CN102699321B - 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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CN102699321B
CN102699321B CN201210190080.2A CN201210190080A CN102699321B CN 102699321 B CN102699321 B CN 102699321B CN 201210190080 A CN201210190080 A CN 201210190080A CN 102699321 B CN102699321 B CN 102699321B
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layer
microsphere
coupling structure
metal carbonyl
carbonyl coat
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CN102699321A (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

Plasma coupled structure microballoon and preparation method thereof for a kind of surface-enhanced Raman
Technical field
The present invention relates to the material in a kind of biological medicine, the separated detection technique of fine chemicals field and preparation method thereof, particularly, relate to a kind of surface-enhanced Raman 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, in chemistry, biological medicine, in detecting, is widely used.At present, there have been a lot of methods can prepare the substrate with SERS effect.For example, the nano level metal film that the coarse precious metal surface of the most common electrochemical deposition, sputter form, the metal-sol of preparation etc.In said method, metal-sol preparation method is the simplest, and enhancement effect is high, and in SERS detects, application is more extensive.But the nano particle particle size that gold, silver colloidal sol obtains is controlled difficulty, and very easily reunite, particularly, after adding thing to be detected, colloidal sol is more unstable, finally causes the poor repeatability of SERS signal, cannot realize quantitative analysis.
In recent years, utilize hollow silver microballoon to replace metal-sol to be used to Raman detection, such as the old intelligent grade (CN 101905330 A) of keeping of Shanghai Communications University, by reacting with ascorbic acid after streptococcus thermophilus is mixed with silver nitrate, obtain hollow silver microballoon.Although this class base material has good Raman to strengthen effect, cannot recycle after these substrate one-time detection of being prepared by noble metal.Therefore, the magnetic nucleocapsid structure microballoon of tool is used in again SERS 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 not with respect to silver (450 nm), and independent silver particles does not have the biocompatibility that gold particle is good, these shortcomings all will affect in the utilization aspect biological medicine Raman detection.So Jin Heyin is carried out compound, utilize between them long-range or the resonance of short distance conjugation, can improve the sensitivity of Raman technology 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 as follows:
A plasma coupled structure microballoon for surface-enhanced Raman, described plasma coupled structure microballoon be take magnetic microsphere as kernel, in described kernel outside, successively forms metal carbonyl coat I, nonmetal separation layer and metal carbonyl coat II; The thickness of described metal carbonyl coat I or metal carbonyl coat II is 0～50 nm, and the thickness of described nonmetal separation layer is 0～100 nm; The particle diameter of described plasma coupled structure microballoon is 300～1000 nm, and specific saturation magnetization is 10～50 emu/g.
The thickness of described nonmetal separation layer is 10～30 nm.
Described magnetic microsphere is tri-iron tetroxide (Fe 3o 4) microballoon.
Described metal carbonyl coat I or metal carbonyl coat II are the metal shells that gold or silver deposit by interfacial reaction.
Described nonmetal separation layer refers to the intermediate layer of the two kinds of Shell Materials in interval, comprises nonmetallic materials in general sense, as silica (SiO 2), titanium oxide (TiO 2), the inorganic material such as zinc oxide (ZnO), the macromolecular materials such as polystyrene (PS), PMA (PMMA), polyelectrolyte, shitosan.
A preparation method for plasma coupled structure microballoon for surface-enhanced Raman, comprises the steps:
(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, 150～200 ℃ of solvent heat treatment, prepare Fe 3o 4magnetic microsphere;
(2) utilize the direction of growth of the polyvinylpyrrolidone restriction metal of molecular weight 5000～70000, the Fe finally making in step (1) 3o 4magnetic microsphere surface forms fine and close metal carbonyl coat I, obtains complex microsphere;
(3) by sol-gal process, nonmetal separation layer is coated on the complex microsphere that step (2) obtains;
(4) on the complex microsphere surface of processing through step (3), by the method for self assembly layer by layer, introduce seed metallization, by interface growth, form metal shell, i.e. metal carbonyl coat II; The method of described self assembly layer by layer refers to 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 described step (3) is SiO 2layer, utilizes ethyl orthosilicate to form colloidal sol in the solution of second alcohol and water, and a certain amount of microballoon be impregnated in described colloidal sol, and the complex microsphere superficial growth that utilizes the base catalysts such as ammoniacal liquor, NaOH, KOH to obtain in step (2) forms fine and close SiO 2layer.
In described step (4), cationic polyelectrolyte generally has: PAH (PAH), polymine (PEI), diallyl dimethyl ammoniumchloride (PDDA) etc., anionic polyelectrolyte can be selected PSS (PSS), polyacrylic acid (PAA) etc.
Utilize Electrostatic Absorption by metal cation (as Ag +, Cu 2+deng) be adsorbed in anionic polymer surface, and metallate ion is (as AuCl 4 -, PtCl 6 2-deng) be adsorbed in cationic polyelectrolyte surface.By reducing agent (as NaBH 4, KBH 4deng) metal ion is reduced into metallic particles, be about to seed metallization and introduce complex microsphere surface, finally by interface growth, form metal shell, as the karat gold reducing process the present invention relates to, the microballoon that adds ADSORPTION OF GOLD seed in the karat gold solution configuring, the reduction of utilizing formaldehyde by 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 apply aspect Raman detection, by prepared complex microsphere is immersed in to 10 -4～10 -9in the RdB aqueous solution of mol/L, by magnet adsorption, converge, direct-detection is assembled the Raman signal of microballoon.
The present invention prepares special controlled, the new technology of the material structure of design, raw material is simple, equipment energy consumption is low, has magnetic separating property, can be applicable to bio-separation and detect, and during for detection of Raman enhancement effect, its detection can reach 10 -9mol/L; The present invention is applicable to photochemical catalysis, and the fields such as disease detection and food security can be realized the realization separation such as biological medicine molecule and SERS are detected to integrated application prospect simultaneously.Regulate the thickness of each layer, prepare multifunction magnetic gold and silver long-range plasma resonance microballoon.
Accompanying drawing explanation
Fig. 1 is Fe in embodiment 3 3o 4@Ag-SiO 2-Au complex microsphere forming process schematic diagram;
Fig. 2 is the TEM figure of different composite microballoon in embodiment 3 processes, and a is Fe 3o 4@Ag, b is Fe 3o 4@Ag-SiO 2, c is Fe 3o 4@Ag-SiO 2the TEM figure of-Au;
Fig. 3 is Fe in embodiment 3 3o 4@Ag-SiO 2-Au detects 10 -4～10 -9mol/L RdB Raman spectrogram.
The specific embodiment
Below in conjunction with embodiment, further illustrate content of the present invention, but these embodiment do not limit the scope of the invention.
Embodiment 1
The preparation method of plasma coupled structure microballoon for surface-enhanced Raman, comprises the steps:
(a) solvent hydro-thermal legal system is for Fe 3o 4magnetic microsphere
Take successively ferric trichloride 0.650 g, water acetic acid sodium 1.000 g, trisodium citrate 0.250 g, gets 20 mL
Ethylene glycol, is stirred to solution homogeneous.Solution is transferred in 50 mL water heating kettles to 200 ℃ of hydro-thermal 10 h.Naturally cool to room temperature, with ethanol and water washing, obtain Fe 3o 4the average-size of magnetic microsphere is 330 nm.
(b) Ag layer is coated
Take 0.200g Fe 3o 4, 0.100g AgNO 3with 2.500g PVP-K30, measure 24 mL ethylene glycol,
At 100 ℃, react 12 hours.With ethanol and deionized water washing, desciccate obtains Fe 3o 4@Ag complex microsphere.About 9 nm of Ag layer thickness.@represents nucleocapsid structure, and the material before@represents nuclear material ,@expression Shell Materials below, and represent successively shell structurre from the inside to the outside from left to right.
(c) SiO 2being coated of layer
Weigh 0.2g Fe 3o 4@Ag powder, is scattered in 10 mL water, gets 40 mL ethanol, adds 0.14 mL
Concentrated ammonia liquor, finally adds 0.57 mL ethyl orthosilicate, 25 ℃ of 8 hours reaction time.After question response finishes, use magnet separated, washing, desciccate obtains Fe 3o 4@Ag-SiO 2complex microsphere.The SiO preparing 2layer thickness is about 90 nm.
(d) Au layer is coated
Weigh 0.2g Fe 3o 4@Ag-SiO 2powder adds PAH 7 mL of 2g/L, and ultrasonic 30 minutes, separation was washed
Wash.Add 0.1% HAuCl 47 mL, adsorb separating, washing after 30 minutes.Finally add 0.1M NaBH 4solution, reacts 30 minutes, and washing is dry.Preparation karat gold solution.Take 0.100g K 2cO 3in 600 mL, add 400 mL water, stir 10 minutes.Add 1% HAuCl 46 mL, continue to stir 30 minutes.Get the above-mentioned dried powder of 0.2g, ultrasonic 30 minutes.Finally add 0.035 mL HCHO, react 30 minutes, separating, washing, the dry end product Fe that obtained 3o 4@Ag-SiO 2-Au.About 5 nm of Au layer thickness.
(e) particle diameter approximately 540 nm of final complex microsphere, specific saturation magnetization is 15 emu/g, to the Raman signal of RdB is minimum, detects 10 -6mol/L.
Embodiment 2
The preparation method of plasma coupled structure microballoon for surface-enhanced Raman, comprises the steps:
(a) solvent hydro-thermal legal system is for Fe 3o 4magnetic microsphere is as above-described embodiment 1.
(b) be directly coated Ag layer and Au layer, intermediate layer is cancelled.Specific implementation method is as step (b) in embodiment 1 and step (d).
(c) particle diameter approximately 360 nm of final complex microsphere, specific saturation magnetization is 45 emu/g, to the Raman signal of RdB is minimum, detects 10 -7mol/L.
Embodiment 3
The preparation method of plasma coupled structure microballoon for surface-enhanced Raman, comprises the steps:
(a) solvent hydro-thermal legal system is for Fe 3o 4magnetic microsphere is as above-described embodiment 1.
(b) coated Ag layer.Specific implementation method is as the step of embodiment 1 (b).If Fig. 2 a is at Fe 3o 4surface has formed one deck Ag layer, i.e. Fe 3o 4@Ag, about 9 nm of its thickness.
(c) reduce consumption and the reaction time of ethyl orthosilicate coated thin SiO 2layer.Method of operating is as follows: weigh 0.2g Fe 3o 4@Ag powder, is scattered in 10 mL water, gets 40 mL ethanol, adds 0.14 mL concentrated ammonia liquor, finally adds 0.14 mL ethyl orthosilicate, 25 ℃ of 6 hours reaction time.After question response finishes, use magnet separated, washing, desciccate obtains Fe 3o 4@Ag-SiO 2complex microsphere.The SiO forming 2about 15 nm(of layer are as Fig. 2 b)
(d) coated Au layer.Specific implementation method is as the step of embodiment 1 (d).As Fig. 2 c can see golden particle at microballoon at outermost layer, about 5 nm of its Au layer thickness.
(e) particle diameter approximately 420 nm of final complex microsphere, specific saturation magnetization is 37 emu/g, as Fig. 3 detects 10 to the Raman signal of RdB is minimum -9mol/L.

Claims (3)

1. a preparation method for plasma coupled structure microballoon for surface-enhanced Raman, comprises the steps:
(1) ferric trichloride 0～1.0g, sodium acetate 0～1.0g, trisodium citrate 0～0.25g and ethylene glycol 0～20mL are stirred, 150～200 ℃ of solvent heat treatment, prepare Fe 3o 4magnetic microsphere;
(2) utilize the direction of growth of the polyvinylpyrrolidone restriction metal of molecular weight 5000～70000, the Fe finally making in step (1) 3o 4magnetic microsphere surface forms fine and close metal carbonyl coat I, obtains complex microsphere;
(3) by sol-gal process, nonmetal separation layer is coated on the complex microsphere that step (2) obtains;
(4) on the complex microsphere surface of processing through step (3), by the method for self assembly layer by layer, introduce seed metallization, by interface growth, form metal shell, i.e. metal carbonyl coat II; The method of described self assembly layer by layer refers to 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 thickness of described metal carbonyl coat I or metal carbonyl coat II is that the thickness of 0～50nm and described metal carbonyl coat I and metal carbonyl coat II is not all 0, and the thickness of described nonmetal separation layer is 0～100nm and is not 0; The particle diameter of described plasma coupled structure microballoon is 300～1000nm, and specific saturation magnetization is 10～50emu/g.
2. preparation method according to claim 1, is characterized in that, the nonmetal separation layer of described step (3) is SiO 2layer, utilizes ethyl orthosilicate to form colloidal sol in the solution of second alcohol and water, and a certain amount of microballoon be impregnated in described colloidal sol, and the complex microsphere superficial growth that utilizes base catalyst to obtain in step (2) forms fine and close SiO 2layer.
3. preparation method according to claim 1, it is characterized in that, in described step (4), cationic polyelectrolyte is PAH, polymine or diallyl dimethyl ammoniumchloride, and anionic polyelectrolyte is PSS 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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