JPS6232944B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an iontophoresis device that selectively infiltrates mineral ions necessary for a living body from outside the body. BACKGROUND ART Cell constituent substances are contained in predetermined concentrations in the living bodies of animals and plants, such as the human body, and if the balance is disrupted, normal biological functions cannot be maintained. For example, the sodium and potassium ion concentration ratios [Na ⁺ ]/[K ⁺ ] are maintained at different constant values inside and outside of animal cells, and as the intracellular sodium ion concentration increases, blood pressure increases, and conversely, potassium ion concentration increases. It has the property of lowering blood pressure as the ion concentration increases. Furthermore, when the concentration of magnesium ions in plant cells decreases, chlorophyll production is inhibited, resulting in abnormal growth. Similarly, when the concentration of iron and copper ions in animal cells decreases, anemia occurs. In addition to adjusting the concentration of these elements originally contained in living organisms, there are also elements that are not normally contained in living tissues but are important in the sense that they promote self-activation of living organisms. Examples include germanium ions and silicon ions, which have recently attracted attention as inducers of interferon and macrophages. If these semiconductor elements are selectively taken into the body at appropriate concentrations,
Preferred therapeutically. The ingestion of necessary elemental ions as described above has conventionally been carried out by internal administration of food or medicine, absorption of nutrients through the roots, or external application such as injection or application. However, absorption through biological cell membranes and plasma membranes is limited because it occurs within the scope of biological mechanisms. Direct injection methods such as injections are also effective in the sense of delivering prescribed drugs into the skin of a living body, but biological mechanisms work in terms of absorption of the injected drugs into living cells, so this is not always possible. However, it may not be as effective. In order to solve these problems and selectively supply necessary mineral ions from outside the body into living cells, the present inventor developed a "mineral ion permeator" that utilizes a type of biological battery phenomenon.
was first applied for (Special Publication No. 55979, Showa 61). The present invention has been made in order to selectively, effectively, and stably supply the above-mentioned semiconductor ions useful to living bodies into living cells. Like the prior invention, the present invention also utilizes the action of a biological battery. In the prior invention, a conductive mineral that generates desired permeated ions and a conductive mineral that has a higher standard unipolar potential than the mineral are electrically connected directly or indirectly, and the two types of conductive minerals are connected directly or indirectly. By pressing each mineral surface against the living body's skin surface and forming a closed circuit through the living body, we were able to generate mineral ions using redox reactions and allow the ions to penetrate into the living body. In this case, the generation of permeating ions and the in-vivo penetration of the generated ions depend on the standard unipolar potential difference between the two types of conductive minerals, so in order to promote this action even more effectively, it is necessary to Connecting a DC power source between the two types of conductive minerals in such a direction that the generated conductive mineral side is biased positively,
Extremely effective. Of the two types of conductive minerals mentioned above, the mineral A with a lower standard unipolar potential is a semiconductor single crystal, and the electrical connection between A and B constitutes an effective ion permeator that meets the purpose of the present invention. In other words, as shown in Figure 6, even if the conductive mineral A with a higher standard unipolar potential is a non-metallic electric material such as metal or carbon, {a}, if the A is a semiconductor crystal, {b} Also, a potential barrier occurs at the electrical junction between A and B. In Figure 6, B is a non-doped n for simplicity.
Although the type semiconductor single crystal and A are p-type semiconductor single crystals, of course other conductivity type combinations are also the same. In Figure 6 a, there is a so-called Schottky barrier at the interface, and in case b, there is a heterojunction barrier at the interface. In both cases, the conduction band bottom (energy Ec) of A and B becomes discontinuous at the interface, and the interface area of B The carrier depletion layer is spreading. Figure 6 shows an energy band diagram when the electric circuit including this junction is not closed (in a state of thermal equilibrium). When a closed circuit is formed, as shown in FIG. 7, the potential barrier at the interface A and B is lowered by the positive electrode effect of A, and a large number of carrier electrons flow from the conduction band of B to A. The electrons flowing into the instep flow from the instep into the body via the skin surface of the body via the crimping point. In case b, a part of the electrons flowing into A from B recombine with holes and disappear inside the p-type semiconductor crystal A. In the living body, mineral ions (e.g. Fe ³⁺ ions) are generated by electrons injected in the region directly below the shell.
A reduction reaction (Fe ³⁺ →Fe ²⁺ ) occurs. However, there is no inflow of electrons from the living body to the cathode (B) side. This is because the Schottky barrier formed at the interface between the biological skin surface and B is biased in the opposite direction due to the positive electrode effect of B, as shown in Figure 7 a and b. This is because electrons accumulate at the interface. The semiconductor crystal is Inside Otsu, the defect level Ed is activated mainly by receiving thermal energy and light energy from the outside, and ionization occurs in the process shown in the figure. Electrons and holes generated by ionization flow in the direction of the arrows due to concentration diffusion, but the semiconductor crystal O is in an unstable state due to the catalytic action of the living body at the contact surface with the living body. A part of the holes that flow into the interface region do not flow into the biological skin surface as carriers, but instead flow into the biological contact atomic surface containing holes (i.e., the cation surface).
dissociates from the crystal lattice as cations and leaches into the body. The cations dissociated from the semiconductor crystal A penetrate into the living body by concentration diffusion. As explained above using the energy band diagram, an electrical junction of two types of conductive minerals with different standard unipolar potentials is used as a conductive mineral B with a lower standard unipolar potential, for example, in the present embodiment. When it is constructed by selecting a semiconductor single crystal such as germanium, tin, or copper selenide as shown in
Ionization occurs within the semiconductor crystal due to energy band discontinuity at the interface, and holes flow to the interface with the biological skin surface to form a cation atomic surface in the interface region, resulting in the formation of cations (cations). ) is likely to occur. However, if two types of conductive minerals with different standard unipolar potentials are both non-semiconductor crystals (for example, two types of metals, or one type of metal and one type of carbon or other non-metallic mineral), as shown in Figure 8. As shown in Figure 2, when attached to a living body, a continuous energy band (conduction band) is created.
Because of the inclination, the electron current flows along the closed circuit of B → A → Living body → B. As a result, the atomic plane of A in the interface region between A and the biological skin surface is neutralized by electrons supplied from the living body, so that the cationization ratio becomes extremely small. That is, although such a combination is effective as a current source, it is not very effective as an ion source. Although semiconductor crystal B is treated as a single crystal in FIGS. 6 and 7, a cation generation effect similar to that of a single crystal can be obtained even with a polycrystal whose grain boundary size is sufficiently large compared to the diffusion length of minority carriers. However, in the case of polycrystals with small grain boundaries or polycrystals containing internal strain (such as mixed sintered bodies), the grain boundaries inside the crystals are active and act as recombination centers, so the Electrons generated in the ionization process
Hole pairs are trapped at grain boundaries and cannot contribute to the mechanism in which holes flow to the interface with the biological skin surface and generate cations. Therefore, it is unsuitable as a cation source in such cases. By the way, the living body also performs temperature regulation and metabolism (skin respiration, sweating, etc.) through the skin surface, and the skin surface is constantly exposed to the outside world, so the hydrogen ion index (PH) at the skin surface is Easily changeable. The purified skin surface (epithelium) is almost neutral (very weakly alkaline), but when waste products are removed from the body through sweating, the skin becomes weak due to the action of various weak acidic substances such as uric acid. The face is
It is slightly acidic with a pH of about 6. In addition, the components of sweat include PH
It also contains alkaline substances such as ammonia to regulate the water content, and its chemical composition is a complex mixture of weakly acidic and alkaline substances. Therefore,
Metals that come into contact with the skin of a living body are affected by this. In particular, base metals with a strong tendency to ionize can be dissolved in aqueous solutions containing these chemicals (i.e. sweat, etc.).
It is easily oxidized by contact with other materials, and the surface is likely to be coated with an oxide film. The higher the temperature, the more acidic and acidic substances contained in sweat and waste products.
The higher the concentration of alkaline chemicals, the more conspicuous the progression, and it is especially noticeable on the skin of mammals such as humans. At oxidized metal surfaces, the standard monopolar potential decreases and biocell action is inhibited. For this,
Among the aforementioned "mineral ion permeators" of the prior application, the permeators using base metals with a relatively large tendency to ionize (minerals with a relatively low standard unipolar potential) had the disadvantage of not being able to withstand continuous use for long periods of time. Of the two types of conductive mineral electrodes that make up the penetrator, at the cathode, the atomic surfaces that come into contact with the skin are ionized and the generated ions penetrate into the living body, so fresh atomic surfaces are exposed each time. Therefore, although the deterioration is relatively small, the atomic surface of the anode is particularly susceptible to oxidation because the same atomic surface is constantly in contact with the skin surface unless metal ions are deposited in the body. Some of these oxides may irritate the skin of a living body and cause undesirable effects such as "rash" on the living body. The present invention was made in order to solve the problems of the "mineral ion permeator" of the prior application. In order to achieve this objective, the present invention uses noble metals (platinum, gold, rhodium, iridium, palladium, and alloys thereof). Precious metals are generally resistant to pH changes and are chemically stable, so as shown in the examples below, they not only show no deterioration even after long-term use, but also have a high standard single-electrode potential, making it difficult to configure cathodes. It has the advantage that the potential difference with the semiconductor crystal increases, and therefore the concentration of ions that permeate into the living body increases. The noble metal for the anode can be used in the form of a molasses, but it may also be formed into a thin film on another conductive material by a method such as vapor deposition. The present invention will be described in detail below based on examples. (Example 1) Diameter 5mm, flat part thickness 2mm, cone part maximum thickness 1mm
An undoped n-type single crystal germanium conical pellet (purity 99.999%) 1 was prepared, and a ring made of insulating ceramics 2 having a thickness of 1 mm and a height of 2 mm was tightly attached to the outer periphery of the flat part. Furthermore, a ring made of metal 3 having a standard monopolar potential higher than that of germanium and having a thickness of 2 mm and a height of 2 mm was closely attached to the outer periphery of the ceramic ring. On the bottom surface of the non-conical side of this triple pellet,
An aluminum film 4 with a thickness of about 3000A is deposited on the bottom surface so that the germanium pellet 1 and the metal 3 are electrically connected, and an adhesive tape 5 is placed on the deposition surface.
was pasted. The adhesive tape 5 serves as a means for skin contact. Skin fittings were made in which the metal 3 was pure copper (Case A) and pure gold (Case B), and experiments were conducted to compare their attachment to the skin of a living body. After carefully shaving the hair on the thigh of the dog's right leg, the above-mentioned skin fitting tool was crimped onto the skin surface of this area so that germanium 1 and metal 3 were simultaneously brought into skin contact. Eight specimens were used in the mounting test, with four specimens each serving as Case A and Case B subjects. For all specimens, before attaching the skin attachment device, the area to be attached was cleaned with alcohol, and the skin surface was cleaned before being attached to the skin. A fixed amount (2 c.c.) of blood was repeatedly collected over time from a vein at a depth of about 10 mm directly below the point where the skin fitting was attached, and the germanium concentration in the blood was examined. Blood tests conducted before the start of the experiment showed that the germanium concentration in the blood of all eight samples was below the detection limit. The wearing experiment continued for 360 hours, during which time all eight specimens remained wearing the skin fittings. FIG. 2 illustrates the time course of germanium concentration in blood for Case A and Case B. The number in the diagram is 4
Indicates the average value of the samples. As is clear from Figure 2, when copper is used as the metal on the anode side (Case A), the blood concentration of germanium reaches almost its peak value (approximately 100 ppm) 216 hours after the start of the experiment; concentration decreased. On the other hand, when gold is used as the anode metal (Case B), the blood germanium concentration reaches saturation approximately 360 hours after the start of the experiment, reaching over 250 ppm. After the experiment was completed, the skin fittings were removed from each specimen and the metal surface of the skin fittings was examined. In Case A, where copper was used as the metal 3, the surface of the copper anode was darkened, and some parts of the skin fittings were darkened. Although the gold anode had changed color to blue-green, no change was observed in the gold anode. Therefore, it is considered that the peak of the blood germanium concentration curve in case A in FIG. 2 is mainly caused by a decrease in electromotive force due to surface oxidation of the copper anode.
Further, the difference in blood germanium concentration between Case A and Case B is considered to be due to the difference in the atmospheric stability of the anode metal used and the difference in standard monopolar potential. Figure 2 clearly shows the superiority of noble metal anodes in mineral ion permeators. (Example 2) As shown in Fig. 3, a polycrystalline Sn plate 6 of 1 cm square and 0.5 mm thick with an average grain boundary size of 200 μm and a metal 3 having a higher standard unipolar potential than the polycrystalline Sn plate 6 were made of copper. The wires 7 were soldered together, and the two metal plates containing the copper wires 7 were pasted and fixed with adhesives 5 with an interval of 2 mm between them. This skin attachment was attached to a mouse to examine the ion penetration effect. After carefully shaving the hair on the lower limbs of the mouse and cleaning it with alcohol, apply metal 3 to the area.
A different type of skin fitting was attached. When metal 3 is rhodium (Case C), palladium (Case D), gold and silver 1:1 alloy (Au50at%,
Three mouse specimens were prepared for each of the cases of Ag50at%) (Case E) and Copper (Case F), and were fitted with the skin fittings at almost the same time. After installation
After 280 hours had elapsed, each skin attachment was removed, and the mouse leg meat immediately below the Sn plate 6 (up to a depth of about 5 mm below the epidermis) was removed and analyzed to measure the tin concentration. As a result, depending on the type of metal 3,
Concentration differences as shown in the table were detected. The values in the table represent the average value of three samples in each case. From the lower limb meat of mice that did not have skin attachments attached,

[Table] Since Sn was not detected (below the detection limit), this result is considered to indicate the effect of mineral ion penetration by the skin fitting, but when copper, which has a relatively large ionization tendency, was used as metal 3. The concentration of tin contained in (Case F) is conspicuously low. When the metal parts of each skin joint were inspected after the experiment, the surface of the Sn plate 6 was uniformly cloudy, but no change was observed in the Rh anode in case C and the Pd anode in case D. . The Au/Ag alloy anode in case E was slightly darkened. In addition, the Cu anode in Case F had a significant degree of blackening to the extent that it lost its metallic luster, and some parts had turned blue-green. In case F, some "sores" were observed on the mouse mounting area. These are the results of oxidation of Ag and Cu in the alloy due to metabolic effects on the mouse skin surface. In particular, the oxidation of copper, which has a strong tendency to ionize, is severe, and as a result, the biological battery action expires early after the skin fitting is attached, and the generation and penetration of Sn ions is suppressed, resulting in a conspicuous concentration in case F. It is estimated that the value has decreased. Similar to the previous example, the results in Table 1 also show the excellent effects of using a noble metal anode. Furthermore, the reason why there is a difference in the penetration effect of tin between noble metal anodes is as follows.
This is thought to be due to the difference in standard monopolar potential. (Example 3) Two spheres (diameter 3 mm) each made of a copper selenide single crystal 8 and a metal 3 with a higher standard unipolar potential are welded together using solder 9 as shown in Figure 4. An ion permeation experiment was carried out by firmly pressing the stems of Japanese butterbur with a needle 5. When metal 3 is pure copper (Case G), when it is platinum (Case H), and when the surface of a copper ball with a diameter of 3 mm is coated using the sputtering method, the thickness is approximately
Five specimens were prepared for each case of 3000A iridium (Case I), and the ion permeation conditions were examined after 200 hours had elapsed by attaching the specimens at almost the same time. After the experiment was completed, the skin fitting was removed from the specimen, and immediately a 1 cm long stem including the attachment area was cut and the selenium concentration in the stem was measured by physical analysis along with the stem of a comparative specimen that was not attached. Table 2 shows the average selenium concentration of the five samples prepared for each case. The selenium concentration contained in the comparative sample without the skin fitting was below the detection limit (1 ppm). The fact that selenium was found in the sample no matter which skin contact tool was used shows the usefulness of the ``mineral ion permeator''.

[Table] In other words, compound ions Cu ₂ Se are generated directly under the copper selenide cathode 8 of these skin joints, penetrate and diffuse into the butterbur stems, and the Cu ₂ Se ions are further converted into Cu ions and Se ions in the butterbur water solution. It is thought that it was ionized. On the other hand, inside the butterbur stalk directly below the anode metal 3,
Reduction of mineral ions (such as copper ions) contained in butterbur must have occurred. but,
As the data in Table 2 shows, case G and case H
(or case I), there is a significant difference in the selenium concentration contained in butterbur. The reason for this is thought to be mainly due to the stability of the anode metal 3 used for the skin joint. In fact, when we inspected the metal surface of the leather fitting removed from the brush, we found that the copper anode in case G had turned black, while the noble metal anodes in cases H and I showed no change at all. Considering the very large difference in selenium concentration, it is predicted that the copper anode was oxidized quite early after installation, causing the biological battery to stop functioning and preventing copper selenide ions from penetrating into the butterbur stems. be done. Because the butterbur's biological mechanism works, it is thought that the selenium ions that once entered at a fairly high concentration were excreted in the latter half of the experiment period. (Embodiment 4) On the other hand, a DC power source 11 is attached to the skin contact tool shown in FIG. 4 through a series variable resistor 10 so that the copper selenide single crystal 8 side is biased positively and the metal 3 side is biased negatively. Then, a skin fitting with the structure shown in Fig. 5 was made. In order to compare the ion penetration effect with the skin contact tool shown in Fig. 4, the anode metal 3 was made of platinum, which is the same as in Case H of the previous example, and a penetration experiment was carried out by applying pressure to the stem of a butterbur growing on the ground. Summer. After applying the skin contact tool 5 times so that the copper selenide single crystal 8 and the metal (platinum) 3 are crimped to the butterbur stem at the same time, the variable resistor 10 is operated to apply approximately 1 mA to the closed circuit including the butterbur stem. It was biased so that an electric current could flow through it. After 200 hours of attachment, the skin attachment was removed and a 1cm long stem including the attached part was cut and analyzed. The selenium concentration in all 5 samples reached over 10,000 ppm. It has been shown that the ion penetration by the skin joint of the present invention is extremely effective. As described in detail in the above embodiments, the skin contact tool of the present invention makes it possible to perform selective ion penetration into a living body stably, harmlessly, and effectively by employing a noble metal anode. By using the skin contact tool of the present invention, growth promotion and treatment of a living organism, or metal ion exchange can be performed continuously for a long period of time from outside the living body. Note that the above embodiments describe only a part of the present invention, and if the skin attachment device of the present invention is applied not only to a part of the skin surface of a living body but also to the entire skin surface, the ion concentration in the living body can be adjusted more easily. It is obvious that this can be done quickly.

[Brief explanation of the drawing]

Figures 1 and 3 to 5 are cross-sectional views of the main parts of the skin fitting used in different embodiments of the present invention, and Figure 2 shows the use of the skin fitting shown in Figure 1. Figures showing the experimental data, Figure 6 a, b, Figure 7 a,
b and FIG. 8 are explanatory diagrams of the present invention. In the figure, 1...Germanium pellets, 2
...Insulating ceramics, 3...Metal with a higher standard monopolar potential than the mineral that generates penetrating ions, 5: Adhesive tape (for example, porcelain tape), 6: Sn
Board, 7...Copper wire, 8...Copper selenide, 9...Solder, 11...DC power supply.

Claims (1)

[Scope of Claims] 1. Consists of a conductor electrically connecting two types of conductive minerals having different standard unipolar potentials, and a skin contact means affixed to the conductor; Among the conductive minerals, the mineral with a higher standard unipolar potential (hereinafter referred to as A) is one type selected from the group consisting of platinum, gold, rhodium, iridium, and palladium, or an alloy of metals included in this group. , an ion permeator in which a mineral with a lower standard unipolar potential (hereinafter referred to as B) is a source of ions to be penetrated made of semiconductor crystals, and A and B are each used in skin contact with a living body. 2. An ion permeator in which a DC power source is connected between the two types of conductive minerals described in claim 1 in a direction that biases B positively and A negatively.