CN115651525B - Glucose diffusion-limited polymer outer membrane and preparation method and application thereof - Google Patents
Glucose diffusion-limited polymer outer membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of biosensors, and particularly provides a glucose diffusion-limited polymer outer membrane, a preparation method and an application thereof, wherein the glucose diffusion-limited polymer outer membrane comprises the following components in percentage by dry weight of the membrane being 100 percent: 70-90% of polyurethane, 1-3% of 3-aminopropyltriethoxysilane, 5-15% of hydrophilic material and 1-10% of oxygen-enriched material. The research of the invention finds that the polymer outer membrane formed by polyurethane, 3-aminopropyl triethoxysilane, hydrophilic material and oxygen-enriched material in a specific mass percentage can greatly reduce the signal change caused by external interference (stirring) and low oxygen condition while widening the detection range of the sensor, thereby further improving the accuracy of the detection result.
Description
Technical Field
The invention relates to the technical field of biosensors, in particular to a glucose diffusion-limited polymer outer membrane and a preparation method and application thereof.
Background
Diabetes is a common endocrine disease, is classified as one of three diseases in the world due to high morbidity and serious complications, and the key point for treating diabetes is to quickly, accurately and stably monitor the blood sugar concentration in a patient. The successful development of continuous blood glucose monitoring (CGM) system based on glucose sensor provides an effective way to solve the problem. In order to improve the linear working range and the operation stability of the glucose sensor, an important method is to cover a layer of high molecular polymer film with selective permeability on the surface of glucose oxidase of the glucose sensor to be used as a glucose diffusion limiting outer film, so that the glucose concentration on the surface of the glucose oxidase is lower than that in a body, and the catalytic action of glucose molecules and the glucose oxidase is controlled by glucose diffusion, thereby achieving the purpose of improving the linear response range of the glucose sensor.
Continuous blood glucose monitoring (CGM) systems based on first generation sensor technologies face the most central problems: how to ensure that the detection result of the sensor is accurate and precise and is not influenced by other co-reactants (such as oxygen deficiency). First, the interstitial fluid O of normal human tissue 2 The concentration (0.2-0.3 mM) is far lowerAt glucose concentrations (about 5-10 mM), especially those of diabetic patients with blood glucose concentrations above 20 mM, this results in an enzyme catalysis rate dependent on O 2 Rather than glucose, ultimately leads to a narrow sensor detection range and severe deviation of the results. Therefore, CGM glucose-limiting outer membrane technology is of critical importance. The sensor outer membrane technology has the main functions of: (1) limiting glucose diffusion; (2) stabilizing the oxygen concentration in the sensor and preventing the interference of external impurities; (3) improving the biocompatibility of the sensor with the tissue interface; (4) protect the sensor, strengthen the biomechanical characteristic of the sensor. Therefore, CGM has a very high demand for the outer membrane technology, and the outer membrane material and the outer membrane technology are one of the key bottlenecks in the development of CGM.
The existing CGM sensor adopts an outer membrane technology to widen the linear detection range, but the signal change caused by external interference (stirring) is not equal to 20-50 percent, even higher; hypoxia can cause signal changes of 30% -200%, etc. Therefore, to realize the large-scale commercialization of the CGM sensor as soon as possible, not only a wide linear detection range but also, more importantly, an ability to resist external environmental fluctuations and reduce the influence of low oxygen concentration on the sensor detection signal are to be realized.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of low detection accuracy of the glucose sensor under the conditions of external environment interference and low oxygen in the prior art, thereby providing a practical glucose diffusion-limiting polymer outer membrane, and a preparation method and application thereof.
The invention provides a glucose diffusion limiting polymeric outer membrane comprising, based on 100% dry weight of the membrane:
70-90% of polyurethane, 1-3% of 3-aminopropyltriethoxysilane, 5-15% of hydrophilic material and 1-10% of oxygen-enriched material.
The polyurethane may be polyether polyurethane, and may be prepared by conventional method in the art or may be available commercially, such as but not limited to, model SG-85A available from Luborun corporation.
Further, the hydrophilic material is selected from one or more of polyvinylpyrrolidone, polyethylene glycol, 3- [ N, N-dimethyl- [2- (2-methylpropane-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt and 2-methacryloyloxyethyl phosphorylcholine.
Among them, polyvinylpyrrolidone having an average molecular weight of 10,000 to 1,600,000, such as but not limited to polyvinylpyrrolidone having an average molecular weight of 1,300,000, available from Sigma-Aldrich company under the type K90, is used.
The polyethylene glycol has an average molecular weight of 2,000-20,000, such as but not limited to polyethylene glycol 20000, which is available from Sigma-Aldrich company, and has an average molecular weight of 20,000.
Further, the oxygen-enriched material is selected from one or more of ethyl cellulose, amino-terminated polydimethylsiloxane, polycarbonate, polytrimethyl-1-propane and polyimide.
Of these, amino-terminated polydimethylsiloxanes having an average molecular weight of 1,000 to 5,000, such as, but not limited to, those available from Sigma-Aldrich having an average molecular weight of 1,000, are used in the detailed description.
Further, the hydrophilic material is polyvinylpyrrolidone or polyethylene glycol.
Further, the film comprises the following components in percentage by dry weight of the film of 100 percent:
75% of polyether polyurethane, 2% of 3-aminopropyltriethoxysilane, 15% of polyvinylpyrrolidone and 8% of amino-terminated polydimethylsiloxane.
Further, the thickness of the outer polymer film is 1 to 50 μm, preferably 7 to 25 μm, and more preferably 14 to 16 μm.
Further, the glucose permeability coefficient of the outer polymeric membrane is 1E-12 cm 2 /s ~ 1E-8 cm 2 (ii)/s, the outer polymer membrane limiting the glucose diffusion ratio of 10 to 1000:1.
the invention also provides a preparation method of the glucose diffusion limiting polymer outer membrane, which comprises the following steps:
adding polyurethane, 3-aminopropyltriethoxysilane, a hydrophilic material and an oxygen-enriched material into a solvent for mixing to obtain a polymer solution, and coating the polymer solution on the surface of the sensor to obtain the glucose diffusion-limited polymer outer membrane.
The coating method can be, but is not limited to, dip coating, spin coating, spray coating, hand coating, and the like.
Further, the solvent used comprises tetrahydrofuran and absolute ethanol in a volume ratio of 85-95.
Further, the solid content of the polymer solution is 1 to 10% by weight.
The invention also provides a glucose sensor, which comprises the glucose diffusion limiting polymer outer membrane or the glucose diffusion limiting polymer outer membrane prepared by the preparation method.
1. The glucose diffusion limiting polymer outer membrane provided by the invention comprises the following components in percentage by dry weight of the membrane of 100 percent: 70-90% of polyurethane, 1-3% of 3-aminopropyltriethoxysilane, 5-15% of hydrophilic material and 1-10% of oxygen-enriched material. The research of the invention finds that the polymer outer membrane formed by polyurethane, 3-aminopropyltriethoxysilane, hydrophilic material and oxygen-enriched material in a specific mass percentage can widen the detection range of the sensor, more importantly, can greatly reduce the signal change caused by external interference (stirring) and low oxygen condition, and further improve the accuracy of the detection result.
2. The glucose diffusion limiting polymer outer membrane provided by the invention comprises the following components in percentage by dry weight of the membrane of 100 percent: 75% of polyether polyurethane, 2% of 3-aminopropyltriethoxysilane, 15% of polyvinylpyrrolidone and 8% of amino-terminated polydimethylsiloxane. The polymer outer membrane obtained by adopting the formula can better reduce the signal change caused by external interference (stirring) and low oxygen condition.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is the effect of external disturbance (stirring) conditions in experimental example 1 of the present invention on the current signal of the CGM sensor provided in example 1;
FIG. 2 is the effect of the hypoxic condition in Experimental example 2 of the present invention on the current signal of the CGM sensor prepared in example 1;
FIG. 3 is a chronoamperometric curve and response time T95 for glucose detection using the CGM sensor provided in example 1 in Experimental example 3 of the present invention;
FIG. 4 is a schematic view of the structure of a glucose sensor in example 1 of the present invention;
reference numerals:
1. a glucose diffusion limiting polymeric outer membrane; 2. an electrode layer; 3. an enzyme sensor layer.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not indicate specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The present embodiment provides a glucose sensor, as shown in fig. 4, comprising a biosensor, and a glucose diffusion limiting polymer outer membrane 1 coated on the surface of the biosensor, wherein the biosensor comprises an electrode layer 2 and an enzyme sensor layer 3, wherein both the electrode layer and the enzyme sensor layer can adopt the conventional technology, for example, the electrode layer can adopt a metal layer catalyzing hydrogen peroxide, not limited to platinum and platinum-based alloy, the present embodiment adopts platinum metal, the enzyme sensor layer is made by crosslinking glucose oxidase and glutaraldehyde, and the glucose diffusion limiting polymer outer membrane is coated on the surface of the enzyme sensor layer.
Wherein, the raw materials of the glucose diffusion limiting polymer outer membrane comprise 75 g of polyether polyurethane (SG-85A), 2 g of 3-aminopropyltriethoxysilane, 15 g of polyvinylpyrrolidone (K90) and 8g of amino-terminated polydimethylsiloxane.
The preparation method comprises the following steps: weighing raw materials, adding a solvent, and uniformly mixing to obtain a polymer solution. Wherein, the solvent adopts tetrahydrofuran and absolute ethyl alcohol with the volume ratio of 90. And coating the polymer solution on the surface of the sensor, and standing at normal temperature to obtain the glucose diffusion limiting polymer outer membrane. The coating is dip coating, and the parameters of a dip coater are as follows: the descending speed is 3000 mu m/s; the time is 5 s; pulling 3500 μm/s; the number of pulls was 5 times, and the thickness of the outer film of the glucose diffusion limiting polymer obtained was 15 μm (scanning electron microscope).
Example 2
Only differs from example 1 in that polyethylene glycol 20000 is used instead of polyvinylpyrrolidone.
Example 3
The only difference from example 1 is that 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt is used instead of polyvinylpyrrolidone.
Example 4
The only difference from example 1 is that 2-methacryloyloxyethyl phosphorylcholine is used instead of polyvinylpyrrolidone.
Example 5
The only difference from example 1 was that the dip coater was pulled 3 times at a pull rate of 1000. Mu.m/s, the solid content of the polymer solution was 6% by weight, and the outer film of the glucose diffusion limiting polymer obtained had a thickness of 7 μm.
Example 6
The only difference from example 1 was that the dip coater was pulled 8 times at a speed of 5000. Mu.m/s, the polymer solution had a solid content of 4wt%, and the resulting glucose diffusion limiting polymer outer membrane had a thickness of 25 μm.
Example 7
The only difference from example 1 is that the starting materials for the glucose diffusion limiting polymer outer membrane included 90 g of polyether urethane (SG-85A), 1 g of 3-aminopropyltriethoxysilane, 5 g of polyvinylpyrrolidone (K90) and 4 g of amino terminated polydimethylsiloxane.
Example 8
The only difference from example 1 is that the starting materials for the glucose diffusion limiting polymer outer membrane included 80 g of polyether urethane (SG-85A), 2 g of 3-aminopropyltriethoxysilane, 10 g of polyvinylpyrrolidone (K90) and 8g of amino-terminated dimethylpolysiloxane.
Comparative example 1
The difference from example 1 was only that the raw material of the glucose diffusion limiting polymer outer membrane was different, and in this comparative example, 50 g of cellulose acetate and 50 g of cellulose acetate butyrate were included.
Comparative example 2
The only difference from example 6 is that the glucose diffusion limiting polymer outer membrane is composed of 60 g of polyether urethane (SG-85A), 2 g of 3-aminopropyltriethoxysilane (3-aminopropyl-triethoxysilane), 30 g of polyvinylpyrrolidone (K90) and 8g of amino-terminated polydimethylsiloxane as the raw materials.
Comparative example 3
The only difference from example 5 is that the glucose diffusion limiting polymer outer membrane was made from materials including polyether urethane (SG-85A) 65 g, 3-aminopropyltriethoxysilane 2 g, polyvinylpyrrolidone (K90) 25 g and amino terminated polydimethylsiloxane 8g.
Comparative example 4
The only difference from example 1 is that the starting materials for the glucose diffusion limiting polymer outer membrane included polyether urethane (SG-85A) 60 g, 3-aminopropyltriethoxysilane 2 g, polyvinylpyrrolidone (K90) 30 g and amino terminated polydimethylsiloxane 8g.
Experimental example 1 influence of stirring and non-stirring on detection Signal
The glucose sensors prepared in each of the examples and comparative examples were tested for their effect on glucose response with and without agitation, test method: the method comprises the steps of adopting an electrochemical workstation of a two-electrode system, placing a glucose sensor probe in Phosphate Buffered Saline (PBS) solution with the pH value of 7, applying a potential of 0.6V vs Ag/AgCl by using a working electrode, sequentially adding glucose solution with a certain concentration (4 mM glucose solution is added every time and 6 times) into stirred electrolyte (the stirring speed is 200 rpm), stopping stirring after the glucose solution is added, and calculating the change rate of steady-state current response under stirring and under non-stirring. Taking example 1 as an example, the relationship between current density and Time (Time) is shown in fig. 1.
The results of the tests, as shown in the following table:
as can be seen from the above table, compared with comparative examples 1 to 4, the signal change rate of each example of the present invention is significantly reduced, which indicates that the signal change rate is more stable under the interference condition, and the accuracy of the detection result is significantly improved.
As can be seen from comparison of examples 1-2 with 3-4, the present invention can further reduce the signal change rate under the interference condition by using polyvinylpyrrolidone or polyethylene glycol as the hydrophilic material, especially polyvinylpyrrolidone.
As can be seen from the comparison of example 1 with examples 5 to 6, the present invention can further reduce the signal change rate under interference conditions by limiting the outer film thickness to a preferable range.
As can be seen from the comparison of example 1 with examples 7 and 8, the present invention can further reduce the rate of change of signal under interference conditions by limiting the mass percentages of polyurethane and hydrophilic material to the preferred ranges.
Experimental example 2 Effect on detection signals in Normal oxygen region and Low oxygen region
The glucose sensors prepared in each of the examples and comparative examples were tested for their effect on glucose response under continuous stirring at normal and low oxygen concentrations, test method: an electrochemical workstation of a two-electrode system is adopted, a glucose sensor probe is placed in Phosphate Buffered Saline (PBS) solution with the pH value of 7, the potential applied by a working electrode is 0.6V vs Ag/AgCl, then glucose solution with the concentration of 2,3.5 and 3.5 mM is sequentially added into continuously stirred electrolyte (the stirring speed is 200 rpm), the oxygen concentration in the electrolyte is 6.7 mg/dL, the solution is subjected to oxygen removal to 0.6 mg/dL, current signals before and after oxygen removal are recorded, and the normal oxygen concentration and the low oxygen concentration and the change rate of the sensor response to the glucose current under the same glucose concentration are calculated. The current density (current sensitivity) vs. Time (Time) for example 1 is shown in FIG. 2 by continuing to add glucose solution at a concentration of 3.5,7 mM at an oxygen concentration of 0.6 mg/dL.
The overall test results, as shown in the following table:
as can be seen from the above table, compared with comparative examples 1 to 4, the signal change rate of each example of the present invention is significantly reduced, which indicates that the signal change rate is more stable under the interference condition, and the accuracy of the detection result is significantly improved.
As can be seen from comparison of example 1 with examples 2 to 4, the present invention can further reduce the rate of change of signal under the interference condition by using polyvinylpyrrolidone as a hydrophilic material.
As can be seen from the comparison of example 1 with examples 5 to 6, the present invention can further reduce the signal change rate under interference conditions by limiting the outer film thickness to a preferable range.
As can be seen from the comparison of example 1 with examples 7 and 8, the present invention can further reduce the rate of change of signal under interference conditions by limiting the mass percentages of polyurethane and hydrophilic material to the preferred ranges.
Experimental example 3 in the low oxygen region, the sensor measures the relevant parameters of the detection signal
The glucose sensors prepared in examples 1 to 4, 6 to 8 and comparative examples 2 to 4 were tested for their response to glucose by the CGM sensor under continuous stirring, test method: the glucose sensor probe is placed in phosphate buffered saline (PBS buffer) with the pH value of 7 by adopting an electrochemical workstation of a two-electrode system, the potential of 0.6V vs Ag/AgCl is applied to a working electrode, then glucose solution with certain concentration (4 mM glucose solution is added each time and 12 times are added) is sequentially added into the stirred electrolyte (the stirring speed is 200 rpm), the solution is deoxidized to reduce the oxygen concentration from 6.7 mg/dL to 0.6 mg/dL and is stabilized, and a timing current curve is measured. Taking example 1 as an example, the relationship between current density and Time (Time) is shown in fig. 3.
The results of the tests, as shown in the following table:
as can be seen from the above table, compared with comparative examples 2-4, the linear correlation coefficient of each example of the invention is improved, the linear relationship is good, the accuracy of the detection result is obviously improved, and the maximum value of the glucose linear response is more than or equal to 36 mM. In particular, in examples 1-2, the maximum response reached 44 mM or more, while the response time was appropriate between 110 and 160 s.
Since the test range of the glucose linear response in this experiment was 0 to 48 mM, the glucose sensors of examples 1 and 6 to 8 showed good linear relationship at 48 mM, and therefore, the maximum value of the glucose linear response was recorded as 48 mM or more.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (7)
1. A glucose diffusion limiting polymeric outer membrane comprising, based upon 100% dry weight of the membrane:
75-90% of polyurethane, 1-3% of 3-aminopropyltriethoxysilane, 5-15% of a hydrophilic material and 1-10% of an oxygen-enriched material, wherein the polyurethane is polyether polyurethane, the thickness of the outer polymer membrane is 14-16 μm, and the hydrophilic material is polyvinylpyrrolidone or polyethylene glycol.
2. The glucose diffusion limiting polymeric outer membrane of claim 1, comprising, based on 100% dry weight of the membrane:
75% of polyether polyurethane, 2% of 3-aminopropyltriethoxysilane, 15% of polyvinylpyrrolidone and 8% of amino-terminated polydimethylsiloxane.
3. The glucose diffusion limiting polymer outer membrane of claim 1, wherein the oxygen rich material is selected from one or more of ethyl cellulose, amino terminated polydimethylsiloxane, polycarbonate, polytrimethyl-1-propane and polyimide.
4. A method of forming the glucose diffusion limiting polymeric outer membrane of any of claims 1-3, comprising the steps of:
adding polyurethane, 3-aminopropyltriethoxysilane, a hydrophilic material and an oxygen-enriched material into a solvent for mixing to obtain a polymer solution, and coating the polymer solution on the surface of the sensor to obtain the glucose diffusion-limited polymer outer membrane.
5. The method of claim 4, wherein the solvent comprises tetrahydrofuran and absolute ethanol in a volume ratio of 85-95.
6. The method of claim 4 or 5, wherein the polymer solution has a solid content of 1-10wt%.
7. A glucose sensor comprising the glucose-diffusion limiting polymer outer film according to any one of claims 1 to 3 or the glucose-diffusion limiting polymer outer film produced by the production method according to any one of claims 4 to 6.
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| CN101184851A (en) * | 2005-05-17 | 2008-05-21 | 雷迪奥米特医学公司 | Enzyme sensor including a water-containing spacer layer |
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| US5322063A (en) * | 1991-10-04 | 1994-06-21 | Eli Lilly And Company | Hydrophilic polyurethane membranes for electrochemical glucose sensors |
| US7226978B2 (en) * | 2002-05-22 | 2007-06-05 | Dexcom, Inc. | Techniques to improve polyurethane membranes for implantable glucose sensors |
| CN101018599A (en) * | 2004-08-16 | 2007-08-15 | 诺和诺德公司 | Multiphase biocompatible semi-permeable membrane for biosensors |
| EP3794135A1 (en) * | 2018-05-16 | 2021-03-24 | Medtronic MiniMed, Inc. | Thermally stable glucose limiting membrane for glucose sensors |
| CN113083647B (en) * | 2019-12-23 | 2023-06-27 | 浙江荷清柔性电子技术有限公司 | Polymer diffusion limiting membrane layer, preparation method thereof and glucose sensor |
| CN113354993A (en) * | 2021-07-15 | 2021-09-07 | 乐普（北京）医疗器械股份有限公司 | Hydrophilic coating, preparation method and coating firmness testing method |
| CN115417963B (en) * | 2022-09-19 | 2024-09-13 | 苏州百孝医疗科技有限公司 | Biocompatible polycarbonate polyurethane, preparation method and application thereof |
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| WO2006018425A2 (en) * | 2004-08-16 | 2006-02-23 | Novo Nordisk A/S | Multiphase biocompatible semi-permeable membrane for biosensors |
| CN101184851A (en) * | 2005-05-17 | 2008-05-21 | 雷迪奥米特医学公司 | Enzyme sensor including a water-containing spacer layer |
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