CN108645827B - Ultra-sensitive NO sensor based on simplified microstructure optical fiber - Google Patents

Ultra-sensitive NO sensor based on simplified microstructure optical fiber Download PDF

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CN108645827B
CN108645827B CN201810450829.XA CN201810450829A CN108645827B CN 108645827 B CN108645827 B CN 108645827B CN 201810450829 A CN201810450829 A CN 201810450829A CN 108645827 B CN108645827 B CN 108645827B
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cdte
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CN108645827A (en
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丁莉芸
吴伟
林海涛
余莎
徐冰
黄�俊
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Wuhan University of Technology WUT
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    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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Abstract

The invention discloses a sensing optical fiber for detecting NO concentration in a living body, wherein the sensing optical fiber is provided with an open pore channel, the surface of the open pore channel adopts a chemical bonding mode to fix a NO fluorescent probe, the NO fluorescent probe is a quantum dot bonded on the open pore channel, and the quantum dot is a semiconductor quantum dot containing Cd element. The surface of the open pore of the optical fiber is functionalized (hydroxylated and silanized), so that the surface of the optical fiber has a group which can be chemically bonded with the NO fluorescent probe, and the NO fluorescent probe is directly fixed on the surface of the open pore. The problems that the fluorescent probe generated by physical methods such as electrostatic action, van der waals force and the like is easy to leak and separate can be effectively solved. The NO fluorescent probe selected by the invention is a self-made high-performance semiconductor quantum dot (CdTe quantum dot, CdS quantum dot, CdTe/CdS core-shell structure quantum dot), and the stability and the sensitivity of the NO sensor are greatly improved.

Description

Ultra-sensitive NO sensor based on simplified microstructure optical fiber
Technical Field
The invention belongs to the technical field of biological detection and clinical medical detection, relates to a micro optical fiber biosensor for detecting NO concentration in a living body, and particularly relates to preparation of a NO fluorescent probe.
Background
Nitric Oxide (NO), a unique vasoactive substance, is involved in and mediates a variety of physiological and pathological processes in the central nervous system, and is an important messenger and effector molecule in the body. The NO level can be used as one of important indexes for researching various physiological functions of nerves, immunity, digestion and the like, and various diseases and pathologies of heart, cerebral vessels, diabetes, tumors, obesity and the like. If the direct measurement of the NO content in human body can be realized, the mechanism of regulating and controlling the physiological and pathological processes of a plurality of important diseases by NO can be disclosed, and the NO level in the human body can be regulated by NO donor drugs or enzyme inhibitors, which has great significance for early diagnosis and treatment of a plurality of diseases of human beings.
NO is free radical small molecule gas with simple structureThe protein is extremely unstable, has fat solubility, can freely pass through cell membranes, and has great difficulty in detecting the concentration of NO in human bodies through experiments. This is because the amount of NO is normally very small, and only 1 to 200attomol (1attomol 10) is released per cell on average-18mol) and too fast metabolism (half-life period of 5-60 s), and the expression condition of NO at that time is difficult to reflect by detecting after obtaining a sample. Currently, there are two methods for detecting the concentration of NO: (1) the indirect detection method is to detect the metabolic product nitrous acid or nitrous acid ester by using NO synthetase induction. Since the induction of the expression of the synthase and the production of the metabolite take a certain time, the detection of the concentrations of the synthase and the metabolite does not completely reflect the concentration of NO at that time. (2) A direct detection method comprising: electron paramagnetic resonance spectroscopy (EPR), chemiluminescence, mass spectrometry, fluorescence, electrochemical sensors, and the like. The first three detection methods are generally low in sensitivity, complex in operation, high in sample treatment requirement, long in time consumption and high in cost; although the last two methods can monitor the concentration of NO in real time, the preparation process has high requirements, the signal detection system is complex, the stability is poor, and the practical application of the method is greatly limited.
The optical fiber biological sensing technology is a microanalysis technology which has high sensitivity and can carry out remote real-time analysis in recent ten years. The optical fiber biosensor is an analytical measuring device that selectively converts biological information of an analysis object into an optical signal that is easily measured by an analytical instrument, and can perform real-time, on-line detection of a single (or multiple) kinds of objects, and has become an important detection means for various kinds of biomass, molecules, and ions. The method has the characteristics of high detection precision, quick response, strong anti-interference capability and the like. Through years of development, substantial progress is made in developing fiber NO sensors by modifying the NO recognition sensitive layer (i.e., the sensing layer) at the end of the fiber.
Currently, there are many kinds of fiber optic NO sensors reported in literature and related to the intersection of various disciplines, mainly including: chemiluminescent, absorptive, fluorescent, and the like. Compared with other types of optical fiber NO sensors, the fluorescent optical fiber NO sensor has higher sensitivity and quicker response, is more beneficial to commercialization, and is one of effective means for realizing high-sensitivity real-time quick detection of NO. However, the following problems are commonly existed in the existing fluorescent type optical fiber NO sensor: 1. the detection sensitivity is low compared with the level of NO in organisms. Usually, a NO recognition sensitive layer is fixed at the end part of an optical fiber, and the loading capacity of the fluorescent probe is limited due to the small effective area of the end surface of the optical fiber; and the fluorescence signal is generated by the excitation of an evanescent field of the end face of the optical fiber, so that the excited fluorescence signal is weak due to the small energy of the evanescent field under the general condition, and the sensitivity of the sensor is greatly limited. 2. Lack the ability to identify analytes with high selectivity. At present, the most commonly used NO fluorescent probes are organic dyes, and in most cases, the excitation spectra of the organic dyes are narrow, and the fluorescent characteristic spectra are wide and low in intensity; the most serious defects are poor photochemical stability, photobleaching and photolysis, which causes poor stability of the optical fiber NO sensor. 3. The detection object and the sensing probe are in an open environment, and the fluorescent probe is easy to leak under the influence of molecular diffusion, so that the stability of the sensor is poor.
With the development of optical fiber transmission theory and manufacturing process, micro-structured optical fiber (MOF) has become a research hotspot in the field of optical fiber sensing. As the number of the channels adopted by the micro-structured optical fiber increases, the difficulty of fixing the biological sensitive material on the inner wall of the micro-structured optical fiber also increases, and the selection of the fixing method of the sensitive material is more limited. Researchers in recent years simplify the porous channel of the traditional microstructure optical fiber, and the micro-pore of the traditional microstructure optical fiber, which penetrates through the whole volume, provides a good reaction site for biological detection, and provides possibility for preparing a new generation of optical fiber biosensor with high sensitivity, high stability and quick response. Compare traditional optic fibre biosensor, the biosensor based on simplify micro-structure optic fibre has extremely outstanding advantage: (1) the sensitivity is obviously improved. The simplified microstructure optical fiber has a relatively large internal specific surface area which can be used for loading a sensitive material, and the sensitive material has a sufficiently large contact area with an object to be detected, so that the sensitivity of the optical fiber sensing probe can be effectively improved; (2) the stability is obviously improved. The detection of the object to be detected is carried out in the micro-channel of the MOF sensing probe, so that the collection amount of a sample can be greatly reduced, and the problems that a sensitive layer of the traditional optical fiber sensing probe is exposed outside and is easy to damage and leak and the like are solved; (3) and flexibly designing the distribution, the diameter and the duty ratio of the inner pore channels of the MOF to optimize the sensing performance.
Disclosure of Invention
Aiming at the problems of low sensitivity, poor stability and the like of the existing optical fiber NO sensor, the invention prepares high-performance quantum dots as NO fluorescent probes; a simplified microstructure optical fiber is selected and quantum dots are fixed on the surface of an open pore channel by adopting a chemical bonding method, so that the novel NO optical fiber sensor is developed.
The technical scheme of the invention comprises the following contents:
the sensing optical fiber is provided with an open pore channel, the surface of the open pore channel adopts a chemical bonding mode to fix a NO fluorescent probe, the NO fluorescent probe is a quantum dot bonded on the open pore channel, and the quantum dot is a semiconductor quantum dot containing Cd element.
According to the technical scheme, the fluorescent probe is a CdTe quantum dot, a CdS quantum dot or a CdTe/CdS core-shell quantum dot.
According to the technical scheme, the sensing optical fiber is provided with two symmetrically arranged open pore channels.
According to the technical scheme, the sensing optical fiber is provided with an open pore channel.
The invention also provides an optical fiber biosensor for detecting the concentration of NO in a living body, which is characterized by comprising a light source, a sensing optical fiber and an information acquisition and data processing system, wherein the sensing optical fiber is the sensing optical fiber of the technical scheme.
The method also provides a preparation method of the sensing optical fiber for detecting the concentration of NO in the organism, which is characterized by comprising the following steps:
1) preparing quantum dots for bonding on the open pore channels, wherein the quantum dots are semiconductor quantum dots containing Cd elements;
2) selecting two micro-structure optical fibers with open pore channels, and carrying out hydroxylation and silanization on the surfaces of the open pore channels;
3) under the action of the cross-linking agent, the prepared quantum dots are directly fixed on the surfaces of the open pore channels in a chemical bond mode.
According to the technical scheme, the quantum dots are CdTe quantum dots, CdS quantum dots or CdTe/CdS core-shell quantum dots.
In connection with the above technical scheme, the preparation method of the CdTe quantum dots comprises the following steps:
1) introducing high-purity N2Fully removing air in the condensing reflux device within half an hour;
2) adding CdCl2Adding the solution into a three-neck flask, adding 180-220 mg of trisodium citrate dihydrate under magnetic stirring, and sequentially adding 6-8 mL of Na2TeO3Solution, 90-100 mL of water, 95-105 mg of L-cysteine and 125-135 mg of NaBH4Obtaining a mixed solution;
3)N2under protection, heating the mixture solution to 70-90 ℃, and condensing in a spiral reflux device for 40-50 min;
4) after condensing and refluxing, naturally cooling to room temperature under the protection of nitrogen to obtain CdTe quantum dots;
in connection with the technical scheme, the preparation method of the CdS quantum dot comprises the following steps:
1) introducing high-purity N2Fully removing air in the condensing reflux device within half an hour;
2) adding CdCl2Adding the solution into a three-neck flask, and adding 180-220 mg of trisodium citrate dihydrate under magnetic stirring; then sequentially adding 1-2 mmol of thiourea, 90-100 mL of water, 95-105 mg of L-cysteine and 125-135 mg of NaBH4Obtaining a mixed solution;
3)N2under protection, heating the mixture solution to 70-90 ℃, and condensing in a spiral reflux device for 40-50 min;
4) and after condensation and reflux, naturally cooling to room temperature under the protection of nitrogen to obtain the CdS quantum dots.
In connection with the technical scheme, the preparation method of the CdTe/CdS core-shell quantum dot comprises the following steps:
1) introducing high-purity N2Fully removing air in the condensing reflux device within half an hour;
2) adding CdCl2Adding the solution into a three-neck flask, and adding 180-220 mg of trisodium citrate dihydrate under magnetic stirring; then adding 6-8 mLNa in sequence2TeO3Solution, 90-100 mL of water, 95-105 mg of L-cysteine and 125-135 mg of NaBH4Obtaining a mixed solution;
3)N2under protection, heating the temperature of the mixture solution to 70-90 ℃, condensing the mixture solution in a spiral reflux device for 30-40 min, dissolving 1-2 mmol of thiourea in a small amount of deionized water, and injecting the solution into a reaction device to continue reacting for 20-30 min;
4) after condensation and reflux, the CdTe/CdS core-shell structure quantum dot is obtained by naturally cooling to room temperature under the protection of nitrogen.
The invention has the beneficial effects that:
(1) the invention prepares a high-performance water-soluble semiconductor quantum dot as a NO fluorescent probe, and improves the sensitivity to NO, thereby increasing the sensitivity to NO detection.
(2) The invention selects simplified micro-structure optical fibers with different structures, functionalizes (hydroxylates and silanizes) the surface of an open pore channel of the micro-structure optical fiber, enables the surface to have a group which can be chemically bonded with quantum dots containing Cd of the NO fluorescent probe, directly fixes the NO fluorescent probe on the surface of the open pore channel, can effectively avoid the problems of easy leakage, separation and the like of the fluorescent probe which is usually generated by physical methods such as electrostatic action, van der Waals force and the like, and improves the stability and the repeatability of the sensor.
(3) The NO optical fiber sensor utilizes the open large air hole channel of the simplified microstructure optical fiber as a micro-reaction tank, so that the fluorescent probe fixed on the surface of the NO optical fiber is in contact with NO to react quickly, and the response time is prolonged; meanwhile, the effective area of the sensitive layer is obviously increased, and the sensitivity of the sensor is improved.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIGS. 1a and 1b are cross-sectional views of two simplified microstructured optical fibers.
Fig. 2 shows that quantum dots are fixed on the surface of the open channel of the optical fiber by means of chemical bonds.
FIG. 3 is a schematic diagram of NO detection by CdTe/CdS core-shell quantum dots fixed on the surface of the open pore of the microstructure optical fiber.
Fig. 4 is a diagram of an experimental setup for a NO sensor based on a simplified microstructured optical fiber.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention discloses a sensing optical fiber for detecting NO concentration in a living body, as shown in figure 3, the sensing optical fiber is provided with an open pore channel, the surface of the open pore channel adopts a chemical bonding mode to fix a NO fluorescent probe, the NO fluorescent probe is a quantum dot bonded on the open pore channel, and the quantum dot is a semiconductor quantum dot containing Cd element. Cd element is very sensitive to NO, and quantum dots containing the Cd element can react quickly when in contact with NO. Therefore, the semiconductor quantum dots containing Cd are used as NO fluorescent probes, so that the fluorescent probes fixed on the surfaces of the open pore channels can be rapidly contacted with NO to react, and the response time is prolonged; meanwhile, the effective area of the sensitive layer is obviously increased, and the sensitivity of the sensor is improved.
In the embodiment of the invention, the fluorescent probe is a CdTe quantum dot, a CdS quantum dot or a CdTe/CdS core-shell quantum dot (namely a quantum dot compounded by two materials, namely CdTe and CdS).
As shown in FIG. 1a, an embodiment of the present invention has an open channel in the sensing fiber. As shown in FIG. 1b, another embodiment of the present invention selects a sensing fiber having two open channels symmetrically disposed thereon.
As shown in fig. 4, the optical fiber biosensor for detecting the NO concentration in a living body according to the present invention includes a light source (optionally a laser), a sensing optical fiber, and an information collecting and data processing system (optionally a spectrometer), wherein the sensing optical fiber is the sensing optical fiber according to the above embodiment. Laser light is emitted from a light source through a filter, a portion of the light enters a microstructure sensing optical fiber (MOF) through a microscope objective, and a portion of the light enters a spectrometer. The sensing optical fiber is placed in an environment to be detected, the concentration of NO in the environment can influence the quantum dots fixed on the open pore channel of the sensing optical fiber, the fluorescence signal changes, and the signal change can be displayed on a spectrometer, so that the purpose of detecting the concentration of NO in an organism is achieved.
The preparation method of the sensing optical fiber for detecting the concentration of NO in a living body, disclosed by the invention, as shown in figure 2, comprises the following steps:
1) preparing quantum dots for bonding on the open pore channels, wherein the quantum dots are semiconductor quantum dots containing Cd elements;
2) selecting two micro-structure optical fibers with open pore channels, and carrying out hydroxylation and silanization on the surfaces of the open pore channels;
3) under the action of the cross-linking agent, the prepared quantum dots are directly fixed on the surfaces of the open pore channels in a chemical bond mode.
The quantum dots can be selected from CdTe quantum dots, CdS quantum dots or CdTe/CdS core-shell quantum dots.
Example 1
The preparation steps of each quantum dot are introduced as follows:
(1) and preparing CdTe quantum dots.
Introducing high-purity N2Half an hour, the air in the reflux condenser was sufficiently removed. Adding CdCl2Adding the solution into a three-neck flask, and adding 200mg of trisodium citrate dihydrate under magnetic stirring; then 8mLNa is added in sequence2TeO3Solution, 92mL of water, 100mg of L-cysteine and 130mg of NaBH4。N2The mixture solution was cooled to 80 ℃ under protection and condensed in a spiral reflux apparatus for 50 min. After condensing and refluxing, the CdTe quantum dots are naturally cooled to room temperature under the protection of nitrogen to obtain the CdTe quantum dots.
(2) And (3) fixing the NO fluorescent probe on the surface of the open pore channel of the microstructure optical fiber.
The semiconductor quantum dots prepared in step (1) are fixed on the surface of the open pore channels of the microstructured optical fiber shown in fig. 1 (a). Firstly, functionalizing, namely hydroxylating and silanizing the surface of an open pore channel of the microstructure optical fiber; then, under the action of a cross-linking agent, the prepared semiconductor quantum dots are directly fixed on the surfaces of the open pore channels in a chemical bond mode, and the specific steps are shown in fig. 2.
(3) And detecting NO by the ultra-sensitive NO sensor based on the micro-structured optical fiber.
Fig. 4 shows an experimental setup diagram of a microstructure fiber-based ultrasensitive NO sensor. 473nm excitation light is coupled to the optical fiber sensor probe to excite the semiconductor quantum dot sensitive layer to emit fluorescence, the fluorescence is transmitted along the optical fiber, and after the semiconductor quantum dot reacts with NO, the fluorescence signal (intensity or phase shift) changes. The change of the fluorescence signal of the sensor probe is tracked and recorded in real time by using the spectrometer, so that the high-sensitivity real-time monitoring of the NO concentration is realized.
Example 2
The method is the same as that of example 1 except that the microstructured optical fiber shown in fig. 1(a) in step (2) of example 1 is changed to the microstructured optical fiber shown in fig. 1(b) having two enlarged air holes.
The microstructure fiber of fig. 1(b) has 2 open large air hole channels as a micro-reaction cell, which can make the fluorescent probe fixed on the surface of the fiber react with NO quickly in contact, thereby increasing the response time; meanwhile, the effective area of the sensitive layer is obviously increased, and the sensitivity of the sensor is improved.
Example 3
The implementation method is the same as that of the example 1 except that the CdTe quantum dots obtained in the step (1) in the example 1 are changed into the CdS quantum dots.
The preparation method of the CdS quantum dot comprises the following steps: introducing high-purity N2Half an hour, the air in the reflux condenser was sufficiently removed. Adding CdCl2Adding the solution into a three-neck flask, and adding 200mg of trisodium citrate dihydrate under magnetic stirring; then 0.0974g of thiourea, 92mL of water, 100mg of L-cysteine and 130mg of NaBH were added in that order4。N2The mixture solution was cooled to 80 ℃ under protection and condensed in a spiral reflux apparatus for 50 min. And after condensation and reflux, naturally cooling to room temperature under the protection of nitrogen to obtain the CdS quantum dots.
Example 4
Except that the CdTe quantum dots obtained in the step (1) in the embodiment 1 are changed into CdTe/CdS core-shell structure quantum dots, the other implementation methods are the same as the embodiment 1.
Preparing CdTe/CdS core-shell structure quantum dots: introducing high-purity N2Half an hour, the air in the reflux condenser was sufficiently removed. Adding CdCl2Adding the solution into a three-neck flask, and adding 200mg of trisodium citrate dihydrate under magnetic stirring; then 8mLNa is added in sequence2TeO3Solution, 92mL of water, 100mg of L-cysteine and 130mg of NaBH4。N2The mixture solution was cooled to 80 ℃ under protection and condensed in a spiral reflux unit for 30 min. A small amount of deionized water was added to the reaction apparatus to dissolve 0.0974g of thiourea (about 1.28mmol), and the reaction was continued for 20 min. After condensation and reflux, the CdTe/CdS core-shell structure quantum dot is obtained by naturally cooling to room temperature under the protection of nitrogen.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.

Claims (10)

1. A sensing optical fiber for detecting the concentration of NO in a living body is characterized in that the sensing optical fiber is provided with an open pore channel, the surface of the open pore channel is hydroxylated and silanized, and under the action of a cross-linking agent, the surface of the open pore channel adopts a chemical bonding mode to fix a NO fluorescent probe, wherein the NO fluorescent probe is a quantum dot bonded on the open pore channel, and the quantum dot is a semiconductor quantum dot containing Cd element.
2. The sensing optical fiber for detecting the concentration of NO in a living organism according to claim 1, wherein the semiconductor quantum dots are CdTe quantum dots, CdS quantum dots or CdTe/CdS core-shell quantum dots.
3. The optical sensing fiber for detecting the concentration of NO in a living organism according to claim 1, wherein the optical sensing fiber has two open channels symmetrically arranged.
4. The sensing fiber for detecting the concentration of NO in a living organism according to claim 1, wherein the sensing fiber has an open channel therein.
5. An optical fiber biosensor for detecting NO concentration in organism, which comprises a light source, a sensing optical fiber and an information acquisition and data processing system, wherein the sensing optical fiber is the sensing optical fiber according to any one of claims 1-4.
6. A method for preparing a sensing optical fiber for detecting NO concentration in a living body is characterized by comprising the following steps:
1) preparing quantum dots for bonding on the open pore channels, wherein the quantum dots are semiconductor quantum dots containing Cd elements;
2) selecting two micro-structure optical fibers with open pore channels, and carrying out hydroxylation and silanization on the surfaces of the open pore channels;
3) under the action of the cross-linking agent, the prepared quantum dots are directly fixed on the surfaces of the open pore channels in a chemical bond mode.
7. The method according to claim 6, wherein the quantum dot is a CdTe quantum dot, a CdS quantum dot or a CdTe/CdS core-shell quantum dot.
8. The preparation method of claim 7, wherein the CdTe quantum dots are prepared by the following method:
1) introducing high-purity N2Fully removing air in the condensing reflux device within half an hour;
2) adding CdCl2Adding the solution into a three-neck flask, adding 180-220 mg of trisodium citrate dihydrate under magnetic stirring, and sequentially adding 6-8 mL of Na2TeO3Solution, 90-100 mL of water, 95-105 mg of L-cysteine and 125-135 mg of NaBH4Obtaining a mixed solution;
3）N2under protection, heating the mixture solution to 70-90 ℃, and condensing in a spiral reflux device for 40-50 min;
4) after condensing and refluxing, the CdTe quantum dots are naturally cooled to room temperature under the protection of nitrogen to obtain the CdTe quantum dots.
9. The preparation method according to claim 7, wherein the CdS quantum dot is prepared by the following steps:
1) introducing high-purity N2Fully removing air in the condensing reflux device within half an hour;
2) adding CdCl2Adding the solution into a three-neck flask, and adding 180-220 mg of trisodium citrate dihydrate under magnetic stirring; then sequentially adding 1-2 mmol of thiourea, 90-100 mL of water, 95-105 mg of L-cysteine and 125-135 mg of NaBH4Obtaining a mixed solution;
3）N2under protection, heating the mixture solution to 70-90 ℃, and condensing in a spiral reflux device for 40-50 min;
4) and after condensation and reflux, naturally cooling to room temperature under the protection of nitrogen to obtain the CdS quantum dots.
10. The preparation method according to claim 7, wherein the CdTe/CdS core-shell quantum dot is prepared by the following method:
1) introducing high-purity N2 for half an hour, and fully removing air in the condensation reflux device;
2) adding CdCl2Adding the solution into a three-neck flask, and adding 180-220 mg of trisodium citrate dihydrate under magnetic stirring; then adding 6-8 mLNa in sequence2TeO3Solution, 90-100 mL of water, 95-105 mg of L-cysteine and 125-135 mg of NaBH4Obtaining a mixed solution;
3）N2under protection, heating the temperature of the mixture solution to 70-90 ℃, condensing the mixture solution in a spiral reflux device for 30-40 min, dissolving 1-2 mmol of thiourea in a small amount of deionized water, and injecting the solution into a reaction device to continue reacting for 20-30 min;
4) after condensation and reflux, the CdTe/CdS core-shell structure quantum dot is obtained by naturally cooling to room temperature under the protection of nitrogen.
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