Histamine detection nano sensing needle based on doped graphene

Abstract

The utility model relates to a histamine detection nano sensing needle based on doped graphene. The histamine detection nano sensing needle comprises a stainless steel acupuncture needle; the surface of a needle tip at the front end of the stainless steel acupuncture needle is sequentially covered with a gold film subjected to electrochemical deposition, and a graphene layer and a cerium oxide coating which are manually dispensed on the surface of the gold film; the surface of the needle rod of the stainless steel acupuncture needle is covered with an insulating film layer. According to the nano sensing needle, the defect that a polymer sensitive film formed by a traditional coating mode is easy to fall off is overcome, the combination is very firm, and the polymer sensitive film cannot fall off after entering a body, so that the stability of the nano sensing needle can be greatly improved, nondestructive in-vivo measurement is realized, and the acquired signal is stable and real.

Description

Technical Field

[0001] The present application relates to the technical field of sensor preparation, and in particular to a histamine detection nanosensor needle based on doped graphene. Background Art

[0002] Acupoints are the initial response site of acupuncture effects and play a vital role in the effectiveness of acupuncture. Acupuncture stimulation of acupoints can cause the local release of a variety of biochemical substances in the acupoint area, such as histamine. [2] , 5-HT [3] 、Ca2+ [4] etc., and then start the neuro-endocrine-immune regulatory network, thus producing a wide range of regulatory effects. Therefore, the analysis of various biochemical substances in the acupoint microenvironment will greatly advance the research on the acupoint activation mechanism of acupuncture effect.

[0003] However, traditional methods cannot effectively explore it, so sensor needles have become a sharp weapon for studying meridian acupuncture points. For example, sensor needles can measure the three-dimensional structure of acupuncture points and meridians and the molecular events that occur there. Sensor needles are needle-shaped sensors made from traditional Chinese medicine acupuncture needles. They are a combination of acupuncture and sensor technology. Compared with other biomedical sensors, sensor needles can achieve in-body, positioning, fixed-point, real-time, and dynamic measurements without or with minimal loss. They can be used as sensors and actuators. And it is inexpensive, easy to operate, and disposable; in addition, it has many fields of use. In addition to traditional Chinese medicine, it can also be used in environmental protection, chemical industry, agriculture, forestry, animal husbandry, sideline production, and fishery industries.

[0004] Traditional sensing needles are mainly composed of acupuncture needles, sensitive membranes, gold-plated membranes and insulating membranes, and their basic principles are basically the same as other sensors. Among them, the selection and coating of sensitive materials are key technologies, which basically determine the performance of the sensing needles. However, the sensitive membranes of the sensing needles developed at this stage are mostly polymer materials, and the fixation of the sensitive membrane on the surface of the acupuncture needle base is carried out in a coating manner, which not only makes the sensitive membrane on the surface of the acupuncture needle relatively thick and uneven in thickness, but also causes the sensitive membrane to easily fall off after contacting with the physiological fluids in the body when the acupuncture needle enters the body, thereby seriously affecting the stability and reproducibility of the sensing needle detection.

[0005] Therefore, there is an urgent need to provide a histamine detection nanosensor needle based on doped graphene to solve the technical problems mentioned above. Utility Model Content

[0006] Based on this, a histamine detection nanosensor needle based on doped graphene is provided, which overcomes the disadvantage that the polymer sensitive film formed by the traditional coating method is easy to fall off. The bonding is very strong and will not cause falling off after entering the body, thereby greatly improving the stability of the nanosensor needle.

[0007] On the one hand, a histamine detection nanosensor needle based on doped graphene is provided, comprising: a stainless steel acupuncture needle; the needle tip surface at the front end of the stainless steel acupuncture needle is sequentially covered with a gold film deposited by electrochemical deposition and a graphene layer and a cerium oxide coating manually drop-coated on the surface of the gold film; the needle shaft surface of the stainless steel acupuncture needle is covered with an insulating film layer.

[0008] Optionally, the distance between the leading edge of the insulating film layer and the needle tip of the stainless steel acupuncture needle is 1 to 3 cm.

[0009] Optionally, the distance between the leading edge of the insulating film layer and the needle tip of the stainless steel acupuncture needle is 1 cm.

[0010] Optionally, the thickness of the cerium oxide coating is set to 30-60 nm.

[0011] Optionally, the insulating film layer is an epoxy resin layer.

[0012] Compared with the prior art, the beneficial effects of this application are:

[0013] The present application sequentially covers the tip surface of the front end of the stainless steel acupuncture needle with an electrochemically deposited gold film, a graphene layer manually drop-coated on the gold film surface, and a cerium oxide layer, and covers the needle shaft surface of the acupuncture needle with an insulating film layer. The acupuncture needle has a relatively sensitive specific detection range and response value for histamine and has high sensitivity. The preparation is simple and convenient, and the disadvantage of the polymer sensitive film formed by the traditional coating method that it is easy to fall off is overcome. The bonding is very firm and will not cause falling off after entering the body, thereby greatly improving the stability of the nanosensor needle. More importantly, a cerium oxide layer is added, and the cerium oxide layer has an electrocatalytic effect and enhances the electrochemical signal. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 Schematic diagram of the structure of the histamine detection nanosensor needle based on doped graphene in this embodiment.

[0015] Figure numerals: 1. stainless steel acupuncture needle; 2. gold film; 3. graphene layer; 4. cerium oxide coating; 5. insulating film layer. DETAILED DESCRIPTION

[0016] In order to make the purpose, technical solution and advantages of the present application more clearly understood, the present application is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0017] It should be noted that the illustrations provided in this embodiment only illustrate the basic concept of the present application in a schematic manner, and therefore the drawings only show components related to the present application rather than being drawn according to the number, shape and size of components in actual implementation. In actual implementation, the type, quantity and proportion of each component may be changed at will, and the component layout may also be more complicated.

[0018] The structures, proportions, sizes, etc. illustrated in the drawings of this specification are only used to match the contents disclosed in the specification so as to facilitate understanding and reading by persons familiar with this technology. They are not used to limit the conditions under which this application can be implemented, and therefore have no substantive technical significance. Any structural modification, change in proportion or adjustment of size, without affecting the effects and purposes that can be achieved by this application, should still fall within the scope of the technical contents disclosed in this application.

[0019] The directions or positional relationships indicated by the terms "upper", "lower", "left", "right", "middle", "longitudinal", "lateral", "horizontal", "inner", "outer", "radial", "circumferential" and the like in this specification are based on the directions or positional relationships shown in the drawings and are only for the convenience of simplifying the description. They do not indicate or imply that the devices or elements referred to must have a specific direction, be constructed and operate in a specific direction, and therefore cannot be understood as limiting the present application. In addition, the terms "first" and "second" are used for descriptive purposes only and cannot be understood as indicating or implying relative importance.

[0020] The embodiment of the present application provides a histamine detection nanosensor needle based on doped graphene, which is mainly aimed at the shortcomings of the prior art that the polymer material sensitive film is not firmly bonded to the surface of the acupuncture needle base and is easy to fall off, affecting the detection stability and detection sensitivity, and then provides a histamine detection nanosensor needle with good detection stability, a relatively sensitive specific detection range and response value for histamine, and high sensitivity.

[0021] The following is a detailed description of a histamine detection nanosensor needle based on doped graphene provided in this embodiment. Please refer to Figure 1 As shown, it includes: a stainless steel acupuncture needle 1, on the needle tip surface of the front end of the stainless steel acupuncture needle 1, a gold film 2 deposited by electrochemical deposition and a graphene layer 3 and a cerium oxide coating 4 manually drop-coated on the surface of the gold film 2 are sequentially covered; on the needle shaft surface of the stainless steel acupuncture needle 1, an insulating film layer 5 is covered.

[0022] In the present embodiment, the tip surface of the front end of the stainless steel acupuncture needle 1 is sequentially covered with an electrochemically deposited gold film 2 and a graphene layer 3 and a cerium oxide layer 4 manually drop-coated on the surface of the gold film 2, and the needle shaft surface of the stainless steel acupuncture needle 1 is covered with an insulating film layer 5. Since the graphene layer 3 is prepared on the surface of the stainless steel acupuncture needle 1 by an electrochemical reduction method, the disadvantage of the polymer sensitive film formed by the traditional coating method that it is easy to fall off is overcome, and the bonding is very strong, and it will not cause falling off after entering the body, thereby greatly improving the stability of the nanosensor needle, and realizing non-destructive in vivo measurement, and the collected signal is stable and real; at the same time, since graphene and cerium oxide are nanomaterials and are very thin, when they are used to modify the acupuncture needle, there is no obvious change in the thickness of the needle tip before and after modification, and the conductivity is very good. The histamine detection nanosensor needle constructed by them has a large specific surface area, a high detection sensitivity, and a relatively sensitive specific detection range and response value for histamine. According to literature reports, the detection limit range of the relevant histamine sensor needle is 1.98-5585.59nmo l / L, while the detection limit of the histamine detection nanosensor needle in the present application is in the range of 0.19-1.9nmo l / L.

[0023] In this embodiment, it should be noted that the distance between the front edge of the insulating film layer 5 on the needle shaft of the stainless steel acupuncture needle 1 and the needle tip is 1 to 3 cm. Preferably, the distance between the front edge of the insulating film layer 5 on the needle shaft of the stainless steel acupuncture needle 1 and the needle tip is 1 cm, so that the sensing contact area can be increased, there are more contact sites, and setting 1 cm is more in line with clinical needle insertion requirements.

[0024] It should also be noted that the thickness of the cerium oxide coating 4 is set to 30-60 nm, and the thickness of the needle tip of the stainless steel acupuncture needle 1 does not change significantly before and after being modified by the nanomaterial cerium oxide coating 4, and the conductivity is very good.

[0025] It should also be noted that the insulating film layer 5 is an epoxy resin layer, which has excellent chemical resistance, especially alkali resistance, strong paint film adhesion, especially to metal, and good heat resistance and electrical insulation.

[0026] The preparation method of the histamine detection nanosensor needle based on doped graphene in this embodiment is also described below, which includes the following steps:

[0027] Step 201, pretreatment of acupuncture needles: grind the stainless steel acupuncture needles, wash them, and then blow dry them with nitrogen for later use. Specifically, the acupuncture needles are grinded with suede, and then ultrasonically washed in anhydrous ethanol and ultrapure water respectively, and then blow dried with nitrogen for later use.

[0028] Step 202, modification of gold particles: using chloroauric acid solution as electrolyte, pretreated acupuncture needles as working electrodes, and Pt wire as auxiliary electrodes, a constant potential deposition method is used to deposit metal gold particles on the tips of acupuncture needles at 50° C., the deposition potential of the constant potential deposition is 0.4 V, and the deposition time is 50 s;

[0029] Step 203, modification of graphene (GP): manually applying graphene (GP) dropwise to the tip of the acupuncture needle modified with nano-gold particles, and performing high temperature annealing;

[0030] Step 204, coating the needle body with an insulating layer: coating the needle shaft of the acupuncture needle except for the needle tip modified with graphene with an insulating layer and drying it at 20-25° C.; the length of the gold-plated needle tip retained is 1 cm.

[0031] Step 205, modification of cerium oxide (CeO2): prepare a saturated cerium oxide solution using cerium oxide powder and DMF solution, immerse the modified part in the saturated cerium oxide solution, take it out after one day, and dry it.

[0032] The performance of the histamine detection nanosensor needle based on doped graphene is characterized below. The specific experiments and results are as follows:

[0033] Potassium ferrocyanide solution was used as electrolyte, and bare acupuncture needles and acupuncture needles with gold particles deposited on their surfaces were used as working electrodes, Pt wire was used as auxiliary electrode, and Ag / AgCl was used as reference electrode. Cyclic voltammetry was used to scan 1 circle at a potential of -1 to 0.4 V, with a scan rate of 100 mV / s. The cyclic voltammetry curves of the three were significantly different. Among them, the traditional stainless steel acupuncture needles had almost no obvious electrochemical curve, which was due to the poor electrochemical properties and weak conductivity of bare acupuncture needles; the second was the acupuncture needles modified with nano-gold particles, which was due to the enhanced conductivity after the gold particles were deposited on their surfaces; the best electrochemical curve was the histamine detection nanosensor needle obtained above, which was due to the fact that graphite would further enhance the conductivity, and cerium oxide had the function of electrocatalysis and enhancing electrochemical signals.

[0034] Histamine solution was used as electrolyte, and the above-obtained histamine detection nanosensor needle was used as working electrode, Pt wire as auxiliary electrode, and Ag / AgCl as reference electrode. Cyclic voltammetry was used to scan 10 cycles at a potential of -1 to 0.4 V, with a scanning rate of 100 mV / s. The obtained cyclic voltammetry curve trace signal was very stable with almost no fluctuation, indicating that the three modified layers of gold particles, graphene, and cerium oxide were firmly combined on the surface of the acupuncture needle, with high stability and not easy to fall off.

[0035] Finally, the modified histamine detection nanosensor needle was placed in a 0-100 mg / L histamine solution, with the above-obtained histamine detection nanosensor needle as the working electrode and the saturated calomel electrode as the reference electrode, and the DPV method was used for scanning measurement, with a potential of -1 to 0.4 V. As the histamine concentration increased, the peak value gradually increased, and within the concentration range (0-100 mg / L), the current value changed significantly. Further, the response current value of the histamine detection nanosensor needle in different histamine solutions was taken as the ordinate, and the histamine concentration was taken as the abscissa, and a linear curve 1 was obtained by fitting: Y=8.11907(±0.04452)-0.05746(±0.01652)X, where Y is the response current value, X is the histamine concentration, and the fitting coefficient R 2 is 0.85811, and the linear response range is 0-5 mg / L; Linear curve 2: Y = 8.46 (± 0.01964) -0.00406 (± 2.96923E-4) X, Y is the response current value, X is the histamine concentration, and the fitting coefficient R 2 The linear response range is 25-100 mg / L. This result shows that the histamine detection nanosensor of the present application has a good response to the histamine solution.

[0036] The implementation principle of this embodiment: In this application, the needle tip surface of the front end of the stainless steel acupuncture needle 1 is sequentially covered with an electrochemically deposited gold film 2, a graphene layer 3 and a cerium oxide coating 4 manually drop-coated on the surface of the gold film 2, and the needle shaft surface of the stainless steel acupuncture needle 1 is covered with an insulating film layer 5. The histamine detection nanosensor needle obtained in this way has a firm bond, good stability, and a relatively sensitive specific detection range and response value for histamine.

[0037] The technical features of the above embodiments may be combined arbitrarily. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0038] The above-described embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be construed as limiting the scope of the patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent application shall be subject to the attached claims.

Claims

1. A histamine detection nanosensor needle based on doped graphene, characterized in that: include: Stainless steel acupuncture needle (1); The needle tip surface at the front end of the stainless steel acupuncture needle (1) is sequentially covered with a gold film (2) deposited by electrochemical deposition, a graphene layer (3) obtained by manual drop coating and high temperature annealing, and a cerium oxide coating (4); The surface of the needle shaft of the stainless steel acupuncture needle (1) is covered with an insulating film layer (5).

2. The histamine detection nanosensor needle based on doped graphene according to claim 1, characterized in that: The distance between the front edge of the insulating film layer (5) and the needle tip of the stainless steel acupuncture needle (1) is 1 to 3 cm.

3. The histamine detection nanosensor needle based on doped graphene according to claim 2, characterized in that: The distance between the front edge of the insulating film layer (5) and the needle tip of the stainless steel acupuncture needle (1) is 1 cm.

4. The histamine detection nanosensor needle based on doped graphene according to claim 1, characterized in that: The thickness of the cerium oxide coating (4) is set to 30-60 nm.

5. The histamine detection nanosensor needle based on doped graphene according to claim 1, characterized in that: The insulating film layer (5) is an epoxy resin layer.

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