CN102944543B - Method and device for detecting ultra trace sample based on surface-enhanced Raman spectroscopy - Google Patents
Method and device for detecting ultra trace sample based on surface-enhanced Raman spectroscopy Download PDFInfo
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method and device for detecting an ultra trace sample based on surface-enhanced Raman spectroscopy (SERS). The device disclosed herein comprises an SERS optrode and a sample adaptive positioner having a groove structure with super-hyophobic characteristics. The method disclosed herein is characterized in that: a sample solution adheres to a super-hyophobic substrate without infiltration to form spherical liquid drops, but the sample solution adheres to the SERS optrode with infiltration; with the evaporation of the solvent, the sample liquid drops turns smaller and leave the super-hyophobic surface, solutes are concentrated and deposited at the head of the SERS optrode, thus the unit area concentration of the detected object is raised, and high-sensitivity analysis is realized. According to the invention, the amount (10-20 muL) of the required sample solution is few, the analysis sensitivity is high (e.g. the actual detection limit of pesticide Hostathion is only 20pg.), the method disclosed herein can be widely applied in the analysis and detection of trace materials in the fields of homeland security, environmental monitoring, food safety, medical health, etc.
Description
Technical field
The present invention relates to Molecular Spectral Analysis detection field, be specifically related to utilize auroral poles technology and the super lyophobic material of optical fiber as SERS carrier, and auroral poles induction evaporation pre-concentration analytical technology based on super lyophobic material.
Background technology
Illumination is mapped on material elastic scattering and inelastic scattering occurs, and the scattered light of elastic scattering is the composition identical with excitation wavelength, and inelastically scattered scattered light has the composition long and shorter than excitation light wave, is referred to as Ramam effect; Because vibrational spectrum is the fingerprint of material molecule, the Raman spectrometer of making according to Ramam effect can be for accurate qualitative discriminating sample.The analytical approach of Raman spectrum does not generally need sample to carry out pre-treatment, and easy and simple to handle in analytic process, and minute is short, is a kind of analytical technology that can simultaneously carry out to sample quantitative and qualitative analysis, has application prospect very widely.But, its lower sensitivity has limited the large-scale application of this technology.
Surface enhanced raman spectroscopy (SERS) is a kind of high sensitivity spectral analysis technique growing up along with Nano-technology Development in the nineties in 20th century.The same with Raman spectrum, SERS can be for accurate qualitative discriminating sample.SERS has the sensitivity for analysis of superelevation, and more common Raman analysis sensitivity improves approximately 10 orders of magnitude, can analyze the little molecule that arrives, and arrives greatly the research object of cellular level.In prior art, SERS detects generally three kinds of modes: in sample solution, add nano material, and induced nano particle assembles to form SERS focus; In SERS substrate, directly drip sample solution, allow it sprawl, to be dried and to analyze; And SERS auroral poles is inserted to sample solution collection signal etc.Aforesaid way has shortcomings.For example, directly drip the mode reappearance extreme difference of nano particle; In SERS substrate, drip sample and depend on SERS substrate, simultaneously because sample can be sprawled in substrate, unit area sample concentration can be restricted, i.e. sensitivity meeting is lower.SERS auroral poles has good execute-in-place prospect, but required sample size is still in mL level, and sensitivity has room for promotion.In general, these three kinds of modes are also had any problem for the detection of composition in (surpassing) trace samplings, can not obtain enough accurate results.
At the bottom of having there is super-hydrophobic SERS dual-functional group in document recently.Its ultimate principle is when sample solution drop is in SERS substrate when evaporation drying, because substrate has super-hydrophobicity, very little [the Xu et al of drop contact area (the final distribution area of solute), Journal of Physical Chemistry C, 115 (2011) 9977.], solute even wherein can shrink and be concentrated to a bit [De Angeliset al, Nat Photon, 5 (2011) 682.] with drop.Therefore, the per unit area concentration of final analysis is just greatly improved, and has report to show to have the auxiliary SERS substrate in super-hydrophobic interface not have super-hydrophobic auxiliary substrate sensitivity to improve approximately 1～4 order of magnitude.
But, existing difunctional SERS substrate also has more defect.Wherein topmost problem is because final concentrated point is less, must find by high-performance microscope, and this not only needs skilled operative technique, more needs the time.These shortcomings make it be difficult to become a kind of analysis in situ of maturation.In addition, the manufacturing technology with the SERS substrate of higher enhancer also depends on micro-nano process technology, and cost is also higher.Finally, at the bottom of existing dual-functional group, all belong to super hydrophobic material, extract and usually with an organic solvent treat analytic sample in on-the site analysis.This just makes the existing technology scope of application be limited to.Therefore, also need one can with Portable Raman spectrometer coupling, the same concentrated trace of super lyophoby performance or the ultratrace composition sample molecule of utilizing is to improve sensitivity for analysis, but can realize preferably Sample location, required sample solution is at μ L level SERS analysis device, for Homeland Security, environmental monitoring, food security and medicine and hygiene fields.
Summary of the invention
In view of this, the object of this invention is to provide a kind of adaptive location Surface enhanced raman spectroscopy analysis device, can realize preferably Sample location, thereby in analytical solution, do not need larger amount of solution (μ L level) when composition, utilize concentrated trace or the ultratrace composition analyzed of super lyophoby interface assisted evaporative, be applicable to Homeland Security, environmental monitoring, food security and medicine and hygiene fields.
The method that detects ultratrace sample based on surface-enhanced Raman of the present invention, comprises the following steps:
A drips testing sample solution in super lyophobic group basal surface, forms spherical droplets;
B simultaneously SERS auroral poles immerses spherical droplets from drop top, and solution droplets diminishes gradually and concentrates after due to solvent evaporation and is deposited on SERS auroral poles head;
C utilizes surface-enhanced Raman spectroscopy to record solutes content and obtains the solutes content in solution.
Further, SERS auroral poles is multimode or the single-mode fiber that end self assembly has any one or two kinds of combinations in gold, silver, gold-silver alloy nanoparticles;
Further, SERS auroral poles self assembly structure processing formation through the following steps:
Plastics cushion is removed in I optical fiber one end;
It is in 1:3 hydrogen peroxide-concentrated sulfuric acid solution that the optical fiber end described in step I is soaked in volume ratio by II, processes 10-120 minute for constant temperature 30-80 degree Celsius;
III step II optical fiber end after treatment is soaked in coupling agent-organic solvent solution of volumn concentration 1-10% more than 10 hours;
IV is placed in 0.1 ~ 3 mM nano-particle solution by optical fiber end after treatment step III and soaks more than 24 hours;
V is placed in volumn concentration 2-10% coupling agent solution by optical fiber end after treatment step IV and soaks more than 20 minutes;
VI is placed in nano particle by optical fiber end after treatment step V and soaks more than 1 hour;
VII repeating step V and VI, until obtain the required nano particle number of plies;
VIII is placed in vacuum or atmosphere of inert gases by the optical fiber of the Nanoparticle Modified of acquisition and within the scope of 80-140 degree Celsius, heats and within 20-60 minute, obtain SERS auroral poles;
Further, the coupling agent solution in step V is any one or the two or more potpourri in the ethanolic solution of amino silane hydrating solution, hydrosulphonyl silane hydrating solution and dimercaptan;
Further, the optical fiber cover top layer of SERS auroral poles optical fiber end after treatment is super-hydrophobic layer or super-hydrophobic-oleophobic layer, the surface enhancement that fiber core end is Nanoparticle Modified;
Further, in step II, it is in 1:3 hydrogen peroxide-concentrated sulfuric acid solution that optical fiber end is soaked in to volume ratio, 80 degrees Celsius of processing of constant temperature 30 minutes;
In step III, optical fiber end be soaked in the ethanol of hydrophobic compound of volumn concentration 1-10% or acetone soln in more than 10 hours;
In step IV, optical fiber end is placed in the water-organic solvent solution that contains silver nitrate and trisodium citrate more than 24 hours; Wherein, the concentration of silver nitrate is 0.1mM to 10mM, and the concentration of silver nitrate and the concentration ratio of trisodium citrate are 0.2 to 2; Organic solvent is any one or the two or more potpourri in methyl alcohol, ethanol, isopropyl alcohol and acetonitrile; Organic solvent and water volume ratio are 0.05 to 2;
In step IV, optical fiber after treatment imports 632.8 Ear Mucosa Treated by He Ne Laser Irradiations of 2-30mW at the optical fiber other end, and the reaction time is 2-30min;
Further, hydrophobic compound be alkylchlorosilane, containing one or more the potpourri in fluoroalkyl Group chlorsilane, flucride siloxane and stearic acid;
Further, at the bottom of super lyophobic group, be the sand paper substrate that surface has super-hydrophobic layer or super-hydrophobic-oleophobic layer;
Further, being configured to by coated abrasive surface coating nanometer polytetrafluorethylenano nano powder at the bottom of super lyophobic group, then obtain at 100-200 degree Celsius of scope internal heating curing.
The invention also discloses a kind of device that detects ultratrace sample based on surface-enhanced Raman, comprise and have the Raman spectrometer of SERS auroral poles and the sample adaptive location device of level and smooth groove type structure, described sample adaptive location device opening upwards and SERS auroral poles are just to its inside surface minimum point; Sample adaptive location device inside surface is super-hydrophobic substrate.
Beneficial effect of the present invention: portable self-adapted locating surface of the present invention strengthens Raman spectrum analysis device, adopt super lyophobic group bottom structure, maximum feature is to use SERS auroral poles to induce the evaporation and concentration at super lyophoby interface compared with existing SERS-super-hydrophobic double-functional material, thereby makes the directed concentrated auroral poles head that is gathered in of solute.Therefore, the present invention, without utilizing the concentrated point of large-scale microscope search, can combine with existing Portable Raman spectrometer, thereby greatly improve the sensitivity of on-the site analysis, be applicable to ultratrace sample, be applicable to Homeland Security, environmental monitoring, food security and medicine and hygiene fields; The sample adaptive location device of groove type structure, and auroral poles is just to its minimum point, and sample is positioned at low spot after splashing into sample adaptive location device under Action of Gravity Field, because amount is less, thereby be easy to smooth evaporating solvent, thereby in auroral poles head concentrating sample composition to be detected.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is apparatus of the present invention structural principle schematic diagram;
Fig. 2 is auroral poles of the present invention and substrate the first structural principle;
Fig. 3 is auroral poles of the present invention and substrate the second structural principle;
Fig. 4 is the process schematic diagram that auroral poles is induced super-hydrophobic interfacial process;
The SERS spectrogram of the Raman microprobe Nai Er indigo plant that Fig. 5 the present invention obtains.
Embodiment
Fig. 1 is apparatus of the present invention structural principle schematic diagram, Fig. 2 auroral poles of the present invention and substrate knot principle meaning, and Fig. 3 is the process schematic diagram that auroral poles is induced super-hydrophobic interfacial process, the SERS spectrogram of the Raman microprobe Nai Er indigo plant that Fig. 4 the present invention obtains;
As shown in Figure 3, detect the method for ultratrace sample based on surface-enhanced Raman, comprise the following steps:
A drips testing sample solution in super lyophobic group basal surface, forms spherical droplets; Dripping is the amount of conventional titration experiments;
B simultaneously SERS auroral poles immerses spherical droplets from drop top, and solution droplets diminishes gradually and concentrates after due to solvent evaporation and is deposited on SERS auroral poles head;
C utilizes surface-enhanced Raman spectroscopy to record solutes content and obtains the solutes content in solution.
As shown in Figure 4, after sample solution 18 drips in the super-hydrophobic layer 13 on 7 surfaces at the bottom of super lyophobic group, formation is approximate spherical, and is positioned at all the time bottom with volatilization; Finally, because auroral poles 5 has water wettability, when solution narrows down to a certain degree, when its capillary force is enough to customer service gravity, drop can be adsorbed on auroral poles head and the most at last solute 19 deposition on it, form SERS21 by incident laser 20.
In the present embodiment, SERS auroral poles is multimode or the single-mode fiber that end self assembly has any one or two kinds of combinations in gold, silver, gold-silver alloy nanoparticles; The present embodiment is silver.
In the present embodiment, SERS auroral poles through the following steps self assembly builds processing formation:
I optical fiber end is removed plastics cushion.
It is in 1:3 hydrogen peroxide-concentrated sulfuric acid solution that optical fiber end is soaked in volume ratio by II, processes 10-120 minute for constant temperature 30-80 degree Celsius;
III step II optical fiber end after treatment is soaked in coupling agent-organic solvent solution of volumn concentration 1-10% more than 10 hours;
IV is placed in 0.1 ~ 3 mM nano-particle solution by optical fiber end after treatment step III and soaks more than 24 hours;
V is placed in volumn concentration 2-10% coupling agent solution by optical fiber end after treatment step IV and soaks more than 20 minutes;
VI is placed in nano particle by optical fiber end after treatment step V and soaks more than 1 hour;
VII repeating step V and VI, until obtain the required nano particle number of plies;
VIII is placed in vacuum or atmosphere of inert gases by the optical fiber of the Nanoparticle Modified of acquisition and within the scope of 80-140 degree Celsius, heats and within 20-60 minute, obtain SERS auroral poles; Inert gas adopts as N
2, Ar; In the present embodiment, temperature is 100 degrees Celsius, and the heat time is 40 minutes;
In the present embodiment, the coupling agent solution in step V is any one or the two or more potpourri in the ethanolic solution of amino silane hydrating solution, hydrosulphonyl silane hydrating solution and dimercaptan; The present embodiment is selected dimercaptan, certainly can adopt amino silane hydrating solution and hydrosulphonyl silane hydrating solution to substitute, and through test, effect is identical.
In the present embodiment, in step II, it is in 1:3 hydrogen peroxide-concentrated sulfuric acid solution that optical fiber end is soaked in to volume ratio, 80 degrees Celsius of processing of constant temperature 30 minutes; Certainly, constant temperature can be within the scope of 30-80 degree Celsius, and the processing time can, within the scope of 10-120 minute, all can be realized goal of the invention;
In step III, optical fiber end be soaked in the ethanol of hydrophobic compound of volumn concentration 1-10% or acetone soln in more than 10 hours; In the present embodiment, selecting volumn concentration is 5%; Certainly, within the scope of volumn concentration 1-10%, there is no obvious difference;
In step IV, optical fiber end is placed in the water-organic solvent solution that contains silver nitrate and trisodium citrate more than 24 hours; Wherein, the concentration of silver nitrate is 0.1mM to 10mM, and the concentration of silver nitrate and the concentration ratio of trisodium citrate are 0.2 to 2, is 1 in the present embodiment; Organic solvent is any one or the two or more potpourri in methyl alcohol, ethanol, isopropyl alcohol and acetonitrile; Organic solvent and water volume ratio are 0.05 to 2, and the present embodiment is 0.8;
In step IV, optical fiber after treatment imports 632.8 Ear Mucosa Treated by He Ne Laser Irradiations of 2-30mW at the optical fiber other end, and the reaction time is 2-30min, does not coexist within the scope of this and adjusts according to laser intensity.
In the present embodiment, hydrophobic compound is alkylchlorosilane, containing one or more the potpourri in fluoroalkyl Group chlorsilane, flucride siloxane and stearic acid, the present embodiment is selected alkylchlorosilane, with alkylchlorosilane being replaced containing fluoroalkyl Group chlorsilane, flucride siloxane and stearic acid, experiment acquired results is basic identical.
In the present embodiment, it at the bottom of super lyophobic group, is the sand paper substrate that surface has super-hydrophobic layer or super-hydrophobic-oleophobic layer; Sand paper adopts abrasive paper for metallograph, has super-hydrophobic layer or super-hydrophobic-oleophobic layer at the working surface of sand paper; Have flexible characteristic, adaptability is stronger.
In the present embodiment, being configured to by coated abrasive surface coating nanometer polytetrafluorethylenano nano powder at the bottom of super lyophobic group, then obtain at 100-200 degree Celsius of scope internal heating curing.
As depicted in figs. 1 and 2, the invention also discloses a kind of device that detects ultratrace sample based on surface-enhanced Raman, comprise and have the Raman spectrometer of SERS auroral poles and the sample adaptive location device of level and smooth groove type structure, described sample adaptive location device opening upwards and SERS auroral poles are just to its inside surface minimum point; Sample adaptive location device inside surface is super-hydrophobic substrate.
In the embodiment in figure 1,1 is portable computer; 2 is Portable Raman spectrometer; 3 is special optical fiber conversion connector; 4 for connecting optical fiber; 5 is SERS auroral poles; 6 is sample solution; 7 is the super lyophoby of groove type interface; 8 is support.Wherein, the laser that Portable Raman spectrometer 2 sends enters SERS auroral poles through 3 and 4 switchings.After sample solution 6 evaporates on super lyophoby concave surface 7, its solute will be gathered in the just end of the auroral poles 5 to concave surface center.The SERS signal of its generation returns along original optical path, is converted to electric signal and is included by computing machine 1 after 2 light-splitting processing; The effect at super lyophoby interface 7 is to ensure that in solution, solute is only concentrated at SERS auroral poles 5 heads, the same with auroral poles 5, is core of the present invention.
As shown in Figure 2, also comprise support 8, SRES auroral poles 5, and super lyophoby concave surface 7.Described sample adaptive location device 7 opening upwards and auroral poles 5 are just to its inside surface minimum point, auroral poles 5 and sample adaptive location device 7 all need to have fixing location structure, the just minimum point to sample adaptive location device 7 inside surfaces of auroral poles after stationary positioned, the mechanical system that can adopt prior art, does not repeat them here; The present invention is simple and compact for structure, and auroral poles 5 is formed by optical fiber, and optical fiber is born transmission excitation laser and SERS signal simultaneously; SERS auroral poles is extremely low to the requirement of sample preparation (sampling) and instrument light path, and cheapness can abandon, and has greatly reduced cost.
In the present embodiment, auroral poles 5 can be by two kinds of implementations:
Preferably as shown in Figure 2,9 is fiber core to structure; 10 is fiber reflection layer; 11 is plastic protective layer; 12 is the metal nano material that gold, silver, copper etc. can produce SERS; 13 is the super lyophobic layers of concave surface; 8 is support; 15 is solution droplets; 16 is incident light; 14 is the SERS signal reflecting; 18 is auroral poles super-hydrophobic layer; Noble metal nanometer material is not coated whole optical fiber head, but after first modified optical fiber being become to lyophoby performance, forms in fibre core original position.Owing to only having, the nano material at fibre core position is hydrophilic, and in the time that drop is adsorbed on auroral poles, solute will only deposit at fibre core position; Therefore, its major advantage be unit area after evaporation and concentration sample (solute) concentration by have compared with scheme 1 at least one order of magnitude increase (with fibre core 60 μ m, fibre diameter 200 μ m calculate,
Metal nano material 12 can be various metal nano material, but taking the enhancement effect of the irregular nanocrystal of Ag as best, repeatedly after self assembly, forms the SERS substrate of high sensitivity and high reliability.
The another kind of embodiment of auroral poles 5 can be the coated whole optical fiber head of metal nano material.
In the present embodiment, described sample adaptive location device 13 is fixedly connected on support 14, is detachable fixed connection structure, is threaded connection or clamping all can.Auroral poles 5 can adopt hard sheath to install, and makes optical fiber have good intensity, convenient location; Easy accessibility, simply compact; Fixed form can make comparatively simple physical construction, until fix and have a good locating effect.
Fig. 5 is the analysis result of the present invention to Raman microprobe Nai Er indigo plant.From top to bottom, a is (2ppb Nai Er indigo plant) in solution; B is (10 μ L 2ppt Nai Er indigo plant) after concentrated, and sample size is only 20 to fly gram.
Experiment shows, the present invention during compared to independent use SERS auroral poles sensitivity improve approximately 3 orders of magnitude, needed sample size is reduced to 10 μ L simultaneously, is applicable to the analysis of ultratrace sample.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (7)
1. a method that detects ultratrace sample based on surface-enhanced Raman, is characterized in that: comprise the following steps:
A drips testing sample solution in super lyophobic group basal surface, forms spherical droplets;
B simultaneously SERS auroral poles immerses spherical droplets from drop top, and solution droplets diminishes gradually and concentrates after due to solvent evaporation and is deposited on SERS auroral poles head; SERS auroral poles is multimode or the single-mode fiber that end self assembly has any one or two kinds of combinations in gold, silver, gold-silver alloy nanoparticles;
C utilizes surface-enhanced Raman spectroscopy to record solutes content and obtains the solutes content in solution;
SERS auroral poles through the following steps self assembly builds processing formation:
Plastics cushion is removed in I optical fiber one end;
It is in 1:3 hydrogen peroxide-concentrated sulfuric acid solution that the optical fiber end described in step I is soaked in volume ratio by II, processes 10-120 minute for constant temperature 30-80 degree Celsius;
III step II optical fiber end after treatment is soaked in coupling agent-organic solvent solution of volumn concentration 1-10% more than 10 hours;
The nano-particle solution that optical fiber end after treatment step III is placed in 0.1～3 mM/every liter by IV is soaked more than 24 hours;
V is placed in volumn concentration 2-10% coupling agent solution by optical fiber end after treatment step IV and soaks more than 20 minutes;
VI is placed in nano-particle solution by optical fiber end after treatment step V and soaks more than 1 hour;
VII repeating step V and VI, until obtain the required nano particle number of plies;
VIII is placed in vacuum or atmosphere of inert gases by the optical fiber of the Nanoparticle Modified of acquisition and within the scope of 80-140 degree Celsius, heats and within 20-60 minute, obtain SERS auroral poles.
2. the method that detects ultratrace sample based on surface-enhanced Raman according to claim 1, is characterized in that: the coupling agent solution in step V is any one or the two or more potpourri in the ethanolic solution of amino silane hydrating solution, hydrosulphonyl silane hydrating solution and dimercaptan.
3. the method that detects ultratrace sample based on surface-enhanced Raman according to claim 2, it is characterized in that: the optical fiber cover top layer of SERS auroral poles optical fiber end after treatment is super-hydrophobic layer or super-hydrophobic-oleophobic layer, the surface enhancement that fiber core end is Nanoparticle Modified.
4. the method that detects ultratrace sample based on surface-enhanced Raman according to claim 3, is characterized in that: in step II, it is in 1:3 hydrogen peroxide-concentrated sulfuric acid solution that optical fiber end is soaked in to volume ratio, 80 degrees Celsius of processing of constant temperature 30 minutes;
In step III, optical fiber end is soaked in the ethanol of hydrophobic compound of volumn concentration 1-10% or acetone soln more than 10 hours;
In step IV, optical fiber end is placed in the water-organic solvent solution that contains silver nitrate and trisodium citrate more than 24 hours; Wherein, the concentration of silver nitrate is 0.1mM to 10mM, and the concentration of silver nitrate and the concentration ratio of trisodium citrate are 0.2 to 2; Organic solvent is any one or the two or more potpourri in methyl alcohol, ethanol, isopropyl alcohol and acetonitrile; Organic solvent and water volume ratio are 0.05 to 2;
In step IV, optical fiber after treatment imports 632.8 Ear Mucosa Treated by He Ne Laser Irradiations of 2-30mW at the optical fiber other end, and the reaction time is 2-30min.
5. the method that detects ultratrace sample based on surface-enhanced Raman according to claim 4, is characterized in that: hydrophobic compound is alkylchlorosilane, containing one or more the potpourri in fluoroalkyl Group chlorsilane, flucride siloxane and stearic acid.
6. the method that detects ultratrace sample based on surface-enhanced Raman according to claim 1, is characterized in that: at the bottom of super lyophobic group, be the sand paper substrate that surface has super-hydrophobic layer or super-hydrophobic-oleophobic layer.
7. the method that detects ultratrace sample based on surface-enhanced Raman according to claim 6, it is characterized in that: being configured to by coated abrasive surface coating nanometer polytetrafluorethylenano nano powder at the bottom of super lyophobic group, then obtain at 100-200 degree Celsius of scope internal heating curing.
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| CN113138186A (en) * | 2021-05-27 | 2021-07-20 | 福建师范大学 | Super-hydrophobic automatic positioning SERS spectrum detection platform and preparation method and application thereof |
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