CN101936906B - Carrier, kit and surface enhanced Raman spectroscopy analysis method - Google Patents
Carrier, kit and surface enhanced Raman spectroscopy analysis method Download PDFInfo
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- CN101936906B CN101936906B CN2009100867788A CN200910086778A CN101936906B CN 101936906 B CN101936906 B CN 101936906B CN 2009100867788 A CN2009100867788 A CN 2009100867788A CN 200910086778 A CN200910086778 A CN 200910086778A CN 101936906 B CN101936906 B CN 101936906B
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Abstract
The invention provides a carrier. The carrier comprises a supporting body (11) and at least one analysis unit, wherein each analysis unit comprises a liquid removing structure, a porous substrate layer (12) and an enhancement layer (14); the porous substrate layer (12) and the enhancement layer (14) are positioned above the liquid removing structure; the liquid removing structure is positioned in the supporting body (11) or positioned on the surface of the supporting body (11); the enhancement layer (14) is positioned on the surface of the porous substrate layer (12); the liquid removing structure is used for receiving liquid from the porous substrate layer (12); and the enhancement layer (14) is used for enhancing Raman scattering intensity. The invention also provides a kit containing the carrier and a method for performing surface enhanced Raman spectroscopy analysis by using the carrier. The carrier provided by the invention can obviously enhance a Raman scattering signal, has high sensitivity, and can perform quantitative analysis by adding an internal standard substance or external standard substance.
Description
Technical field
The kit that the present invention relates to a kind of carrier and comprise said carrier in addition, the invention still further relates to and uses said carrier to carry out the method for SERS analysis and the purposes of said carrier.
Background technology
Any material all is made up of one or more chemical constitution.Chemical analysis is method and a process of analyzing single or complicated compound chemical structure, composition and quantity.Therefore chemical analysis is significant in agricultural, manufacturing industry, commerce and trade, health care and public health and daily life.Therefore, carry out like a raging firely about the research of chemical analysis aspect.
Raman spectrum (RS) and infrared spectrum (IR) belong to molecular vibration spectrum together, but their mechanism is different: infrared spectrum is the characteristic absorption of molecule to infrared light, and Raman spectrum then is that molecule is to scattering of light (being Raman scattering).Raman scattering is the inelastic scattering of photon.When light by atom or molecular scattering, wherein most of photon is by elastic scattering (Rayleigh scattering), the photon of this scattering has identical energy (frequency) and wavelength with the photon of incident light.Yet the photon of sub-fraction scattered light has different frequencies with the photon of incident light, and is usually less than or is higher than the frequency of incident light photon.Because the frequency shifting of Raman diffused light changes corresponding to the energy state of electronics in the molecule, so Raman spectroscopy just becomes people and studies one of new tool of molecular structure.The forties in 20th century, because at that time technical device level limits, also owing to the developing rapidly of infrared spectrum technology, Raman spectrum once was at low ebb the stage.Early 1960s, the Raman spectrum that appears as of laser instrument provides desirable light source, adds the development of computing machine, and one that laser Raman spectroscopy is progressively become in the molecular spectroscopy is enlivened branch.
SERS (SERS) is a kind of variant of Raman spectrum analysis technology, is a kind of technology responsive to the metal surface.If molecule approaches the special metal surface on the position, because the additional-energy transmission between molecule and the metallic surface electronics, the intensity of Raman signal can greatly be increased, and enhancer can be up to 10
14To 10
15, this makes this technology can be used for surveying individual molecule.In order to carry out SERS, said analyte molecule is attracted on the nano level roughened metal surface, to detect the Raman scattering of enhancing.Gold is typically to be used for the metal that surperficial Raman spectrum strengthens with silver, because their plasma resonance frequency is positioned at visible light and near-infrared radiation frequency range.Metallic copper, nickel, platinum, iron and aluminium also can be used for SERS.
Compare infrared spectrum and fluorescent technique, SERS (SERS) can provide abundant molecular structure information; Compare mass spectrum, SERS is relatively cheap, volume is little.Present known use SERS carries out chemico-analytic method has two kinds.First method be with the solid matter that does not have Liquid Absorption or watertightness such as metal, pottery or glass as carrier, the mixed liquor that will contain testing sample and metal nanoparticle places on the surface of this carrier, detects with laser Raman spectrometer then.The method measuring result error is bigger, is difficult to operation.Second method equally with the solid matter that do not have Liquid Absorption or watertightness such as metal, pottery or glass as carrier; Different is at first metal nano material to be fixed on the surface of this carrier; Then the solution of testing sample is placed on the surface of carrier of metal nanoparticle, and analyze with Raman spectrometer.Yet there is weak, the low shortcoming of sensitivity of Raman signal in the method.And test sample is a liquid in testing process in above-mentioned two kinds of methods, and can not concentrate, thereby causes that Raman signal is weak, sensitivity is lower, therefore can not be used for quantitative test.
Summary of the invention
The objective of the invention is for the SERS method that overcomes prior art exists that Raman signal is unstable, sensitivity is low, operating difficulties and can not be used for the defective of quantitative test, provide a kind of and can make that SERS analyzes that Raman signal is stable, highly sensitive, operation facility and the carrier that can carry out quantitative test.
Another object of the present invention provides the kit that comprises above-mentioned carrier and uses above-mentioned carrier to carry out the method that SERS is analyzed.
The invention provides a kind of carrier; Wherein, Said carrier comprises supporter and at least one analytic unit, and each analytic unit comprises that porous matrix layer and enhancement layer are positioned at except that on the liquid structure except that liquid structure, porous matrix layer and enhancement layer; The said liquid structure of removing is arranged in said supporter or is positioned on the said supporting body surface; Said enhancement layer is positioned on the said porous matrix layer material surface, and the said liquid structure of removing is used to receive the liquid from the porous matrix layer, and said enhancement layer is used to strengthen Raman scattering intensity.
The present invention also provides a kind of kit; Wherein, This method comprises that the solution with testing sample loads on the carrier, measures the Raman spectrum of testing sample, wherein then; Said carrier is a carrier provided by the invention, and the method that loads on the carrier is added on the enhancement layer of said carrier for the solution with testing sample.
Inventor of the present invention discovers; Though the first method of prior art can strengthen the Raman scattering signal to a certain extent owing to the adding of metal nanoparticle; But when analyzing testing sample,, make metal nanoparticle depart from the laser focal plane of Raman spectrum analysis because the metal nanoparticle in the mixed liquor sinks with Raman spectrometer; Thereby Raman signal is unstable, and sensitivity is very low.Though second method has overcome owing to metal nanoparticle sinks to departing from the defective of laser focal plane; But in the method because testing sample is in solution state and the surface metal nano particle can not mix effectively; Thereby enhancement effect is lower, causes the sensitivity of Raman signal low.
Carrier structure provided by the invention is simple, easy to operate and highly sensitive.When using carrier provided by the invention to carry out chemical analysis; Sample is dropped on the porous matrix layer of said carrier with the form of solution after, remove the liquid structure owing to exist, thereby the solvent in the solution can be blotted rapidly; Composition to be measured in the testing sample is evenly on the reinforcing agent surface attached to enhancement layer; Have concentrating and become the characteristic of fluid sample, thereby can directly be used for analyzing, thereby operation is very easy into solid sample.Through making composition to be measured in the testing sample evenly on the reinforcing agent surface attached to enhancement layer; Avoided the metal nanoparticle sinking on the one hand and caused departing from laser focal plane and Raman signal problem of unstable, low causing of the testing sample concentration that has also solved the prior art existence on the other hand is difficult to test very weak with Raman signal and problem that can't carry out quantitative test.And, use carrier provided by the invention, can jumbo fluid sample be attached on the small size solid surface through removing the liquid structure, and form the solid sample layer, again this sample layer is carried out the sensitivity that Raman spectrum analysis just can significantly improve detection.In addition, according to preferred implementation provided by the invention, can carry out accurate quantitative test to testing sample through adding internal standard compound and external standard.
Description of drawings
Longitudinal section synoptic diagram when Fig. 1 representes removing the liquid structure and being liquid-adsorption layer of carrier provided by the invention;
Longitudinal section synoptic diagram when Fig. 2 representes removing the liquid structure and being the duct of carrier provided by the invention;
Fig. 3 representes that the liquid structure of removing of carrier provided by the invention is the longitudinal section synoptic diagram that liquid-adsorption layer and said carrier also comprise shell;
Fig. 4 representes that the liquid structure of removing of carrier provided by the invention is the longitudinal section synoptic diagram that duct and said carrier also comprise shell;
Vertical view when Fig. 5 representes that carrier provided by the invention comprises shell;
Fig. 6 representes that carrier provided by the invention also comprises the longitudinal section synoptic diagram of filter membrane;
Fig. 7 representes the Raman spectrometer structural representation;
Fig. 8 representes to detect among the embodiment 1 Raman spectrogram that obtains;
Fig. 9 representes to detect among the embodiment 2 Raman spectrogram that obtains;
Figure 10 representes to detect in the Comparative Examples 1 Raman spectrogram that obtains;
Figure 11 represent the middle medicament of embodiment 3 do not decoct preceding, decoct 15 minutes, decoct 30 minutes, decoct 60 minutes, decocted 90 minutes and decoct 120 minutes test result figure.
Figure 12 represent according in the Raman spectrogram of the external standard testing sample of embodiment 4 at 686cm
-1The canonical plotting that the scattering peak intensity at place is formulated;
Figure 13 representes according to 686cm in the Raman spectrum of the specimen C1-C6 of embodiment 5
-1The scattering peak intensity and the 730cm at place
-1The canonical plotting that the ratio of the intensity of the scattering peak at place is formulated.
Embodiment
Do explanation at length below in conjunction with Fig. 1-6 pair of carrier provided by the invention.
Shown in Fig. 1-6; Carrier support 11 provided by the invention and at least one analytic unit; Each analytic unit comprises except that liquid structure, porous matrix layer 12 and enhancement layer 14; Porous matrix layer 12 is positioned at except that on the liquid structure with enhancement layer 14, and the said liquid structure of removing is arranged in said supporter 11 or is positioned on said supporter 11 surfaces, and said enhancement layer 14 is positioned on said porous matrix layer 12 material surface; The said liquid structure of removing is used to receive the liquid from porous matrix layer 12, and said enhancement layer 14 is used to strengthen Raman scattering intensity.
The material of said supporter 11 can be the various solid materials that do not influence test, for example can be metal, plastics, glass or their compound substance.In the present invention, do not test as long as the shape of said supporter 11 has special qualification can put into the Raman scattering appearance with size, for example, said supporter 11 can be rectangular tab or thin rounded flakes.The area of said supporter 11 can be the 1-1000 square centimeter, is preferably the 10-100 square centimeter.The thickness of said supporter 11 can be the 0.5-50 millimeter, is preferably the 1-5 millimeter.
Under preferable case; Said analytic unit is a plurality of, and 2 adjacent analytic units are apart from one another by opening, and a plurality of analytic units can shared one remove the liquid structure; Each analytic unit also can have the independent liquid structure of removing, 2 promptly adjacent analytic units remove the liquid structure apart from one another by opening.In use, each analytic unit can be respectively applied for measures a sample, so the number of analytic unit is many more, and the number of the sample of energy measurement is also many more.Further under the preferable case, said carrier comprises the analytic unit of the parallel distribution of two rows, and the center of same row's analytic unit is on same straight line, and the line of centres of four analytic units that two rows are adjacent forms rectangle or square.In order to reduce the interference between the sample, porous matrix layer 12 minor increment of adjacent two analytic units are the 1-100 millimeter, and said minor increment is meant the minor increment at the edge of adjacent two analytic units.
In one embodiment of the invention, the said liquid structure of removing is liquid-adsorption layer 13a, and said liquid-adsorption layer 13a is positioned at the surface of supporter 11.The liquid absorption of said liquid-adsorption layer 13a is preferably the 1-1000 microlitre, further is preferably the 1-100 microlitre.The material of said liquid-adsorption layer 13a is sponge, absorbency resin, cellulose paper, spun glass or their combination.The thickness of said liquid-adsorption layer is the 0.1-10 millimeter, is preferably the 0.5-5 millimeter.The pick up of said liquid-adsorption layer is 0.1-50, is preferably 0.5-10, and said pick up is meant that the liquid-adsorption layer of unit weight can absorb the maximum weight value of liquid.Said liquid-adsorption layer 13a can cover said supporter 11 fully, also can locally cover said supporter 11.Particularly, under the situation of the said supporter 11 of the local covering of said liquid-adsorption layer, when carrier of the present invention comprised an analytic unit, said liquid-adsorption layer 13a was the block of an area much smaller than supporter; When carrier of the present invention comprised plural analytic unit, said liquid-adsorption layer 13b was plural discontinuous block, and said discontinuous block can have identical or different size and dimension, preferably has identical size and dimension.
In another embodiment of the invention, the said liquid structure of removing is the duct 13b that is arranged in supporter 11.Said duct 13b comprises inlet 13b1 and outlet 13b2, and said inlet 13b1 is positioned at the below of porous matrix layer 12, import among the 13b of duct through said inlet 13b1 from the liquid of porous matrix layer 12, and through said outlet 13b2 derivation supporter 11.When carrier provided by the invention had a plurality of analytic unit, said duct 13b comprised a plurality of inlet 13b1, and each inlet connects an analytic unit separately.In addition, the cross-sectional area of said inlet 13b1 is the 0.1-99% of porous matrix layer 12 area of its corresponding analytic unit.In addition, the number of the inlet that said duct 13b is connected with each analytic unit can be for a plurality of, and when the inlet number under being arranged on each analytic unit was a plurality of, the cross-sectional area sum of each inlet and the sectional area of pipeline all met aforementioned proportion.
In carrier of the present invention, said porous matrix layer 12 is used to assemble reinforcing agent with the formation enhancement layer, and guarantees that liquid can pass through.The upper surface size of said porous matrix layer 12 can be 10 microns-10 millimeters; Be preferably the 0.5-5 millimeter; The upper surface of said porous matrix layer 12 can for the shape of various rules as circular or square; When the upper surface of said porous matrix layer 12 was circle, then the size of said upper surface was meant circular diameter dimension; When the upper surface of said porous matrix layer 12 was rectangle or square, then the size of said upper surface was meant foursquare cornerwise size.Said porous matrix layer 12 can be formed by various porosints; Said porosint can be organic polymer, inorganic material or their compound substance, for example can be in spun glass, cellulose, nylon, porous silicon, fritted glass, porous metals, porous metal oxide and the silicon nanostructure material one or more.Said porous metals can be noble metal such as gold, silver, and said porous metal oxide can be an aluminium oxide.
The thickness of said porous matrix layer 12 is the 0.05-5 millimeter, is preferably the 0.1-0.5 millimeter.The aperture of said porous matrix layer 12 is 10 nanometers-10 micron, is preferably the 25-500 nanometer, further is preferably the 50-250 nanometer, thus said porous matrix layer 12 can the trapped particles size greater than the solid particle in this aperture.In above-mentioned preferred pore diameter range; Can avoid causing reinforcing agent such as metal nanoparticle to be difficult to form enhancement layer too greatly on the one hand through hole because of the aperture; And can prevent that the composition to be measured in the testing sample runs off through hole; Solvent such as the moisture in the milk in the testing sample are got into except that in the liquid structure through hole fast, composition to be measured and reinforcing agent are attached to rapidly on the porous matrix layer 12, form the testing sample layer.The porosity of said porous matrix layer 12 is 1-99%, is preferably 10-90%.In the present invention, said porosity is meant that the volume of hole accounts for the number percent of whole porous matrix layer cumulative volume.
Said porous matrix layer 12 can also can be for discontinuously arranged for continuous distribution.When the liquid structure of removing of said carrier is liquid-adsorption layer 13a and said liquid-adsorption layer 13a when covering said supporter 11 fully, said porous matrix layer 12 can cover said liquid-adsorption layer 13a fully, also can locally cover said liquid-adsorption layer 13a; In addition, comprise that at said carrier a plurality of analytic units and said liquid-adsorption layer 13a are that said porous matrix layer 12 is preferably discontinuously arranged and is corresponding with said liquid-adsorption layer 13a under the discontinuously arranged situation.When the liquid structure of removing of said carrier is duct 13b, and said carrier is when comprising a plurality of analytic unit, and said porous matrix layer 12 is preferably discontinuously arranged and corresponding with the position in said duct.When being discontinuously arranged, can practice thrift the consumption of porous matrix at said porous matrix on the one hand, also can alleviate the weight of whole carrier on the other hand, thereby be more convenient for carrying.
In the present invention, said enhancement layer 14 is used to strengthen Raman scattering intensity, and the thickness of said enhancement layer 14 is the 0.1-1000 micron, is preferably the 1-500 micron.The thickness of said enhancement layer 14 is for being absorbed in the height of bosom to enhancement layer 14 upper surface peaks in the porous matrix layer 12 from reinforcing agent.In said enhancement layer 14, the part that plays main reinforced effects is the upper surface of said enhancement layer 14.Said enhancement layer 14 can form through the method for various routines; For example; Be added on the said porous matrix layer 12 through the solution that will contain reinforcing agent, the liquid that said porous matrix layer 12 makes said solution through and hold back solid particle, thereby form said enhancement layer 14.Said reinforcing agent comprises the potpourri of metal nanoparticle or metal nanoparticle and the material that can make the metal nanoparticle cohesion.Before the formation enhancement layer, said metal nanoparticle is independently preserved with the material that can make the metal nanoparticle cohesion.Wherein, The particle diameter of the said metal nanoparticle of at least 50 weight % is the 5-500 nanometer; Because the particle diameter of metal nanoparticle is little, surface energy is high, thereby in solution, also can reunite even without the said material of metal nanoparticle cohesion that can make; Form bigger particle, thereby be trapped on the porous matrix layer 12 and form enhancement layer.Said metal can be in gold, silver, nickel, platinum, copper, iron and the aluminium one or more; The said material that can make metal nanoparticle cohesion can be in salt, the bronsted lowry acids and bases bronsted lowry one or more; Said acid, alkali and salt are can be through changing the Zeta potential (the inside and outside potential difference (PD) of electron cloud) of the metallic colloid particulate that metal nanoparticle forms, thereby realize the salt of the cohesion of metal nanoparticle, in the bronsted lowry acids and bases bronsted lowry one or more.Said salt can be in chloride (like in sodium chloride, ammonium chloride and the lithium chloride one or more), nitrate (like in ammonium nitrate, sodium nitrate and the potassium nitrate one or more), sulfate (like sodium sulphate) or the phosphate (like dipotassium hydrogen phosphate) one or more; Said acid can be in hydrochloric acid, acetic acid, the citric acid one or more, and said alkali can be NaOH or aqua ammonia.For the raman spectral signal that prevents specimen is as much as possible disturbed, the said material of metal nanoparticle cohesion that can make is preferably sodium chloride and/or lithium chloride.In the present invention; When said reinforcing agent is the potpourri of metal nanoparticle and the material that can make the metal nanoparticle cohesion; The aggregation of said enhancement layer 14 on porous layer hypothallus 12, forming by metal nanoparticle and the material that can make the metal nanoparticle cohesion; The method that forms aggregation is following: (1) prepares said metal nanoparticle, and said metal nanoparticle uses with its liquid or colloidal form usually.Said metal nanoparticle liquid is normally through reducing the metal nanoparticle colloidal solution that corresponding metal ion solution metal ion obtains with known method, the metal nanoparticle liquid of formation can be without concentrating or dilution and directly use.Metal ion solution metal ion concentration is normally at 0.01-10 mM/liter (mM), be preferably the 0.1-2 mM/liter.The reductive agent that is used to reduce can be for well known to a person skilled in the art various reductive agents.(2) add the said material of metal nanoparticle cohesion that can make in the metal nanoparticle liquid to; Obtain mixture liquid, it is 1 mM/rise to, 5 mol that the said addition that can make the material of metal nanoparticle cohesion makes its ultimate density in said mixture liquid; (3) add said mixture liquid in the sample well to form enhancement layer 14.In said metal nanoparticle liquid; There is not dilution, concentrating under the situation that reaches solvent evaporates; The concentration of metallic atom can be represented by the concentration of metallic ion, and the concentration of said metallic ion is meant that original metal ion solution mixes the back with reductant solution but the concentration of the metallic ion of reduction reaction when not beginning.Yet; Because metal nanoparticle is normally obtained by many metallic atoms gatherings, and the size of metal nanoparticle is relevant with the concentration of GOLD FROM PLATING SOLUTION metal nano-particle, under the identical situation of other condition; The concentration of GOLD FROM PLATING SOLUTION metal nano-particle is high more; The particle diameter of the metal nanoparticle of gained is big more, and the concentration of GOLD FROM PLATING SOLUTION metal nano-particle is low more, and the particle diameter of the metal nanoparticle of gained is more little; And under the certain situation of the total amount of metallic atom, the particle diameter of metal nanoparticle is big more, and the number of metal nanoparticle is just few more, also is that the concentration of metal nanoparticle is low more.Because the number of metal nanoparticle and measurement of concetration inconvenience; And under the certain situation of the total amount of metallic atom; The concentration of metal nanoparticle is relevant with the particle diameter of metal nanoparticle again; Therefore, generally the number or the concentration of metal nanoparticle are not measured, but embodied through the particle diameter of metal nanoparticle.Inventor of the present invention finds, with respect to the sectional area of per 1 square millimeter of sample well, uses the particle diameter of at least 50% said metal nanoparticle of about 20-35 microlitre can effectively realize the object of the invention as the metal nanoparticle liquid of 5-500 nanometer.Therefore; Under the preferable case; With respect to the sectional area of per 1 square millimeter of sample well, use the particle diameter of at least 50% said metal nanoparticle of about 20-35 microlitre to be the metal nanoparticle liquid of 5-500 nanometer, for example; For the circular sample hole of sample well diameter, use the above-mentioned metal nanoparticle liquid of 4-7 microlitre at 0.5 millimeter (about 0.2 square millimeter).Said process can be accomplished before carrier uses or fulfil ahead of schedule and deposit subsequent use.
In a kind of preferred implementation of the present invention, carrier provided by the invention also comprises shell 15, and said shell 15 is fixed on the supporter 11, a space forming surface of said shell 15 and supporter 11, and analytic unit is positioned at this space; Said shell 15 comprises opening 16, the position corresponding to said analytic unit of at least one said opening.This opening 16 be positioned at the sample well that analytic unit under this opening promptly is configured for carrying the Raman analysis sample.Said shell 15 can be used for porous matrix layer 12 and liquid-adsorption layer 13a are fixed on the supporter 11, and is used to form the sample well of this carrier.Particularly when said carrier comprises above-mentioned a plurality of analytic unit, said shell 15 can be fixed on discontinuous enhancement layer 14, porous matrix layer 12 and liquid-adsorption layer 13a on the supporter 11, forms a plurality of analytic units.Through the fixation of shell 15, need not bonding agent between each parts of said carrier and can realize effective applying.The material of said shell 15 can be various flexible materials, for example can be plastic sheet or metal forming such as aluminium foil, Copper Foil or goldleaf, and the thickness of said shell 15 can be the 1-500 micron.
When said carrier comprises one or more analytic unit, said analytic unit be positioned at said opening 16 under, the size of analytic unit is not less than the size of said opening 16.
In the present invention, the shape in the cross section of the shape of the opening 16 of said shell and analytic unit can match and also can mismatch.Under the preferable case; The shape in the opening 16 of said shell and the cross section (also being the cross section of porous matrix layer) of analytic unit is circle; The size of said opening 16 is 1 micron-10 millimeters, further is preferably the 0.1-5 millimeter, and the sectional area of said porous matrix layer is preferably 1.01-50 times of said opening 16 sectional areas; Can guarantee that like this testing sample can all be positioned on the porous matrix layer 12, can also make testing sample fully concentrated.For the ease of quantitative test with carry out repeated detection, the opening 16 of said shell and the number of analytic unit are preferably 2-12 separately.
Further under the preferable case, said carrier also comprises filter membrane 17, and said filter membrane 17 covers on the opening 16 of said shell 14, and said filter membrane is used to hold back big molecule such as protein, and the molecular cut off of said filter membrane is more than 10000.Said molecular cut off is meant the molecular weight of minimum solute in the solute that can be lived by membrane retention.The material of said filter membrane 17 can be regenerated cellulose, nitrocellulose or modified polypropene hollow fiber, and its thickness can be 1 micron to 0.2 millimeter.The size of said filter membrane 17 is greater than the size of the opening 16 of said shell 14.
The method for making of carrier provided by the invention does not have special qualification, holds Raman spectrum analysis with structures of samples as long as can enhancement layer 14, porous matrix layer 12, imbibition structure and supporter 11 are combined to form can be used in.For example; When said carrier to remove the liquid structure be discontinuous liquid-adsorption layer 13a the time; On a surface of supporter 11, form discontinuous liquid-adsorption layer 13a, and correspondingly on each liquid-adsorption layer 13a, adhere to porous matrix layer 12, the mixed liquor that will contain reinforcing agent then is added to respectively on the said porous matrix layer 12; Liquid in the said mixed liquor is through said porous matrix layer 12; Thereby form enhancement layer 14, the shell 15 that the shape that will have opening and opening again and position and said porous matrix layer 12 are complementary is attached on porous matrix layer 12 or the liquid-adsorption layer 13a according to the profile applying of porous matrix layer 12 and liquid-adsorption layer 13a, and is fixed on the supporter 11.When the removing the liquid structure and be duct 13b of said carrier; On the supporting surface of supporter 11, form one or more holes longitudinally, the degree of depth in hole does not run through the thickness of supporter 11, is communicated with said one or more holes longitudinally through horizontal hole then; And said horizontal hole is communicated to the outside of supporter 11; Thereby form the duct 13b that is communicated with, with on the inlet of porous matrix layer 12 attached to vertical hole, the mixed liquor that will contain reinforcing agent then is added to respectively on the said porous matrix layer 12 then; Liquid in the said mixed liquor is through said porous matrix layer 12; Thereby form enhancement layer 14, the shell 15 that the shape that will have opening and opening again and position and said porous matrix layer 12 are complementary is attached on the porous matrix layer 12 according to the profile applying of porous matrix layer 12, and is fixed on the supporter 11.
Carrier provided by the invention in use can make fluid sample be condensed into solid sample to carry out Raman spectrum analysis.Said carrier (before promptly using) in idle process is stored in the closed environment usually, and said closed environment is generally vacuum or fills inert gas such as nitrogen or argon gas, and said closed environment is that the material of glass, plastics, metal etc. forms by material.In use, only need sample directly be placed on the enhancement layer 14 to get final product, therefore, operation is very convenient.
The present invention also provides a kind of kit, and wherein, said kit comprises carrier provided by the invention.Said kit provided by the invention can be used for the chemical analysis such as the Raman spectrum analysis of various routines.
Carrier provided by the invention and kit can be used for the solid sample analysis; Also can be used for the analysis of fluid sample; But because as stated; When analyzing liquid sample, particularly more can embody advantage of the present invention during the content of the trace in the analyzing liquid sample or trace constituent, so the present invention is that example is explained carrier of the present invention and used this carrier to carry out the method that SERS is analyzed with the SERS analytical approach of fluid sample.
The present invention also provides a kind of SERS analytical approach; This method comprises that the solution with testing sample loads on the carrier; Measure the Raman spectrum of testing sample then; Wherein, said carrier is a carrier provided by the invention, and the method that the solution of testing sample is loaded on the carrier comprises that the solution with testing sample is added on the enhancement layer of said carrier.
In order more effectively to improve the sensitivity of Raman spectrum, preferably in testing sample, add the material that can make the metal nanoparticle cohesion, the testing sample that will contain the material that can make the metal nanoparticle cohesion then is added on the enhancement layer of said carrier.
When said carrier also comprises filter membrane; The method that the solution of testing sample is loaded on the carrier comprises that the solution of testing sample is added on the filter membrane of said carrier; Macromolecular substances is trapped on the filter membrane; Then through filter membrane, solvent is discharged the carrier through the porous matrix layer with except that the liquid structure through the enhancement layer continued for micromolecule testing sample and solvent, and testing sample is then attached on the enhancement layer.
In the circular sample hole analytic unit of 0.5 millimeter (about 0.2 square millimeter), the said consumption that contains the solution of testing sample is generally the 1-100 microlitre, is preferably the 10-20 microlitre at each diameter.
A preferred embodiment of the invention also contains the known internal standard compound of content in said mixed liquor, said internal standard compound is not overlapped with the Raman spectrum of determinand or whole overlapping material for itself producing Raman spectrum and this Raman spectrum.For different testing samples, the kind of internal standard compound maybe be different.Through this optimal way, can realize quantitative test.Particularly; Through the raman spectral signal with the known internal standard compound of content is reference standard; The raman spectral signal and the reference standard of testing sample are compared; Analyze the Raman spectrum characteristic peak intensity (ordinate) of testing sample and the ratio or the difference in height of the Raman spectrum characteristic peak intensity of reference standard, judge that the concentration (or content) of testing sample is higher than or is lower than the concentration (or content) of internal standard compound, even concentration difference roughly (or content difference).
With respect to every liter the mixed liquor that contains testing sample, the consumption of internal standard compound is generally 1 microgram-1 gram, is preferably 10 micrograms-100 milligram.The absolute magnitude of composition to be measured can fly gram (fg) to the scope of nanogram (ng) in each testing sample, even can be single molecules level.That is to say, as long as contain this composition to be measured in the testing sample, even if the content of this composition to be measured be individual molecule, fly to restrain (fg) or nanogram (ng), adopt method of the present invention also can measure.
In addition; In order to realize quantitative test; Can comprise that also the external standard that content is known loads on the said carrier; Measure the enhancing Raman spectrum of external standard then, and the Raman spectrum characteristic peak of this external standard and the Raman spectrum characteristic peak of testing sample are compared, said external standard and testing sample have same or similar Raman spectrum characteristic peak.The method of above-mentioned use external standard also can be called " external standard method ".When using external standard method to carry out quantitative test, preferably use the carrier that comprises two row's sample wells provided by the invention.
For different testing samples, the kind of external standard can be different.Internal standard compound can be identical with external standard, also can be different.
The method that the employing Raman spectrometer is analyzed is for well known to a person skilled in the art method, and is for example, as shown in Figure 7; The carrier that carries testing sample is placed on the worktable 21; Send laser through laser instrument 24, form focused beam through optical filter 23 and through object lens 22, light beam irradiates produces Raman scattering to testing sample; The light signal that Raman scattering produces detects through optical signalling detecting device 25, and detected light signal reads and analyzes through computing machine 26.
SERS analytical approach provided by the invention can be used for the sample of taking from human body, animal, plant, microorganism, food, medicine and environment etc. is detected.
Below through embodiment the present invention is described further.
Embodiment 1
Present embodiment is used to that carrier provided by the invention is described and uses this carrier to carry out the method that SERS is analyzed.
(1) makes carrier
Liquid-adsorption layer 13a is placed on the supporter 11; Then porous matrix layer 12 is placed on the said liquid-adsorption layer 13a; Wherein said supporter 11 is the glass plate of millimeter (wide) * 2,75 millimeters (length) * 25 millimeter (thick); The material of liquid-adsorption layer 13a is that thickness is 0.5 millimeter cellulose paper (pick up is 5), the material of porous matrix layer 12 be the aperture be 200 nanometers, porosity be 50% and thickness be 0.5 millimeter glass fibre membrane.Through rolling they are closely sticked together each other; On said porous matrix layer 12, form enhancement layer 14 then; Said enhancement layer 14 will be through being that reinforcing agent drips of solution that the lithium chloride of 5 mol is formed is added on the glass fibre membrane and forms by the concentration of the silver nano-grain of 5 microlitres and 5 microlitres, and thickness is 1 micron.The particle diameter of above-mentioned silver nano-grain is the 40-80 nanometer, concrete preparation method for the concentration to 20 milliliters boiling be 1.0 mMs/liter AgNO
3Solution in add the sodium citrate (Na of 2 milliliters 1 weight %
3C
6H
5O
72H
2O) solution, and under magnetic agitation, keep the boiling 10 minutes that refluxes, promptly get 22 milliliters silver nano-grain colloid (being silver nano-grain).
(2) detect and analyze
The concentration that makes 10 microlitres is that the WS of the melamine of 10ppm is added on the said carrier, after liquid is filtered dry doubling formation solid layer fast, carries out Raman spectrum and detects, and obtains Raman spectrogram as shown in Figure 8.In Fig. 8, at 686cm
-1Scattering peak (the 686cm at place
-1The place scattering peak be the characteristic peak of melamine) raman scattering intensity be 28365.
Embodiment 2
Present embodiment is used to that carrier provided by the invention is described and uses this carrier to carry out the method that SERS is analyzed.
(1) makes carrier
To make said carrier with embodiment 1 identical method; Different is; Said enhancement layer 14 is through will (particle diameter of silver nano-grain is the 40-80 nanometer by the silver nano-grain of 5 microlitres; The preparation method is with embodiment 1) and the concentration of 2.5 microlitres be that reinforcing agent drips of solution that the lithium chloride of 5 mol is formed is added on the glass fibre membrane and forms, thickness is 0.5 micron.
(2) detect and analyze
The WS of getting 10 microlitre concentration and be the melamine of 10ppm mixes with 2.5 microlitre lithium chlorides (5 mol), and is added on the said carrier, filters dry doubling fast at liquid and carries out the Raman spectrum detection after forming solid layer, obtains Raman spectrogram as shown in Figure 9.In Fig. 9, at 686cm
-1Scattering peak (the 686cm at place
-1The place scattering peak be the characteristic peak of melamine) raman scattering intensity be 62370.With with embodiment 1 inequality be that lithium chloride (make can with the material of metal nanoparticle cohesion) adds in two batches.
Comparative Examples 1
The concentration that makes 10 microlitres is that (particle diameter of silver nano-grain is the 40-80 nanometer for the WS and the silver nano-grain of 5 microlitre lithium chlorides (5 mol) and 5 microlitres of melamine of 10ppm; The preparation method is with embodiment 1) mixing material; Draw the said mixing material of 10 microlitres then, and directly adopt Raman spectrometer that it is carried out Raman spectrum and detect to obtain Raman spectrogram shown in figure 10.In Figure 10, at 686cm
-1Scattering peak (the 686cm at place
-1The place scattering peak be the characteristic peak of melamine) raman scattering intensity be 2463.
Through with embodiment 1 and 2 and the testing result of Comparative Examples 1 compare explanation, adopt carrier provided by the invention can make SERS sensitivity strengthen more than 10 times.Particularly when make can be added on the said carrier with the material (like lithium chloride) of metal nanoparticle cohesion the time in batches, surperficial Raman spectrum sensitivity strengthens more remarkable, can be up to more than 20 times.
Embodiment 3
Present embodiment is used to that carrier provided by the invention is described and uses this carrier to carry out the method for SERS analysis and the application of studying at traditional Chinese medicine.
(1) makes carrier as shown in Figure 3
(2) preparation of testing sample
Chinese medicine prescription to being made up of 5 gram matrimony vines, the 5 gram Radixs Astragali, 10 gram Radix Codonopsis, 3 gram Radix Angelicae Sinensis, the 7 gram tubers of multiflower knotweed, 10 gram Huai Shan, 8 gram Poria cocos, the 3 gram barks of eucommia and the 5 Keshan fruit of medicinal cornels decocts, and 1 milliliters of liquid of the decoction gained during get decoction respectively 0 minute, 15 minutes, 30 minutes, 60 minutes, 90 minutes and 120 minutes is as testing sample 1,2,3,4,5 and 6.
(3) Raman spectrum detects
Above-mentioned testing sample 1-6 is repeated once separately, and get 10 microlitres respectively, and correspondingly be added to separately in 12 sample wells of carrier of above-mentioned (1) gained.Liquid in each sample well is filtered dry doubling fast and on enhancement layer, is formed after the black solid layer fast, carries out Raman spectrum successively and detects, and the one of which testing result is shown among Figure 11 in each sample of testing sample 1-6.
(4) interpretation of result
Shown in figure 11, internal standard compound is at 720cm
-1Scattering peak appears in the position at place, and the intensity at this peak is the strongest, 1320cm
-1The scattering of position is unimodal to be weakened along with decocting time gradually, and this is unimodal at 1300cm when decocting 30 minutes
-1Locate to derive an acromion, 1600-1650cm
-1The scattering of position is bimodal to be occurred when decocting 30 minutes and reaches the strongest, and the intensity at this peak weakens greatly when decocting 90 minutes.This shows; The chemical constitution of the concoction that above-mentioned Chinese medicine prescription obtains after decocting can change along with the variation of decocting time; And, show that said Chinese medicine prescription chemical constitution information in the gained concoction when decocting 30-60 minute is the abundantest because the raman spectral information that when decocting 30-60 minute, records is maximum.
Embodiment 4
Present embodiment is used to that carrier provided by the invention is described and uses this carrier to carry out the method that SERS is analyzed.
(1) makes carrier as shown in Figure 6
Supporter 11 is the plastic plate of millimeter (wide) * 5,80 millimeters (length) * 30 millimeter (thick); The aperture of duct 13b is 1.0 millimeters; The material of porous matrix layer 12 be the aperture be 1 micron, porosity be 20% and thickness be 3 millimeters glass fibre membrane; Enhancement layer 14 through will by the hydrochloric acid solution of 0.1 mole of 5 microlitre and 5 microlitre gold nano grains (particle diameter of gold nano grain is the 40-80 nanometer, concrete preparation method comprise the concentration to 20 milliliters boiling be 1.0 mMs/liter HAuCl
4Solution in add the sodium citrate (Na of 2 milliliters 1 weight %
3C
6H
5O
72H
2O) solution, and under magnetic agitation, keep the boiling 10 minutes that refluxes, promptly get 22 milliliters of gold nano grain colloids (being gold nano grain); And use required amount to test) the reinforcing agent drips of solution formed is added on the glass fibre membrane and forms; Thickness is 1 micron, and the material of shell 15 is that thickness is 0.15 millimeter laminated plastic sheet material, totally 12 of sample wells (number that also is the analytic unit of porous matrix formation is 12); Be arranged in two parallel rows along this plastic plate length direction; Spacing between two rows is 20 millimeters, and the spacing of adjacent two sample wells of same row is 10 millimeters, and sample well is that diameter is 1 millimeter a circular port.It is that 3 millimeters, thickness are 10 microns regenerated cellulose film (molecular cut off is more than 10000) that the sample well top is placed with diameter.
(2) preparation of external standard specimen
Respectively the melamine of 0 microgram, 5 micrograms, 20 micrograms, 50 micrograms, 100 micrograms and 200 micrograms is added in the amino-acid nutrition liquid that does not contain melamine (being produced by Xiamen Ji Ren bio tech ltd) of 10 grams (10 milliliters); Make the melamine external standard specimen of 0ppm, 0.5ppm, 2ppm, 5ppm, 10ppm and 20ppm, with the sample that so makes as the external standard specimen.
(3) preparation of testing sample
Get the two unknown seed amino acid nutrient solution testing samples (A and B) of content of melamine, use the amino-acid nutrition liquid sample that do not contain melamine that the concentration of testing sample is diluted to 1/2,1/10 and 1/100 separately; Thereby obtain 6 sample A1, A2, A3, B1, B2 and B3, as shown in table 1 below,
Table 1
| Sample | Dilute strength |
| A1 | 1/2 |
| A2 | 1/10 |
| A3 | 1/100 |
| B1 | 1/2 |
| B2 | 1/10 |
| B3 | 1/100 |
(4) Raman spectrum detects
Above-mentioned 6 external standard specimen and 6 testing samples are got 10 microlitres respectively; Be added in 12 sample wells of above-mentioned carrier; Under pull of vacuum, the liquid in each sample well is filtered dry doubling fast and on enhancement layer, is formed after the solid layer fast, carries out Raman spectrum successively and detects.
(5) interpretation of result
In the Raman spectrogram of external standard specimen and testing sample, at 686cm
-1The position enhancing scattering peak (686cm of varying strength all appears
-1Place's scattering peak is the characteristic peak of melamine).According in the Raman spectrogram of external standard testing sample at 686cm
-1The scattering peak intensity at place makes canonical plotting shown in figure 12, and wherein concrete data are as shown in table 2 below.Test result and the analysis result of testing sample A1-A3 and B1-B3 are as shown in table 3 below.
Table 2
| Content of melamine (ppm) | 686cm
-1The intensity of place's |
| 0 | 10 |
| 0.5 | 500 |
| 2 | 2000 |
| 5 | 5000 |
| 10 | 9000 |
| 20 | 13000 |
Table 3
Because the A2 value is in the centre of typical curve (A1 and A3 be high-end and low side at typical curve), so the content of melamine is confirmed as 100ppm among the sample A.Because the value of B1, B2 and B3 is all at 500 times, so the content of melamine is confirmed as less than 1ppm among the sample B.
Present embodiment is used to that carrier provided by the invention is described and uses this carrier to carry out the method that SERS is analyzed.
(1) makes carrier as shown in Figure 3
To make said carrier with embodiment 3 identical methods.
(2) contain the preparation of the specimen of internal standard compound
Get the unknown two kinds of testing samples (A and B) of content of melamine; Respectively with the concentration dilution to 1/2,1/5 and 1/10 of above-mentioned two kinds of testing samples (A and B), make 6 testing samples (A1, A2, A3, B1, B2 and B3) with the milk that does not contain melamine altogether.
The milk that does not contain melamine is organized as C; Be divided into 6 samples (C1, C2, C3, C4, C5 and C6); To the melamine that wherein adds known quantity, making wherein, the content of melamine is respectively 0.2ppm, 0.5ppm, 1ppm, 2ppm, 10ppm and 20ppm respectively.
In addition,, be added to respectively in above-mentioned 12 samples as internal standard compound with adenine, making wherein, the content of adenine is 5ppm.
Making these milk that contain melamine and adenine 12000 rev/mins of following centrifugings 5 minutes respectively, is that 10 millimeters, thickness are 50 microns regenerated cellulose film (molecular cut off is more than 10000) through diameter, obtains cleaner liquid.The 10 microlitre cleaner liquids of respectively asking for mix with the lithium chloride of 5 moles of 5 microlitres, mix (particle diameter of silver nano-grain is the 40-80 nanometer, and the preparation method is with embodiment 1) then with 5 microlitre silver nano-grains, make 12 specimen.
(4) Raman spectrum detects
The above-mentioned specimen that contains internal standard compound is respectively got 20 microlitres also be added to respectively in 12 sample wells of above-mentioned carrier, the liquid in each sample well is filtered dry doubling fast and on enhancement layer, is formed after the solid layer fast, carries out Raman spectrum successively and detects.
(5) interpretation of result
In the Raman spectrogram of specimen, melamine strengthens scattering peak at 686cm
-1The place, adenine strengthens scattering peak at 730cm
-1The place, and calculate 686cm in the Raman spectrum of C1-C6 respectively
-1The scattering peak intensity and the 730cm at place
-1The ratio of the intensity of the scattering peak at place, its result is shown in the following table 4, and it is shown in figure 13 to formulate typical curve.
Table 4
| Melamine (ppm) | Ratio (686cm -1/730cm -1) |
| 0.2 | 0.1 |
| 1 | 0.25 |
| 2 | 0.5 |
| 5 | 1.25 |
| 10 | 2 |
| 20 | 2.5 |
Through calculating 686cm among specimen A1, A2, A3, B1, B2 and the B3
-1/ 730cm
-1Ratio (686cm
-1The scattering peak intensity and the 730cm at place
-1The ratio of the intensity of the scattering peak at place), obtain 686cm among the A3
-1/ 730cm
-1Ratio is 2.2 (686cm among A1 and the A2
-1/ 730cm
-1Ratio is all greater than 3), 686cm among the B1
-1/ 730cm
-1Ratio is 0.2 (686cm among B2 and the B3
-1/ 730cm
-1Ratio is all less than 0.1).Therefore, respectively with the 686cm of A3
-1/ 730cm
-1The 686cm of ratio (2.2) and B1
-1/ 730cm
-1Ratio (0.2) finds the value (content of melamine) of corresponding horizontal ordinate as ordinate in Figure 13, wherein, the value of the horizontal ordinate that A3 is corresponding is 15ppm, and the value of the horizontal ordinate that B1 is corresponding is 0.8ppm.In addition, because A3 is diluted to 1/10, B1 is diluted to 1/2, and therefore, the content that can correspondingly calculate melamine among the sample A is 150ppm, and the content of melamine is 1.6ppm among the sample B.
This shows, adopt the method for carrier provided by the invention and SERS analysis can carry out quantitative test.
Claims (16)
1. carrier; It is characterized in that; Said carrier comprises supporter (11) and at least one analytic unit, and each analytic unit comprises that porous matrix layer (12) and enhancement layer (14) are positioned at except that on the liquid structure except that liquid structure, porous matrix layer (12) and enhancement layer (14); The said liquid structure of removing is arranged in said supporter (11) or is positioned on said supporter (11) surface; Said enhancement layer (14) is positioned on said porous matrix layer (12) surface, and the said liquid structure of removing is used for receiving the liquid from porous matrix layer (12), and said enhancement layer (14) is used to strengthen Raman scattering intensity.
2. carrier according to claim 1; Wherein, Said analytic unit is a plurality of, and the enhancement layer (14) of 2 adjacent analytic units and porous matrix layer (12) be apart from one another by opening, and shared one of a plurality of analytic units remove liquid structure or each analytic unit and have the independent liquid structure of removing.
3. carrier according to claim 1 and 2, wherein, the said liquid structure of removing is liquid-adsorption layer (13a), said liquid-adsorption layer (13a) is positioned at the surface of supporter (11).
4. carrier according to claim 3, wherein, the liquid absorption of said liquid-adsorption layer (13a) is the 1-1000 microlitre, and the thickness of said liquid-adsorption layer (13a) is the 0.1-10 millimeter, and the pick up of said liquid-adsorption layer (13a) is 0.1-10.
5. carrier according to claim 1 and 2, wherein, the said liquid structure of removing is for being arranged in the duct (13b) of supporter (11).
6. carrier according to claim 5; Wherein, Said duct (13b) comprises inlet (13b1) and outlet (13b2); Said inlet (13b1) is positioned at the below of porous matrix layer (12), imports in the duct (13b) through said inlet (13b1) from the liquid of porous matrix layer (12), and through said outlet (13b2) derivation supporter (11).
7. carrier according to claim 1 and 2, wherein, the thickness of said enhancement layer (14) is the 0.1-1000 micron.
8. carrier according to claim 7, wherein, said enhancement layer (14) is formed by reinforcing agent.
9. carrier according to claim 8, wherein, said reinforcing agent comprises metal nanoparticle or independent metal nanoparticle of preserving and the material that can make the metal nanoparticle cohesion.
10. carrier according to claim 9, wherein, the particle diameter of the said metal nanoparticle of at least 50 weight % is the 5-500 nanometer, said metal is one or more in gold, silver, copper, nickel, platinum, iron and the aluminium; The said material that can make the metal nanoparticle aggegation is in acid, alkali and the salt one or more.
11. carrier according to claim 1 and 2, wherein, said carrier also comprises shell (15), and said shell (15) is fixed on the supporter (11), a space forming surface of said shell (15) and supporter (11), and analytic unit is positioned at this space; Said shell (15) comprises opening (16), and at least one said opening is corresponding to the position of said analytic unit.
12. carrier according to claim 11, wherein, said carrier also comprises filter membrane (17), and said filter membrane (17) covers on the opening (16) of said shell (15), and the molecular cut off of said filter membrane is more than 10000.
13. a kit is characterized in that, said kit comprises any described carrier among the claim 1-12.
14. SERS analytical approach; This method comprises that the solution with testing sample loads on the carrier; Measure the Raman spectrum of testing sample then; It is characterized in that said carrier is any described carrier among the claim 1-12, the method that loads on the carrier is added on the enhancement layer of said carrier for the solution that will contain testing sample.
15. method according to claim 14 wherein, also contains the known internal standard compound of content in the said mixed liquor, said internal standard compound is not overlapped with the Raman spectrum of determinand or whole overlapping material for itself producing Raman spectrum and this Raman spectrum.
16. method according to claim 14; Wherein, This method comprises that also the external standard that content is known loads on the said carrier; Measure the Raman spectrum of external standard then, and the Raman spectrum of this external standard and the Raman spectrum of testing sample are compared, said external standard and testing sample have same or similar Raman spectrum characteristic peak.
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| CN102221542A (en) * | 2011-03-24 | 2011-10-19 | 华南师范大学 | Method for detecting Clenbuterol by applying competitive SERS (Surface-Enhanced Raman Scattering) and application thereof |
| WO2013109280A1 (en) * | 2012-01-19 | 2013-07-25 | Hewlett-Packard Development Company, L.P. | Molecular sensing device |
| WO2014025034A1 (en) | 2012-08-10 | 2014-02-13 | 浜松ホトニクス株式会社 | Surface-enhanced raman scattering unit |
| WO2014025035A1 (en) | 2012-08-10 | 2014-02-13 | 浜松ホトニクス株式会社 | Surface-enhanced raman scattering element |
| US9863884B2 (en) | 2012-08-10 | 2018-01-09 | Hamamatsu Photonics K.K. | Surface-enhanced Raman scattering element, and method for producing same |
| CN108827928B (en) | 2012-08-10 | 2021-12-24 | 浜松光子学株式会社 | Surface enhanced Raman scattering unit and using method thereof |
| CN104076023B (en) * | 2014-07-22 | 2017-01-18 | 中国人民解放军第三军医大学第一附属医院 | Body fluid Raman spectrum testing device |
| GB201418483D0 (en) * | 2014-10-17 | 2014-12-03 | Johnson Matthey Plc | Analytical method and composition |
| CN104406953B (en) * | 2014-11-21 | 2017-10-27 | 中国科学院电子学研究所 | Uniform Raman detection chip of large area of perforated membrane enhanced sensitivity and preparation method thereof |
| CN106153598B (en) * | 2015-04-23 | 2024-02-13 | 北京嘉信怡达科技有限公司 | A thin slice fixing device and short-term test raman spectrometer for short-term test |
| CN104914089B (en) * | 2015-06-18 | 2017-10-27 | 清华大学 | The method for carrying out semi-quantitative analysis to trace mixture with SERS |
| EP3353535A4 (en) * | 2016-02-29 | 2019-06-26 | Hewlett-Packard Development Company, L.P. | Surface enhanced raman spectroscopy sample carrier |
| CN106979942B (en) * | 2017-05-04 | 2020-07-07 | 华中师范大学 | Raman spectrum analysis method for individual quantification of solid-phase synthesized compound combinatorial library and application thereof |
| CN113466202A (en) * | 2021-06-18 | 2021-10-01 | 上海应用技术大学 | On-site rapid detection method for pesticide residues in fruit and vegetable samples |
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