CN102699321A - Plasma coupling structure microsphere for surface-enhanced Raman scattering (SERS) and manufacturing method thereof - Google Patents

Plasma coupling structure microsphere for surface-enhanced Raman scattering (SERS) and manufacturing method thereof Download PDF

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CN102699321A
CN102699321A CN2012101900802A CN201210190080A CN102699321A CN 102699321 A CN102699321 A CN 102699321A CN 2012101900802 A CN2012101900802 A CN 2012101900802A CN 201210190080 A CN201210190080 A CN 201210190080A CN 102699321 A CN102699321 A CN 102699321A
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layer
microsphere
metal carbonyl
coupled structure
carbonyl coat
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CN102699321B (en
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朱以华
沈建华
杨晓玲
范开才
钟华
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East China University of Science and Technology
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Abstract

The invention relates to a plasma coupling structure microsphere for surface-enhanced Raman scattering (SERS). By the plasma coupling structure microsphere, a magnetic microsphere serves as a kernel, and a metal cladding I, a nonmetallic isolating layer and a metal cladding II are formed outside the kernel one by one, wherein the metal cladding I or the metal cladding II has the thickness of 0 to 50nm; the nonmetallic isolating layer has the thickness of 0 to 100nm; and the plasma coupling structure microsphere has the particle size of 300 to 1,000nm and the specific saturation magnetization of 10 to 50emu/g. The plasma coupling structure microsphere is simple in manufacturing method and controllable in product structure, the obtained microsphere can be suitable for biological separation and detection, and when the microsphere is used for detecting a Raman-enhanced effect, the detection rate can reach 10<-9> mol/L; and moreover, the plasma coupling structure microsphere is applied to the fields of photochemical catalysis, disease detection, food safety and the like, and the application prospect integrating separation and SERS detection on biological medical molecules and the like can be realized.

Description

A kind of surface-enhanced Raman is with plasma coupled structure microballoon and preparation method thereof
Technical field
The present invention relates to material of a kind of biological medicine, fine chemicals separation detection technical field and preparation method thereof, particularly, relate to a kind of surface-enhanced Raman with magnetic microsphere of Ag-Au long-range plasma coupled structure and preparation method thereof.
Background technology
SERS (SERS) has overcome the low shortcoming of common Raman technology sensitivity, can improve Raman signal, can realize Single Molecule Detection, is widely used in detecting in chemistry, biological medicine.At present, there have been a lot of methods can prepare substrate with SERS effect.For example, the coarse precious metal surface of the most common electrochemical deposition, the nano level metal film of sputter formation, the metal-sol of preparation etc.In the said method, the metal-sol preparation method is the simplest, and enhancement effect is high, in SERS detects, uses more extensive.But, the nano particle particle size control difficulty that gold, silver colloidal sol obtains, and very easily reunite, particularly after adding thing to be detected, colloidal sol is more unstable, finally causes the poor repeatability of SERS signal, can't realize quantitative analysis.
In recent years, utilize the hollow silver microballoon to replace metal-sol to be used to raman detection, for example the old intelligent grade (CN 101905330 A) of keeping of Shanghai Communications University obtains the hollow silver microballoon through streptococcus thermophilus is mixed the back with silver nitrate with the ascorbic acid reaction.Though this type base material has good Raman reinforced effects, can't recycle after these substrate one-time detection by the noble metal preparation.Therefore, the nucleocapsid structure microballoon that has magnetic is used in SERS again, and technical (Langmuir 2009,25 (18), 10782 – 10787; Anal. Biochem. 2009,391,24 – 30).But; Single golden structural material SPECTRAL REGION is limited in 600 nm to far infrared; Extensive inadequately with respect to silver (450 nm), and independent silver particles does not have the good biocompatibility of gold particle, these shortcomings all will influence the utilization aspect the biological medicine raman detection.So Jin Heyin is carried out compound, utilize between them the resonance of long-range or short distance conjugation, can improve Raman technology sensitivity and utilization scope ( Adv. Funct. Mater. 2010 , 20, 1954 – 1961; J. Mater. Chem., 2010, 20, 3688 – 3693).
Summary of the invention
The present invention is directed to the deficiency of above-mentioned existing SERS material structure, design a kind of multilayer microballoon and application process aspect raman detection thereof with magnetic kernel and gold and silver long-range plasma coupled structure.Concrete technical scheme is following:
A kind of surface-enhanced Raman is with plasma coupled structure microballoon, and said plasma coupled structure microballoon is kernel with the magnetic microsphere, successively forms metal carbonyl coat I, nonmetal separation layer and metal carbonyl coat II in said kernel outside; The thickness of said metal carbonyl coat I or metal carbonyl coat II is 0～50 nm, and the thickness of said nonmetal separation layer is 0～100 nm; The particle diameter of said plasma coupled structure microballoon is 300～1000 nm, and specific saturation magnetization is 10～50 emu/g.
The thickness of said nonmetal separation layer is 10～30 nm.
Said magnetic microsphere is tri-iron tetroxide (Fe 3O 4) microballoon.
Said metal carbonyl coat I or metal carbonyl coat II are the metal shells that gold or silver deposit through interfacial reaction.
Said nonmetal separation layer is meant the intermediate layer of two kinds of shell materials at interval, comprises nonmetallic materials in general sense, like silica (SiO 2), titanium oxide (TiO 2), zinc oxide inorganic material such as (ZnO), macromolecular materials such as polystyrene (PS), PMA (PMMA), polyelectrolyte, shitosan.
A kind of surface-enhanced Raman comprises the steps: with the preparation method of plasma coupled structure microballoon
(1) ferric trichloride 0～1.0 g, sodium acetate 0～1.0 g, trisodium citrate 0～0.25 g and ethylene glycol 0～20 mL are stirred, prepare Fe 150～200 ℃ of solvent heat treatment 3O 4Magnetic microsphere;
(2) utilize the direction of growth of the polyvinylpyrrolidone restriction metal of molecular weight 5000～70000, the Fe that makes in step (1) at last 3O 4The magnetic microsphere surface forms fine and close metal carbonyl coat I, obtains complex microsphere;
(3) through sol-gal process nonmetal separation layer is coated on the complex microsphere that step (2) obtains;
(4) introduce seed metallization on the complex microsphere surface of handling through the method for self assembly layer by layer, form metal shell, i.e. metal carbonyl coat II through interface growth through step (3); The method of said self assembly layer by layer is meant that the polyelectrolyte layer of sandwich tape opposite charges is that cationic polyelectrolyte, one deck are alternately absorption assembling of anionic polyelectrolyte by one deck.
The nonmetal separation layer of said step (3) is SiO 2Layer utilizes ethyl orthosilicate in the solution of second alcohol and water, to form colloidal sol, and a certain amount of microballoon impregnated in the said colloidal sol, and the complex microsphere superficial growth that utilizes base catalysts such as ammoniacal liquor, NaOH, KOH to obtain in step (2) forms fine and close SiO 2Layer.
In the said step (4) generally there be cationic polyelectrolyte: PAH hydrochloride (PAH), polymine (PEI), diallyl dimethyl ammoniumchloride (PDDA) etc., anionic polyelectrolyte can be selected for use and gather 4-styrene sulfonate (PSS), polyacrylic acid (PAA) etc.
Utilize Electrostatic Absorption with metal cation (like Ag +, Cu 2+Deng) be adsorbed in the anionic polymer surface, and the metallate ion is (like AuCl 4 -, PtCl 6 2-Deng) be adsorbed in the cationic polyelectrolyte surface.Through reducing agent (like NaBH 4, KBH 4Deng) metal ion is reduced into metallic particles; Be about to seed metallization and introduce the complex microsphere surface; Form the metal shell through interface growth at last; As the karat gold reducing process that the present invention relates to, in the karat gold solution that configures, add the microballoon of ADSORPTION OF GOLD seed, the reduction of utilizing formaldehyde with golden layer growth at microsphere surface.Its introduce seed and interface growth method and existing bibliographical information similar ( Biosens. Bioelectron., 2012,34,132-136).
The present invention relates to above-mentioned multifunction magnetic gold and silver long-range plasma resonance microballoon and aspect raman detection, use, through the prepared composite microballoon is immersed in 10 -4～10 -9In the RdB aqueous solution of mol/L, converge through magnet absorption, directly the Raman signal of detection of aggregation microballoon.
The present invention prepare the material structure of design special controlled, technology is novel, raw material is simple, equipment energy consumption is low, has the magnetic separating property, can be applicable to that bio-separation detects, its detection can reach 10 when being used to detect the Raman enhancement effect -9Mol/L; The present invention is applicable to photochemical catalysis, and fields such as disease detection and food security can realize realizations such as biological medicine molecule separation and SERS are detected incorporate application prospect simultaneously.Regulate the thickness of each layer, preparation multifunction magnetic gold and silver long-range plasma resonance microballoon.
Description of drawings
Fig. 1 is Fe among the embodiment 3 3O 4Ag-SiO 2-Au complex microsphere forming process sketch map;
Fig. 2 is the TEM figure of different composite microballoon in embodiment 3 processes, and a is Fe 3O 4Ag, b are Fe 3O 4Ag-SiO 2, c is Fe 3O 4Ag-SiO 2The TEM figure of-Au;
Fig. 3 is Fe among the embodiment 3 3O 4Ag-SiO 2-Au detects 10 -4～10 -9Mol/L RdB Raman spectrogram.
The specific embodiment
To combine embodiment further to illustrate content of the present invention below, but these embodiment do not limit protection scope of the present invention.
Embodiment 1
Surface-enhanced Raman comprises the steps: with the preparation method of plasma coupled structure microballoon
(a) solvent Hydrothermal Preparation Fe 3O 4Magnetic microsphere
Take by weighing ferric trichloride 0.650 g successively, water acetic acid sodium 1.000 g, trisodium citrate 0.250 g gets 20 mL
Ethylene glycol is stirred to the solution homogeneous.Solution is transferred in the 50 mL water heating kettles 200 ℃ of hydro-thermal 10 h.Naturally cool to room temperature,, obtain Fe with ethanol and water washing 3O 4The average-size of magnetic microsphere is 330 nm.
(b) coating of Ag layer
Take by weighing 0.200g Fe 3O 4, 0.100g AgNO 3With 2.500g PVP-K30, measure 24 mL ethylene glycol,
100 ℃ were reacted 12 hours down.With ethanol and deionized water washing, desciccate promptly obtains Fe 3O 4The Ag complex microsphere.About 9 nm of Ag layer thickness.Represent nucleocapsid structure, represent nuclear material at preceding material, the expression shell material of back, and represent shell structurre successively from the inside to the outside from left to right.
(c) SiO 2The coating of layer
Weighing 0.2g Fe 3O 4The Ag powder is scattered in the 10 mL water, gets 40 mL ethanol, adds 0.14 mL
Concentrated ammonia liquor adds 0.57 mL ethyl orthosilicate at last, 25 ℃ of 8 hours reaction time.After question response finishes, use magnet to separate, washing, desciccate promptly obtains Fe 3O 4Ag-SiO 2Complex microsphere.The SiO for preparing 2Layer thickness is about 90 nm.
(d) coating of Au layer
Weighing 0.2g Fe 3O 4Ag-SiO 2Powder adds PAH 7 mL of 2g/L, and ultrasonic 30 minutes, separation was washed
Wash.The HAuCl of adding 0.1% 47 mL adsorb separating, washing after 30 minutes.Add 0.1M NaBH at last 4Solution reacted 30 minutes, and washing is dry.Preparation karat gold solution.Take by weighing 0.100g K 2CO 3In 600 mL, add 400 mL water, stirred 10 minutes.Add 1% HAuCl 46 mL continue to stir 30 minutes.Get the above-mentioned dried powder of 0.2g, ultrasonic 30 minutes.Add 0.035 mL HCHO at last, reacted 30 minutes, separating, washing, drying has obtained end product Fe 3O 4Ag-SiO 2-Au.About 5 nm of Au layer thickness.
(e) about 540 nm of particle diameter of final complex microsphere, specific saturation magnetization is 15 emu/g, detects 10 to the Raman signal of RdB is minimum -6Mol/L.
Embodiment 2
Surface-enhanced Raman comprises the steps: with the preparation method of plasma coupled structure microballoon
(a) solvent Hydrothermal Preparation Fe 3O 4Magnetic microsphere such as above-mentioned embodiment 1.
(b) directly coat Ag layer and Au layer, the intermediate layer is cancelled.Step (b) and step (d) among practical implementation method such as the embodiment 1.
(c) about 360 nm of particle diameter of final complex microsphere, specific saturation magnetization is 45 emu/g, detects 10 to the Raman signal of RdB is minimum -7Mol/L.
Embodiment 3
Surface-enhanced Raman comprises the steps: with the preparation method of plasma coupled structure microballoon
(a) solvent Hydrothermal Preparation Fe 3O 4Magnetic microsphere such as above-mentioned embodiment 1.
(b) coat the Ag layer.The step of practical implementation method such as embodiment 1 (b).Like Fig. 2 a at Fe 3O 4The surface has formed one deck Ag layer, i.e. Fe 3O 4Ag, about 9 nm of its thickness.
(c) consumption and the reaction time of reduction ethyl orthosilicate, coat thin SiO 2Layer.Method of operating is following: weighing 0.2g Fe 3O 4The Ag powder is scattered in the 10 mL water, gets 40 mL ethanol, adds 0.14 mL concentrated ammonia liquor, adds 0.14 mL ethyl orthosilicate at last, 25 ℃ of 6 hours reaction time.After question response finishes, use magnet to separate, washing, desciccate promptly obtains Fe 3O 4Ag-SiO 2Complex microsphere.The SiO that forms 2Layer about 15 nm (like Fig. 2 b)
(d) coat the Au layer.The step of practical implementation method such as embodiment 1 (d).Can see golden particle, its Au layer thickness about 5 nms at microballoon at outermost layer like Fig. 2 c.
(e) about 420 nm of particle diameter of final complex microsphere, specific saturation magnetization is 37 emu/g, detects 10 like Fig. 3 to the Raman signal of RdB is minimum -9Mol/L.

Claims (8)

1. a surface-enhanced Raman is characterized in that with plasma coupled structure microballoon, and said plasma coupled structure microballoon is kernel with the magnetic microsphere, successively forms metal carbonyl coat I, nonmetal separation layer and metal carbonyl coat II in said kernel outside; The thickness of said metal carbonyl coat I or metal carbonyl coat II is that the thickness of 0～50 nm and said metal carbonyl coat I or metal carbonyl coat II is not 0 simultaneously, and the thickness of said nonmetal separation layer is 0～100 nm; The particle diameter of said plasma coupled structure microballoon is 300～1000 nm, and specific saturation magnetization is 10～50 emu/g.
2. plasma coupled structure microballoon according to claim 1 is characterized in that the thickness of said nonmetal separation layer is 10～30 nm.
3. plasma coupled structure microballoon according to claim 1 is characterized in that said magnetic microsphere is tri-iron tetroxide (Fe 3O 4) microballoon.
4. plasma coupled structure microballoon according to claim 1 is characterized in that, said metal carbonyl coat I or metal carbonyl coat II are the metal shells that gold or silver deposit through interfacial reaction.
5. plasma coupled structure microballoon according to claim 1 is characterized in that said nonmetal separation layer is silica, titanium dioxide, zinc oxide, polystyrene, PMA, polyelectrolyte or shitosan.
6. the arbitrary described surface-enhanced Raman of claim 1～5 comprises the steps: with the preparation method of plasma coupled structure microballoon
(1) ferric trichloride 0～1.0 g, sodium acetate 0～1.0 g, trisodium citrate 0～0.25 g and ethylene glycol 0～20 mL are stirred, prepare Fe 150～200 ℃ of solvent heat treatment 3O 4Magnetic microsphere;
(2) utilize the direction of growth of the polyvinylpyrrolidone restriction metal of molecular weight 5000～70000, the Fe that makes in step (1) at last 3O 4The magnetic microsphere surface forms fine and close metal carbonyl coat I, obtains complex microsphere;
(3) through sol-gal process nonmetal separation layer is coated on the complex microsphere that step (2) obtains;
(4) introduce seed metallization on the complex microsphere surface of handling through the method for self assembly layer by layer, form metal shell, i.e. metal carbonyl coat II through interface growth through step (3); The method of said self assembly layer by layer is meant that the polyelectrolyte layer of sandwich tape opposite charges is that cationic polyelectrolyte, one deck are alternately absorption assembling of anionic polyelectrolyte by one deck.
7. preparation method according to claim 6 is characterized in that, the nonmetal separation layer of said step (3) is SiO 2Layer utilizes ethyl orthosilicate in the solution of second alcohol and water, to form colloidal sol, and a certain amount of microballoon impregnated in the said colloidal sol, and the complex microsphere superficial growth that utilizes base catalyst to obtain in step (2) forms fine and close SiO 2Layer.
8. preparation method according to claim 6; It is characterized in that; Cationic polyelectrolyte is PAH hydrochloride, polymine or diallyl dimethyl ammoniumchloride in the said step (4), and anionic polyelectrolyte is to gather 4-styrene sulfonate or polyacrylic acid.
CN201210190080.2A 2012-06-11 2012-06-11 Plasma coupling structure microsphere for surface-enhanced Raman scattering (SERS) and manufacturing method thereof Expired - Fee Related CN102699321B (en)

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CN103286312A (en) * 2013-05-08 2013-09-11 复旦大学 Surface-common-enhanced fluorescence surface-enhanced Raman multi-layer core-shell structure composite particles and preparation method of particles
CN103409750A (en) * 2013-08-15 2013-11-27 南京邮电大学 Arrayed silver nanorods with surface-modifying gold nanoparticles and preparation method thereof
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CN104162665A (en) * 2014-08-29 2014-11-26 华东理工大学 Gold-organic silicon-gold multilayer core-shell nano-structure and preparing method and application thereof
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CN104807802A (en) * 2015-04-03 2015-07-29 南京邮电大学 Surface enhanced raman scattering base and in-situ growth method thereof
CN107245196A (en) * 2017-06-22 2017-10-13 成都爱兴生物科技有限公司 Multilayer assembles the preparation method of micron size polystyrene magnetic composite microsphere
CN108827929A (en) * 2018-04-17 2018-11-16 华东理工大学 A kind of SERS probe and preparation method thereof based on MOFs
CN109470683A (en) * 2018-10-23 2019-03-15 江苏大学 A method of 2,4-D is carried out with SERS substrate combination multiple linear regression model and is quickly detected
CN112683871A (en) * 2021-01-05 2021-04-20 武双 Soil chromium ion content detection method
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CN103409750A (en) * 2013-08-15 2013-11-27 南京邮电大学 Arrayed silver nanorods with surface-modifying gold nanoparticles and preparation method thereof
CN103409750B (en) * 2013-08-15 2015-08-19 南京邮电大学 Array type Silver nanorod of a kind of finishing gold nano grain and preparation method thereof
CN103504454A (en) * 2013-09-11 2014-01-15 江南大学 Food dipping method based on strong electrolyte ion current controlled by function signal
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CN104086719A (en) * 2014-07-02 2014-10-08 齐鲁工业大学 Preparation method of ferroferric oxide/polystyrene/silver nano-composite particles
CN104128603A (en) * 2014-08-13 2014-11-05 厦门大学 Metal nanoparticle wrapped by zirconium-based porous shell and preparing method of metal nanoparticle
CN104162665B (en) * 2014-08-29 2017-01-11 华东理工大学 Gold-organic silicon-gold multilayer core-shell nano-structure and preparing method and application thereof
CN104162665A (en) * 2014-08-29 2014-11-26 华东理工大学 Gold-organic silicon-gold multilayer core-shell nano-structure and preparing method and application thereof
CN104181144A (en) * 2014-09-10 2014-12-03 齐鲁工业大学 Preparation method of ferroferric oxide/polystyrene/titanium dioxide/silver nanometer composite material
CN104807802A (en) * 2015-04-03 2015-07-29 南京邮电大学 Surface enhanced raman scattering base and in-situ growth method thereof
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CN107245196A (en) * 2017-06-22 2017-10-13 成都爱兴生物科技有限公司 Multilayer assembles the preparation method of micron size polystyrene magnetic composite microsphere
CN108827929A (en) * 2018-04-17 2018-11-16 华东理工大学 A kind of SERS probe and preparation method thereof based on MOFs
CN109470683A (en) * 2018-10-23 2019-03-15 江苏大学 A method of 2,4-D is carried out with SERS substrate combination multiple linear regression model and is quickly detected
CN112683871A (en) * 2021-01-05 2021-04-20 武双 Soil chromium ion content detection method
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