Acupuncture needles that adsorb toxic heavy metal ions, and methods for manufacturing and applying the same.

Abstract

A group of inventions relates to the field of medical devices. A method for producing needles with adsorption properties is described by depositing an iron oxide coating onto the needle by atomic layer deposition. An acupuncture needle for reflex therapy, consisting of a handle and shaft made of metal material, is placed in a reactor where a vacuum is created at a pressure of approximately 10 mbar ± 0.1 mbar and a temperature of 150 ± 0.2 °C, then a ferrocenecarboxylic acid precursor in the form of vapor is delivered to the reactor, then nitrogen is added to the reactor and degassed to the initial pressure, and this process is repeated in pulse mode until a specific coating thickness is formed. The use of ferrocenecarboxylic acid as a precursor for producing an Fe3O4 coating is described. An acupuncture needle for adsorbing toxic heavy metal ions is described with a coating of Fe3O4 nanofilm thickness of 14 nm ± 0.1 nm, and the nanofilm has the appearance of a nanosieve as shown in Figure 1b. The use of acupuncture needles for adsorbing metal ions is described. The technical achievement of this invention is the development of a method for attaching a magnetic separation film of Fe3O4 to the surface of an acupuncture needle, which is simpler and less expensive in terms of methodology and technique, thereby imparting adsorption properties to the acupuncture needle. The needle of this invention makes it possible to adsorb toxic heavy metal ions such as cadmium, arsenic, manganese, cesium, aluminum, iron, cobalt, nickel, chromium, mercury, lead, copper, zinc, beryllium, antimony, thallium, bismuth, osmium, tin, molybdenum, zirconium, titanium, vanadium, molybdenum, and gallium.

Description

Technical Field

[0001] This solution relates to the fields of medicine and medical devices, and more particularly to a acupuncture needle for performing acupuncture treatment procedures that promote the adsorption and removal of toxic heavy metal particles (ions) from the human body.

[0002] The acupuncture needle for reflexology, which is the subject of the patent claim, comprises a handle and a shaft, and the contact part of the shaft is coated with magnetic nanoparticles of iron oxide Fe3O4 and / or γ-Fe3O4.

[0003] The present invention also relates to a method for manufacturing such a needle by attaching an iron oxide coating to the acupuncture needle by atomic layer deposition.

[0004] The technical achievement of the present invention is to make the adsorption characteristics for removing toxic substances containing toxic heavy metal particles (ions) from the human body more extensive by attaching a magnetic nanoparticle coating, and to develop a method for attaching a magnetic separation film of Fe3O4 with a specific thickness to the surface of the acupuncture needle, which is simpler and thus cheaper in terms of technique and technology. In view of the fact that the resulting improved acupuncture needle has extensive adsorption characteristics including adsorption characteristics for metal ions of cadmium, arsenic, manganese, cesium, aluminum, iron, cobalt, nickel, chromium, mercury, lead, copper, zinc, beryllium, antimony, thallium, bismuth, osmium, tin, molybdenum, zirconium, titanium, vanadium, molybdenum, gallium, the present invention can be used to remove heavy metals and toxins from the human body without any side effects on the human body, even as the traditional acupuncture needle used in acupuncture therapy. The acupuncture needle of the present invention can be used to purify the body for both therapeutic purposes and for daily preventive use.

Background Art

[0005] Prior art, RU 2674985 C2, registered on December 14, 2018, provides a method for applying a coating to a surgical needle. This method involves immersing the surgical needle in a silicon coating solution bath by moving the needle in a silicon coating solution bath with the needle tip facing upward while the needle is placed on a carrier, removing the needle from the coating bath, directing an airflow towards the needle at an angle of approximately + / - 20° with respect to the longitudinal central axis of the distal end of the needle, thereby ensuring that a sufficient amount of silicon coating solution is retained at the tip of the needle, thereby applying the silicon coating to the surgical needle mounted on the carrier, and solidifying the silicon coating. The silicon coating solution comprises polydimethylsiloxane having vinyl-terminated groups, polymethylsiloxane having metal-terminated groups, a platinum complex having a binder, namely methylhydrosiloxane, divinyltetramethyldisiloxane, and ethylcyclohexanol, and an organic solvent.

[0006] In the publication, ХАФИЗОВ А. А. et al. установкой с электролитическим катодом", Социально- экономические и технические системы: исследование, проектирование, оптимизация, 2015, vol.1, From pages 25-33 of No. 1 (64), a method for depositing an iron(II,III) oxide coating onto a metal surface by plasma flame sputtering is also known. The key to this method is that a gas (argon, nitrogen, or air) is passed through a burning arc (electrodes, electrolyte, and copper nozzle) between two electrodes. Because the burning arc is high energy, gas atoms lose electrons from their outer shells. As a result, an ion-electron gas or plasma is generated. The temperature of the plasma jet reaches 3000-5000°C. Powdered material is delivered to the plasma jet in the area of ​​the nozzle's outlet. As a result, the ejected material is heated, melted, dispersed, and deposited onto the surface of the workpiece. During the ejection process, it is necessary to control the thickness of the sputtered layer, which is 0.1-2 mm for plasma coatings.

[0007] A disadvantage of this method is that it requires controlling the thickness of the metal layer being sputtered, which is typically 0.1 to 2 mm for plasma coatings.

[0008] A prior art technique, RU 2761440 C2, registered on December 8, 2021, describes a method for applying a coating to medical devices that come into contact with tissue, particularly injection needles, by first cleaning and activating the needle surface with accelerated ions, and then performing ion-plasma sputtering with a flow of accelerated gas particles containing organosilicon compounds, followed by ion-plasma sputtering with a flow of accelerated gas particles containing ions (Fe) and / or titanium (Ti) atoms.

[0009] The disadvantage of this method is that it requires the application of an additional pre-coating with organosilicon compounds, which prolongs the process and results in insufficient adhesive strength for the needles.

[0010] In addition, prior art, RU 2717705 C1, registered on March 25, 2020, is known to involve attaching an iron oxide coating to a needle using a gas flame. The size of the Fe3O4 nanoparticle coating is 10-100 nm ± 20%.

[0011] A disadvantage of this method is that the granular composition of iron(II,III) oxide powder used must be uniform for proper adhesion. A wide range of particle sizes significantly impairs the quality and adhesion of the coating.

[0012] The closest analogue to the solution presented herein for a method of producing acupuncture needles with adsorption properties is the solution disclosed in RU 2773965 C1, registered on June 14, 2022. This known solution involves depositing an iron oxide coating onto the acupuncture needle by atomic layer deposition. The acupuncture needle is placed in a reaction chamber, a vacuum is created in the chamber at a pressure of 1–5 mbar, the acupuncture needle is heated to a temperature of 220–280°C, and a cycle is performed in which a bis-η5-cyclopentadienyl iron II (ferrocene) precursor is supplied to the vapor reaction area separately and consecutively for 1–3 seconds at a temperature of 80–100°C with a time delay of 1–3 seconds, and an oxygen reagent gas is supplied at a pressure of 1–3 bar for 5–7 seconds with a time delay of 1–3 seconds. After the above precursor and oxygen have been released, the reactor is degassed to its original pressure by supplying nitrogen. This cycle is carried out until a specific coating thickness of 4-32 nm is formed by at least 600 cycles. This solution ensures a uniform coating, increased adsorption properties, and consequently guarantees that the resulting acupuncture needles have adsorption strength.

[0013] However, there is still a need to provide a method for manufacturing acupuncture needles with adsorption properties that is technically simpler and therefore less expensive, while enabling the production of needles with standardized parameters, particularly coating thickness.

[0014] The closest analogue to the solution presented herein relating to an acupuncture needle having adsorption properties is the solution disclosed in RU 189268 U1, registered on 17 May 2019. A well-known acupuncture needle for reflexology comprises a handle and a shaft, the contact portion of which is coated with magnetic nanoparticles of iron oxide Fe3O4 and / or γ-Fe3O4. The needle adsorbs and removes heavy metal particles from the human body by adhering magnetic nanoparticles of magnetite (Fe3O4) and / or magnethematite (γ-Fe3O4), which are iron oxides. However, there is a demand in the prior art for acupuncture needles with enhanced adsorption properties.

[0015] The acupuncture needle of the present invention has adsorption properties for metal ions of cadmium, arsenic, manganese, cesium, aluminum, iron, cobalt, nickel, chromium, mercury, lead, copper, zinc, beryllium, antimony, thallium, bismuth, osmium, tin, molybdenum, zirconium, titanium, vanadium, molybdenum, and gallium. It has a predetermined coating thickness of 14 nm, and the nanofilm on the surface of the needle is an analogue of a nanosieve in which negative charge accumulates due to the concentration of excess oxygen atoms. Individual regions with magnetic susceptibility are formed within the film by forming magnetically responsive iron oxide crystals. When blood containing metal ions enters these regions, the metal ions are adsorbed.

[0016] A method for adsorbing and removing heavy metal particles from the human body is known from RU 2717705 C1, registered on March 23, 2020. Acupoints are determined for this purpose. At least 15 needles for reflex therapy are inserted into acupoints throughout the body, and at least 15 needles for reflex therapy are inserted locally into acupoints according to the affected organ. The acupuncture needles for reflex therapy are used with handles and shafts made of metal. At least the contact portion of the shaft is coated with magnetic nanoparticles of magnetite (Fe3O4) and / or magnethematite (γ-Fe3O4), which are iron oxides. The needles are removed after 30 to 90 minutes. This method improves overall human health by adsorbing and removing heavy metals from the body's blood and lymphatic flow, thereby reducing the concentration of heavy metals in the body.

[0017] However, when using acupuncture needles with adsorption properties, it is necessary to broaden the range of heavy metals and toxins that are removed.

[0018] The comprehensive solution covered by the claims solves the problem of this application. [Prior art documents] [Patent Documents]

[0019] [Patent Document 1] RU 2674985 C2 [Patent Document 2] RU 2761440 C2 [Patent Document 3] RU 2717705 C1 [Patent Document 4] RU 2773965 C1 [Patent Document 5] RU 189268 U1 [Non-patent literature]

[0020] [Non-Patent Document 1] KHAFIZOV A. A. et al., "Spraying ferromagnetic powder onto steel using an electrodeless plasma installation", Socio-economic and technical systems: research, design, optimization, 2015, vol.1, No.1(64), pp. 25-33

Summary of the Invention

Problems to be Solved by the Invention

[0021] The object of the present invention is to create a unique magnetic separation coating of Fe3O4 in the shape of a nano sieve.

[0022] The technical result is to develop a method for attaching a magnetic separation film of Fe3O4 to the surface of acupuncture needles, which is simpler and thus cheaper methodologically and technically, and to impart adsorption characteristics to the acupuncture needles.

[0023] The object of the present invention is solved, and the technical result is achieved by using a novel precursor, namely ferrocenecarboxylic acid.

Means for Solving the Problems

[0024] The present invention relates to a method for manufacturing an acupuncture needle having adsorption characteristics and having a coating of a magnetic separation film of Fe3O4 with a thickness of 14 nm ± 0.1 nm on the surface. The coating is deposited by the atomic layer deposition method of an iron oxide coating. The acupuncture needle for reflexology, which is composed of a handle and a shaft made of a metal material, is placed in a reactor that is fabricated at a vacuum of a pressure value of about 10 mbar ± 0.1 mbar and a temperature of 150 ± 0.2 °C. Then, the ferrocenecarboxylic acid precursor is delivered to the reactor in the form of vapor.

[0025] The reactor is then filled with nitrogen and degassed to its original pressure, and this process is repeated in pulse mode until the desired coating thickness is achieved.

[0026] This method allows for the formation of individual regions with magnetic susceptibility within the film by creating a needle with a 14 nm ± 0.1 nm thick Fe3O4 magnetic separation film coated in the shape of a nanosieve, where regions with negative charge accumulation exist due to the concentration of excess oxygen atoms, and by forming magnetically responsive iron oxide crystals. When blood containing metal ions enters these regions, the metal ions are adsorbed through three mechanisms.

[0027] The mechanism involves magnetic separation. Magnetically responsive ions (cobalt, nickel, chromium, manganese, iron, copper, titanium, osmium) contained in bodily fluids are attracted to the surface of a film in which a regional structure has been formed.

[0028] The mechanism involves physical adsorption (heavy metals and metalloids: cadmium, cesium, lead, mercury, chromium, zinc, antimony, arsenic, thallium, zirconium). Coulomb interactions between the film surface and cations (metal ions) capture metal ions from the blood, which are then retained on the film surface; in other words, the metal ions are embedded in the film's cavities.

[0029] Chemical adsorption (copper, zinc, nickel, aluminum, cobalt, beryllium, bismuth, tin, molybdenum, vanadium, gallium). Chelation of similar compounds through the formation of chemical bonds. When a bond is formed between an ion and the oxygen atom of the film, the ion is "firmly" held on the surface.

[0030] Furthermore, it is shown that significant adsorption occurs in an improved needle with an iron(II,III) oxide coating thickness of 14 nm.

[0031] Accordingly, the present invention also relates to acupuncture needles manufactured by this method, which have adsorption properties for metal ions of cadmium, arsenic, manganese, cesium, aluminum, iron, cobalt, nickel, chromium, mercury, lead, copper, zinc, beryllium, antimony, thallium, bismuth, osmium, tin, molybdenum, zirconium, titanium, vanadium, molybdenum, and gallium, and which have a specific film coating thickness of 14 nm ± 0.1 nm.

[0032] Furthermore, since a key feature for achieving the technical success, namely the production of nanosieve-shaped films as shown in Figure 1b, is the use of a novel precursor, namely ferrocenecarboxylic acid, the present invention also relates to the use of a ferrocenecarboxylic acid precursor for obtaining a coating of Fe3O4 films.

[0033] The method of the present invention employs specific applications, and therefore both the claimed method and the claimed application are designated for manufacturing (obtaining) the claimed acupuncture needle.

[0034] Another invention, which is the subject of the patent claims, is the use of needles for adsorbing metal ions.

[0035] The surface morphology of the film was examined using a backscattered electron microscope. [Brief explanation of the drawing]

[0036] [Figure 1a] Figure 1a is a backscattered electron microscope image of an unmodified acupuncture needle. [Figure 1b] Figure 1b is a backscattered electron microscope image of an acupuncture needle with a 14 nm layer of iron(III) oxide attached to it. [Modes for carrying out the invention]

[0037] As can be seen in Figure 1b, a porous Fe3O4 film with a thickness of 14 nm is formed.

[0038] The acceptable temperature deviation is 0.2°C, and the acceptable pressure deviation is 0.1 mbar (1%).

[0039] Example 1: Manufacturing of acupuncture needles with adsorption properties The acupuncture needles were placed in the reactor, air was drawn in until the pressure reached approximately 10 mbar, and the reactor was heated to 150°C. The needles in the reactor were heated to a predetermined temperature, and then the ferrocenecarboxylic acid precursor was added as vapor to the area where the needles were placed. After being introduced into the reaction zone, the ferrocenecarboxylic acid underwent thermal decomposition as shown in the following equation.

[0040] [ka]

[0041] [ka]

[0042] The vapor obtained by evaporating the precursor (η5-C5N5)2FeCOOH (ferrocenecarboxylic acid) was heated at 60°C for 400 ms and continuously supplied. After each addition of the precursor, the reactor was filled with nitrogen for 1 second to degas it back to the initial pressure. This process was repeated in pulse mode, with each cycle lasting 9 seconds. The number of cycles was 180. As a result, a coating with a thickness of 14 nm was obtained.

[0043] The reactor used was the TFS200 from Beneq (Finland), a state-of-the-art piece of equipment. This reactor is a closed, circular container with a diameter of 200 mm and a height of 3 mm. A vacuum was created inside the reactor to a specific pressure using a pump, achieving a maximum pressure of approximately 10 mbar. A heating element on the outside of the container maintained the desired temperature inside the reactor.

[0044] In the method of the present invention, the temperature is lower compared to the method using ferrocene, because the ferrocene carboxylic acid precursor used decomposes.

[0045] In contrast to using ferrocene and oxygen, when ferrocenecarboxylic acid is used, the oxygen contained in the CO2 molecules produced by the peroxide reaction plays the role of oxygen. Therefore, using this precursor significantly reduces the process time.

[0046] The crucial difference between the claimed method and known methods is: - By heating the substrate to a temperature of 150°C, it becomes possible to use a more volatile ferrocenecarboxylic acid precursor. - By using ferrocenecarboxylic acid, the reaction can be carried out without the use of an external oxygen source. - By using an internal oxygen source, it becomes possible to maximize the utilization of ferrocenecarboxylic acid to produce the desired iron(III) oxide. That is the case.

[0047] Example 2: Adsorption of mercury ions Mercury ion adsorption was performed using an improved acupuncture needle coated with 14 nm thick iron(II,III) oxide. A predetermined total mercury ion concentration equal to 3 μg / l was prepared by diluting monovalent or divalent mercury ions (50 / 50) from a national standard sample into the customer's blood. Next, a 14 nm thick needle was placed in the prepared "blood" solution with a mercury ion concentration of 3 μg / l. After adsorption, the ion concentration in the "blood" solution was measured using a Shimadzu AA-7000 atomic absorption spectrophotometer. A concentration change of 0.4% was shown, and the adsorption capacity (Γ) was 0.45 μg / g.

[0048] Example 3: Adsorption of lead ions A test solution with a lead ion concentration of 2 μg / l was prepared, and adsorption was performed for 1 hour using an improved acupuncture needle coated with 14 nm thick iron(II,III) oxide. After adsorption, the ion concentration in the solution was measured using a Shimadzu AA-7000 atomic absorption spectrophotometer. The adsorption process was shown to occur at a very low level of 0.011%, and the adsorption capacity (Γ) was 0.034 μg / g.

[0049] Example 4: Adsorption of cesium ions A test solution with a cesium ion concentration of 2.7 μg / l was prepared, and adsorption was performed for 1 hour using an improved acupuncture needle coated with 14 nm thick iron(II,III) oxide. After adsorption, the ion concentration in the solution was measured using a Shimadzu AA-7000 atomic absorption spectrophotometer. The adsorption process was shown to occur at a very low level of 0.035%, and the adsorption capacity (Γ) was 0.11 μg / g.

[0050] Therefore, compared to the closest analogue, the method of applying the coating is simplified. On the one hand, this method allows the reactor temperature to be reduced from 220-280°C to 150°C and the precursor supply temperature from 80-100°C to 60°C, thereby reducing electricity costs. On the other hand, by using a novel precursor, the use of an external oxygen source can be eliminated, which also reduces costs. In this case, the needle coating has the appearance of a nanosieve, as shown in Figure 1b.

[0051] Compared to the closest analogue, the adsorption characteristic of the needle in the present invention at a comparable thickness of mercury ion coating was 0.45 μg / g, while that of the closest analogue was 0.32.

Claims

1. Fe ３ O ４ A method for manufacturing acupuncture needles having coating and adsorption properties, - An acupuncture needle for reflex therapy, consisting of a handle and shaft made of metal, is placed in a reactor where a vacuum is created at a pressure of 10 mbar ± 0.1 mbar and a temperature of 150 ± 0.2°C. - Next, ferrocenecarboxylic acid in vapor form is delivered to the reactor, and Next, nitrogen is filled into the reactor and degassed to the initial pressure, and this process is performed by Fe ３ O ４ The cycle is repeated in pulse mode until a specific thickness of 14 nm ± 0.1 nm of the nanofilm coating is formed, and the nanofilm has the appearance of a nanosieve as shown in Figure 1b. A method that includes this.

2. Fe ３ O ４ A needle for adsorption of metal ions, obtained by the method described in claim 1, wherein the thickness of the coating of the nanofilm is 14 nm ± 0.1 nm, and further, the nanofilm has the appearance of a nanosieve as shown in Figure 1b.

3. Fe ３ O ４ The application of the acupuncture needle for metal ion adsorption according to claim 2, wherein the thickness of the nanofilm coating is 14 nm ± 0.1 nm, and further, the nanofilm has the appearance of a nanosieve as shown in Figure 1b.

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