TWI521099B - A method of electrochemical synthesis for photoluminescence sensors of oxygen and glucose - Google Patents

Description

Electrochemical synthesis method of optical oxygen and glucose sensor

The present invention relates to a method for fabricating an oxygen and glucose sensor; and more particularly to an electrochemical synthesis method for an optical oxygen and glucose sensor.

Oxygen detection is very important in many areas. For example, the needs of oxygen detection can be seen in different fields such as electronics, chemical industry, aquaculture, environmental pollution monitoring, and healthcare.

In prior art studies, bismuth (III) metal-defective compounds were formed into micrometer-sized crystals in a self-assembled manner, which was applied to small oxygen sensors, but the self-assembly method took several days. It is not easy to control the experimental conditions, which is not conducive to the demand of a large number of industrial production.

On the other hand, glucose sensors can be used in the fields of biology, medicine, food, etc. The more important application is to monitor the blood sugar concentration of diabetic patients. However, most of the sensor materials or detection methods will be applied in practice. There are one or more limitations such as low sensitivity, low accuracy, low stability, long reaction time and technical complexity.

Therefore, the present invention hopes that the manufacturing method of the glucose sensor of the prior art can be improved to enable the glucose sensor to achieve a better detection effect, and the present invention is more desirable to develop. The existing glucose sensor enables it to have the advantages of being convenient to carry, efficiently combining with enzymes, rapid reaction, a small amount of sample, etc., and these improvements of the present invention are important in the basic reaction mechanism and the intended practical application. of.

A disadvantage of the general electrochemical synthesis method is, for example, an organic solvent is used in consideration of factors such as solubility of a ligand, conductivity, and the like, but an organic solvent generally has a higher electric resistance than an aqueous solution. The invention changes the conventional synthesis method and finds a better control condition to shorten the time required for synthesizing the crystal, achieves the purpose of mass production, and applies the synthesized crystal to the oxygen and glucose sensor. Especially useful in the detection of blood oxygen and blood sugar.

Therefore, the present invention proposes an electrochemical synthesis method of an optical oxygen and glucose sensor for improving the existing oxygen and glucose sensor manufacturing methods, and finding a better control condition to shorten the manufacturing oxygen and glucose sensing. The time required to synthesize crystals and the goal of mass production is further applied to the detection of oxygen and glucose sensors in the blood.

The present invention utilizes an electrochemical method for synthesizing a ruthenium (III)-zinc(II) complex compound, the crystal light source thereof being a metal to ligand charge transfer, and the present invention utilizes the crystal light source to match The polymer (Ir-Zn _e ) is applied to the oxygen and glucose sensors, and the reaction time, voltage and temperature can be controlled by electrochemical synthesis to control the detection of oxygen; under optimized conditions (30 ° C , 5V, 1h), the oxygen detection capacity is K _sv =3.55atm ^-1 , and the LOD is 0.41%; the invention is also applied to glucose sensing, and respectively for impact factors, including buffer solution concentration, pH value, interference The substance, stability and temperature effects regulate the detection of glucose. The detectable glucose in the present invention has a linear range of 0.1 mM to 6 mM and a LOD of 0.05 mM, thereby making it possible to replace the material of the anion and the anode metal. The sensing range of oxygen and glucose sensors.

The invention synthesizes crystals by electrochemical method, and uses an external electric field to accelerate the speed of crystal formation, thereby achieving the effect of rapidly synthesizing crystals. The invention develops and utilizes an electrochemical method to shorten the time required for synthesizing crystals, and achieves efficient production of crystals. [ZnL ₂ ]. 3DMF. 5H ₂ O (referred to as Ir-Zn _{e in the} present invention), wherein L is a ruthenium (III) complex, and the crystal Ir-Zn _e can be directly applied as an oxygen sensor, and can be further The crystal Ir-Zn _e- binding enzyme is used for detecting glucose, and the fiber-optic fluorometer can be used as the light-receiving sensor. The present invention forms a glucose sensor by a combination of layer structures, and the first layer is cerium oxide. The sol-gel-bound Ir-Zn _{e is} called the Ir-Zn _e layer, the second layer is laid on the eggshell membrane and is called the Ir-Zn _e -E layer, and the second layer is proved to retain the enzyme activity as an enzyme. The buffer layer of Ir-Zn _e , the third layer of enzyme encapsulated in the spherical calcium oxalate is called Ir-Zn _e -EA layer, and finally successfully applied to glucose sensing in blood glucose.

The optical oxygen sensor of the invention is a phosphorescent molecule synthesized by mixing cerium (III)-zinc metal ions as a sensor part, and the phosphorescent light is emitted when the phosphorescent molecules collide with oxygen, so that the phosphorescence is emitted, The life cycle changes, so it can be used for oxygen detection.

The principle of the phosphorescent glucose sensor is to use glucose oxidase, which converts glucose into gluconic acid in an aerobic environment, and consumes oxygen in the process, and in the same environment, when there is a substance that is excited by light and emits phosphorescence, the light is emitted. The intensity is enhanced by the consumption of oxygen, and the degree of enhancement of the light is proportional to the concentration of glucose, and the concentration line is tested to determine the concentration of glucose in the solution.

The present invention utilizes an improved electrochemical synthesis method in which a specific metal electrode is used at the anode, a voltage is applied to the two electrodes, and the metal ions are released from the electrolyte. The base combines to form a crystal, because the applied voltage provides energy to overcome the free energy of the reaction, and the reaction time is shortened, and the electrochemical synthesis method can be a continuous manufacturing process, and the invention has a relatively fast speed compared to other hydrothermal synthesis methods and the like. The synthesis speed is also relatively flexible in terms of synthesis conditions, and the reaction temperature, time, voltage, etc. can be controlled, which is very advantageous for further industrial use.

Therefore, the invention not only has the advantages of the electrochemical synthesis method, for example, the electrochemical synthesis method can rapidly synthesize the crystal reduction time; compared with the hydrothermal synthesis method and the microwave synthesis method, the electrochemical reaction is in a relatively mild synthetic environment; The manufacturing method of the present invention can be adjusted to control the manufacturing conditions more, for example, the rate of release of metal ions, the concentration of metal ions, the concentration of ligands, and the like can be controlled.

In the present invention, a novel application of the optical glucose sensor, the present invention utilizes glucose oxidase to convert oxygen to glucose (β-D-glucose) into gluconic acid (D-gluconic acid), which consumes oxygen. The characteristics are as follows: [Formula 1] glucose oxidation chemical reaction formula, the enzyme is combined with the electrochemically synthesized crystal of the present invention to form an optical glucose sensor, and glucose oxidase (Glucose Oxidase, GOx) is added after adding glucose solution. Oxidized glucose in turn consumes oxygen, and the crystal is enhanced in the absence of oxygen extinction, and the concentration of the glucose solution can be estimated by the degree of enhancement of the intensity of the light.

In addition, the optical glucose sensor of the present invention fixes the enzyme in a suitable solid carrier, which can contribute to the improvement of stability and activity, and develops and improves the existing glucose sensor to make it convenient to carry. Efficient combination of enzymes, rapid response, trace amounts The advantages of sample volume and so on are important in the basic reaction mechanism and the intended application.

Different from the current various oxygen sensors, the optical oxygen sensor of the present invention is a detection method that does not consume oxygen, and the oxygen content can be known by visually observing the change of the light intensity. More or less, it is possible to further utilize the change in light intensity to push back the concentration of oxygen.

The invention has the advantages of being free from biological autofluorescence, and the phosphorescent glucose sensor of the invention can realize the advantages of simple and rapid detection, and has high sensitivity and correctness combined with the optical enzyme detecting system. Easy to operate and low error.

10‧‧‧ thermostat

20‧‧‧Power supply

30‧‧‧Anode

40‧‧‧ cathode

50‧‧‧Agitator

60‧‧‧Nitrogen bottle

70‧‧‧Electrochemical reaction tank

LH ₂ ‧‧‧Reactants

Ir-Zn _e ‧‧‧ product crystal

1 a schematic view of a synthetic crystalline-based embodiment of an electrochemical test device according to an embodiment of the present invention Ir-Zn _e crystals.

Figure 2 is a diagram showing the electrochemical synthesis reaction of an Ir-Zn _e crystal according to the present invention.

FIG third embodiment of the system according to the present invention Ir-Zn crystals _e FEG scanning electron microscope and energy dispersive spectrometer of illustration.

FIG schematic view showing a first engagement crystal Ir-Zn electrochemical test device of the present invention according to the embodiment of _e crystals, as shown in FIG. 1, the present invention is electrochemically synthetic crystalline Ir-Zn _e Case experimental apparatus comprises a thermostat The tank 10 provides a stable reaction temperature; the power supply 20 provides a voltage and current for electrochemical reaction; the anode 30 is a zinc metal sheet, and the metal mesh to be coated may be, for example, a stainless steel mesh; and the cathode 40 is zinc. a metal sheet, wherein the anodized metal sheet can also be replaced with a different metal electrode material; the stirring device 50 maintains the electrolyte concentration to reduce the concentration polarization; the nitrogen bottle 60 provides nitrogen; the electrochemical reaction tank 70, and the electrolyte is placed therein. MTBS (methyltributylammonium methyl sulfate) is soluble in organic solvents as an electrolyte.

The invention provides an electrochemical synthesis method of an optical oxygen sensor. The experimental step of electrochemically synthesizing crystal Ir-Zn _e comprises cutting a zinc metal sheet into, for example, 5 cm (length) × 1 cm (width). ×0.3mm (thickness), wherein the anode and cathode metal sheets can also be replaced with different metal electrode materials; if the metal sheets are reused, a pretreatment can be performed first, for example, using a grinder to remove oxides on the surface with water and acetone. Rinse and then dry with nitrogen; then, the stainless steel mesh coated zinc metal sheet is fixed on the fixing piece, for example, fixed on the glass slide, and the distance between the two glass slides is, for example, 25 mm; then the positive and negative electrodes are respectively clipped Zinc metal sheet; then insert the electrode into the electrolytic cell containing the electrolyte to fill the nitrogen gas to stir the magnet to the maximum, apply the set voltage, time and temperature; wherein the step of disposing the electrolyte comprises 100mg LH ₂ , 1g MTBS is dissolved in 80mL DMF and 25mL H ₂ O mixed solution to be completely dissolved, poured into the electrochemical reaction tank, and filled with nitrogen for 30 minutes to drive out other gases; when the reaction time is completed, it will be treated by electrochemical synthesis reaction The anode metal sheet is taken out together with the metal mesh coated thereon, and the cleaning method can be cleaned, for example, by washing with water and alcohol and then drying with nitrogen; finally, a plurality of Ir-Zn _e crystals formed on the metal mesh are formed. It is an optical oxygen sensor.

2 is an electrochemical synthesis reaction diagram of an Ir-Zn _e crystal embodiment according to the present invention. As shown in FIG. 2, the present invention uses the Ir-Zn _e crystal as an example to synthesize a reactant LH ₂ , the chemical formula thereof. Is Ir(ppy) ₂ (H ₂ dcbpy)PF ₆ (ppy=2-phenylpyridine, H ₂ dcbpy=4,4′-dicarboxy- ₂ , 2′-bipyridine), thereby obtaining the electrochemical synthesis reaction of the present invention The synthesized product crystal Ir-Zn _e has a chemical formula of [ZnL ₂ ]. 3DMF. 5H ₂ O (ORTEP structure), L is a ruthenium (III) complex.

Unless otherwise specified, the experimental drugs of the present invention can be purchased from Sigma-Aldrich or Alfa Aesar, and the solvent used for the reaction, unless otherwise specified, is used directly after opening. Wherein LH ₂ is a ruthenium metal compound Ir(ppy) ₂ (H ₂ dcbpy) PF ₆ (ppy=2-phenylpyridine, H ₂ dcbpy=4,4'-dicarboxy-2,2'-bipyridine); MTBS is Tributylmethylammonium methyl sulfate (Sigma-Aldrich); DMF is N , N- Dimethyl formamide (Sigma-Aldrich).

Preparation of other drugs: Preparation of Tri-EOS solution, 0.58 mL TEOS, 1.224 mL Tri-EOS, 0.4 mL 0.1 M HCl, 1.25 mL EtOH, stirred for 1 hour, uniformly mixed and then added 3.5 mL of EtOH and stirred for 1 hour. Preparation of sodium alginate solution containing glucose oxidase: 40 mg of sodium alginate was dissolved in 1 mL of DI H ₂ O, and 5 mg of glucose oxidase (GOx) was dissolved in 1 mL of 100 mM PBS buffer solution of pH=7, respectively, after dissolution. The glucose oxidase solution was added to the sodium alginate solution and mixed well. 100mM, pH = 7 phosphate buffer solution (phosphate buffer solution; PBS) is formulated, taking 3.549g NaH ₂ PO _4. H ₂ O, 3.450 g of Na ₂ HPO ₄ , was placed in 250 mL, and mixed into a solution having a pH of 7.

The method of the present invention can synthesize different phosphorescent coordination polymers by replacing different materials of the anode and cathode metal to prepare oxygen and glucose sensors with different detection ranges. When the anode-anode metal sheet of the method of the invention is replaced with a different metal electrode material, the crystal product has the general formula Ir-X, and X represents different metal electrode material ions, wherein the cathode or anode metal sheet includes, for example, zinc or cadmium. a metal such as silver, platinum, nickel, iron, lead, mercury or titanium, which may also include, for example, a composite alloy electrode, such as a silver/silver chloride electrode, a silver/carbon electrode or a zinc oxide/carbon electrode, Or it may include, for example, a metal oxide material such as ruthenium oxide (RuO ₂ ), manganese oxide (MnO ₂ ), lead oxide (PbO ₂ ) or nickel oxide (NiO), or the like.

Taking the Ir-Zn _e crystal as an example, the step of fabricating the glucose sensor of the present invention comprises cutting a metal mesh of 2 mm×2 mm, comprising the Ir-Zn _e crystal formed by the method of the invention, and Put in a 1.5 mL microcentrifuge tube; add 2 μL of Tri-EOS solution; centrifuge for five minutes and then open the lid of the microcentrifuge tube for 2 hours to form a combination with silica sol-gel. Ir-Zn _e layer; the solid carrier such as the eggshell membrane is washed with deionized water, the eggshell membrane having a diameter of 2.13 mm is cut, and the eggshell membrane is laid on the Ir-Zn _e layer in the microcentrifuge tube to form an Ir -Zn _e -E layer; adding 2 μL of sodium alginate solution containing glucose oxidase, centrifuging for five minutes; adding 200 μL of 0.2 M calcium chloride solution and centrifuging for ten minutes to form Ir-Zn _e -EA layer; The optical glucose sensor is completed after the calcium solution is removed.

The solid carrier which can be used in the method of the present invention may be a biofilm or a polymer film or the like in addition to the eggshell membrane, and the biofilm may be, for example, a bamboo film, a cellulose film or a fish gill. A Tri-EOS polymer film or a Tri-EOS polymer film centered on a boron atom.

The electrochemical synthesis method voltage of the present invention includes 5 to 30 volts (V), the time includes 2 minutes to 2 hours, and the temperature includes 10 to 50 ° C. In the portion where the synthesis reaction time is changed, the present invention has a fixed voltage at 20V. The temperature changes at 40 ° C from 2 minutes to 4 hours. During the synthesis, it is found that the crystal size increases with the increase of the reaction time, and the crystals attached to the metal mesh are more, up to 1 hour. When the maximum is reached, the crystal size will become smaller with time. The crystal is the smallest at 4 hours and the amount of crystals attached to the metal mesh is much less. It is speculated that the reason may be that the more metal ions are released as the reaction time increases. The more and the larger the crystal, the more the crystal will fall from the metal net when it grows to a certain extent. Therefore, the larger crystal falls on the metal net, leaving only small crystals on the metal network. , so metal online The average crystal size becomes smaller.

In the detection effect of the optical oxygen sensor of the invention, it is found that the oxygen detection effect in the synthesis reaction time of the electrochemical synthesis method is the best in 1 hour, because the crystals are larger and larger in the unit area of the metal mesh. The effect of collision with oxygen is relatively good, so the oxygen detection capability is relatively large. The present invention optimizes the oxygen detection capability of the crystal by changing the experimental conditions of the electrochemical synthesis method, and the measured K _SV is 3.55 atm ^{. 1} , K _SV is a Stern-Volmer constant, which is often used in dynamic extinction studies. A linear relationship can be obtained from the relationship between the intensity of the light emission and the quantum yield and the concentration of the matting agent. When the K _SV value is larger, , indicating that the better the matting effect, the closer the matting material is to the sample, so it is a better oxygen detecting sensor.

In the application of the present invention, it has been found that in the effect of sensing oxygen, the present invention utilizes the Stern-Volmer equation to discuss the oxygen detection ability in the time, temperature and voltage of the electrochemical synthesis method during synthesis. The synthesis reaction conditions of the electrochemical synthesis method have an optimized oxygen detection ability K _SV = 3.55 atm ^-1 at a reaction time of 1 hour, a reaction temperature of 30 ° C, and a reaction voltage of 5 V, and the effect is found in the time portion in one hour. Preferably, because as the electrochemical reaction time increases, the more crystals are attached to the metal mesh and the larger the crystal, the better the crystals per unit area when measuring the oxygen detecting ability. It is found that the effect of 30 ° C is better in the temperature portion. The faster the metal ions are released as the temperature increases, the more crystals are formed but the crystals are formed directly in the electrolyte without adhering to the metal mesh. The effect of 5V is found in the voltage portion because the faster the metal ions are released as the voltage increases, the more crystals are formed but the crystals are formed directly in the electrolyte and do not adhere to the metal mesh.

The invention utilizes an electrochemical method to shorten the time required for synthesizing Ir-X crystals, and achieves efficient production of crystal Ir-X crystals, and [ZnL ₂ ]. 3DMF. 5H ₂ O (Ir-Zn _e crystal) is taken as an example, applied to an oxygen sensor, and further Ir-Zn _{e is} used to detect glucose and use a fiber-optic fluorometer as a sensor. The layer structure is combined into a glucose sensor, the first layer is a cerium oxide sol gel combined with Ir-Zn _e called an Ir-Zn _e layer, and the second layer is a flat layer of fresh eggshell film called Ir -Zn _e -E layer, the second layer proved to maintain the enzyme activity as a buffer layer for the enzyme and Ir-Zn _e , and the third layer of enzyme is encapsulated in the spherical calcium oxalate called Ir-Zn _e -EA layer Finally, it was successfully applied to glucose sensing in blood glucose.

FIG third embodiment of the system according to the present invention Ir-Zn crystals _e FEG scanning electron microscope and the energy dispersive spectrometer illustrated, as shown in FIG 3, wherein (a) is a scanning Ir-Zn _e EDS SEM Photo (b) is an EDS analysis map of Ir-Zn _e . The present invention uses a field emission gun scanning electron microscope and an energy dispersive spectrometer/direction image microscope (Field Emission Scanning electron microscope additional Energy Dispersive Spectrometer and Orientation Image Microscopy; FEG- SEM+EDS+OIM), commissioned by Ms. Li Yuanci, a technician of the Taiwan University's Valuable Instrument Center, to determine the instrument brand and model number is LEO 1530. In this example, the electrochemical synthesis method of the present invention is at 40 ° C, 20 V, 3 hours. The Ir-Zn _e crystal synthesized under the experimental conditions, Fig. 3 (a) shows that the Ir-Zn _e crystal can be observed as a flaky crystal in the SEM, and the third graph (b) shows that in the EDS analysis map. found signal with zinc iridium proved synthesized crystals of Ir-Zn _e comprising these two elements, it was confirmed the electrochemical synthesis method of the present invention results based synthetic crystalline Ir-Zn _e consistent.

LH ₂ ‧‧‧Reactants

Ir-Zn _e ‧‧‧ product crystal

Claims (19)

An electrochemical synthesis method of an optical oxygen sensor, comprising: coating a metal mesh on an anode metal sheet and fixing it on a fixing piece, and fixing a cathode metal piece of the same material as the anode metal piece to another Fixing a chip; connecting a positive electrode and a negative electrode of a power supply to the anode metal piece and the cathode metal piece; the anode metal piece to which the positive electrode is connected and the cathode metal to which the negative electrode is connected The sheet is placed in an electrolytic cell containing an electrolyte and filled with nitrogen and stirred, and subjected to an electrochemical synthesis reaction by applying a set voltage, a time and a temperature, wherein the voltage is 5 to 30 volts (V), The time includes 2 minutes to 2 hours and the temperature includes 10 to 50 ° C. The electrolyte includes one LH ₂ , and the LH ₂ includes Ir(ppy) ₂ (H ₂ dcbpy) PF ₆ (ppy=2- Phenylpyridine, H ₂ dcbpy=4,4′-dicarboxy-2,2′-bipyridine); and the anode metal sheet treated by the electrochemical synthesis reaction together with the metal mesh coated thereon is cleaned and treated, The plurality of Ir-X crystals formed on the metal mesh are optical oxygen sensing , Ir-X wherein the plurality of metal ions in crystals X, comprising a metal electrode of the anode or cathode sheet metal ions from the material. According to the electrochemical synthesis method of the optical oxygen sensor of claim 1, wherein when the X is a zinc ion, the Ir-X crystals comprise a plurality of Ir-Zn _e crystals having a chemical formula of [ZnL ₂ ]. 3DMF. 5H ₂ O (ORTEP structure), L is a ruthenium (III) complex. An electrochemical synthesis method of an optical oxygen sensor according to claim 1, wherein the material of the anode or cathode metal sheet comprises zinc, cadmium, silver, platinum, nickel, iron, Lead, mercury or titanium. An electrochemical synthesis method of an optical oxygen sensor according to claim 1, wherein the material of the anode or cathode metal sheet comprises a composite alloy electrode. An electrochemical synthesis method of an optical oxygen sensor according to claim 4, wherein the composite alloy electrode comprises a silver/silver chloride electrode, a silver/carbon electrode or a zinc oxide/carbon electrode. An electrochemical synthesis method of an optical oxygen sensor according to claim 1, wherein the material of the anode or cathode metal sheet comprises a metal oxide material. An electrochemical synthesis method of an optical oxygen sensor according to claim 6 wherein the metal oxide material comprises ruthenium oxide (RuO ₂ ), manganese oxide (MnO ₂ ), lead oxide (PbO ₂ ) or oxidation. Nickel (NiO). An electrochemical synthesis method of an optical oxygen sensor according to claim 1 or 2, wherein the electrolyte is formulated to include 100 mg (mg) of one LH ₂ and one gram (g) of an MTBS (methyltributylammonium methyl sulfate) dissolved in 80 ml (mL) of a mixed solution of DMF ( N , N -Dimethyl formamide) and 25 ml (mL) of water (H ₂ O), after being completely dissolved, poured into the electrolytic cell. Inject nitrogen into the other gases. An electrochemical synthesis method of an optical oxygen sensor according to claim 1, wherein the fixing piece comprises a slide glass. An electrochemical synthesis method of an optical oxygen sensor according to claim 1, wherein the metal mesh comprises a stainless steel metal mesh. An electrochemical synthesis method of an optical oxygen sensor according to claim 1, wherein the method further comprises removing the surface oxygen from the anode metal piece or the cathode metal piece. Pretreatment of the compound. An electrochemical synthesis method of an optical glucose sensor, comprising: combining a plurality of crystal Ir-X formed by the electrochemical synthesis method according to any one of claims 1 to 11 with a plurality of enzymes That is, an optical glucose sensor is formed, wherein the enzymes comprise a plurality of glucose oxidases. An electrochemical synthesis method of an optical glucose sensor according to claim 12, wherein the method of combining the crystal Ir-X with the enzymes comprises: placing the crystal Ir-X into a A microcentrifuge tube is added with a Tri-EOS solution, and after centrifugation, the lid of the microcentrifuge tube is opened to stand to form an Ir-X crystal sol gel layer combined with silica sol-gel ( Ir-X layer); a solid carrier is laid on the Ir-X layer in the microcentrifuge tube to form a buffer layer (Ir-XE layer); a sodium alginate solution containing a plurality of glucose oxidases is added 2 μL (μL) after centrifugation; adding 200 μL of 0.2 M calcium chloride solution and centrifuging to form an enzyme layer (Ir-XEA layer); and removing the calcium chloride solution to complete an optical glucose Sensor. An electrochemical synthesis method of an optical glucose sensor according to claim 13 wherein the solid carrier comprises a biofilm or a polymer film. An electrochemical synthesis method of an optical glucose sensor according to claim 14, wherein the biofilm comprises an eggshell membrane, a bamboo membrane, a cellulose membrane or a fish gill. Electrochemical synthesis of optical glucose sensors according to item 14 of the patent application The polymer film comprises a Tri-EOS polymer film centered on a ruthenium atom or a Tri-EOS polymer film centered on a boron atom. An electrochemical synthesis method of an optical glucose sensor according to claim 13 wherein the preparation of the Tri-EOS solution comprises 0.58 mL of TEOS (Tetraethyl orthosilicate) and 1.224 mL of Octyl-triEOS (triethoxy(octyl)-silane). After stirring 0.4 mL of 0.1 M HCl and 1.25 mL of EtOH, add 3.5 mL of EtOH and stir until homogeneous. According to the electrochemical synthesis method of the optical glucose sensor of claim 13, wherein the sodium alginate solution containing the glucose oxidase comprises 40 mg of sodium alginate dissolved in 1 mL of deionized water to form a brown algae Sodium citrate solution, 5 mg glucose oxidase (GOx) was dissolved in 1 mL of 100 mM pH=7 PBS buffer solution (Phosphate-Buffered Saline) to form a glucose oxidase solution. The glucose oxidase solution was added to the sodium alginate solution and mixed well. An electrochemical synthesis method of an optical glucose sensor according to claim 18, wherein the preparation of the PBS buffer solution comprises 0.1 M NaH ₂ PO ₄ . H ₂ O and 0.1 M Na ₂ HPO _{4 were} prepared.