CN1306099A

CN1306099A - Process for preparing surface plasma resonance response chip by wet chemical method

Info

Publication number: CN1306099A
Application number: CN 00133099
Authority: CN
Inventors: 金永东; 董绍俊
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2000-11-14
Filing date: 2000-11-14
Publication date: 2001-08-01
Anticipated expiration: 2020-11-14
Also published as: CN1166812C

Abstract

A wet and chemical process for preparing surface plasma resonance (SPR) response substrate is disclosed. The self-assembled single-layer film of nm gold particles on aminopropyl trimethoxysilane modified glass chip is used as catalysis template. The chlorauri acid/oxyammonia is used as chemical gold-plating liquid. The uniform plating can be controlled in nm class by controlling reaction time and shaking the plating liquid. Its advantages are high responsibility and repeatability.

Description

The wet chemical preparation method of surface plasma resonance response chip

The invention belongs to the wet chemical preparation method of surface plasma resonance response chip.

(surface plasmon resonance, SPR) spectrum is a kind of strong research tool of on-the-spot real-time characterization solid/liquid interfaces to surface plasma body resonant vibration.Because SPR specific refractory power and variation in thickness to its boundary material in the hundreds of nanometer range is very responsive, in the more than ten years in the past, the SPR technology is used widely as a kind of interface analysis means.It not only can be used to measure the optical characteristics of SPR on the metallic film, and can study formation and the physical property that the surface is adsorbed film and molecule, for example effects such as the absorption of LB film, gas molecule and protein adsorption, simultaneously can also provide interactional dynamic information between liquid phase molecule and the surperficial fixed molecule, as part one acceptor interaction, Study on biocompatibility, drug screening, DNA hybridization or the like.Especially the release of the early 1990s BIAcore SPR commodity instrument, make the SPR technology as a kind of need not mark, directly, in real time, the biomolecular interaction analysis means of original position, and be used widely in field of biology.Aspect chemical, the SPR technology also has been used to LB film, self-organized film, interaction of biomacromolecules and electrochemistry SPR research.The key of SPR technology is that the thickness that needs preparation to be deposited on the thin slide is the golden film (or other precious metal) of 45-60 nanometer, in order to the excitating surface plasmon.Up to the present, nearly all SPR response chip all is to obtain by vacuum evaporation (or ion sputtering) dry method.This not only needs expensive vacuum evaporation system, and during operational cost, simultaneously the pattern and the thickness wayward (Pamela A.Mosier-Bossand Steven H.Lieberman, Applied Spectroscopy.1999,53,867.) of film.In addition, in order to improve the adhesive power between gold or other precious metal and the slide, often need first evaporation one deck chromium (or other metal) before the gold evaporation film.Because the electrochemistry of chromium is polluted, this has brought unfavorable factor for again electrochemistry SPR research.

The wet chemical preparation method that the purpose of this invention is to provide a kind of surface plasma resonance response chip.This method is at first based on the self-assembly of golden nanometer particle on TSL 8330 (APTMS) modification slide, be catalytic templating with this nanoparticle unitary film then, by the even growth of electroless plating technology at nanoscale scope inner control gold film, reach required pattern and thickness, thereby obtain good spr signal response.This legal system is equipped with the SPR response chip fully based on solution, and not only cost is low, simple to operate, and good, the favorable reproducibility of the substrate that makes response, is easy to popularize use in general wet-chemical laboratory.

We have used particle diameter to be about the golden nanometer particle of 2.5 nanometers as the nucleation site among the present invention, on the slide that APTMS modifies, form a fine and close individual layer film of nanoparticles by self-assembly, control the golden film surface coverage that electroless plating subsequently increases with this, and, make golden film in conjunction with more firm so as to improving bond strength amino in gold and the TSL 8330 molecule.Subsequently, control the concentration and the plated film time of chemical gold plating liquid, can under room temperature, control the thickness of gold-plated film in the nanoscale scope.In addition,, can prevent golden film island growth effectively, thereby golden film is evenly being increased along slide normal direction last layer one deck by agitation of solutions, final obtain definition intact, surfaceness is greatly about the even golden film of 2-3nm.

The present invention will approach slide glass earlier through the chromic acid lotion soaked overnight, and be 3: 1 dense H 70 ℃ volume ratio ₂SO ₄/ 30%H ₂O ₂After soaking 10-30min in the mixing solutions, clean with deionized water and spectroscopically pure methanol rinse, immerse then and carry out the processing of slide silanization in the 4-8ml methanol solution that contains the 0.4-0.8ml TSL 8330 after 12-18 hour, take out the slide of silanization, clean with methanol rinse, and immerse immediately with Trisodium Citrate reduction preparation, average particulate diameter is about in the gold sol of 2.0-3.0nm, assembled 12-18 hour.Take out slide, promptly immerse after washing is clean in the gold plating liquid that 4-8ml contains the hydrochloro-auric acid that oxyammonia that concentration is 0.1-1mM and concentration is 0.05-0.15%, evenly shake, the room temperature controlling reaction time can obtain the spr signal response chip of golden film thickness at 45-60nm at 10 ± 1min.The atomic force microscope pattern characterizes and shows that the surface definition of golden film is intact, and surfaceness is about 2-3 nanometer.

The SPR response chip of the present invention's preparation is fully based on solution, and is easy and simple to handle, favorable reproducibility, and the dried preparation when desirable cost lattice costliness, operational cost, carrying out SPR research for the wet-chemical laboratory provides to make things convenient for a shortcut.Because the golden film of this method preparation combines firmly with slide, and does not have the pollution of chromium,, help to promote the development of electrochemistry SPR for the electrochemistry SPR research of rising provides convenience.In addition, this method is owing to have the ability that evenly increases at nanoscale scope inner control gold film, and method is not subjected to the restriction of substrate shape, size etc., therefore has certain universality, can be used as class methods, be used to make electrochemistry, self-assembly and SPR response chip.

Embodiment provided by the invention is as follows: embodiment 1: get once chromic acid lotion, 3: 1 dense H ₂SO ₄/ 30%H ₂O ₂The slide that mixing solutions embathed, further handle through the APTMS silanization, after gold sol soaks self-assembly, immersing 6ml immediately contains in the gold plating liquid that oxyammonia that concentration is 0.4mM and concentration are 0.1% hydrochloro-auric acid, under the situation of evenly shaking, in room temperature controlling reaction time 9 minutes, promptly obtain the intact spr signal response chip of definition that golden film thickness is equivalent to 45nm.

Embodiment 2: get once chromic acid lotion, 3: 1 dense H ₂SO ₄/ 30%H ₂O ₂The slide that mixing solutions embathed, further handle through the APTMS silanization, after gold sol soaks self-assembly, immersing 6ml immediately contains in the gold plating liquid that oxyammonia that concentration is 0.4mM and concentration are 0.1% hydrochloro-auric acid, under the situation of evenly shaking, in room temperature controlling reaction time 11 minutes, can obtain the intact spr signal response chip of definition that golden film thickness is equivalent to 60nm.

Embodiment 3: get the spr signal response chip that a slice adopts the inventive method preparation, it as working electrode, is immersed 0.1MH ₂SO ₄In the aqueous solution, in-0.2-+1.4V potential range, carry out the cyclic voltammetric electrochemistry experiment, can obtain classical cyclic voltammetric rational curve pollution-free, that definition is intact with the 0.1V/s sweep velocity, and continuous electric bit scan 30min, curve shape is stable, shows that golden film has electrochemical stability.Embodiment 4: get the spr signal response chip that a slice adopts the inventive method preparation, be used for the small molecules system, as the self-assembly SPR sign of 2mM p-Mercaptoaniline ethanolic soln.Before and after the assembling, 0.15 ° angle has taken place and has changed in the SPR angle, and the peak height of SPR curve and peak width have no significant change, and coincide with notional result.The spr signal response chip that shows this method preparation can be further used for self-assembly SPR research fully.

Claims

1, a kind of wet chemical preparation method of surface plasma resonance response chip is characterized in that thin slide glass through the chromic acid lotion soaked overnight, and is 3: 1 dense H 70 ℃ volume ratio ₂SO ₄/ 30%H ₂O ₂After soaking 10-30min in the mixing solutions, clean with deionized water and spectroscopically pure methanol rinse, immerse then and carry out the processing of slide silanization in the 4-8ml methanol solution that contains the 0.4-0.8ml TSL 8330 after 12-18 hour, take out the slide of silanization, clean with methanol rinse, and immerse with Trisodium Citrate reduction preparation immediately, average particulate diameter is about in the gold sol of 2.0-3.0nm, assembled 12-18 hour, take out slide, promptly immerse after washing is clean in the gold plating liquid that 4-8ml contains the hydrochloro-auric acid that oxyammonia that concentration is 0.1-1mM and concentration is 0.05-0.15%, evenly shake, the room temperature controlling reaction time obtains the spr signal response chip of golden film thickness at 45-60nm at 10 ± 1min.