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CN112986207A - Surface Raman enhanced optical fiber probe and preparation method thereof - Google Patents

Surface Raman enhanced optical fiber probe and preparation method thereof Download PDF

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Publication number
CN112986207A
CN112986207A CN202110146884.1A CN202110146884A CN112986207A CN 112986207 A CN112986207 A CN 112986207A CN 202110146884 A CN202110146884 A CN 202110146884A CN 112986207 A CN112986207 A CN 112986207A
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solution
optical fiber
raman
gold
preparing
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周宇
徐建华
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Hangzhou Supo Technology Co ltd
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Digong Hangzhou Science And Technology Industry Co ltd
Hangzhou Supo Technology Co ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons

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  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention discloses a preparation method of a surface Raman enhanced fiber probe, which comprises the following steps: preparing a seed solution; adding seed solution to HAuCl4Preparing a gold nano star solution by using the solution; processing the surface of the end face of the optical fiber; and covering the surface of the processed optical fiber end surface with gold nano-star.

Description

Surface Raman enhanced optical fiber probe and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of nano biological materials. Specifically, the invention relates to a surface Raman enhanced fiber probe and a preparation method thereof.
Background
The surface raman enhancement (SERS) application is mainly focused in the fields of medicine, biology, homeland security, environmental pollution and food pollution, and is particularly useful for detecting food additives, drugs, pesticides and some contaminants down to the single-molecule level, detecting molecules in biological cells, detecting dangerous explosives, etc., and it has high sensitivity and excellent molecular specificity. The key to successful detection using SERS is the formation of a high gap density of less than 10nm, which can also be referred to as a hot spot. When the detection object is attached to these hot spots, the raman scattering signal will be greatly enhanced.
From an application point of view, standard raman detection instruments are relatively large and not portable. The handheld detection instrument solves the problem of portability, but has limitations for some specific scene pages, for example, in some narrow spaces, the instrument is not easy to enter; dangerous, toxic or explosive substances requiring remote detection; in vivo testing, etc. Therefore, a simple and convenient preparation of the surface enhanced raman scattering active probe is necessary.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a surface Raman enhanced fiber probe, which comprises the following steps:
preparing a seed solution;
adding seed solution to HAuCl4Preparing a gold nano star solution by using the solution;
processing the surface of the end face of the optical fiber; and
and covering the surface of the treated optical fiber end surface with gold nano-star.
In one embodiment of the invention, the citrate solution is added to the boiling HAuCl4To prepare a seed solution.
In one embodiment of the invention, 1.5mL of a 1% citrate solution is added to 10mL of boiling 0.001M HAuCl with stirring at 700rpm4To prepare a seed solution, and after 15 minutes the solution was cooled.
In one embodiment of the present invention, preparing the gold nanostar solution comprises adding a seed solution to HAuCl4Adding acid to adjust the pH value of the solution to acidity, adding a reducing agent and an Ag + ion solution into the solution, centrifuging the obtained solution in a centrifuge, and dispersing the solution in ultrapure water, wherein the acid is hydrochloric acid, and the Ag + ion solution is AgNO3And (3) solution.
In one embodiment of the invention, 2mL of seed solution is added to 200mL of 2.5X 10-4M HAuCl4To the solution, 200. mu.L of 1M HCl was added, and then 400. mu.L of 0.01M AgNO was added while vigorously stirring for 30 seconds3Solution and 1mL ascorbic acid solution, and finally, the solution at 4 degrees C under 4000rpm speed centrifugal 1.5h, then dispersed in ultrapure water, wherein the vigorous stirring of the stirring rotation selectedThe speed was about 1200 rpm.
In one embodiment of the invention, treating the fiber end surface comprises: soaking one end of the optical fiber in a buffer solution for 10 hours under mild stirring, wherein the buffer solution is a solution of 0.1M ethanolamine/0.5M sodium phosphate, and the pH value of the buffer solution is 7.4; then, after washing with 2-propanol, it was soaked for 90 minutes in a 2% solution of 3-aminopropyltrimethoxysilane APTMS in 2-propanol; washing with ultrapure water and absolute ethanol.
In one embodiment of the present invention, covering the gold nanostars on the treated fiber end surface comprises: one end of the treated optical fiber was soaked in the gold nanostar solution for 2 hours, and then washed with ultrapure water and absolute ethanol.
In one embodiment of the present invention, the gold nanostar particles are fixed to the surface of the optical fiber by electrostatic interaction.
According to another embodiment of the present invention, there is provided a surface raman-enhanced fiber optic probe prepared by the above method.
The embodiment of the invention provides a surface Raman enhanced fiber probe and a preparation method thereof. The embodiment of the invention can use the optical fiber, so that the detection is more flexible and convenient, and the gold nano-star particles are used, so that the detection sensitivity is higher. The method has the advantages of simplicity, rapidness, strong repeatability, low cost and the like, and the surface enhanced Raman scattering enhancement factor is high and the detection is sensitive.
Drawings
To further clarify the above and other advantages and features of embodiments of the present invention, a more particular description of embodiments of the invention will be rendered by reference to the appended drawings. It is appreciated that these drawings depict only typical embodiments of the invention and are therefore not to be considered limiting of its scope. In the drawings, the same or corresponding parts will be denoted by the same or similar reference numerals for clarity.
Fig. 1 illustrates a method of fabricating a surface raman scattering enhanced fiber optic probe according to one embodiment of the present invention.
Fig. 2 shows a transmission electron microscopy TEM image of gold nanostars formed by an embodiment of the present invention.
FIG. 3 shows a rhodamine 6G detection spectrum of a surface Raman enhanced fiber probe.
Detailed Description
In the following description, the invention is described with reference to various embodiments. One skilled in the relevant art will recognize, however, that the embodiments may be practiced without one or more of the specific details, or with other alternative and/or additional methods, materials, or components. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of embodiments of the invention. Similarly, for purposes of explanation, specific numbers, materials and configurations are set forth in order to provide a thorough understanding of the embodiments of the invention. However, the invention may be practiced without specific details. Further, it should be understood that the embodiments shown in the figures are illustrative representations and are not necessarily drawn to scale.
Reference in the specification to "one embodiment" or "the embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment.
The optical fiber probe is prepared by covering the surface of the optical fiber with the gold nano-star particles by a chemical method, and has excellent realizable reproducibility and high enhancement factors. Firstly, the surface of the optical fiber is treated by a chemical method, and then the gold nanoparticles are fixed on the surface of one end of the optical fiber by utilizing electrostatic adsorption. The use of gold nanostars as core particles of the SERS tag may provide advantages over gold nanospheres, including a greater SERS enhancement factor due to multiple "hot spots" of the electromagnetic field, making the raman-enhanced signal stronger. Meanwhile, because a large number of 'hot spots' are generated among the gold nano-star particles, the surface enhanced Raman scattering enhancement factor is high, and the detection sensitivity is stronger. At the same time, the use of a large number of nanoparticles allows random adsorption of analytes to be largely avoided or reduced and reproducibility to be largely improved. And the flexibility of light is combined, so that scenes which are difficult to detect by common Raman equipment can be detected more easily.
Fig. 1 illustrates a method of fabricating a surface raman scattering enhanced fiber optic probe according to one embodiment of the present invention.
As shown in fig. 1, first, at step 110, a seed solution is prepared. In one embodiment of the invention, the citrate solution may be added to the boiling HAuCl4To prepare a seed solution.
For example, in one example, 1.5mL of a 1% citrate solution is added to 10mL of boiling 0.001M (mol/L) HAuCl with stirring at 700rpm4To prepare a seed solution, and after 15 minutes the solution was cooled. The citrate can be sodium citrate or the like.
In this step, AuCl in solution4 -The ions are reduced under the action of citrate radicals to generate gold nanospheres with the diameter of about 5nm, and the gold nanospheres are used as seeds for the growth of the gold nanostars.
Next, at step 120, the seed solution is added to HAuCl4And (4) preparing a gold nano star solution. In one embodiment of the invention, the seed solution is the core of the growth of gold nanostars. Adding seed solution to HAuCl4Adding acid to adjust pH of the solution to acidity, adding reducing agent and AgNO to the solution3And (3) solution. Reducing agent to reduce AuCl in solution4 -The ions are reduced and grow on the surface of the gold nanospheres in the seed solution to form the gold nanostars, and Ag + ions have a catalytic action and regulate and control the number and the size of branches on the surface of the gold nanostars.
For example, in one example, 2mL of seed solution is added to 200mL of 2.5X 10-4M HAuCl4To the solution, 200. mu.L of 1M HCl was added. Thereafter, 400. mu.L of 0.01M AgNO was added thereto while vigorously stirring for 30 seconds3Solution and 1mL ascorbic acid solution. Ascorbic acid acts as a reducing agent. Finally, the solution was centrifuged at 4000rpm for 1.5h at 4 ℃ and then redispersed in ultrapure water to form a gold nanostar solution. The agitation speed for vigorous agitation was about 1200 rpm.
Next, at step 130, the fiber end surface is treated. In one embodiment of the invention, first, one end of the fiber is soaked in a buffer solution of 0.1M ethanolamine/0.5M sodium phosphate (an aqueous solution containing 0.1M ethanolamine and 0.5M sodium phosphate) at pH 7.4 for 10 hours with gentle agitation. Then, after washing with 2-propanol, it was soaked for 90 minutes in a 2% (v/v by volume) solution of 3-Aminopropyltrimethoxysilane (APTMS) in 2-propanol (i.e., the volume ratio of APTMS in 2-propanol was 2%). Thereafter, the mixture was washed with ultrapure water and absolute ethanol. The surface of the optical fiber is provided with a large number of silicon hydroxyl groups (Si-OH), APTMS is used as a coupling agent, and the groups of APTMS are hydrolyzed and then react with the silicon hydroxyl groups on the surface of the optical fiber to form Si-O-Si bonds, so that APTMS molecules are fixed on the surface of the optical fiber, and the tail ends of the APTMS molecules are provided with amino groups, thereby enabling the modified surface of the optical fiber to be positively charged.
At step 140, gold nanostars are coated on the treated fiber end surface. One end of the treated optical fiber was soaked in the gold nanostar solution for 2 hours, and then washed with ultrapure water and absolute ethanol. The gold nanostar particles are fixed to the surface of the optical fiber due to electrostatic interaction.
Next, the surface of the manufactured optical fiber probe is subjected to surface raman enhanced detection.
Will 10-4M rhodamine 6G (R6G) ethanol solution is dripped on the surface of the prepared optical fiber probe. After 10 minutes, the substrate was washed with water and ethanol on the surface and dried at room temperature. All Raman and SERS spectra were recorded using an InVia Renishaw Raman spectrometer and a 633nm HeNe laser exposed for 10s under a 50 x objective lens. The laser power was set to 0.5 mW.
Fig. 2 shows a transmission electron microscopy TEM image of gold nanostars formed by an embodiment of the present invention. As shown in FIG. 2, the diameter of the gold nanostar core formed by the method of the embodiment of the present invention is 38. + -.4 nm, the length of the branch structure is in the range of 7. + -.3 nm, and the number of branches is in the range of 8. + -.4. The zeta potential of the gold nanostar particles was in the range-41.8 ± 0.98mV, due to the electronegativity of the surface for the citrate ion coverage. As described above, in step 130, the treated fiber end face is positively charged, while the gold nanostar surface is negatively charged. Under the electrostatic action, the gold nano-star particles are fixed on the surface of the optical fiber.
FIG. 3 shows a rhodamine 6G detection spectrum of a surface Raman enhanced fiber probe. As shown in FIG. 3, when rhodamine 6G is used as a standard detection substance to perform detection by using the basic group, the characteristic spectrum of the substrate can be obviously obtained, and a strong signal is obtained.
The embodiment of the invention provides a surface Raman enhanced fiber probe and a preparation method thereof. The embodiment of the invention can use the optical fiber, so that the detection is more flexible and convenient, and the gold nano-star particles are used, so that the detection sensitivity is higher. The method has the advantages of simplicity, rapidness, strong repeatability, low cost and the like, and the surface enhanced Raman scattering enhancement factor is high and the detection is sensitive.
While various embodiments of the present invention have been described above, it should be understood that they have been presented by way of example only, and not limitation. It will be apparent to persons skilled in the relevant art that various combinations, modifications, and changes can be made thereto without departing from the spirit and scope of the invention. Thus, the breadth and scope of the present invention disclosed herein should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.

Claims (10)

1. A method for preparing a surface Raman enhanced fiber probe comprises the following steps:
preparing a seed solution;
adding seed solution to HAuCl4Preparing a gold nano star solution by using the solution;
processing the surface of the end face of the optical fiber; and
and covering the surface of the treated optical fiber end surface with gold nano-star.
2. The method of fabricating a surface-raman-enhanced fiber probe according to claim 1, characterized by adding a citrate solution to boiling HAuCl4To prepare a seed solution.
3. The method of preparing a surface raman-enhanced fiber optic probe of claim 2, wherein 1.5mL of 1% citrate solution is added to 10mL of boiling 0.001M HAuCl with stirring at 700rpm4To prepare a seed solution, and after 15 minutes the solution was cooled.
4. The method of making a surface raman-enhanced fiber optic probe according to any one of claims 1-3, wherein preparing the gold nanostar solution comprises adding a seed solution to HAuCl4Adding acid to adjust the pH value of the solution to acidity, adding a reducing agent and an Ag + ion solution into the solution, centrifuging the obtained solution in a centrifuge, and dispersing the solution in ultrapure water, wherein the acid is hydrochloric acid, and the Ag + ion solution is AgNO3And (3) solution.
5. The method of preparing a surface raman-enhanced fiber optic probe according to any one of claims 1 to 3, wherein 2mL of the seed solution is added to 200mL of 2.5 x 10-4M HAuCl4To the solution, 200. mu.L of 1M HCl was added, and then 400. mu.L of 0.01M AgNO was added while vigorously stirring for 30 seconds3The solution and 1mL ascorbic acid solution, and finally, the solution is centrifuged at 4000rpm for 1.5h at 4 ℃ and then redispersed in ultrapure water, wherein vigorous stirring is selected at a stirring speed of about 1200 rpm.
6. The method of manufacturing a surface raman enhanced fiber probe according to claim 1, wherein the processing of the fiber end surface comprises: soaking one end of the optical fiber in a buffer solution for 10 hours under mild stirring, wherein the buffer solution is a solution of 0.1M ethanolamine/0.5M sodium phosphate, and the pH value of the buffer solution is 7.4; then, after washing with 2-propanol, it was soaked for 90 minutes in a 2% solution of 3-aminopropyltrimethoxysilane APTMS in 2-propanol; washing with ultrapure water and absolute ethanol.
7. The method of claim 6, wherein the surface of the optical fiber has a plurality of silicon hydroxyl groups (Si-OH), and the APTMS is used as a coupling agent, and the group of the APTMS is hydrolyzed and reacts with the silicon hydroxyl groups on the surface of the optical fiber to form Si-O-Si bonds, so that the APTMS molecule is immobilized on the surface of the optical fiber, and the end of the APTMS molecule has an amino group, thereby positively charging the modified surface of the optical fiber.
8. The method of manufacturing a surface raman enhanced fiber probe according to claim 1, wherein the covering of the gold nanostars on the treated fiber end surface comprises: one end of the treated optical fiber was soaked in the gold nanostar solution for 2 hours, and then washed with ultrapure water and absolute ethanol.
9. The method of claim 8, wherein the gold nanostar particles are immobilized to the surface of the optical fiber by electrostatic interaction.
10. A surface raman-enhanced fiber optic probe prepared by the method of any one of claims 1-9.
CN202110146884.1A 2021-02-03 2021-02-03 Surface Raman enhanced optical fiber probe and preparation method thereof Pending CN112986207A (en)

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