CN107057257B - A kind of surface enhanced Raman scattering substrate of pH response type template assemblies, preparation method and the method using the substrate detection molecules - Google Patents

A kind of surface enhanced Raman scattering substrate of pH response type template assemblies, preparation method and the method using the substrate detection molecules Download PDF

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CN107057257B
CN107057257B CN201710260419.4A CN201710260419A CN107057257B CN 107057257 B CN107057257 B CN 107057257B CN 201710260419 A CN201710260419 A CN 201710260419A CN 107057257 B CN107057257 B CN 107057257B
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gold
substrate
raman scattering
preparation
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CN107057257A (en
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吴义平
张霞
杨本宏
刘伟芳
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Hefei University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0806Silver
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0831Gold
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

Abstract

The present invention relates to a kind of surface enhanced Raman scattering substrate of pH response type template assemblies, preparation method and utilize the method for the substrate detection molecules.Template on its Raman scattering substrate is the poly- divinyl pyridine sensitive to pH, noble metal gold or silver particles are modified in template, template, which adjusts to generate with pH value, to be shunk and expands, while gold or Nano silver grain gap in dynamic regulation substrate, to form adjustable hot spot;Nano silver grain size is 25~35nm, and the size of composite substrate is about 1 μm.Substrate SERS " hot spot is adjustable " prepared by the present invention drops into testing molecule effectively in substrate " hot spot " range.It selects the polymer of pH sensitivity as template, is mixed with gold, silver nanoparticle and testing molecule, adjust the pH value of solution, can dynamically adjust SERS hot spot.

Description

A kind of surface enhanced Raman scattering substrate of pH response type template assemblies, preparation method And the method using the substrate detection molecules
Technical field
The present invention relates to Surface enhanced Raman scattering technology and relevant detection methods, are specifically related to a kind of pH response Surface enhanced Raman scattering substrate, preparation method and the method using the substrate detection molecules of type template assemblies.
Background technique
It is abundant to be capable of providing testing molecule because having high detection sensitivity for Surface enhanced Raman spectroscopy (SERS) technology Finger print information has been acknowledged as a kind of advanced analysis and detection method.Noble metal gold, silver nanoparticle is often by as SERS Substrate is detected, the plasma resonance between nanoparticle can generate strong electromagnetic field, amplify the Raman signal of testing molecule. Research shows that gap relationships of the enhancing of this signal often between noble metal nano particles are close: on the one hand, working as noble metal When nanoparticle gap is less than 10nm, the electromagnetic field that plasma resonance generates sharply is reinforced, and forms effective SERS hot spot;Separately On the one hand, this SERS hot spot has its effective range, and only when testing molecule is fallen in this hotspot range, the Raman signal of generation is It can largely improve, reach highly sensitive detection.
In existing research, most of detection is all that the noble metal gold, silver nanoparticle that will be synthesized is mixed with testing molecule, Then it is added drop-wise to progress SERS detection on silicon wafer, after this method is simple, but gold, silver Nano sol is added dropwise on silicon wafer, Mutual gap is not regulated and controled, i.e., gap is uneven, and the hotspot's distribution range of formation is big, and testing molecule falls into hot spot Probability it is small, the sensitivity of detection and homogeneity all it is difficult to ensure that.Some studies the synthesis for being dedicated to SERS substrate, right Noble metal nano particles are assembled, and can control in the gap of noble metal nano particles in 10nm hereinafter, still requirement of experiment It is higher, it is difficult to be widely used.
Summary of the invention
It is uneven the technical problem to be solved by the present invention is to overcome existing SERS substrate " hot spot " and molecule is difficult to fall into heat It the problems such as technical deficiency of point effective range, provides a kind of SRES " hot spot is adjustable ", testing molecule is made effectively to drop into base Surface enhanced Raman scattering substrate, preparation method and the utilization substrate inspection of pH response type template assemblies in bottom " hot spot " range The method for surveying molecule.
To achieve the goals above, the technical scheme adopted by the invention is as follows: a kind of surface of pH response type template assemblies Enhance Raman scattering substrate, the template on Raman scattering substrate is the poly- divinyl pyridine sensitive to pH, is modified in template There are noble metal gold or a silver particles, template, which adjusts to generate with pH value, shrinks and expansion, while gold in dynamic regulation substrate or silver are received Rice corpuscles gap, to form adjustable hot spot;Nano silver grain size is 25~35nm, and the size of composite substrate is about 1 μm.
A method of the surface enhanced Raman scattering substrate preparing pH response type template assemblies, first with initiator and Crosslinking agent synthetic polymer template recycles reduction of sodium citrate agent synthesis gold or Nano silver grain, it is molten to adjust polymer template The pH value of liquid is acidity, and gold, silver nanoparticle is mixed to get the adjustable surface enhanced Raman scattering substrate of hot spot.
Preferably, polymer template the preparation method comprises the following steps: the pure water of 50mL is added in the three-necked flask of 250mL, water Bath is heated to 80 DEG C, is passed through nitrogen purification, and the polymer monomer of 0.55g is added after 30min -- divinyl pyridine and 0.04g's Crosslinking agent -- methylene diacrylamine rapidly joins the potassium peroxydisulfate of 0.050g as initiator after mixing 10min, gathers Reaction is closed to start;Solution becomes cloudy after 5~15min of reaction, reacts 80 DEG C of constant temperature lasting 1h;Then stirring is cooled to room temperature, and is Removal some of which oligomer and unconverted monomer carry out resulting polymer solution with the revolving speed of 5000r/min Centrifugation, time 10min is rear to use second distillation water washing 3 times, each ultrasound 10min, by resulting poly- divinyl pyridine point It is dispersed in 50mL ultrapure water stand-by.It is milky when polymer template is shunk, is colorless and transparent when expansion.
Preferably, gold or Nano silver grain the preparation method comprises the following steps: by the secondary distilled water of 99mL, 1mL concentration be 1% chlorine Auric acid or silver nitrate, are added sequentially in the three-necked flask of 250mL, magnetic agitation, and heating water bath is rapidly added matter to after boiling Measuring score is 1% sodium citrate solution 1mL as reducing agent, obtained gold or Nano silver grain;With secondary water supersound washing 3 It is secondary, it is dispersed in the distilled water of 10mL stand-by.Sodium citrate is again simultaneously stabilizer, so that gold, silver nanoparticle is stablized and deposits It is saving for a long time.Obtained aurosol is claret, and silver sol is celadon.
Preferably, surface enhanced Raman scattering substrate the preparation method comprises the following steps: take the polymer template of 0.5mL, use 0.1mol/ The salt acid for adjusting pH value of L takes 0.5mL gold or silver nanoparticle colloidal sol to be added in polymer template solution, fills to acid (about 3) Divide mixing.Finally add certain density testing molecule crystal violet, magnetic agitation 5min.Conventionally, by mixed liquor It is added drop-wise on silicon wafer, detects testing molecule SERS signal.
A method of using the surface enhanced Raman scattering substrate detection molecules of pH response type template assemblies, by polymer Template, gold or silver nanoparticle colloidal sol mix under acidic environment with testing molecule, and the pH value for then adjusting mixed solution is alkalinity, with The contraction of template, gold or Nano silver grain gap reduce, testing molecule by effectively be locked in gold or Nano silver grain between, It has been in it in SERS hotspot range, detection signal measuring obtains the SERS spectrogram of the testing molecule.
Surface enhanced Raman scattering substrate, preparation method and the utilization substrate inspection of pH response type template assemblies of the invention The method for surveying molecule, the principles of science analysis are as follows:
One, select divinyl pyridine as monomer, as crosslinking agent, potassium peroxydisulfate is used as to be drawn methylene diacrylamine Send out agent, the poly- divinyl pyridine polymerizeing as template, this polymer in acid medium since amino is positively charged, phase Repulsion is generated between mutually, therefore polymer is swelling state, when gradually adjusting solution to alkalinity, the proton of amino is gradually dissociated, The positive charge of polymer belt is reduced to last not charged, and repulsion constantly reduces, therefore polymer is gradually received by original swelling state Contracting, volume-diminished.
Two, the selected monomer of polymer template, crosslinking agent and initiator, the signal generated in SERS detection is weaker, The detection of testing molecule will not be had an impact or be interfered.
Three, gold, silver Nano sol is obtained using reduction of sodium citrate gold chloride or silver nitrate, preparation method is simple, fits Preferably save for a long time.When SERS is detected, Nano silver grain is mixed with polymer template, by adjusting the pH value of solution, not only Nano silver grain gap can effectively be regulated and controled, form dynamic SERS hot spot, meanwhile, testing molecule can be locked effectively It is to generate strong SERS signal within the scope of SERS, reach highly sensitive detection between gold, silver nanoparticle.
Compared with the existing technology, beneficial effects of the present invention performance is as follows:
1), in traditional technology synthesis SERS substrate, gold, silver nanoparticle gap cannot effectively be adjusted, obtained SERS Hot spot is uneven, and the SERS signal of generation is unstable, influences the sensitivity of detection.And existing SERS substrate is realized to gold, silver The assemble method of nanoparticle is all relatively complicated, most of all quickly to form " hot spot ", and substrate prepared by the present invention The method of SERS " hot spot is adjustable " is simple, selects the polymer of pH sensitivity as template, with gold, silver nanoparticle and to be measured point Son mixing, adjusts the pH value of solution, can dynamically adjust SERS hot spot.
2), the method for preparation method of the invention and detection molecules is simple, has a vast market application prospect.
Detailed description of the invention
With reference to embodiments with attached drawing to the surface enhanced Raman scattering substrates of pH response type template assemblies of the invention, It preparation method and makes and being discussed further using the method for the substrate detection molecules.
Fig. 1 is the signal that substrate of the invention prepared and carried out to testing molecule Raman spectrum method for detecting surface reinforcement Figure.As seen in Figure 1, gel template is mixed with noble metal nano particles and testing molecule in the expanded state, after The pH value of solution is adjusted, gel template is shunk, and not only reduces the noble metal nano particles gap wherein modified, the SERS of formation Hot spot increases;Meanwhile testing molecule is locked in noble metal nano particles and is formed by hotspot range, SERS detection sensitivity It improves.
The optical photograph and polymer molecule that Fig. 2 is polymer template synthesized in SERS substrate of the invention are with molten Molecule structure change and the contraction generated and dilating principle schematic diagram when liquid pH value changes.As seen in Figure 2, polymer After HCl is added in template, keeps protonated amino positively charged, generate repulsion between each other, template is swelling state, shows nothing Color transparence;When the alkalinity for the pH for adjusting solution, proton is neutralized, and the mutual repulsion of molecule reduces, and template gradually tapers up, It is rendered as milky.This dilation process has good invertibity.
It is formed after polymer (A), Nano silver grain (B) and its mixing in Fig. 3 SERS substrate prepared by the present invention The TEM of compound substrate (C) schemes and its corresponding UV-visible spectrum (D).As seen in Figure 3, Yin Na Rice corpuscles is modified in gel template, and the obvious red shift of silver-colored absorption peak, illustrates Nano silver grain in the composite substrate of formation Gap shrinks.
Specific embodiment
Embodiment 1
Step 1: polymer template the preparation method comprises the following steps:
The pure water of 50mL is added in the three-necked flask of 250mL, heating water bath is passed through nitrogen purification, 30min to 80 DEG C Polymer monomer -- crosslinking agent of divinyl pyridine and 0.04g -- methylene diacrylamine of 0.55g, mixing are added afterwards After 10min, the potassium peroxydisulfate of 0.050g is rapidly joined as initiator, polymerization reaction starts.Solution after 5~15min of reaction It becomes cloudy, reacts 80 DEG C of constant temperature lasting 1h.Then stirring is cooled to room temperature, in order to remove some of which oligomer and unpolymerized Monomer, resulting polymer solution is centrifuged with the revolving speed of 5000r/min, time 10min, after use secondary distilled water Washing 3 times, each ultrasound 10min, resulting poly- divinyl pyridine is dispersed in 50mL ultrapure water for use.
Step 2: Nano silver grain the preparation method comprises the following steps:
The secondary distilled water of 99mL, the silver nitrate that 1mL concentration is 1% are added sequentially in the three-necked flask of 250mL, Magnetic agitation, heating water bath are rapidly added the sodium citrate solution 1mL that mass fraction is 1% as reducing agent, obtain to after boiling To Nano silver grain size be about 35nm.With secondary water supersound washing 3 times, it is dispersed in the distilled water of 10mL for use, obtains The silver sol arrived is celadon.
Step 3: the preparation of surface enhanced Raman scattering substrate and SERS detection:
The polymer template for taking 0.5mL takes 0.5mL silver-colored with the salt acid for adjusting pH value of 0.1mol/L to acid (about 3) Nano sol is added in polymer template solution, is sufficiently mixed.Finally add certain density testing molecule crystal violet, magnetic Power stirs 5min.Conventionally, mixed liquor is added drop-wise on silicon wafer, detects testing molecule SERS signal.
Embodiment 2
Step 1: polymer template the preparation method comprises the following steps:
The pure water of 50mL is added in the three-necked flask of 250mL, heating water bath is passed through nitrogen purification, 30min to 80 DEG C Polymer monomer -- crosslinking agent of divinyl pyridine and 0.04g -- methylene diacrylamine of 0.55g, mixing are added afterwards After 10min, the potassium peroxydisulfate of 0.050g is rapidly joined as initiator, polymerization reaction starts.Solution after 5~15min of reaction It becomes cloudy, reacts 80 DEG C of constant temperature lasting 1h.Then stirring is cooled to room temperature, in order to remove some of which oligomer and unpolymerized Monomer, resulting polymer solution is centrifuged with the revolving speed of 5000r/min, time 10min, after use secondary distilled water Washing 3 times, each ultrasound 10min, resulting poly- divinyl pyridine is dispersed in 50mL ultrapure water for use.
Step 2: gold nanoparticle the preparation method comprises the following steps:
The secondary distilled water of 99mL, the gold chloride that 1mL concentration is 1% are added sequentially in the three-necked flask of 250mL, Magnetic agitation, heating water bath are rapidly added the sodium citrate solution 1mL that mass fraction is 1% as reducing agent, obtain to after boiling To gold nanoparticle size be about 40nm.With secondary water supersound washing 3 times, it is dispersed in the distilled water of 10mL for use, obtains The aurosol arrived is claret.
Step 3: the preparation of surface enhanced Raman scattering substrate and SERS detection:
The polymer template for taking 0.5mL takes 0.5mL golden with the salt acid for adjusting pH value of 0.1mol/L to acid (about 3) Nano sol is added in polymer template solution, is sufficiently mixed.Finally add certain density testing molecule crystal violet, magnetic Power stirs 5min.Conventionally, mixed liquor is added drop-wise on silicon wafer, detects testing molecule SERS signal.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention Design or beyond the scope defined by this claim, be within the scope of protection of the invention.

Claims (6)

1. a kind of surface enhanced Raman scattering substrate of pH response type template assemblies, it is characterised in that: on its Raman scattering substrate Template be the poly- divinyl pyridine sensitive to pH, be modified in template noble metal gold or silver particles, template adjusted with pH value It generates and shrinks and expand, while gold or Nano silver grain gap in dynamic regulation substrate, to form adjustable hot spot.
2. a kind of method for the surface enhanced Raman scattering substrate for preparing pH response type template assemblies as described in claim 1, It is characterized in that, first with initiator and crosslinking agent synthetic polymer template, recycles reduction of sodium citrate agent synthesis gold or silver Nanoparticle, the pH value for adjusting polymer template solution is acidity, and gold, silver nanoparticle is mixed adjustable to get hot spot Surface enhanced Raman scattering substrate.
3. preparation method as claimed in claim 2, which is characterized in that polymer template the preparation method comprises the following steps:
The pure water of 50mL is added in the three-necked flask of 250mL, heating water bath is passed through nitrogen purification, adds after 30min to 80 DEG C Enter the polymer monomer of 0.55g -- crosslinking agent of divinyl pyridine and 0.04g -- methylene diacrylamine, mixes 10min Afterwards, the potassium peroxydisulfate of 0.050g is rapidly joined as initiator, polymerization reaction starts;
Solution becomes cloudy after 5~15min of reaction, reacts 80 DEG C of constant temperature lasting 1h;Then stirring is cooled to room temperature, in order to remove it In some oligomer and unconverted monomer, resulting polymer solution is centrifuged with the revolving speed of 5000r/min, the time Rear to use second distillation water washing 3 times for 10min, resulting poly- divinyl pyridine is dispersed in 50mL by each ultrasound 10min It is stand-by in ultrapure water.
4. preparation method as claimed in claim 3, which is characterized in that gold or Nano silver grain the preparation method comprises the following steps:
By the secondary distilled water of 99mL, the gold chloride or silver nitrate that 1mL concentration is 1%, it is added sequentially to the three-necked flask of 250mL In, magnetic agitation, heating water bath is rapidly added the sodium citrate solution 1mL that mass fraction is 1% and is used as reduction to after boiling Agent, obtained gold or Nano silver grain;With secondary water supersound washing 3 times, it is dispersed in the distilled water of 10mL stand-by.
5. preparation method as claimed in claim 4, which is characterized in that surface enhanced Raman scattering substrate the preparation method comprises the following steps:
The polymer template for taking 0.5mL takes 0.5mL gold or silver nanoparticle colloidal sol with the salt acid for adjusting pH value of 0.1mol/L to acidity It is added in polymer template solution, is sufficiently mixed.
6. a kind of surface enhanced Raman scattering substrate detection molecules using pH response type template assemblies as described in claim 1 Method, which is characterized in that polymer template, gold or silver nanoparticle colloidal sol are mixed under acidic environment with testing molecule, then adjusted The pH value for saving mixed solution is alkalinity, and with the contraction of template, gold or Nano silver grain gap reduce, and testing molecule is effective It is locked between gold or Nano silver grain, has been in it in SERS hotspot range, detection signal measuring obtains the testing molecule SERS spectrogram.
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CN108120709B (en) * 2017-12-25 2020-09-18 合肥工业大学 Capillary micro-droplet metal ball detection method for surface enhanced Raman spectroscopy
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CN112683878A (en) * 2020-12-21 2021-04-20 山东大学 Method for detecting pH of solution based on surface enhanced Raman effect
DE102021127233A1 (en) 2021-10-20 2023-04-20 Endress+Hauser Conducta Gmbh+Co. Kg Sensor for measuring a pH value of a measuring liquid
CN115746360B (en) * 2022-11-24 2023-12-12 无锡学院 Flexible surface-enhanced Raman scattering substrate with adjustable gap, and preparation method and application thereof

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