CN102608304A - Surface-modified sensing element and surface modifying method thereof - Google Patents
Surface-modified sensing element and surface modifying method thereof Download PDFInfo
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- CN102608304A CN102608304A CN2011100304380A CN201110030438A CN102608304A CN 102608304 A CN102608304 A CN 102608304A CN 2011100304380 A CN2011100304380 A CN 2011100304380A CN 201110030438 A CN201110030438 A CN 201110030438A CN 102608304 A CN102608304 A CN 102608304A
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Abstract
The invention relates to a surface modifying method of a sensing element. The method comprises the following steps of: providing a sensing element, wherein the surface of the sensing element is provided with a metal film; utilizing isopropyl alcohol plasmas to form a surface modification layer with multiple carboxyl on the metal film of the sensing element; and forming a polyacrylic layer on the surface modification layer, wherein the polyacrylic acid of the polyacrylic layer is grafted with carboxyl of the surface modification layer. The invention provides the surface-modified sensing element.
Description
Technical field
The invention relates to a kind of sensing element and surface modification method thereof, refer to a kind of sensing element and surface modification method thereof that increases key knot molecular density and uniformity coefficient that be applicable to especially through surfaction through surfaction.
Background technology
In recent years, sensing element has just like become trend in application such as the biological Molecular Detection of medical diagnosis and thickness detections.In biological Molecular Detection, need fixed biologically property molecule (immobilized bio-molecules) on the sensing element usually, via reacting between biological molecule and the sample to be tested, impel signal to change, to measure the kind and the content of sample to be tested.
Then need carry out upgrading to metal coating earlier when the metal coating on optics sensing element surface if need with biological molecular binding.Traditional biological surface modification technology; Be the optics sensing element that will desire upgrading, be soaked in 11-sulfydryl undecanoic acid (11-mercaptoundecanoic acid, MUA); Utilize the electron pair on the 11-sulfydryl undecanoic acid element sulphur; Form stable coordination bond with the outer field empty orbital of metallic atom, make at last to have carboxyl (COOH) on the metal coating, reach the effect of upgrading metal coating.Then; Utilize 1-ethyl-3-(3-dimethylamino-propyl) carbodiimides (N-(3-Dimethylaminopropyl)-N '-ethyl-carbodiimide; EDC)/hydroxy-succinamide (N-hydroxy-succinimide; NHS) coupling active agent makes the carboxyl key knot on biological molecule and the metal coating, reaches the purpose of fixed biologically property molecule.
Yet; This kind is soaked in the chemical modification method of 11-sulfydryl undecanoic acid, and it needs to soak for a long time reaction, and normal even inadequately because of metal coating surface hydrophilicity behind the upgrading; And the upgrading result is had a greatly reduced quality; Can't reach expected effect originally, thereby have the processing procedure time tediously long, roll up the experiment instability and reduce conforming shortcoming.
Therefore; If can develop the surface modification method that a kind of sensing element; Make the metal coating of sensing element have uniform surface hydrophilicity, and then promote the detecting characteristic, sensitivity etc. of sensing element, the accuracy in the time of so will more helping to improve biological Molecular Detection.
Summary of the invention
Fundamental purpose of the present invention is that a kind of surface modification method of sensing element is being provided, and can increase carboxyl quantity, the lifting surface hydrophilic characteristic on sensing element surface, and then strengthen biological molecule immobilization effect.
For reaching above-mentioned purpose, an aspect of the present invention provides a kind of surface modification method of sensing element, may further comprise the steps: a sensing element is provided, and wherein, this sensing element surface has a metallic film; Utilize the isopropyl alcohol plasma, on this metallic film of this sensing element, formation one has the surfaction layer of a plurality of carboxyls; And on this surfaction layer, form a polyacrylic acid layer, wherein, the polyacrylic acid of this polyacrylic acid layer is the said carboxyl that grafts on this surfaction layer.
In the surface modification method of the above-mentioned sensing element of the present invention; After the isopropyl alcohol plasma treatment; Can make the metallic film surface of sensing element have carboxyl (COOH); Therefore the follow-up polyreaction of then utilizing is impelled acrylic acid-graftedly on above-mentioned carboxyl, on sensing element, forms the polyacrylic acid layer.Wherein,, can be 1 minute to 30 minutes, perhaps 5 to 15 minutes for the time of plasma upgrading; When implementing the plasma upgrading, wattage or pressure intensity also must be arranged in pairs or groups with plasma species, processing time each other.
Sensing element compared to simple use isopropyl alcohol plasma treatment upgrading; The present invention is through the sensing element of isopropyl alcohol plasma treatment and acroleic acid polymerization reaction treatment; The surface will have more and more equally distributed carboxyl; Have higher water wettability simultaneously, so help generate subsequent rerum natura molecule and carry out immobilization, and then improve the sensitivity and the sensing property of sensing element.
In the surface modification method of the above-mentioned sensing element of the present invention, the kind of sensing element does not have particular restriction, can be the optical fiber sensing element for example; In addition, the kind of the metallic film that it is surperficial is not special to be limited, but in order to make the optical fiber sensing element that better reaction arranged, it can be gold thin film or silver-colored film, gold thin film generally commonly used.In addition, the thickness of film is not restriction also, preferable can be between 20 to 80nm, for example 40 ± 5nm.In addition, the formation method of film does not also have special qualification, can use this area to know the normal method of using of the knowledgeable usually, for example electroplates, and perhaps is arranged in film via nano metal ball.
Therefore; Carry out surfaction of the present invention if the sensing area surface is had the optical fiber sensing element of metallic film; Then biological molecule is fixed in the sensing area; So just, (surface plasmon resonance, optical principle SPR) is carried out sensor operation to sample to be tested to surface plasma body resonant vibration capable of using.
The surface modification method of the above-mentioned sensing element of the present invention, can be further comprising the steps of: on this polyacrylic acid layer, form a biological molecular layer, wherein, the biological molecule of this biological molecular layer be to be binding on polyacrylic carboxyl in this polyacrylic acid layer.
Above-mentioned biological molecule can be antibody, antigen, ferment, tissue part or individual cells etc.For example; The characteristic of utilizing a-protein or seralbumin to combine with antibody Fc part (Fc region); A-protein or seralbumin are fixed on the metallic film as biological molecule, and the follow-up antibody that provides again combines with a-protein or seralbumin, so just can pick out selectivity antigen by antibody; Therefore the optics sensing element of handling through above-mentioned steps; Just can be via the antibody of a-protein or seralbumin combination, the corresponding antigen of selectivity identification detects specific antigen and concentration thereof.
In the surface modification method of the above-mentioned sensing element of the present invention, the biological molecule of this biological molecular layer is under the existence of coupling active agent, carries out the key knot with this polyacrylic acid layer.Wherein, the group that organizes of the optional free 1-ethyl-3-of this coupling active agent (3-dimethylamino-propyl) carbodiimides, hydroxyl fourth two vinegar amine and combination thereof.
In the surface modification method of the above-mentioned sensing element of the present invention, graft on the polyacrylic acid of said carboxyl, can use acrylic acid to form in the irradiation of ultraviolet light is following.In other words; Under the irradiation of ultraviolet light; Make acrylic acid carry out graft polymerization reaction (grafting polymerization), and then form polyacrylic acid grafted said carboxyl, impel to have more and more equally distributed carboxylic-acid functional base on the sensing element in this surfaction layer.
Another object of the present invention is a kind of sensing element through surfaction to be provided, can to have better detecting characteristic and sensitivity etc., and then the accuracy when promoting for biological Molecular Detection.
For reaching above-mentioned purpose, another aspect of the present invention provides a kind of sensing element through surfaction, comprising: a sensing element, and its surface has a metallic film; One has the surfaction layer of a plurality of carboxyls, is positioned on this metallic film of this sensing element, and wherein, this surfaction layer is to utilize the isopropyl alcohol plasma to form; And a polyacrylic acid layer, be positioned on this surfaction layer, wherein, the polyacrylic acid of this polyacrylic acid layer is the said carboxyl that grafts on this surfaction layer.
The above-mentioned sensing element through surfaction of the present invention can also comprise: a biological molecular layer, be positioned on this polyacrylic acid layer, and wherein, the biological molecule of this biological molecular layer is to be binding on polyacrylic carboxyl in this polyacrylic acid layer.Particularly, this biological molecule does not have special qualification, can be a-protein or seralbumin for example.In addition, the biological molecule of this biological molecular layer is to be tied with this polyacrylic acid layer key by the coupling active agent.
Above-mentioned in the sensing element of surfaction in the present invention, this metallic film is a gold thin film or silver-colored film; In addition, forming this polyacrylic acid layer is to use acrylic acid under the irradiation of ultraviolet light, to carry out.
In sum, the present invention utilizes isopropyl alcohol plasma surface modification technology to combine acrylic acid-grafted polymerization technique, promotes processing procedure stability, effectively operating key knot molecular density.Wherein,, have numerous, equally distributed carboxyl-functional base, and its porosity is low by the formed surfaction layer of isopropyl alcohol plasma, good for the tack and the spreadability of the metallic film of sensing element; Add acrylic acid-grafted polymerization; On the surfaction layer, form the polyacrylic acid layer; Impel the sensing element surface to have more, carboxyl-functional base distribution more uniformly; Therefore significantly promote surface hydrophilicity, increase the immobilization that carboxyl quantity can be beneficial to generate subsequent rerum natura molecule simultaneously, and then strengthen the detection effect and the degree of accuracy of sensing element.
Description of drawings
For further specifying content of the present invention, will enumerate below that embodiment and conjunction with figs. specify as after, wherein:
Figure 1A to 1D is the schematic flow sheet for the surfaction method of sensing element in the embodiment of the invention one.
Fig. 1 E is the schematic flow sheet for the surfaction method of sensing element in the embodiment of the invention two.
Fig. 2 A is in the Test Example of the present invention, the fourier transform infrared spectrogram on the sensing element of comparative example one surface.
Fig. 2 B is in the Test Example of the present invention, the fourier transform infrared spectrogram on the sensing element of embodiment one surface.
Embodiment
Below be embodiment of the present invention to be described, have the knack of this technological personage and can understand other advantage of the present invention and effect easily by the content that this instructions disclosed by particular specific embodiment.The present invention also can be implemented or used by other different specific embodiment, and each item details in this instructions also can be based on different viewpoints and application, under spirit of the present invention, carries out various modifications and change not being contrary to.
These accompanying drawings are the synoptic diagram of simplification in the embodiments of the invention.Only these icons only show the element relevant with the present invention, the non-aspect during for actual enforcement of the element that it showed, and component number, the shape equal proportion during its actual enforcement is an optionally design, and its component placement kenel complicacy more.
Embodiment one
Seeing also Figure 1A to 1D, is the schematic flow sheet for the surface modification method of sensing element of the present invention.
At first, shown in Figure 1A, a sensing element 20 is provided, wherein, these sensing element 20 surfaces have a metallic film 21.In present embodiment, this sensing element 20 is the optical fiber sensing element, and for example side is thrown formula optical fiber sensing element, and its surface has a sensing area, by the method for depositing metal films such as sputter, golden film is set as this metallic film 21 on the sensing area surface.
Then, shown in Figure 1B, utilize the isopropyl alcohol plasma, on this metallic film 21 of this sensing element 20, formation one has the surfaction layer 23 of a plurality of carboxyls.In present embodiment, this isopropyl alcohol plasma is to utilize following mode to carry out: use isopropyl alcohol as unstrpped gas, feed in the vacuum discharge tube; Treat isopropyl alcohol after discharge is dissociated, split into various activity chemistry species, again behind complicated chemical reaction; Resultant of reaction is deposited on these metallic film 21 upper surfaces of this sensing element 20; Formation has the surfaction layer 23 of a plurality of carboxyls, and this metallic film 21 of this sensing element 20 of upgrading makes its surface have numerous carboxyls thus.Wherein, utilize the formed surfaction layer 23 of this method, its thin thickness, whole porosity are low, and evenly are covered in these metallic film 21 surfaces of this sensing element 20.
Shown in Fig. 1 C and Fig. 1 D, use acrylic acid for another example, under the irradiation of ultraviolet light, utilize graft polymerization reaction, make acrylic monomers graft on the carboxyl of this surfaction layer 23, let polymerizable acrylic monomer form a polyacrylic acid layer 24 simultaneously as monomer.
Embodiment two
At first.Of embodiment one, carry out upgrading to the surface of sensing element 20, make metallic film 21 surfaces of sensing element 20 form surfaction layer 23 and polyacrylic acid layer 24.
Then, shown in Fig. 1 E, use the coupling active agent, impel the activated carboxylic of polyacrylic acid layer 24, and a plurality of biological molecules 25 are provided, impel the amido of biological molecule 25 and the carboxyl key knot of polyacrylic acid layer 24, and form a biological molecular layer.In present embodiment, employed coupling active agent is 1-ethyl-3-(3-dimethylamino-propyl) carbodiimides.
Comparative example one
Similar embodiment one described method, but only use the isopropyl alcohol plasma, carry out surfaction to metallic film 21 surfaces of sensing element 20.
Test Example
By fourier transform infrared spectrum analysis (Fouri er transform infrared spectroscopy analysis; FTIP analysis); Test to comparative example one and embodiment one prepared sensing element; Its result is respectively shown in Fig. 2 A and Fig. 2 B; Wherein, Fig. 2 A shows the fourier transform infrared spectrogram on the sensing element surface of comparative example one (only passing through the isopropyl alcohol plasma surface treatment), and Fig. 2 B is the fourier transform infrared spectrogram on the sensing element surface of demonstration embodiment one (handling through isopropyl alcohol plasma and acrylic acid-grafted polymeric surface).
Can know by collection of illustrative plates; Compared to a comparative example one through the isopropyl alcohol plasma surface treatment; Through the embodiment one of isopropyl alcohol plasma and the processing of acrylic acid-grafted polymeric surface, its sensing element surface has more carboxyl and reaches like other water wettability functional group quantity such as hydroxyls.
In sum, the sensing element surface is if evenly form a metallic film by sputter, and this sensing element just can produce surface plasma resonance.If after utilizing the formation of isopropyl alcohol plasma treatment upgrading to have the surfaction layer of carboxyl on the metallic film; Utilize acrylic acid as monomer again; Quicken to excite acrylic acid-grafted carboxyl with ultraviolet light, aggregate into polyacrylic acid between acrylic monomers simultaneously, and form a polyacrylic acid layer in the surfaction layer; Just can reach the functional group who changes metallic film on the sensing element by mixed chemical film framework of the present invention.Because surperficial carboxyl quantity increases, just can reach the immobilized effect of enhancing generate subsequent rerum natura molecule, increase the water-wet behavior on surface simultaneously.In addition,, and then can increase the detection effect, promote and detect degree of accuracy and reaction velocity owing to the immobilized effect of biological molecule can be strengthened.
The foregoing description only is to explain for ease and give an example, and the interest field that the present invention advocated is from should being as the criterion so that the claim scope is said, but not only limits to the foregoing description.
Claims (12)
1. the surface modification method of a sensing element may further comprise the steps:
One sensing element is provided, and wherein, this sensing element surface has a metallic film;
Utilize the isopropyl alcohol plasma, on this metallic film of this sensing element, formation one has the surfaction layer of a plurality of carboxyls; And
On this surfaction layer, form a polyacrylic acid layer, wherein, this polyacrylic acid layer polyacrylic acid grafted in the said carboxyl of this surfaction layer.
2. surface modification method as claimed in claim 1, further comprising the steps of: on this polyacrylic acid layer, form a biological molecular layer, wherein, the biological molecular binding of this biological molecular layer is polyacrylic carboxyl in this polyacrylic acid layer.
3. surface modification method as claimed in claim 2, wherein, this biological molecule is a-protein or seralbumin.
4. surface modification method as claimed in claim 2, wherein, the biological molecule of this biological molecular layer carries out the key knot with this polyacrylic acid layer under the existence of coupling active agent.
5. surface modification method as claimed in claim 1, wherein, this metallic film is a gold thin film or silver-colored film.
6. surface modification method as claimed in claim 1 wherein, grafts on the polyacrylic acid of said carboxyl, is to use acrylic acid to form in the irradiation of ultraviolet light is following.
7. sensing element through surfaction comprises:
One sensing element, its surface has a metallic film;
One has the surfaction layer of a plurality of carboxyls, is positioned on this metallic film of this sensing element, and wherein, this surfaction layer is to utilize the isopropyl alcohol plasma to form; And
One polyacrylic acid layer is positioned on this surfaction layer, and wherein, the polyacrylic acid of this polyacrylic acid layer is the said carboxyl that grafts on this surfaction layer.
8. the sensing element through surfaction as claimed in claim 7 also comprises: a biological molecular layer, be positioned on this polyacrylic acid layer, and wherein, the biological molecular binding of this biological molecular layer is polyacrylic carboxyl in this polyacrylic acid layer.
9. the sensing element through surfaction as claimed in claim 8, wherein, this biological molecule is a-protein or seralbumin.
10. the sensing element through surfaction as claimed in claim 8, wherein, the biological molecule of this biological molecular layer is to be tied with this polyacrylic acid layer key by the coupling active agent.
11. the sensing element through surfaction as claimed in claim 7, wherein, this metallic film is a gold thin film or silver-colored film.
12. the sensing element through surfaction as claimed in claim 7 wherein, forms this polyacrylic acid layer and is to use acrylic acid under the irradiation of ultraviolet light, to carry out.
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| CN2011100304380A CN102608304A (en) | 2011-01-19 | 2011-01-19 | Surface-modified sensing element and surface modifying method thereof |
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| CN2011100304380A CN102608304A (en) | 2011-01-19 | 2011-01-19 | Surface-modified sensing element and surface modifying method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070207552A1 (en) * | 1998-08-14 | 2007-09-06 | Holland Biomaterials Group B.V. | Device for investigating chemical interactions and process utilizing such device |
| US20100285512A1 (en) * | 2007-11-27 | 2010-11-11 | Daniel Regis | Functionalized biochips for spr-ms coupling |
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2011
- 2011-01-19 CN CN2011100304380A patent/CN102608304A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070207552A1 (en) * | 1998-08-14 | 2007-09-06 | Holland Biomaterials Group B.V. | Device for investigating chemical interactions and process utilizing such device |
| US20100285512A1 (en) * | 2007-11-27 | 2010-11-11 | Daniel Regis | Functionalized biochips for spr-ms coupling |
Non-Patent Citations (2)
| Title |
|---|
| GUERIN等: "《Plasma polymerization of thin films: correlateions between plasma chemistry and thin film character》", 《LANGMUIR》 * |
| JUNFENG ZHANG: "《Covalent attachment of polymer thin layers to self-assembled monolayers on gold surface by graft polymerization》", 《 THIN SOLID FILMS》 * |
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Application publication date: 20120725 |