CN100502778C - In-vivo real time photosensitive blood sodium ion sensor and preparation method thereof - Google Patents
In-vivo real time photosensitive blood sodium ion sensor and preparation method thereof Download PDFInfo
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- CN100502778C CN100502778C CNB2005101107312A CN200510110731A CN100502778C CN 100502778 C CN100502778 C CN 100502778C CN B2005101107312 A CNB2005101107312 A CN B2005101107312A CN 200510110731 A CN200510110731 A CN 200510110731A CN 100502778 C CN100502778 C CN 100502778C
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Abstract
The invention discloses a real-time photosensitive blood sodium ion sensor and making method, which is made of common optical fiber and blood sodium ion sensing film on the bottom of optical fiber. The invention integrates high-degree biological solubility of phosphorus Choline polymer and protein adhesive proof and high-sensitivity electrochemical luminous material, which can analyze and detect real-time sodium ion in the blood in vivo.
Description
Technical field
The present invention relates to medical apparatus and instruments and material field, be specifically related to a kind of at vivo real time photosensitive blood sodium ion sensor and preparation method thereof
Background technology
Along with the continuous development of modern medicine, during the clinical emergency treatment patient, particularly clinical critical patient's rescue need be to the electrolyte of human body, comprises that blood sodium ion value etc. carries out long Wicresoft and detect in real time.Present employed method and sodium ion gauge are principle with the electrode method mainly.After being faced with used pick off always and blood contacting certain hour, its surface also exists the difficult problem of similar biological pollution by protein adherences such as platelet and cause the problem of inefficacy at the pick off of application such as other field such as bioreactor.
Phosphocholine is the main component of the outer phospholipid head part of biological cell membrane, the polymer that contains the phosphocholine group has been applied to bio-medical material and apparatus surface, can reduce the foreign body reaction that produces when contacting with body fluid such as blood, tear film and urine etc. effectively.The phosphocholine group is polar, and the existing positive charge of its intramolecule also has negative charge, and molecule is electroneutral generally.It has intensive hydrophilic, can reduce protein effectively in its surperficial reversible adhesion.The polymer of being reported at present that contains the phosphocholine group mainly by 2-methylacryoyloxyethyl-2 '-trimethylamine ethyl phosphonic acid ester inner salt (MPC) forms with other monomer copolymerizations, research is arranged, the MPC copolymer has been applied to the medical apparatus surface that cardiac stent, interposing catheter and hemodialysis membrane etc. and blood of human body directly contact, improve the blood compatibility of apparatus, reduce proteinic adhesion in blood coagulation and the blood.But also there is not this base polymer to be applied to the report of vivo implantation type electrochemiluminescence material at present.
Summary of the invention
The objective of the invention is to overcome the defective that present blood sodium ion detects apparatus, provide a kind of at vivo real time photosensitive blood sodium ion sensor and preparation method thereof.
The present invention experiences film 2 by ordinary optic fibre 1 with the blood sodium ion that is coated on optical fiber connector and makes at vivo real time photosensitive blood sodium ion sensor.
Described blood sodium ion is experienced film and is made up of highly sensitive electrochemiluminescence material and the polymer that contains the phospholipid group.This polymer is applied to the optical fibers end, connects light source, and the fluorescence filter disc, the photocell receiving device can assemble small-sized blood sodium ion analyzer.
The present invention combines the high degree of biocompatibility of phosphocholine polymer and anti-protein adhesion property and high sensitivity electrochemiluminescence material, the electrochemical luminous sensor that preparation has stable against biological contamination usefulness can be used for real-time analysis detection blood sodium ion in the organism.
The present invention is the chemiluminescence that is excited by electrochemical reaction at vivo real time photosensitive blood sodium ion sensor, is used for the analyzing and testing of blood sodium ion, has high sensitivity.This highly sensitive electrochemiluminescence material is fixed to electrode or optical fiber surface, can saves mass expensive reagent, simplify the operation and apparatus structure, help enlarging the range of application of instrument.
Compare with known traditional sodium ion instrument, pick off of the present invention can be measured blood sodium ion in the body real-time continuous, has long service life, and measuring range is wide, is swift in response good reproducibility, steady performance.
Preparation method of the present invention realizes as follows:
1) sodium ion electrochemiluminescence material is dissolved in certain solvent,
In the embodiments of the invention, Sodium Green is dissolved in the methanol, SodiumGreen/ methanol ratio is 0.3～0.5 mg/ml;
2) in above-mentioned solution, add the polymer solution that contains the phospholipid group, mix homogeneously,
In the embodiments of the invention, every milligram of Sodium Green and 400～800 milligrams of copolymers are dissolved in the same solution, after the filtration, add entry in gained solution, stir 1.5～3 microliters of water/10 milligram copolymer;
3) with the end of solution coat at optical fiber, heat treatment is 5 hours in 70 degree baking ovens after, and with solvent evaporates, the sodium ion that forms 0.2～0.3 millimeters thick is experienced film, obtains at vivo real time photosensitive blood sodium ion sensor.
The present invention be applicable to can be in solvent dissolved sodium ion electrochemiluminescence material and phospholipid polyalcohol.Wherein highly sensitive electrochemiluminescence material comprises Sodium green (tetra (tetramethylammonium) salt), SBFI (tetraammonium salt), wherein preferred especially Sodium green.
Among the present invention the employed polymer that contains the phospholipid group be 2-methylacryoyloxyethyl-2 '-trimethylamine ethyl phosphonic acid ester inner salt (MPC) contains the monomeric copolymer of polymerizable groups with other, this copolymerization system 2-methylacryoyloxyethyl-2 '-in trimethylamine ethyl phosphonic acid ester inner salt (MPC) and the following monomer one or more carry out free-radical polymerized obtaining: acrylic or methacrylic dialkylaminobenzoic acid (methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, octadecyl) ester, acrylic or methacrylic acid hydroxy methacrylate, acrylic or methacrylic acid hydroxy propyl ester, acrylic or methacrylic acid glycol ester, acrylic or methacrylic acid glycol methyl ether ester, acrylic or methacrylic acid polyethylene glycol ester, acrylic or methacrylic acid polyethylene glycol methyl ether ester, vinyl pyrrolidone, vinylacetate, silane coupler such as γ-(methacryloxy) propyl trimethoxy silicane of containing two keys, γ-(methacryloxy) propyl-triethoxysilicane or the like.
Description of drawings
Fig. 1 is at the vivo real time photosensitive blood sodium ion sensor sketch map,
Wherein 1 is optical fiber, the 2nd, and blood sodium ion is experienced film.
The specific embodiment
Embodiment 1:
30 gram MPC, 68 gram butyl methacrylates, 2 gram γ-(methacryloxy) propyl trimethoxy silicanes and 0.1 gram initiator A IBN are dissolved in the dehydrated alcohol, slowly feed argon deoxygenation in 1 hour.Place 70 ℃ of waters bath with thermostatic control then, stir reaction down 24 hours.After reaction finishes, solution is cooled to room temperature, purifies 2 times with a large amount of normal hexane precipitations; At room temperature with the precipitate vacuum drying collected 24 hours.Obtain containing copolymer 90 grams of phospholipid group.
5 milligrams of Sodium Green are dissolved in 10 ml methanol, getting the above-mentioned copolymer that contains the phospholipid group of 0.4 gram is dissolved in the same solution, after the filtration, in gained solution, add 20 microliters of water, with the end of solution coat at optical fiber, heat treatment is 5 hours in 70 degree baking ovens, with solvent evaporates after stirring, the sodium ion that forms thin layer is experienced film, promptly gets the stable against biological contamination Fibre Optical Sensor that can be used for measuring sodium ion value in blood or the rich in proteins solution.
Embodiment 2:
15 gram MPC, 10 gram metering system acid polyethylene glycol (molecular weight 360) methyl ether esters, 10 gram methacrylic acid glycol methyl ether esters, 63 gram lauryl methacrylates, 2 gram γ-(methacryloxy) propyl trimethoxy silicanes and 0.1 gram initiator A IBN are dissolved in dehydrated alcohol/oxolane (volume ratio 50/50) solution, slowly feed argon deoxygenation in 1 hour.Place 70 ℃ of waters bath with thermostatic control then, stir reaction down 24 hours.After reaction finishes, solution is cooled to room temperature, purifies 2 times with a large amount of normal hexane precipitations; At room temperature with the precipitate vacuum drying collected 24 hours.Obtain containing copolymer 92 grams of phospholipid group.
3 milligrams of Sodium Green are dissolved in 5 ml methanol, getting the above-mentioned copolymer that contains the phospholipid group of 0.2 gram is dissolved in the same solution, after the filtration, in gained solution, add 10 microliters of water, after stirring with the end of solution coat at optical fiber, heat treatment is 5 hours in 70 degree baking ovens, with solvent evaporates, promptly gets the stable against biological contamination Fibre Optical Sensor that can be used for measuring blood or rich in proteins solution sodium ion value.
Embodiment illustrated and that discuss is only used for demonstrating use known for inventor best mode of the present invention to those skilled in the art in this description.Any content in the description all can not be thought limiting the scope of the invention.Can make amendment and do not exceed scope of the present invention above embodiment, by above explanation, this be conspicuous for those skilled in the art.Therefore it should be understood that in the scope of claims and equivalent thereof, can the mode different implement the present invention with above specific descriptions.
Claims (6)
1, a kind of at vivo real time photosensitive blood sodium ion sensor, it is characterized in that experiencing film by ordinary optic fibre with the sodium ion that is coated on optical fiber connector makes, described sodium ion is experienced film and is made up of sodium ion electrochemiluminescence material and the polymer that contains the phospholipid group; The described polymer that contains the phospholipid group is 2-methylacryoyloxyethyl-2 '-trimethylamine ethyl phosphonic acid ester inner salt and silane coupler that contains two keys and other monomeric copolymer.
2, according to claim 1 at vivo real time photosensitive blood sodium ion sensor, it is characterized in that described sodium ion electrochemiluminescence material is Sodium green or SBFI.
3, according to claim 1 at vivo real time photosensitive blood sodium ion sensor, it is characterized in that the described silane coupler that contains two keys is selected from γ-(methacryloxy) propyl trimethoxy silicane or γ-(methacryloxy) propyl-triethoxysilicane.
4, according to claim 1 at vivo real time photosensitive blood sodium ion sensor, it is characterized in that described can with 2-methylacryoyloxyethyl-2 '-trimethylamine ethyl phosphonic acid ester inner salt and be selected from alkyl acrylate or alkyl methacrylate with other monomer of the silane coupler copolymerization that contains two keys, Hydroxyethyl Acrylate or methacrylic acid hydroxyl ethyl ester, acrylic acid hydroxy propyl ester or methacrylic acid hydroxyl propyl ester, acrylic acid glycol ester or methacrylic acid glycol ester, acrylic acid glycol methyl ether ester or methacrylic acid glycol methyl ether ester, polyalkylene glycol acrylate ester or methacrylic acid macrogol ester, polyalkylene glycol acrylate methyl ether ester or methacrylic acid methoxypolyethylene glycol ester, wherein one or more of vinyl pyrrolidone or vinylacetate.
5, according to claim 4 at vivo real time photosensitive blood sodium ion sensor, it is characterized in that the alkyl in the described alkyl methacrylate is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl or octadecyl.
6, the preparation method at vivo real time photosensitive blood sodium ion sensor of claim 1 is characterized in that by following step:
1) sodium ion electrochemiluminescence material Sodium Green is dissolved in methanol solvate, SodiumGreen/ methanol ratio is 0.3～0.5 mg/ml;
2) in above-mentioned solution, add the polymer solution that contains the phospholipid group, mix homogeneously, every milligram of SodiumGreen and 400～800 milligrams of polymer are dissolved in the same solution, after the filtration, in gained solution, add entry, stir, 1.5～3 microliters of water/10 milligram polymer;
3) with the end of solution coat at optical fiber, heat treatment is 5 hours in 70 degree baking ovens, and with solvent evaporates, the sodium ion that forms 0.2～0.3 millimeters thick is experienced film, obtains at vivo real time photosensitive blood sodium ion sensor.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101107312A CN100502778C (en) | 2005-11-24 | 2005-11-24 | In-vivo real time photosensitive blood sodium ion sensor and preparation method thereof |
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| CNB2005101107312A CN100502778C (en) | 2005-11-24 | 2005-11-24 | In-vivo real time photosensitive blood sodium ion sensor and preparation method thereof |
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| CN1969749A CN1969749A (en) | 2007-05-30 |
| CN100502778C true CN100502778C (en) | 2009-06-24 |
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| CNB2005101107312A Expired - Fee Related CN100502778C (en) | 2005-11-24 | 2005-11-24 | In-vivo real time photosensitive blood sodium ion sensor and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5136033A (en) * | 1987-08-24 | 1992-08-04 | Allied-Signal Inc. | Ion selective fluorogenic reagents |
| US5462989A (en) * | 1990-11-07 | 1995-10-31 | Mauze; Ganapati R. | Fiber optic potassium ion sensor |
-
2005
- 2005-11-24 CN CNB2005101107312A patent/CN100502778C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5136033A (en) * | 1987-08-24 | 1992-08-04 | Allied-Signal Inc. | Ion selective fluorogenic reagents |
| US5462989A (en) * | 1990-11-07 | 1995-10-31 | Mauze; Ganapati R. | Fiber optic potassium ion sensor |
Non-Patent Citations (2)
| Title |
|---|
| 《Hemocompatibility of human whole blood on polymers withaphospholipid polar group and its mechanism》. Kazuhiko Ishihara,Hiroko Oshida,etc.Journal of Biomedical Materials Research,Vol.26. 1992 * |
| 《Sodium Green as a Potential Probe for IntracellularSodiumImaging Based on Fluorescence Lifetime》. Henryk Szmacinski and Joseph R. Lakowicz.ANALYTICAL BIOCHEMISTRY,Vol.250. 1997 * |
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