；
It reacts finally, the ammonium hydroxide that the concentration that 0.5mL is added is 0.1mol/L stirs 12 hours at normal temperature, passes through after reaction Magnetic separation collects both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates are washed with water 3 times.
Both sexes γ-the Fe of the package golden shell of unilateral side prepared by this step2O3||SiO2Two-sided hybrid particulates can be stored in room Warm environment is more than half a year, and property pattern is unchanged, as shown in Figure 1.
Through transmission electron microscope photo as shown in figure 3, the spheric granules in figure as synthesizes obtained both sexes γ-Fe2O3 ||SiO2Two-sided hybrid particulates, wherein white hemisphere is SiO2Side, relative color are deeper for Fe2O3Side, color are most deep It is to be wrapped in SiO2The golden shell of side.The lower left corner is the both sexes γ-Fe for not superscribing golden shell in figure2O3||SiO2Two-sided hydridization Particle, SiO2Side superscribes the both sexes γ-Fe of golden shell2O3||SiO2Two-sided hybrid particulates are concentrated mainly on the upper right corner in figure.
Step 3: configuring silver-colored reducing solution
Take the AgNO that the concentration of 1mL is 0.01mol/L3PVP aqueous solution (the MW that aqueous solution and the mass fraction of 1mL are 1% 30000) it is sufficiently mixed, is kept in dark place, as silver-colored reducing solution.
Step 4: test substance is handled
Test substance specifically uses 4- aminothiophenol, does not do any pretreatment, will contain 10-5The test substance of mol/L Both sexes γ-Fe after the modification of the step of aqueous solution 1mL is mixed with 1mL silver reducing solution, added 40mg two2O3||SiO2It is two-sided miscellaneous Change particle, be ultrasonically treated 1min, add 10mL toluene, is ultrasonically treated 2min.Two of toluene and water are separated into after ultrasound not Same phase, and the interface between toluene and water forms the both sexes γ-Fe of self assembly2O3||SiO2The thin layer of two-sided hybrid particulates, i.e., Form a large amount of miniature vesicas.
Finally the resulting mixed solution containing a large amount of miniature vesicas is placed under 20W ultraviolet lamp and is irradiated 0.5 hour.
The partial size of embodiment miniature vesica obtained is in tens microns.The minimum body of required test substance aqueous solution Product can be reduced to 1 μ L.
Step 5: Magneto separate
Solution is drawn by strong magnet, by the resulting a large amount of miniature vesica traction enrichments of step 4, and is made micro- Type vesica and organic solvent separation.
Step 6: SERS is detected
A drop for drawing 5 μ L from the resulting a large amount of miniature vesicas of step 5 with liquid-transfering gun drips to surface-enhanced Raman It scatters on (SERS) substrate, carries out Surface enhanced Raman scattering (SERS) detection.
Fig. 4 is using embodiment 1 based on both sexes γ-Fe2O3||SiO2The highly sensitive SERS molecule of two-sided hybrid particulates Detection method carries out the Raman spectrogram that Raman signal detection obtains to 4- aminothiophenol.4- aminothiophenol used when detection Concentration be 10-5mol/L.Figure 4, it is seen that there is good SERS signal enhancement effect using method of the invention, The Raman signal intensity of its peak value reaches 5000.The minimum concentration that can be detected is 10-8Mol/L, and embodiment repeats 5 More than secondary, as a result without significant change.
Embodiment 2
Step 1: synthesis both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates
With embodiment 1.
Step 2: golden shell selectively package both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates
With embodiment 1.
Step 3: configuring silver-colored reducing solution
Take 1mL 2%AgNO3Aqueous solution instills the aqueous solution of 2% ammonium hydroxide in oscillation dropwise, heavy until what is initially generated It forms sediment until just dissolving, obtains silver-colored reducing solution.
Step 4: test substance is handled
Test substance specifically uses 4- aminothiophenol, does not do any pretreatment, will contain 10-5The test substance 4- of mol/L The glucose solution that the aqueous solution 1mL and 0.5mL silver reducing solution of aminothiophenol, the mass fraction of 0.5mL are 1% is mixed Both sexes γ-Fe after two modification of the step of closing, 40mg is added2O3||SiO2Two-sided hybrid particulates are ultrasonically treated 1min, add 10mL toluene is ultrasonically treated 2min.Two different phases of toluene and water, and the interface between toluene and water are separated into after ultrasound Form the both sexes γ-Fe of self assembly2O3||SiO2The thin layer of two-sided hybrid particulates forms a large amount of miniature vesicas.
The resulting mixed solution containing a large amount of miniature vesicas is finally placed in 60 DEG C of heating water bath 5min.
Step 5: Magneto separate
With embodiment 1.
Step 6: SERS is detected
With embodiment 1.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (10)

1. a kind of highly sensitive SERS molecular detecting method based on both sexes nano particle, it is characterised in that: comprise the following steps that
1) both sexes γ-Fe is synthesized2O3||SiO2Two-sided hybrid particulates: preparation γ-Fe2O3||SiO2Two-sided hybrid particulates simultaneously carry out original Position is modified, obtains both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates；
2) to both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates carry out golden shell modification: in both sexes γ-Fe2O3||SiO2Two-sided hydridization The side hemisphere surface of particle wraps up layer gold；
3) silver-colored reducing solution is configured: by AgNO3It is added to acquisition argentiferous reducing solution in PVP solution；
4) to test substance processing: test substance being mixed with silver-colored reducing solution, organic solvent is added, adds step 2) modification Both sexes γ-Fe afterwards2O3||SiO2Two-sided hybrid particulates form miniature vesica after ultrasonic treatment, then will be to containing miniature vesica Mixed solution photo-reduction or be heat-treated, silver-colored reducing solution reacts inside miniature vesica, generates silver and receives Rice corpuscles；
5) Magneto separate: externally-applied magnetic field traction separates miniature vesica with organic solvent, and enrichment obtains miniature vesica；
6) SERS spectrogram detects: carrying out detection with the resulting miniature vesica of step 5) and obtains Surface enhanced Raman scattering spectrogram.
2. a kind of highly sensitive SERS molecular detecting method based on both sexes nano particle as described in claim 1, feature Be: the test substance in the step 3) is mixed when not making any pretreatment with silver-colored reducing solution.
3. a kind of highly sensitive SERS molecular detecting method based on both sexes nano particle as described in claim 1, feature Be: the organic solvent is toluene.
4. a kind of highly sensitive SERS molecular detecting method based on both sexes nano particle as described in claim 1, feature It is: in the step 2), to both sexes γ-Fe2O3||SiO2The Fe of two-sided hybrid particulates2O3Side superscribe one layer 5~ The golden shell of 10nm thickness.
5. a kind of highly sensitive SERS molecular detecting method based on both sexes nano particle as described in claim 1, feature Be: in the step 4), carrying out photo-reduction processing is to be placed in mixed solution under ultraviolet lamp to irradiate.
6. a kind of highly sensitive SERS molecular detecting method based on both sexes nano particle as described in claim 1, feature Be: in the step 4), carrying out heating reduction treatment is to be placed in mixed solution under water-bath to heat.
7. a kind of highly sensitive SERS molecular detecting method based on both sexes nano particle as described in claim 1, feature Be: the step 1) specifically uses closed reactor, has synthesized two by a step flame assistant spray thermal decomposition manner Property γ-Fe2O3||SiO2Two-sided hybrid particulates:
S1, precursor solution, ferric nitrate and orthosilicic acid tetrem are prepared in ethanol by dissolving ferric nitrate and tetraethyl orthosilicate It is respectively 0.25mol/L and 0.25M mol/L that ester, which is dissolved in the concentration in precursor solution,；
S2, precursor solution is added in reactor with the rate of 5mL/min and is dispersed by oxygen, oxygen rates 0.3m3/ H, oxygen pneumatic 0.15Mpa form fine spray droplet；
S3, hydrogen is added in reactor；Spray droplet is lighted and is supported by hydrogen and oxygen, and the thermal energy for generation of burning is used for γ-Fe2O3||SiO2The thermal decomposition of two-sided hybrid particulates and crystal growth；When burning, hydrogen and oxygen rates are respectively 0.76m3/h、1m3/h；
S4, after combustion continuous stage are added γ-methacryloxypropyl trimethyl silane as modifying agent and carry out in situ change Property, hydrophobic group is grafted to SiO2Hemisphere surface complete it is in-situ modified, to obtain both sexes γ-Fe2O3||SiO2It is double Face hybrid particulates；
S5, by means of vacuum pump, pass through glass fiber filter and collect both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates it is final Product.
8. a kind of highly sensitive SERS molecular detecting method based on both sexes nano particle as described in claim 1, feature It is: the step 2), specifically:
Firstly, being dissolved in PVP containing both sexes γ-Fe2O3||SiO2In the aqueous solution of two-sided hybrid particulates, PVP's is dense in solution Degree unit is to be equivalent to vinylpyrrolidone monomer 0.4mol/L；
Then, the chlorauric acid solution that concentration 0.073mol/L is added forms reaction mixture, so that both sexes γ-Fe2O3||SiO2It is double Face hybrid particulates surface forms PVP-Au3+Colloidal film, Au3+It is 1:100 with the molar ratio of PVP in the reactive mixture；
It is reacted finally, the ammonium hydroxide that the concentration that 0.5mL is added is 0.1mol/L stirs 12 hours at normal temperature, passes through magnetic force after reaction Separate and collect both sexes γ-Fe2O3||SiO2Two-sided hybrid particulates are washed with water 3 times.
9. a kind of highly sensitive SERS molecular detecting method based on both sexes nano particle as described in claim 1, feature It is: the step 4), specifically: test substance does not do any processing, will contain 10-5The aqueous solution of the test substance of mol/L It is mixed with silver-colored reducing solution, the both sexes γ-Fe after adding step 2 modification2O3||SiO2Two-sided hybrid particulates, add first Benzene, ultrasonic treatment；Two different phases of toluene and water are separated into after ultrasound, and the interface between toluene and water forms self assembly Both sexes γ-Fe2O3||SiO2The thin layer of two-sided hybrid particulates forms miniature vesica；Finally contain miniature vesica for resulting Mixed solution be placed under ultraviolet lamp and irradiate or be placed in heating water bath.
10. a kind of highly sensitive SERS molecular detecting method based on both sexes nano particle as described in claim 1, feature Be: the test substance specifically uses 4- aminothiophenol (4-Aminothiophenol).
CN201810916543.6A 2018-08-13 2018-08-13 High-sensitivity SERS molecule detection method based on amphoteric nanoparticles Active CN109283168B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810916543.6A CN109283168B (en) 2018-08-13 2018-08-13 High-sensitivity SERS molecule detection method based on amphoteric nanoparticles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810916543.6A CN109283168B (en) 2018-08-13 2018-08-13 High-sensitivity SERS molecule detection method based on amphoteric nanoparticles

Publications (2)

Publication Number Publication Date
CN109283168A true CN109283168A (en) 2019-01-29
CN109283168B CN109283168B (en) 2020-07-03

Family

ID=65183253

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810916543.6A Active CN109283168B (en) 2018-08-13 2018-08-13 High-sensitivity SERS molecule detection method based on amphoteric nanoparticles

Country Status (1)

Country Link
CN (1) CN109283168B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113533294A (en) * 2021-05-31 2021-10-22 浙江大学 Time domain, space domain and spectrum domain single molecule characterization device based on nanometer gap electrode pair
CN113560595A (en) * 2021-08-06 2021-10-29 山东大学 Preparation method and application of metal-based DNA thermotropic liquid crystal
CN116223475A (en) * 2023-01-03 2023-06-06 上海之江生物科技股份有限公司 Raman nanoparticle lamellar treatment method and application

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090258355A1 (en) * 2008-04-11 2009-10-15 Brookhaven Science Associates, Llc Nanoscale Clusters and Methods of Making Same
KR101195957B1 (en) * 2009-03-26 2012-10-30 한양대학교 에리카산학협력단 Combinational surface-enhanced raman scattering probe and method for detecting target substance by using the same
CN105107482A (en) * 2015-09-11 2015-12-02 中国农业科学院农业质量标准与检测技术研究所 Preparation method for molecular imprinting material and molecular imprinting material prepared through preparation method
CN105147619A (en) * 2015-09-30 2015-12-16 复旦大学 Janus nanometer particle used for monitoring release of two kinds of medicine in real time and preparation method thereof
CN106881465A (en) * 2017-02-17 2017-06-23 桂林理工大学 A kind of preparation method of amphiphilic Janus golden nanometer particles
CN107254307A (en) * 2017-06-13 2017-10-17 山东大学 A kind of silver nanoclusters fluorescence vesica and preparation method thereof and detection Fe3+Application
US20180059026A1 (en) * 2016-08-23 2018-03-01 Optokey, Inc. Surface Enhanced Raman Spectroscopy (SERS) Structure For Double Resonance Output
CN108387746A (en) * 2018-03-02 2018-08-10 浙江大学 A kind of superparamagnetic nanoparticle and preparation method thereof of capture excretion body and specific excretion body electrochemiluminescent immunoassay immue quantitative detection reagent box

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090258355A1 (en) * 2008-04-11 2009-10-15 Brookhaven Science Associates, Llc Nanoscale Clusters and Methods of Making Same
KR101195957B1 (en) * 2009-03-26 2012-10-30 한양대학교 에리카산학협력단 Combinational surface-enhanced raman scattering probe and method for detecting target substance by using the same
CN105107482A (en) * 2015-09-11 2015-12-02 中国农业科学院农业质量标准与检测技术研究所 Preparation method for molecular imprinting material and molecular imprinting material prepared through preparation method
CN105147619A (en) * 2015-09-30 2015-12-16 复旦大学 Janus nanometer particle used for monitoring release of two kinds of medicine in real time and preparation method thereof
US20180059026A1 (en) * 2016-08-23 2018-03-01 Optokey, Inc. Surface Enhanced Raman Spectroscopy (SERS) Structure For Double Resonance Output
CN106881465A (en) * 2017-02-17 2017-06-23 桂林理工大学 A kind of preparation method of amphiphilic Janus golden nanometer particles
CN107254307A (en) * 2017-06-13 2017-10-17 山东大学 A kind of silver nanoclusters fluorescence vesica and preparation method thereof and detection Fe3+Application
CN108387746A (en) * 2018-03-02 2018-08-10 浙江大学 A kind of superparamagnetic nanoparticle and preparation method thereof of capture excretion body and specific excretion body electrochemiluminescent immunoassay immue quantitative detection reagent box

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
YUNFENG LI ET AL.,: "Double-faced g-Fe2O3||SiO2 nanohybrids: flame synthesis, in situ selective modification and highly interfacial activity", 《NANOSCALE》 *
ZHENLI SUN ET AL.: "Multifunctional Fe3O4@SiO2−Au Satellite Structured SERS Probe for Charge Selective Detection of Food Dyes", 《ACS APPL. MATER. INTERFACES》 *
刘凯鸿: "纳米SiO_2颗粒在流体界面的自组装及其对pH的响应性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
刘科 等: "pickering乳液法制备两亲性Janus SiO2纳米粒子", 《天津纺织科技》 *
韩三阳, 等: "Fe 2 0 3A/ u A/ g 磁性核壳纳米粒子的制备及其S E R S 研究", 《第十五届全国光散射学术会议一郑州》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113533294A (en) * 2021-05-31 2021-10-22 浙江大学 Time domain, space domain and spectrum domain single molecule characterization device based on nanometer gap electrode pair
CN113560595A (en) * 2021-08-06 2021-10-29 山东大学 Preparation method and application of metal-based DNA thermotropic liquid crystal
CN113560595B (en) * 2021-08-06 2022-07-01 山东大学 Preparation method and application of metal-based DNA thermotropic liquid crystal
CN116223475A (en) * 2023-01-03 2023-06-06 上海之江生物科技股份有限公司 Raman nanoparticle lamellar treatment method and application

Also Published As

Publication number Publication date
CN109283168B (en) 2020-07-03

Similar Documents

Publication Publication Date Title
Sarfraz et al. Plasmonic gold nanoparticles (AuNPs): properties, synthesis and their advanced energy, environmental and biomedical applications
Fan et al. Functionalized gold nanoparticles: synthesis, properties and biomedical applications
Priyadarshini et al. Gold nanoparticles as efficient sensors in colorimetric detection of toxic metal ions: a review
Dinkel et al. Fast and slow ligand exchange at the surface of colloidal gold nanoparticles
Liu et al. Fe3O4@ graphene oxide@ Ag particles for surface magnet solid-phase extraction surface-enhanced Raman scattering (SMSPE-SERS): from sample pretreatment to detection all-in-one
Jana et al. Enlightening surface plasmon resonance effect of metal nanoparticles for practical spectroscopic application
Chen et al. Au@ ZIF-8 core–shell nanoparticles as a SERS substrate for volatile organic compound gas detection
CN109283168A (en) A kind of highly sensitive SERS molecular detecting method based on both sexes nano particle
Han et al. Magnetic silver hybrid nanoparticles for surface-enhanced resonance Raman spectroscopic detection and decontamination of small toxic molecules
Ali Dheyab et al. Recent advances in inorganic nanomaterials synthesis using sonochemistry: a comprehensive review on iron oxide, gold and iron oxide coated gold nanoparticles
Fang et al. Portable Hg2+ nanosensor with ppt level sensitivity using nanozyme as the recognition unit, enrichment carrier, and signal amplifier
Renard et al. UV-resonant Al nanocrystals: Synthesis, silica coating, and broadband photothermal response
Zhou et al. A novel fluorescence enhanced route to detect copper (II) by click chemistry-catalyzed connection of Au@ SiO2 and carbon dots
Wang et al. Studies of Fe3O4/Ag/Au composites for immunoassay based on surface plasmon resonance biosensor
Lindley et al. Highly tunable hollow gold nanospheres: Gaining size control and uniform galvanic exchange of sacrificial cobalt boride scaffolds
JP4853972B2 (en) Method for detecting target molecules in samples using molecularly imprinted fine particles
CN106053408A (en) Carbon dot fluorescent probe based high sensitive and high selective method for detecting trace silver nano particles in water and/or environment
Semenova et al. Nanostructured silver materials for noninvasive medical diagnostics by surface-enhanced Raman spectroscopy
CN110907425B (en) Surface molecular imprinting SERS sensor based on core-shell structure poly-dopamine coated nano-gold particles and preparation and application thereof
Guleria et al. Glutathione-functionalized organosilicon oxide nanoparticles for bioimaging and forensics
Ma et al. Metal–organic framework-based SERS sensing platforms for life and health detection
Guleria et al. Electron beam mediated synthesis of photoluminescent organosilicon nanoparticles in TX-100 micellar medium and their prospective applications
Zhou et al. Bioinspired one-step synthesis of pomegranate-like silica@ gold nanoparticles with surface-enhanced raman scattering activity
Combs et al. Aptamer‐Assisted Assembly of Gold Nanoframe Dimers
Mao et al. Multifunctional DNA scaffold mediated gap plasmon resonance: Application to sensitive PD-L1 sensor

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
GR01 Patent grant
GR01 Patent grant