CN113466145B - Micro-nano optical fiber sensor for in-situ loading and releasing of medicine and preparation method thereof - Google Patents
Micro-nano optical fiber sensor for in-situ loading and releasing of medicine and preparation method thereof Download PDFInfo
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- 239000013307 optical fiber Substances 0.000 title claims abstract description 95
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- 238000011068 loading method Methods 0.000 title claims abstract description 21
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 9
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- 239000000463 material Substances 0.000 claims abstract description 15
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- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical group [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
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- 241000252506 Characiformes Species 0.000 claims description 3
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- 239000001273 butane Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 3
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 3
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 239000002121 nanofiber Substances 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 2
- AOJJSUZBOXZQNB-TZSSRYMLSA-N Doxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-TZSSRYMLSA-N 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 4
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- 238000001228 spectrum Methods 0.000 description 3
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- 239000002841 Lewis acid Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N2021/0106—General arrangement of respective parts
- G01N2021/0112—Apparatus in one mechanical, optical or electronic block
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention belongs to the technical field of optical fiber sensors, and particularly relates to a micro-nano optical fiber sensor for in-situ loading and releasing of a medicine, which consists of a micro-nano optical fiber and a wrapping layer positioned on the micro-nano optical fiber, wherein the micro-nano optical fiber is made of a photosensitive optical fiber by tapering, the micro-nano optical fiber consists of a beam waist uniform region positioned in the middle, transition regions positioned at two sides of the beam waist uniform region and a normal region connected to the outer end of the transition region, the wrapping layer is grown on the beam waist uniform region in situ, and the wrapping layer is a ZIF-8 material layer loaded with the medicine. The invention combines the micro-nano optical fiber with the biologically active MOFs material, and organically combines the advantages of miniaturization, low cost and high sensitivity of the micro-nano optical fiber with the advantages of high specific surface area and large pore size of the MOFs material, which can load more drug molecules, biodegradability, innocuity, good biocompatibility and the like.
Description
Technical Field
The invention belongs to the technical field of optical fiber sensors, and particularly relates to a micro-nano optical fiber sensor for in-situ loading and releasing of a medicine and a preparation method thereof.
Background
With the development of medical level, there is a higher demand for disease treatment. The drug treatment requires that the drug cannot be released at the focus position with too high concentration and accuracy, so that the injury to body tissues and organs can be avoided. The optical fiber sensor has the advantages of miniaturization, exquisite structure, biocompatibility and the like, and provides a new platform for medicine loading and release. The Metal Organic Frameworks (MOFs) can obtain porous materials with ultrahigh porosity, high thermal stability and chemical stability according to careful selection of components, and have good application prospects in the fields of adsorption, sensing, biological medicine and the like. The mode of combining micro-nano optical fiber technology and nano materials provides new growth power for the development of intelligent sensors. The nano medicine carrying system introduces an optical fiber intelligent detection technology, grows MOFs materials on micro-nano optical fibers in situ, builds a stable novel sensing interface, not only retains the advantages of super high specific surface area, adjustable aperture and the like of the MOFs materials, but also inherits the advantages of the optical fiber technology, is flexible in structural design, can realize safety, simplicity, microminiaturization, no marking and real-time monitoring, and can accurately convey medicines to cancer focus positions and then release the medicines.
Disclosure of Invention
The invention provides a micro-nano optical fiber sensor for in-situ loading and releasing of medicines and a preparation method thereof.
The invention adopts the following technical scheme to achieve the aim:
the micro-nano optical fiber sensor for in-situ loading and releasing of the medicine consists of a micro-nano optical fiber and a wrapping layer positioned on the micro-nano optical fiber, wherein the micro-nano optical fiber is manufactured by tapering a photosensitive optical fiber, the micro-nano optical fiber consists of a beam waist uniform region positioned in the middle, transition regions positioned at two sides of the beam waist uniform region and a normal region connected to the outer end of the transition region, the wrapping layer is grown on the beam waist uniform region in-situ, and the wrapping layer is a ZIF-8 material layer loaded with the medicine.
Further, the length of the transition zone is 4mm, the length of the uniform zone of the beam waist is 10-13mm, and the diameter is 10-15 μm.
Still further, the micro-nano optical fiber is symmetrically bent and arranged about the middle part of the uniform region of the beam waist, and the maximum distance after the uniform region of the beam waist is bent is 0.3 cm to 0.8cm.
A preparation method of a micro-nano optical fiber sensor for in-situ loading and releasing of medicines comprises the following steps:
and step 3, loading the wrapping layer into the uniform beam waist region of the micro-nano optical fiber.
Further, the specific steps of preparing the micro-nano optical fiber by adopting the fusion tapering method in the step 1 are as follows: firstly, the middle position of the photosensitive optical fiber is heated for about 3s through butane flame, and then the micro-nano optical fiber is prepared by accurately and simultaneously moving a displacement platform to carry out uniform tapering.
Still further, the step 2, the surface pretreatment of the micro-nano optical fiber, specifically includes the following steps:
step 2.1, soaking the micro-nano optical fiber for 230min by using 10ml of piranha solution, washing by using deionized water and drying at room temperature for 10min;
step 2.2, soaking the micro-nano optical fiber with 10ml of 1% polystyrene sulfonate solution at room temperature for 1.5 hours, increasing the availability of hydroxyl groups on the surface of the micro-nano optical fiber, washing with absolute ethyl alcohol and drying at room temperature for 10min.
Further, the step 3 of loading the wrapping layer in situ in the uniform region of the beam waist of the micro-nano optical fiber specifically includes the following steps:
step 3.1, weighing the medicines and dissolving the medicines in deionized water to obtain a medicine stock solution;
step 3.2, dissolving 2-methylimidazole in water to obtain a 2-methylimidazole aqueous solution;
step 3.3, dissolving zinc nitrate hexahydrate in water to obtain zinc nitrate hexahydrate solution;
step 3.4, dropwise adding the drug stock solution into the zinc nitrate hexahydrate solution under the room temperature stirring condition with the stirring rate of 1200rpm, stirring for 5 minutes, and then dropwise adding the obtained mixed solution into the 2-methylimidazole aqueous solution under the stirring condition of 1200rpm, and stirring for 10 minutes at room temperature to obtain a drug@MOF solution;
and 3.5, soaking the micro-nano optical fiber in a medicine@MOF solution for 30min, taking out the soaked micro-nano optical fiber, washing unreacted impurities by using deionized water, and drying at 60 ℃ for 30min to obtain the micro-nano optical fiber sensor.
Compared with the prior art, the invention has the following advantages:
1. the invention combines micro-nano optical fiber with 'biologically active MOFs material', organically combines the advantages of miniaturization, low cost and high sensitivity of the micro-nano optical fiber with the advantages of high specific surface area and large pore size of the MOFs material, such as more drug molecules can be loaded, biodegradability, innocuity, good biocompatibility and the like, and provides a new idea for monitoring drug delivery and release in real time by monitoring the drift amount of spectrum under the conditions of drug loading and release and providing a safe and sensitive intelligent sensing technology for drug loading and monitoring drug delivery and release in the process of drug delivery;
2. the invention bends the micro-nano optical fiber to form a probe type structure, has the advantages of simple operation, lower cost and strong anti-interference capability, can accurately convey the loaded medicine to the focus position, and monitors the release process in real time.
3. According to the invention, MOFZIF-8 materials and medicines are grown on the micro-nano optical fiber in situ by adopting a one-step method, so that a stable novel sensing interface is constructed, and the slow release or controllable release of the medicines can be realized safely, simply, conveniently, miniaturized, marker-free and real-time monitored.
Drawings
FIG. 1 is a schematic diagram of a structure used in the present invention;
FIG. 2 is a schematic structural diagram of a micro-nano optical fiber according to the present invention;
FIG. 3 is a graph of sensor spectra and wavelength drift during drug loading according to the present invention;
FIG. 4 is a graph of sensor wavelength shift upon drug release according to the present invention;
in the figure, a broadband light source-1, a micro-nano optical fiber-2, a wrapping layer-3, a spectrometer-4, a beam waist uniform region-201, a transition region-202 and a normal region-203.
Detailed Description
In order to further illustrate the technical scheme of the invention, the invention is further illustrated by the following examples.
As shown in fig. 1 to 2, a micro-nano fiber sensor for in-situ loading and releasing of a drug is characterized in that: the micro-nano optical fiber 2 is made of a photosensitive optical fiber drawing cone, the micro-nano optical fiber 2 consists of a beam waist uniform region 201 positioned in the middle, transition regions 202 positioned at two sides of the beam waist uniform region 201 and a normal region 203 connected to the outer end of the transition region 202, the length of the transition region 202 is 4mm, the length of the beam waist uniform region 201 is 10-13mm, the diameter is 10-15 mu m, the micro-nano optical fiber 2 is symmetrically bent and arranged about the middle of the beam waist uniform region 201, the maximum distance between the bent beam waist uniform regions 201 is 0.3-0.8cm, the wrapping layer 3 grows on the beam waist uniform region 201 in situ, and the wrapping layer 3 is a ZIF-8 material layer loaded with medicines.
A preparation method of a micro-nano optical fiber sensor for in-situ loading and releasing of medicines comprises the following steps:
step 2.1, soaking the micro-nano optical fiber for 230min by using 10ml of piranha solution, washing by using deionized water and drying at room temperature for 10min;
step 2.2, soaking the micro-nano optical fiber with 10ml of 1% polystyrene sulfonate solution at room temperature for 1.5 hours, increasing the availability of hydroxyl groups on the surface of the micro-nano optical fiber 2, washing with absolute ethyl alcohol, and drying at room temperature for 10 minutes;
step 3.1, weighing 20mg of doxorubicin to be co-dissolved in 2mL of deionized water to obtain a drug stock solution;
step 3.2, weighing 1.0g of 2-methylimidazole and dissolving in 4mL of water to obtain a 2-methylimidazole aqueous solution;
step 3.3, weighing 0.1g of zinc nitrate hexahydrate, and dissolving the zinc nitrate hexahydrate in 0.4mL of water to obtain a zinc nitrate hexahydrate solution;
step 3.4, dropwise adding the drug stock solution into a zinc nitrate hexahydrate solution under the room temperature stirring condition with the stirring rate of 1200rpm, stirring for 5 minutes, and then dropwise adding the obtained mixed solution into a 2-methylimidazole aqueous solution under the stirring condition of 1200rpm, and stirring for 10 minutes at room temperature to obtain an doxorubicin@MOF solution;
and 3.5, soaking the micro-nano optical fiber 2 in doxorubicin@MOF solution for 30min, taking out the soaked micro-nano optical fiber 2, flushing unreacted impurities by using deionized water, and drying at 60 ℃ for 30min to obtain the micro-nano optical fiber sensor.
The method for realizing drug release comprises the following steps:
the pH value of the common tumor living environment is weak acidity, and the MOFsZIF-8 material can be degraded in the weak acidity environment, so that the medicine can be released. The drug loaded sensor was immersed in buffers of different pH values (ph=5.0) and the spectral shift was recorded for 60min at a specific time point.
According to the invention, the open metal site of MOFsZIF-8 material or the open Lewis acid or alkali site on ligand is utilized to enable the MOFsZIF-8 material to have stronger interaction with drug molecules, slow release or controllable release of the drug is realized, wavelength drift can be observed through a spectrometer, the spectrum of the sensor during drug loading is observed in FIG. 3, the response is rapid in 10min, and the wavelength drift amount is 31.8nm. In FIG. 4, the MOFsZIF-8 material was observed to degrade to release the drug with a rapid response time of 2min and a wavelength shift of 44nm.
While the principal features and advantages of the present invention have been shown and described, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (6)
1. A micro-nano optical fiber sensor for in-situ loading and releasing of medicines is characterized in that: the optical fiber comprises a micro-nano optical fiber (2) and a wrapping layer (3) positioned on the micro-nano optical fiber (2), wherein the micro-nano optical fiber (2) is manufactured by tapering a photosensitive optical fiber, the micro-nano optical fiber (2) comprises a beam waist uniform region (201) positioned in the middle, transition regions (202) positioned at two sides of the beam waist uniform region (201) and a normal region (203) connected to the outer end of the transition region (202), the wrapping layer (3) grows on the beam waist uniform region (201) in situ, and the wrapping layer (3) is a ZIF-8 material layer loaded with medicines; the transition zone (202) has a length of 4mm, the beam waist uniformity zone (201) has a length of 10-13mm and a diameter of 10-15 μm.
2. A micro-nano fiber sensor for in situ loading and release of a drug according to claim 1, wherein: the micro-nano optical fiber (2) is symmetrically bent and arranged on the middle of the beam waist uniform region (201), and the maximum distance between the bent beam waist uniform region (201) is 0.3 cm to 0.8cm.
3. The method for preparing the micro-nano optical fiber sensor for in-situ loading and releasing of the medicine as set forth in claim 1, which is characterized in that: the method comprises the following steps:
step 1, removing a coating layer from a section of photosensitive optical fiber with the length of 3-4cm, then stably fixing the photosensitive optical fiber on an optical fiber clamp, and preparing the micro-nano optical fiber (2) by adopting a fusion tapering method;
step 2, surface pretreatment of the micro-nano optical fiber (2);
and 3, loading the wrapping layer (3) into a beam waist uniform region (201) of the micro-nano optical fiber (2).
4. A method of preparation according to claim 3, characterized in that: the specific steps of preparing the micro-nano optical fiber (2) by adopting the fusion tapering method in the step 1 are as follows: firstly, the middle position of the photosensitive optical fiber is heated for about 3s through butane flame, and then, the micro-nano optical fiber (2) is manufactured through precisely and simultaneously moving a displacement platform to carry out uniform tapering.
5. A method of preparation according to claim 3, characterized in that: the step 2, the surface pretreatment of the micro-nano optical fiber (2) specifically comprises the following steps:
step 2.1, soaking the micro-nano optical fiber (2) for 30min by using 10ml of piranha solution, washing by using deionized water and drying at room temperature for 10min;
step 2.2, soaking the micro-nano optical fiber (2) with 10ml of 1% polystyrene sulfonate solution at room temperature for 1.5 hours, increasing the availability of hydroxyl groups on the surface of the micro-nano optical fiber (2), washing with absolute ethyl alcohol and drying at room temperature for 10min.
6. A method of preparation according to claim 3, characterized in that: the step 3 is to load the wrapping layer (3) to the beam waist uniform region (201) of the micro-nano optical fiber (2) in situ, and specifically comprises the following steps:
step 3.1, weighing the medicines and dissolving the medicines in deionized water to obtain a medicine stock solution;
step 3.2, dissolving 2-methylimidazole in water to obtain a 2-methylimidazole aqueous solution;
step 3.3, dissolving zinc nitrate hexahydrate in water to obtain zinc nitrate hexahydrate solution;
step 3.4, dropwise adding the drug stock solution into the zinc nitrate hexahydrate solution under the room temperature stirring condition with the stirring rate of 1200rpm, stirring for 5 minutes, and then dropwise adding the obtained mixed solution into the 2-methylimidazole aqueous solution under the stirring condition of 1200rpm, and stirring for 10 minutes at room temperature to obtain a drug@MOF solution;
and 3.5, soaking the micro-nano optical fiber (2) in a medicine@MOF solution for 30min, taking out the soaked micro-nano optical fiber (2), flushing unreacted impurities by using deionized water, and drying at 60 ℃ for 30min to obtain the micro-nano optical fiber sensor.
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