CN101788478B - Optical fibre localization plasma resonance sensing device and system thereof - Google Patents
Optical fibre localization plasma resonance sensing device and system thereof Download PDFInfo
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- CN101788478B CN101788478B CN200910005297XA CN200910005297A CN101788478B CN 101788478 B CN101788478 B CN 101788478B CN 200910005297X A CN200910005297X A CN 200910005297XA CN 200910005297 A CN200910005297 A CN 200910005297A CN 101788478 B CN101788478 B CN 101788478B
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Abstract
The invention relates to an optical fibre localization plasma resonance sensing device and a system thereof. The optical fibre localization plasma resonance sensing system comprises a light source, an optical fibre localization plasma resonance sensing device and a detection unit; the light source provides a light beam incoming to the optical fibre localization plasma resonance sensing device; and the detection unit receives the emergent light of the optical fibre localization plasma resonance sensing device to generate a detection signal. The optical fibre localization plasma resonance sensing device comprises an optical fibre, a precious metal nano particle layer and a thin filter layer, wherein the thin filter layer is a porous material; the aperture or property of the porous material is selected according to the characteristics of the matter to be detected and, at the same time, an interfere source is isolated.
Description
Technical field
The present invention relates to a kind of sensing apparatus and system thereof, particularly relate to a kind of optical fibre localization plasma resonance sensing device and system thereof.
Background technology
At present, localization plasma (or being called the electricity slurry) resonance (Localized PlasmonResonance, LPR) the energy immediate reaction goes out the change of refractive of metal nanoparticle environment of living in, when the localization plasma resonance bands of a spectrum produced change, the spectral distribution of its emergent light or luminous energy can be affected equally.If how the identification unit with selective power in the rice finishing to metal, just have only specific tie substance just can be adsorbed on the Jin Naimi particle surface so in the analytic sample, also just the environment refractive index that the metal nanoparticle is experienced can be had influence on, just narrow spectrum detectability can be reached by this.Further, if metal nanoparticle layer (as gold or silver-colored nanoparticle) is fixed on the optical fiber base material, except effectively reducing the volume of sensor, more can utilize optical fiber repeatedly the phenomenon of total reflection remove to accumulate the variable quantity of LPR signal, the sensing sensitivity of sensor is promoted more.In other words, at light reflex time each time, incident optical signal all can be subjected to the influence of localization plasma resonance and luminous energy is partly absorbed or scattering, therefore when order of reflection is got over repeatedly, the luminous energy decay at this frequency place will add up constantly, therefore also just can reach the purpose of sensitivity lifting.And above-mentionedly develop the sensing element that forms in conjunction with optical fiber base material and localization plasma resonance principle, we just are referred to as optical fibre localization plasma resonance sensing (Fiber-Optic Localized Plasmon Resonance, FO-LPR), after the integration of identification molecule, it is possessing the sensing function of selectivity and high sensitivity simultaneously, therefore the very potential sensing equipment that is developed to instant detection usefulness.Moreover, utilize repeatedly total reflection to go the method for accumulating signal, also can be applicable on the detection technology of surperficial enhanced spectrum, strengthen and Raman scattering (Surface-enhanced Raman Scattering) and surface enhancing fluorescence (Surface-enhanced fluorescence) as the surface.
Though FO-LPR can have instant and highly narrow spectrum detectability, but when being used for the detection of authentic sample, sensor must be directly exposed in the complex environment, this moment is such as cell debris, blood plasma, blood cell, immunocyte even dust and cellulosic or the like interference source, all have an opportunity to be stained with and be bonded at the sensor surface with absorption or mode such as deposition, this moment, the metal nanoparticle will be experienced the variations in refractive index that these covertures cause, and made measurement produce serious deviation.Therefore, if will allow FO-LPR really can be used for the detection of authentic sample, be bound to such an extent that get rid of the phenomenon of the non-specific adsorption that these bulky grain chaff interferences are produced earlier.
Summary of the invention
Because the problem of above-mentioned known techniques, purpose of the present invention is providing a kind of optical fibre localization plasma resonance sensing device and system thereof exactly, to solve the problem relevant with known techniques.
The object of the invention to solve the technical problems realizes by the following technical solutions.According to a kind of optical fibre localization plasma resonance sensing device that the present invention proposes, it comprises: at least one optical fiber; One noble metal nanoparticle layer is fixed on this optical fiber; And one filter thin layer, is a multiple hole material, and coats this optical fiber; Wherein, the aperture of this multiple hole material or character are to do according to the characteristic of a test substance to select also to isolate simultaneously an interference source.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid optical fibre localization plasma resonance sensing device, wherein said optical fiber are the optical fiber of an optical fibre localization plasma resonance (Fiber-Optic Localized Plasmon Resonance).
Aforesaid optical fibre localization plasma resonance sensing device, the zone of peeling off of wherein said optical fiber is a sensing region.
Aforesaid optical fibre localization plasma resonance sensing device, wherein said fiber selection one whole circle divests the optical fiber of shell (cladding) or selects for use a part to divest the optical fiber of shell.
The optical fiber that aforesaid optical fibre localization plasma resonance sensing device, wherein said part divest shell is a D shape optical fiber (D-fiber).
Aforesaid optical fibre localization plasma resonance sensing device can produce fluorescence or Raman diffused light after wherein said noble metal nanoparticle layer and the incident light effect.
Aforesaid optical fibre localization plasma resonance sensing device, wherein said noble metal nanoparticle layer is made up of golden nanoparticle or silver-colored nanoparticle.
Aforesaid optical fibre localization plasma resonance sensing device, the pore size of wherein said filtration thin layer is between 0.2 micron to 20 microns.
Aforesaid optical fibre localization plasma resonance sensing device, the aperture density of wherein said filtration thin layer is between 4 * 10
4Cm
-2To 20 * 10
4Cm
-2
Aforesaid optical fibre localization plasma resonance sensing device, the thickness of wherein said filtration thin layer is between 50 microns to 100 microns.
Aforesaid optical fibre localization plasma resonance sensing device, the molecular weight that dams of wherein said filtration thin layer (MWCO, molecular weight cut off) is less than or equal to 500KDa.
Aforesaid optical fibre localization plasma resonance sensing device, the material of wherein said filtration thin layer is polysulfones (PS, polysulfone), cellulose esters (CE, Cellulose Ester), regenerated cellulose (RC, Regenerated Cellulose), polyethersulfone (PES, polyether sylfone) and poly aromatic ether sulfone (PAES, one polyarylethersulphone) or its combination.
Aforesaid optical fibre localization plasma resonance sensing device also comprises the surface rigid material that punches between wherein said filtration thin layer and this optical fiber, a physical support to be provided and to guide this test substance to specific sensing region.
Aforesaid optical fibre localization plasma resonance sensing device, wherein said surface the punching of rigid material that punch is shaped as a circular opening shape or an elongated gap shape.
Aforesaid optical fibre localization plasma resonance sensing device wherein also comprises at least one conduit, places in this filtration thin layer, and this at least one conduit is in order to importing or flow out this test substance.
Aforesaid optical fibre localization plasma resonance sensing device, wherein said at least one conduit is with this test substance suction or detach this filtration thin layer.
Aforesaid optical fibre localization plasma resonance sensing device, wherein said filtration thin layer screens this test substance and purifying.
Aforesaid optical fibre localization plasma resonance sensing device, wherein said interference source are that a blood cell, a cell debris, immunocyte, dust, cellulosic, bacterium, a local protein, a big molecule, have the stick nature of being stained with or oarse-grained impurity.
Aforesaid optical fibre localization plasma resonance sensing device, the end of wherein said optical fiber plate a minute surface (mirror coating), in order to reflected light signal.
Aforesaid optical fibre localization plasma resonance sensing device, wherein said noble metal nanoparticle layer is fixed on this optical fiber connector, in order to scattering or reflected light signal.
Aforesaid optical fibre localization plasma resonance sensing device, wherein said optical fiber utilize etching mode with core (core) hollow out of this optical fiber connector to form an openwork part, this openwork part comprises a porous material (porous material), and this noble metal is fixed on this porous material.
The object of the invention to solve the technical problems also realizes by the following technical solutions.According to a kind of optical fibre localization plasma resonance sensing system that the present invention proposes, it comprises: an optical fibre localization plasma resonance sensing device comprises: at least one optical fiber; One noble metal nanoparticle layer is fixed on this optical fiber; Reach one and filter thin layer, be a multiple hole material, and coat this optical fiber; One light source provides this optical fibre localization plasma resonance sensing device of light beam incident; And a detecting unit, the emergent light that receives this optical fibre localization plasma resonance sensing device is to produce a detection signal; Wherein, the aperture of this multiple hole material or character are done according to the characteristic of a test substance and are selected also to isolate simultaneously an interference source.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid optical fibre localization plasma resonance sensing system, wherein said optical fiber are the optical fiber of an optical fibre localization plasma resonance (Fiber-Optic Localized Plasmon Resonance).
Aforesaid optical fibre localization plasma resonance sensing system, the zone of peeling off of wherein said optical fiber is a sensing region.
Aforesaid optical fibre localization plasma resonance sensing system, wherein said fiber selection one whole circle divests the optical fiber of shell (cladding) or selects for use a part to divest the optical fiber of shell.
The optical fiber that aforesaid optical fibre localization plasma resonance sensing system, wherein said part divest shell is a D shape optical fiber (D-fiber).
Aforesaid optical fibre localization plasma resonance sensing system can produce fluorescence or Raman diffused light after wherein said noble metal nanoparticle layer and the incident light effect.
Aforesaid optical fibre localization plasma resonance sensing system, wherein said noble metal nanoparticle layer is made up of golden nanoparticle or silver-colored nanoparticle.
Aforesaid optical fibre localization plasma resonance sensing system, the pore size of wherein said filtration thin layer is between 0.2 micron to 20 microns (μ m).
Aforesaid optical fibre localization plasma resonance sensing system, the aperture density of wherein said filtration thin layer is between 4 * 10
4Cm
-2To 20 * 10
4Cm
-2
Aforesaid optical fibre localization plasma resonance sensing system, the thickness of wherein said filtration thin layer is between 50 to 100 microns (μ m).
Aforesaid optical fibre localization plasma resonance sensing system, the molecular weight that dams of wherein said filtration thin layer (MWCO, molecular weight cut off) is less than or equal to 500KDa.
Aforesaid optical fibre localization plasma resonance sensing system, the material of wherein said filtration thin layer is polysulfones (PS, polysulfone), cellulose esters (CE, Cellulose Ester), regenerated cellulose (RC, Regenerated Cellulose), polyethersulfone (PES, polyethersylfone) and poly aromatic ether sulfone (PAES, one polyarylethersulphone) or its combination.
Aforesaid optical fibre localization plasma resonance sensing system also comprises the surface rigid material that punches between wherein said filtration thin layer and this optical fiber, physical support to be provided and to guide this test substance to specific sensing region.
Aforesaid optical fibre localization plasma resonance sensing system, wherein said surface the punching of rigid material that punch is shaped as a circular opening shape or an elongated gap shape.
Aforesaid optical fibre localization plasma resonance sensing system wherein also comprises at least one conduit, places in this filtration thin layer, and this at least one conduit is in order to importing or flow out this test substance.
Aforesaid optical fibre localization plasma resonance sensing system, wherein said at least one conduit is with this test substance suction or detach this filtration thin layer.
Aforesaid optical fibre localization plasma resonance sensing system, wherein said filtration thin layer screens this test substance and purifying.
Aforesaid optical fibre localization plasma resonance sensing system, wherein said interference source are that a blood cell, a cell debris, immunocyte, dust, cellulosic, bacterium, a local protein, a big molecule, have the stick nature of being stained with or oarse-grained impurity.
Aforesaid optical fibre localization plasma resonance sensing system, the end of wherein said optical fiber plate a minute surface (mirror coating), in order to reflected light signal.
Aforesaid optical fibre localization plasma resonance sensing system, wherein said noble metal nanoparticle layer is fixed on this optical fiber connector, in order to scattering or reflected light signal.
Aforesaid optical fibre localization plasma resonance sensing system, wherein said optical fiber utilize etching mode with core (core) hollow out of this optical fiber connector to form an openwork part, this openwork part comprises a porous material (porous material), and this noble metal is fixed on this porous material.
Aforesaid optical fibre localization plasma resonance sensing system, wherein said light source are a laser beam or a light emitting diode (LED).
Aforesaid optical fibre localization plasma resonance sensing system, wherein said detecting unit are a photodiode (Photodiode).
Aforesaid optical fibre localization plasma resonance sensing system wherein also comprises an at least one conduit and a pump (pump), this pump by this at least one conduit with this test substance suction or detach this filtration thin layer.
The present invention compared with prior art has tangible advantage and beneficial effect.By technique scheme, optical fibre localization plasma resonance sensing device of the present invention and system thereof have following advantage and beneficial effect at least:
(1) this optical fibre localization plasma resonance sensing device and system thereof lean on its multiple hole material that filters thin layer, and it can really be applied in the detection of complicated authentic sample.
(2) this optical fibre localization plasma resonance sensing device and system thereof can do selection according to the characteristic of target molecule, only allow the material that desire detects can be penetrating and go into as far as possible, and isolate unnecessary interference source simultaneously.
In sum, the present invention is relevant a kind of optical fibre localization plasma resonance sensing device and system thereof.This optical fibre localization plasma resonance sensing system comprises a light source, an optical fibre localization plasma resonance sensing device and a detecting unit, this light source provides this optical fibre localization plasma resonance sensing device of light beam incident, and this detecting unit receives the emergent light of this optical fibre localization plasma resonance sensing device to produce a detection signal.This optical fibre localization plasma resonance sensing device comprises an optical fiber, a noble metal nanoparticle layer and filters thin layer, this filtration thin layer is a multiple hole material, and wherein the aperture of this multiple hole material or character are done according to the characteristic of test substance and selected also to isolate simultaneously an interference source.The present invention has obvious improvement technically, and has tangible good effect, really is a new and innovative, progressive, practical new design.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of instructions, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.
Description of drawings
Fig. 1 is the synoptic diagram of first embodiment of optical fibre localization plasma resonance sensing device of the present invention.
Fig. 2 is the synoptic diagram of second embodiment of optical fibre localization plasma resonance sensing device of the present invention.
Fig. 3 A is the synoptic diagram of the 3rd embodiment of optical fibre localization plasma resonance sensing device of the present invention.
Fig. 3 B is the structural map of the reflective FO-LPR of optical fibre localization plasma resonance sensing device of the present invention.
Fig. 4 A is the synoptic diagram that the whole circle of the optical fiber of optical fibre localization plasma resonance sensing device of the present invention divests.
Fig. 4 B is the synoptic diagram that the fiber section of optical fibre localization plasma resonance sensing device of the present invention divests.
Fig. 4 C is the sectional view that the fiber section of optical fibre localization plasma resonance sensing device of the present invention divests.
Fig. 4 D is the sensing probe synoptic diagram that the optical fiber connector of optical fibre localization plasma resonance sensing device of the present invention plates a minute surface.
Fig. 4 E is the sensing probe synoptic diagram that the optical fiber connector of optical fibre localization plasma resonance sensing device of the present invention is modified noble metal nanoparticle layer.
Fig. 4 F is that the optical fiber connector core hollow out of optical fibre localization plasma resonance sensing device of the present invention is inserted porous material and modified the sensing probe synoptic diagram of noble metal nanoparticle.
Fig. 4 G is the sensing probe synoptic diagram that the optical fiber connector of optical fibre localization plasma resonance sensing device of the present invention is modified noble metal nanoparticle layer.
Fig. 5 is the synoptic diagram of the 4th embodiment of optical fibre localization plasma resonance sensing system of the present invention.
Fig. 6 is the sensed signal time chart that optical fibre localization plasma resonance sensing system of the present invention changes in conjunction with dialysis technology refractive index.
Fig. 7 A be the aqueous sample that contains interference source PS ball of the present invention after filtration thin layer become the synoptic diagram of clear aqueous solution.
Fig. 7 B is that optical fibre localization plasma resonance sensing system of the present invention signal reaction of PS aqueous solution and its filtrate under the interference source environment carries out sensing.
Fig. 7 C is that optical fibre localization plasma resonance sensing system of the present invention is to different refractivity but the aqueous sample that contains interference source PS ball is carried out the sensed signal time chart.
Fig. 8 A is that optical fibre localization plasma resonance sensing system of the present invention carries out the sensed signal time chart at biochemical molecular under the interference source environment.
8B figure be optical fibre localization plasma resonance sensing system of the present invention under the interference source environment at biochemical molecular carry out sensing get each balance the time signal is carried out data analysis to the concentration logarithm graph of a relation as a result.
Fig. 9 is that optical fibre localization plasma resonance sensing system of the present invention is to the screening of streptomysin and toxamin H and the signal time graph of a relation of sensing function.
1: optical fibre localization plasma resonance sensing device 2: optical fiber
3: noble metal layer 4: filter thin layer
5: 51: the first conduits of conduit
7: minute surface 8: porous material
9: light source 10: detecting unit
11:PS aqueous solution 12: filtrate
13: pure water
Embodiment
Reach technological means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, optical fibre localization plasma resonance sensing device and its embodiment of system, structure, feature and effect thereof that foundation the present invention is proposed are elaborated.
The original intention of this patented invention, be in view of any biochemical sensor no matter be the surface treatment of having passed through how many times, the neither interference that can exempt all impurity in the authentic sample fully is even though the FO-LPR technology has the selectivity of certain ability, equally also lock into the interference of non-specific adsorption.Therefore in order to reduce the unexpected result of this kind, we coat a filtration thin layer that can screen molecular size or characteristic outside the optical fiber of FO-LPR, directly the bulky grain chaff interference is got rid of outside sensing region in the mode of isolating, and the penetrating character of the multiple hole material selectivity of thin layer is filtered in utilization, the analyte that only allows desire detect enters, and in the sensing region of FO-LPR simple cleaner working environment just can have been arranged at this moment.In addition, the thin layer of this screening usefulness is good with being shaped as of hollow column jacket, and the volume of entire combination element is also the smaller the better.
Seeing also shown in Figure 1ly, is the synoptic diagram of first embodiment of optical fibre localization plasma resonance sensing device of the present invention.Resonance sensing device 1 comprises an optical fiber 2 to the optical fibre localization plasma of first embodiment of the invention (or being called the electricity slurry), a noble metal nanoparticle layer 3 and filters thin layer 4.
Above-mentioned optical fiber 2 is the optical fiber of an optical fibre localization plasma resonance, and the peeling zone of this optical fiber is a sensing region; Above-mentioned noble metal nanoparticle layer 3 is made up of golden nanoparticle or silver-colored nanoparticle, and this noble metal nanoparticle layer 3 is fixed on this optical fiber 2; Above-mentioned filtration thin layer 4 is multiple hole materials, and coats this optical fiber 2, wherein also comprises an at least one conduit 5 and a pump (pump), this pump by this at least one conduit 5 with this test substance suction or detach this filtration thin layer 4.The method can reach the action of mass transfer in high efficiency mode, imports or flows out a test substance.This test substance is a biological molecule or a chemical molecular, and the filtration thin layer 4 of this moment similarly is that screen cloth is general, originally complicated analytic sample can be screened and purifying, wherein, the aperture or the character of filtering the multiple hole material of thin layer 4 are to do selection according to the characteristic of this test substance, and isolate an interference source simultaneously.It filters the thin layer aperture density can be between 4 * 10
4Cm
-2To 20 * 10
4Cm
-2(every square centimeter number), its thickness can be between 50 microns to 100 microns (μ m), its molecular weight (MWCO that dams, molecular weight cut off) can be less than or equal to 500KDa, its material be polysulfones (PS, polysulfone), cellulose esters (CE, Cellulose Ester), regenerated cellulose (RC, Regenerated Cellulose), polyethersulfone (PES, polyethersylfone) and poly aromatic ether sulfone (PAES, polyarylethersulphone).This interference source is that a blood cell, a cell debris, immunocyte, dust, cellulosic, bacterium, a local protein, a big molecule, have the stick nature of being stained with or oarse-grained impurity.
Seeing also shown in Figure 2ly, is the synoptic diagram of second embodiment of optical fibre localization plasma resonance sensing device of the present invention.The optical fibre localization plasma resonance sensing device of second embodiment of the invention comprises an optical fiber 2, a noble metal nanoparticle layer 3 and a filtration thin layer 4.Above-mentioned noble metal nanoparticle layer 3 is fixed on this optical fiber 2, this filtration thin layer 4 is multiple hole materials, and coat this optical fiber 2, wherein also comprise first conduit 51 and second conduit 52, it is to place this filtration thin layer interior 4, first conduit 51 is in order to import test substance, and second conduit 52 is in order to derive test substance.This test substance is a biological molecule or a chemical molecular, and the filtration thin layer of this moment similarly is that screen cloth is general, test substance can be screened, wherein, the aperture or the character of filtering the multiple hole material of thin layer 4 are to do selection according to the characteristic of this test substance, and isolate an interference source simultaneously.It is technical that this optical fibre localization plasma resonance sensing device 1 can be used on microdialysis, its microdialysis technology mainly is the sampling design at the outer liquid of active somatic cell, similar artificial blood vessel function, the injury that the pair cell tissue was caused when it can reduce experiment, and in the sampling process of biology inspection product, do not influence the volume of biofluid, so can be used to handle live body (in vivo) simultaneously or (in vitro) the micro-sample that exsomatizes.When seeing through the sampling of microdialysis pipe, must use two liquid conduits simultaneously, be responsible for the importing and the outflow of dislysate, the liquid flow of inner generation this moment, then can make the outer easier FO-LPR of being brought into of the sample surface of filtering substrate, and the existence of dialysis membrane can be isolated in local protein or other big molecules outside the film then, therefore the collected liquid phase of microdialysis technology is worked as totally, therefore also just can reduce the phenomenon of the non-specific adsorption of large granular impurity.When FO-LPR was rendered in the live body detection, the collocation of microdialysis technology can be one and well select.
Seeing also shown in Fig. 3 A, is the synoptic diagram of the 3rd embodiment of optical fibre localization plasma resonance sensing device of the present invention.The optical fibre localization plasma resonance sensing device of third embodiment of the invention comprises an optical fiber 2, a noble metal nanoparticle layer 3 and a filtration thin layer 4.This noble metal nanoparticle layer 3 is fixed on this optical fiber 2, and this filtration thin layer 4 is multiple hole materials, and coats this optical fiber 2, and the filtration thin layer 4 of this moment similarly is that screen cloth is general, test substance can be screened.Because filter the existence of thin layer 4,, make the FO-LPR sensing optical fiber 2 of the inside can be among the more simple environment so the big or complicated material of particle will be isolated in outside this thin layer in the raw sample.In addition, if filtering the selection character or the hole size of thin layer 4 selects proper, it also can be isolated the bacterium or the chip of optical fiber 2 itself with analytic sample, except the pollution that can avoid analytic sample, also can save the puzzlement that must carry out disinfection before the element use simultaneously.Because FO-LPR optical fiber 2 is own because divested the optical fiber shell (cladding) of a part, therefore becomes cracked easily; Also can produce deformation and filter thin layer 4 itself, even cover the surface of optical fiber sensing region because of the pressure of external environment or the influence of gravity.Therefore can insert the suitable surface rigid material 6 that punches filtering thin layer 4 and 2 of FO-LPR optical fiber, so that a good physical support to be provided.For example there are several diameters on a surface approximately greater than the hollow draw point of 0.5 millimeter (mm) aperture, be exactly a kind of fit closely selection, but opening diameter also is not suitable for greater than 5 millimeters, to avoid the anchorage force deficiency of draw point.Shown in Fig. 3 B, structural map for the reflective FO-LPR of optical fibre localization plasma resonance sensing device, it is configured with as the probe, if use the epitheca of pointed draw point as guiding usefulness simultaneously, just can easily reflective LPR probe be penetrated into the particular block that desire detects.Briefly, the draw point of pointed perforate is just like guide (guider), outside the optical fiber 2 that reflection type optical fiber formula localization plasma resonance (RFO-LPR) not only the is provided physical support good, also they can be directed in the specific detection block simultaneously with filtering thin layer 4.In addition, if the firm nothing of the physical strength of sensing element integral body anxiety, the shape of perforate also not necessarily will be based on circular opening so, also can be in the larger area mode, for example the mode of elongated gap is fundamental purpose as the design of hole shape with the speed that promotes the analytic sample mass exchange.
Seeing also shown in Fig. 4 A-Fig. 4 G, is the synoptic diagram of the optical fiber of optical fibre localization plasma resonance sensing device of the present invention.The fiber section of its FO-LPR can be selected the mode (as Fig. 4 A) that divests whole circle shell for use, or use the configuration (as Fig. 4 B) that only divests a part of shell, and its diagrammatic cross-section is shown in Fig. 4 C.The wherein latter's design, because kept part optical fiber shell, make fragile fiber optic core can be subjected to more physical support, therefore physical strength (for example the design of D type optical fiber D-Fiber is exactly to belong to the latter) is preferably arranged, therefore if will develop finer optical fibre localization plasma resonance sensing device the time, the design of using Fig. 4 B will be one and well select.Shown in Fig. 4 D, plate the sensing probe synoptic diagram of a minute surface for the optical fiber connector of optical fibre localization plasma resonance sensing device, utilization plates the mode of a minute surface 7, reflect its light signal, with it immersion or penetrate into particular block, just detection be can finish, the medical treatment or the equipment of instant pick test therefore are more suitable for being developed to.Shown in Fig. 4 E, modify the sensing probe synoptic diagram of noble metal nanoparticle layer 3 for the optical fiber connector of optical fibre localization plasma resonance sensing device, we can be fixed on optical fiber 2 ends with noble metal nanoparticle layer 3, utilize the intensity of scattering or reflected light signal to be used as the sensing principle.Because optical fiber is not by the peeling optical fibre shell, so better mechanical strength can be arranged in this framework.Shown in Fig. 4 F, be optical fiber connector core 11 hollow outs of optical fibre localization plasma resonance sensing device, insert porous material 8 again and modify the sensing probe synoptic diagram of noble metal nanoparticle layer 3.It can use the core 11 part hollow outs of etched mode with optical fiber 2 latter ends, and optical fiber 2 shells 12 of a reservation part, in this space, insert mushy material 8 then, (for example collosol and gel materials such as (sol-gel)) is fixed on these pore surfaces to finish the construction of this type of probe with noble metal nanoparticle layer 3 at last again.At first be to wish, to increase the speed of analytic sample, simultaneously again by the advantage of material high surface, to increase the action of noble metal nanoparticle, to reach better sensing effect in mass transfer by the mushy character of material.Shown in Fig. 4 G, modify the sensing probe synoptic diagram of noble metal nanoparticle layer 3 for the optical fiber connector of optical fibre localization plasma resonance sensing device, utilize chemistry or machining to form pointed (tapered) optical fiber, we can be fixed on optical fiber 2 ends with noble metal nanoparticle layer 3, in order to the fluorescence or the Raman diffused light that produce after collection incident light and the effect of noble metal nanoparticle, and at optical fiber input end collection sensing signal.
Seeing also shown in Figure 5ly, is the synoptic diagram of the 4th embodiment of optical fibre localization plasma resonance sensing system of the present invention.The optical fibre localization plasma resonance sensing system of fourth embodiment of the invention, comprise an optical fibre localization plasma resonance sensing device 1, a light source 9 and a detecting unit 10, this light source 9 can be provides a light beam incident this optical fibre localization plasma resonance sensing device 1, and this detecting unit 10 receives the emergent light of this optical fibre localization plasma resonance sensing device 1 to produce a detection signal.Wherein light source is a laser beam or a light emitting diode (LED), detecting unit is a photodiode (photodiode), though FO-LPR probe-type sensor has excellent sensing function, but when it is applied in the detection of authentic sample, certainly will will run into the interference of serious non-specific adsorption.This is that for example all interference sources such as blood cell, cell debris, cellulosic all have an opportunity to cover on LPR optical fiber 2 surfaces because the composition of authentic sample is very complicated, causes detection signal to produce serious skew.In view of this, we do probe-type FO-LPR sensing system and combine with the microdialysis technology, and the role of perforate draw point is the physical support that is used as element; The microdialysis The Application of Technology allows this element have the ability of optionally taking a sample; Quick, the sensitive sensing function of FO-LPR of arranging in pairs or groups at last, and can develop the instant medical assembly that detects usefulness in the adult.Owing in this combined system liquid conduits is arranged, can be used for importing various medicaments, also can be used for extracting the sample in the element.Even under situation about being necessary, can just can activate or the action of regenerating by the importing of all ingredients to the FO-LPR sensor.If by the interpretation of FO-LPR signal, except learning the relevant message of the state of an illness immediately, more can inject the medicine of suitable dosage subsequently, to reach the function of suiting the remedy to the case.
See also shown in Figure 6ly, it is the sensing of optical fibre localization plasma of the present invention (or be called electricity slurry) resonant sensing system in conjunction with the variation of dialysis technology refractive index.In the experiment of this part, we inject the aqueous sucrose solution of different refractivity in the sample tank, study the influence that each sample causes the LPR signal.Wherein because the existence of dialysis membrane (MW cut-off:100KDa) makes analyte be restricted on mass transfer, so certainly will will provide a method to increase the speed that quality passes.What adopted in this system is that effect is soft, the mode that destructive minimum acceleration is taken a sample, and the sensing system that just adopts the microdialysis method to be set up, the available Fig. 2 of its unitary construction figure does explanation.When the experimental result demonstration increases gradually along with refractive index, LPR optical waveguide signal will slowly reduce, and the slow process stably that drops to of this signal, promptly be to have manifested sample just in filtering thin layer, to carry out the transmission of quality in soft mode, system needs about 1000 seconds time just can reach balance, and the collection of illustrative plates of light signal also presents by the precipitous slow trend that flattens.
See also shown in Fig. 7 A, be the aqueous sample that contains interference source PS ball of the present invention after filtration thin layer become the synoptic diagram of clear aqueous solution.Wherein interference source is that (negative charge is being with on the surface of PS plastic cement ball to polystyrene for Polystyrene, PS) plastic cement ball aqueous solution, therefore can be dispersed in the aqueous solution in the mode of electrostatic repulsion.And the PS ball mainly contained three: the first the interference of LPR sensor, these PS balls because particle is bigger, so have the phenomenon of deposition when leaving standstill; The second, the PS ball itself has negative charge, can be adsorbed on the golden nanoparticle because of the effect of electrostatic force; The 3rd, PS ball solution is white in color, and therefore can change the energy distribution of optical waveguide.Supernatant liquid among Fig. 7 A promptly is that concentration is 2.18 * 10
9The PS ball aqueous solution 11 of beads/mL, but be 200 after how the filtration membrane 4 of rice filters through the aperture, 12 states that present clarification of its filtrate.Fig. 7 B is that penetration optical fibre localization plasma resonance system (TFO-LPR) is to the signal reaction of PS aqueous solution 11 with its filtrate 12, the TFO-LPR system carried out balance before this in pure water 13, when then the filtrate 12 of the clarification among Fig. 7 A being injected sensing system, can find that the LPR signal does not change; But, then can observe rapid signal and descend if directly with in PS aqueous solution 11 injected systems.This is because the PS aqueous solution 11 of white at first can have influence on the evanescent wave energy of optical waveguide, directly cause out the change of light intensity, we can observe the LPR signal and begin to descend gradually in addition, and this may be because the PS ball begins to be deposited on the golden nanoparticle surface and causes.We utilize pure water 11 injected systems for several times at last, wishes the sensing optical fiber surface washing is clean, but we can find that the LPR signal has departed from the balanced signal of its script, confirms to have covered on the golden nanoparticle surface PS ball to a certain degree indirectly.This basic research also shows, using the aperture is 200 filtration membranes of rice how, can be how meter 500 PS balls isolate really with sensing optical fiber and particle diameter, avoids the influence of bulky grain interference source to the LPR signal.In the experiment of this part, we are 2.18 * 10 with concentration
8The PS aqueous solution 11 of beads/mL is as the sample of each different refractivity of solvent configure, so the outward appearance of these samples all is to present white casse.Shown in Fig. 7 C, for the optical fibre localization plasma resonance system to different refractivity but the aqueous sample that contains interference source PS ball is carried out the sensed signal time chart.The purpose of this experiment is to confirm that the LPR sensor can detect under the environment of muddiness really.Experimental technique is to inject different refractivity and muddy aqueous sucrose solution sample in the sample tank, analyze the relation that light intensity and variations in refractive index of optical fiber LPR sensing system then, the result can find when refractive index increases, the LPR signal will decrease, and after 90 seconds, reach balance greatly, the graphic change of signal also comparing class shows and uses the mode that extracts can quicken the mass transfer of analyte inside and outside filtering membrane really like stair-stepping variation.
Seeing also shown in Fig. 8 A, is that optical fibre localization plasma resonance sensing system of the present invention carries out the sensed signal time chart at biochemical molecular under the interference source environment.In order to verify that sensing system that LPR optical fiber collocation filtration membrane is set up has the ability of biochemistry detection, we use the model of biotin-streptomysin (biotin-streptavidin) to do test.The method of experiment is to utilize biotin on the LPR optical fiber surface is modified, and tries to detect film screening streptomysin later after filtration.In the experiment employed filtration membrane be by the aperture by 200 how the cellulose of rice constituted, therefore molecular weight has only the streptomysin (～4 how meter) of 60kDa to enter in the film very wellly in theory, is checked by FIBER OPTIC SENSORS at last.Fig. 8 B promptly is signal is carried out data analysis to the concentration logarithm the graph of a relation as a result when getting each balance, optical waveguide LPR signal when streptomysin (streptavidin) is injected sensor by low concentration toward high concentration, can find when analyte concentration is more and more higher equally, its signal just falls lower and lower, and the figure of LPR signal also presents the figure of similar monolayer adsorption, its signal variation meeting is from the precipitous mitigation that becomes gradually then, and this process approximately needs 1000 seconds time.Relative signal during each balance is 0.9849 to its R value as a result that the concentration logarithm carries out data analysis.The noise of system is 1.7 * 10
-3, we can calculate that its detecting limit is 1.08 * 10 at last
-8G/mL (1.8 * 10
-10M).
Seeing also shown in Figure 9ly, is optical fibre localization plasma resonance sensing system of the present invention to streptomysin (streptavidin) and the screening of toxamin H (anti-biotin) and the signal time graph of a relation of sensing function.In the experiment of this part we to inject molecular weight before this in the sample tank be the toxamin H sample solution of 150kDa, be expected at also that it can not have influence on the variation of LPR signal under the effect of filtration membrane; Then we are replaced as analytic sample the streptomysin solution of each variable concentrations again, because its molecular weight has only 60kDa, therefore expect that also it can penetrate filtration membrane, and can cause the skew of LPR optical waveguide signal.Fig. 9 promptly is an experimental result, wherein number 1 with numbering 2 be respectively that concentration is 1 * 10
-7G/mL and 1 * 10
-6The analytic sample of g/mL toxamin H, the result show the existence of filtering membrane can bring into play really its effect, so toxamin H can not cause the variation of LPR optical waveguide signal.Yet to number 3 to numbering 6 streptomysin during as analytic sample, the signal that the biotin molecule that can see the Jin Naimi surface is caused when recognizing streptomysin has descended.Experimental result confirms, use filtration membrane (MW cut-off, 100kDa) toxamin H (150KDa) that really can molecular weight is bigger is isolated in outside the LPR sensing optical fiber, and can allow that the less streptomysin of molecular weight (60KDa) penetrates, also can utilize at last FO-LPR optical fiber sensing it.
The present invention focus on as how fast, simple mode just finishes the action of sample pre-treatments before optical fibre localization plasma resonance sensing device and system thereof detect, and the difference of the character of the analyte that detects at desire, can select the thin layer of the material of different choice ability for use, to reach the sensing result of greatest benefit as screening usefulness.For example general filtering membrane; just can be in advance with bulky grain or other have be stained with stick nature impurities outside sensing region; by this; will become relatively simple by filtering thin layer screening sample later; therefore the impurity interference cases then can relatively reduce many; the last selective power that just has by optical fibre localization plasma resonance sensing device and system itself thereof again can be detected or the inspection amount at specific analyte.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be not break away from the technical solution of the present invention content, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (45)
1. optical fibre localization plasma resonance sensing device is characterized in that it comprises:
At least one optical fiber;
One noble metal nanoparticle layer is fixed on this optical fiber; And
One filters thin layer, is a multiple hole material, and coats this optical fiber;
Wherein, the molecular weight that dams of described filtration thin layer is less than or equal to 500KDa, and the aperture of described multiple hole material is to do according to the characteristic of a test substance to select also to isolate simultaneously an interference source, and also comprise the surface rigid material that punches between described filtration thin layer and this optical fiber, a physical support to be provided and to guide described test substance to specific sensing region.
2. optical fibre localization plasma resonance sensing device according to claim 1 is characterized in that wherein said optical fiber is the optical fiber of an optical fibre localization plasma resonance.
3. optical fibre localization plasma resonance sensing device according to claim 1 is characterized in that the zone of peeling off of wherein said optical fiber is a sensing region.
4. optical fibre localization plasma resonance sensing device according to claim 1 is characterized in that wherein said fiber selection one whole circle divests the optical fiber of shell or selects for use a part to divest the optical fiber of shell.
5. optical fibre localization plasma resonance sensing device according to claim 4 is characterized in that the optical fiber that wherein said part divests shell is a D shape optical fiber.
6. optical fibre localization plasma resonance sensing device according to claim 1 is characterized in that can producing fluorescence or Raman diffused light after wherein said noble metal nanoparticle layer and the incident light effect.
7. optical fibre localization plasma resonance sensing device according to claim 1 is characterized in that wherein said noble metal nanoparticle layer is made up of golden nanoparticle or silver-colored nanoparticle.
8. optical fibre localization plasma resonance sensing device according to claim 1, the pore size that it is characterized in that wherein said filtration thin layer is between 0.2 micron to 20 microns.
9. optical fibre localization plasma resonance sensing device according to claim 1, the aperture density that it is characterized in that wherein said filtration thin layer is between 4 * 10
4Cm
-2To 20 * 10
4Cm
-2
10. optical fibre localization plasma resonance sensing device according to claim 1, the thickness that it is characterized in that wherein said filtration thin layer is between 50 microns to 100 microns.
11. optical fibre localization plasma resonance sensing device according to claim 1, the material that it is characterized in that wherein said filtration thin layer are one or its combination of polysulfones, cellulose esters and regenerated cellulose.
12. optical fibre localization plasma resonance sensing device according to claim 11 is characterized in that wherein said polysulfones comprises polyethersulfone.
13. optical fibre localization plasma resonance sensing device according to claim 12 is characterized in that wherein said polyethersulfone comprises poly aromatic ether sulfone.
14. optical fibre localization plasma resonance sensing device according to claim 1 is characterized in that wherein said surface the punching of rigid material that punch is shaped as a circular opening shape or an elongated gap shape.
15. optical fibre localization plasma resonance sensing device according to claim 1 is characterized in that wherein also comprising at least one conduit, places in this filtration thin layer, this at least one conduit is in order to importing or flow out this test substance.
16. optical fibre localization plasma resonance sensing device according to claim 15 is characterized in that wherein said at least one conduit is with this test substance suction or detach this filtration thin layer.
17. optical fibre localization plasma resonance sensing device according to claim 1 is characterized in that wherein said filtration thin layer screens this test substance and purifying.
18. optical fibre localization plasma resonance sensing device according to claim 1 is characterized in that wherein said interference source is that a blood cell, a cell debris, immunocyte, dust, cellulosic, bacterium, a local protein, a big molecule, have the stick nature of being stained with or oarse-grained impurity.
19. optical fibre localization plasma resonance sensing device according to claim 1 is characterized in that the end of wherein said optical fiber plates a minute surface, in order to reflected light signal.
20. optical fibre localization plasma resonance sensing device according to claim 1 is characterized in that wherein said noble metal nanoparticle layer is fixed on this optical fiber connector, in order to scattering or reflected light signal.
21. optical fibre localization plasma resonance sensing device according to claim 1, it is characterized in that wherein said optical fiber utilize etching mode with the core hollow out of this optical fiber connector to form an openwork part, this openwork part comprises a porous material, and this noble metal is fixed on this porous material.
22. an optical fibre localization plasma resonance sensing system is characterized in that comprising:
One optical fibre localization plasma resonance sensing device comprises:
At least one optical fiber;
One noble metal nanoparticle layer is fixed on this optical fiber; And
One filters thin layer, is a multiple hole material, and coats this optical fiber;
One light source provides this optical fibre localization plasma resonance sensing device of light beam incident; And
One detecting unit, the emergent light that receives this optical fibre localization plasma resonance sensing device is to produce a detection signal;
Wherein, the molecular weight that dams of described filtration thin layer is less than or equal to 500KDa, and the aperture of described multiple hole material is done according to the characteristic of a test substance and is selected also to isolate simultaneously an interference source, and also comprise the surface rigid material that punches between described filtration thin layer and this optical fiber, a physical support to be provided and to guide described test substance to specific sensing region.
23. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that wherein said optical fiber is the optical fiber of an optical fibre localization plasma resonance.
24. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that the zone of peeling off of wherein said optical fiber is a sensing region.
25. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that wherein said fiber selection one whole circle divests the optical fiber of shell or selects for use a part to divest the optical fiber of shell.
26. optical fibre localization plasma resonance sensing system according to claim 25 is characterized in that the optical fiber that wherein said part divests shell is a D shape optical fiber.
27. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that can producing fluorescence or Raman diffused light after wherein said noble metal nanoparticle layer and the incident light effect.
28. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that wherein said noble metal nanoparticle layer is made up of golden nanoparticle or silver-colored nanoparticle.
29. optical fibre localization plasma resonance sensing system according to claim 22, the pore size that it is characterized in that wherein said filtration thin layer is between 0.2 micron to 20 microns.
30. optical fibre localization plasma resonance sensing system according to claim 22, the aperture density that it is characterized in that wherein said filtration thin layer is between 4 * 10
4Cm
-2To 20 * 10
4Cm
-2
31. optical fibre localization plasma resonance sensing system according to claim 22, the thickness that it is characterized in that wherein said filtration thin layer is between 50 to 100 microns.
32. optical fibre localization plasma resonance sensing system according to claim 22, the material that it is characterized in that wherein said filtration thin layer are one or its combination of polysulfones, cellulose esters and regenerated cellulose.
33. optical fibre localization plasma resonance sensing system according to claim 32 is characterized in that wherein said polysulfones comprises polyethersulfone.
34. optical fibre localization plasma resonance sensing system according to claim 33 is characterized in that wherein said polyethersulfone comprises poly aromatic ether sulfone.
35. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that wherein said surface the punching of rigid material that punch is shaped as a circular opening shape or an elongated gap shape.
36. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that wherein also comprising at least one conduit, places in this filtration thin layer, this at least one conduit is in order to importing or flow out this test substance.
37. optical fibre localization plasma resonance sensing system according to claim 36 is characterized in that wherein said at least one conduit is with this test substance suction or detach this filtration thin layer.
38. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that wherein said filtration thin layer screens this test substance and purifying.
39. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that wherein said interference source is that a blood cell, a cell debris, immunocyte, dust, cellulosic, bacterium, a local protein, a big molecule, have the stick nature of being stained with or oarse-grained impurity.
40. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that the end of wherein said optical fiber plates a minute surface, in order to reflected light signal.
41. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that wherein said noble metal nanoparticle layer is fixed on this optical fiber connector, in order to scattering or reflected light signal.
42. optical fibre localization plasma resonance sensing system according to claim 22, it is characterized in that wherein said optical fiber utilize etching mode with the core hollow out of this optical fiber connector to form an openwork part, this openwork part comprises a porous material, and this noble metal is fixed on this porous material.
43. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that wherein said light source is a laser beam or a light emitting diode.
44. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that wherein said detecting unit is a photodiode.
45. optical fibre localization plasma resonance sensing system according to claim 22 is characterized in that wherein also comprising an at least one conduit and a pump, this pump by this at least one conduit with this test substance suction or detach this filtration thin layer.
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| CN103674923A (en) * | 2012-09-05 | 2014-03-26 | 华东理工大学 | Surface enhanced Raman spectroscopy detection method and device for powder porous material |
| CN103630493A (en) * | 2013-07-23 | 2014-03-12 | 中国科学院电子学研究所 | Raman spectrum measurement system |
| CN106248630A (en) * | 2016-09-06 | 2016-12-21 | 大连理工大学 | The medical biochemical sensor of sonde-type LSPR |
| CN106264556A (en) * | 2016-11-03 | 2017-01-04 | 重庆三峡医药高等专科学校 | A kind of Fiber Optic Sensor Based on Surface Plasmon Resonance inserting blood vessel detection |
| FR3062913B1 (en) * | 2017-02-15 | 2019-04-05 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | METHOD FOR DETECTING A LOCAL REFRACTION INDEX VARIATION OF A DIELECTRIC ENVIRONMENT LOCATED ON THE SURFACE OF AN OPTICAL SENSOR |
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| CN1987425A (en) * | 2005-12-20 | 2007-06-27 | 周礼君 | Surface plasma resonant sensing system and method |
| CN101008608A (en) * | 2006-01-23 | 2007-08-01 | 周礼君 | Testing device containing precious metals, testing system and testing method thereof |
| CN200968934Y (en) * | 2006-06-01 | 2007-10-31 | 河南农业大学 | Fiber surface plasma resonance based soil moisture sensor |
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| CN101008608A (en) * | 2006-01-23 | 2007-08-01 | 周礼君 | Testing device containing precious metals, testing system and testing method thereof |
| CN200968934Y (en) * | 2006-06-01 | 2007-10-31 | 河南农业大学 | Fiber surface plasma resonance based soil moisture sensor |
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