Patent Application
20100209293
The present invention relates to a sterilization method and a sterilization apparatus using plasma, particularly to a technology to enhance a sterilization capability for sterilizing microorganisms present in a liquid or on a surface thereof by adjusting pH by using an atmospheric pressure plasma as a radicals generating source. The present invention is used for sterilization or complete sterilization of medical equipment, food containers, foods, and other articles; sterilization, complete sterilization, and disinfection of wounds; or a sewage treatment and other various cases requiring a sterilization treatment.
Conventionally, the method for sterilizing or completely sterilizing various microorganisms such as bacteria or viruses can be broadly divided into two types, i.e., a physical method (mechanical method) using heat, pressure, or the like, and a chemical method using chemical agents. The physical method includes a high-pressure steam sterilization method (autoclaved sterilization), a gamma sterilization method, an electron beam sterilization method, and the like. The chemical method includes an ethylene oxide gas (EOG) sterilization method, a reduced-pressure hydrogen peroxide plasma sterilization method, and the like.
The physical method is mainly used for complete sterilization of medical equipment. However, since an object to be sterilized is exposed to an extreme physical condition in many cases, the type of object to be sterilized is limited. For example, the autoclave is not applicable to a plastic product that is easily affected by heat, and it is not desirable to sterilize, using gamma rays, materials, precision equipment, or the like that are easily degraded by ultraviolet rays or the like. In addition, a large-scaled apparatus is required in most cases except for using the autoclave, which, in many cases, makes it difficult to choose a place to install the apparatus.
In the case of the chemical method, the chemical agents to be used may exert a harmful influence on the human body. Therefore, a process for securely rendering the agent residue harmless is necessary, which, as a result, requires more cost and time. Particularly, guidance is provided to restrict the use of EOG because it has acute toxicity and a mutagenic property. Especially, when chemical agents are used, complete sterilization in a liquid is difficult. Even if such sterilization is realized, high-concentration chemical agents remain in the liquid as a result. It becomes, then, extremely difficult to detoxify the sterilization agents dissolved in the liquid, i.e., substantially impossible by conventional technologies.
In recent years, on the other hand, investigations for a sterilization method using plasma have been in progress. The plasma is an expression referring to a state of substance in addition to solid, liquid, and gas. Atoms turn into a plasma state consisting of ions and electrons, and acquire a high chemical activity at a high temperature of about 10,000° C. or higher. The plasma is used as a light source represented by a fluorescent lamp or processing used in the semiconductor industry.
Provided as an example of the sterilization method using plasma is the hydrogen peroxide plasma sterilization method (HLPS) as described above. In the HLPS method, a pressure in a chamber is reduced to, for example, as low as 0.3 Torr; hydrogen peroxide is injected and diffused; and high-frequency discharges (10 eV, 13.56 MHz, 400W) by means of air are performed. Thereafter, clean air is blown into the chamber to bring the pressure therein back to the atmospheric pressure. It is said that, according to the HLPS method, sterilization is performed by radicals (OH.) or the like produced by an oxidation action of hydrogen peroxide and the plasma discharges (Non-patent Document 1: “Features and Problems on the Plasma Sterilization and Future Prospect of the New Sterilization using Low-temperature-plasma”, by Kaoru Tamazawa, Bokin Bobai Vol. 32, No. 1, pp. 13-30).
Further, JP-A-2004-290612 discloses a sterilization method which uses hydrogen peroxide as a sterilization chemical agent and combines the same with plasma.
It is also proposed to ignite plasma in a chamber maintained as a vacuum environment after exhausting gas, and sterilize a dried object (Non-patent Document 2: “Plasma Sterilization”, by Masaaki Nagatsu, J. Plasma Fusion Res., vol. 83 , No. 7 (2007) 601-606). Non-patent Document 2 discloses sterilizing medical equipment such as a knife, a scalpel, and a tube disposed in a non-woven fabric that allows gas to pass therethrough but prevents microorganisms from passing therethrough.
According to the conventional sterilization method utilizing a combination of hydrogen peroxide and plasma, what is currently performed is the sterilization by using hydrogen peroxide that, per se, is a powerful microbiocide, and thereafter the plasma is used to decompose and detoxify the hydrogen peroxide.
In addition to this fact, a pressure vessel is required to use plasma under a vacuum environment in a low pressure. The sterilization is performed only in such a pressure vessel, which casts a lot of restrictions in performing the sterilization.
In recent years, atmospheric pressure plasma has been drawing a lot of attention. The conventional plasma is generated, in often cases, under a low pressure, and it is difficult to use it under an ordinary environment. When the plasma is generated under a high pressure such as an atmospheric pressure, the plasma thus generated tends to become a thermal plasma represented by arc plasma used for arc-welding, because particles that are ionized to become plasma, through frequent collisions with neutral gas particles, reach almost a thermal equilibrium state accompanied by an increase in the temperature of neutral gas component. On the other hand, non-equilibrium plasma is attracting attention. The non-equilibrium plasma is chemically active because it has a sufficiently high electron temperature despite a low neutral gas temperature and formed by creating a non-equilibrium state while ingeniously contriving a way to prevent a thermal relaxation state from being generated. The non-equilibrium plasma is sometimes called low-temperature plasma because the neutral gas temperature is about a room temperature, which is significantly low as compared with the electron temperature.
If such a non-equilibrium plasma can be used for sterilization, the practical value thereof is supposed to be extremely high because restrictions for performing sterilization are largely reduced. However, the technology for effectively sterilizing the microorganisms present in a liquid or on a surface thereof has not been established.
The present invention is made in light of the problem described above, and it is an object of the present invention to provide a sterilization method and apparatus with which microorganisms present in a liquid or on a surface thereof can be sterilized effectively.
According to one embodiment of the method of the present invention, plasma is generated in a vicinity of or in a manner to make contact with a liquid whose pH value is adjusted to become 4.8 or lower, and radicals generated by the plasma are made contact with the liquid.
In such a case, it is preferable that the plasma be generated in an atmosphere containing nitrogen gas. The plasma may be generated in the air, instead.
It is preferable that the pH value of the liquid be 4.5 or lower, and more preferable that the pH value be 2 or higher but 3.5 or lower.
Superoxide anion radicals (O2−.) that are generated by the plasma, by making contact with a liquid having a pH value of 4.8 or lower and being diffused in the liquid, react with protons (H+) in the liquid to thereby form hydroperoxy radicals (HOO.). Further, for example, nitrogen and oxygen included in the air are combined together by the action of plasma to thereby form nitrogen oxide such as nitric oxide (NO.) or nitrogen dioxide (NO2.). The nitric oxide (NO.) combines with the hydroperoxy radicals (HOO.) to become peroxynitrite (ONOOH(ONOO−)) having a high microbiocidal activity. A powerful antimicrobial effect is provided by these hydroperoxy radicals (HOO.), peroxynitrite (ONOOH(ONOO−)), and the like.
The present invention may be implemented in various embodiments described below.
To be specific, plasma is generated in a vicinity of or in a manner to make contact with a liquid whose pH value is adjusted to become 4.8 or lower, and radicals (free radicals) generated by the plasma are brought into contact with the liquid.
In the case mentioned above, the plasma is generated in an atmosphere containing nitrogen gas. For example, the plasma is generated in the air.
Further, a method for sterilizing microorganisms present in a liquid or on a surface thereof includes a first step of adjusting a pH value of the liquid to 4.8 or lower and a second step of bringing the liquid into contact with plasma following the first step.
A method for sterilizing microorganisms present on a surface of an object or in a vicinity of the surface includes a step of applying a liquid having a pH value of 4.8 or lower to the surface of the object, and a step of exposing the liquid present on the surface of the object to plasma.
Furthermore, a method for sterilizing microorganisms present on a surface of an object or in a vicinity of the surface includes a step of immersing the object in a liquid having a pH value of 4.8 or lower, and a step of exposing the liquid with the object immersed therein to plasma.
A method for sterilizing microorganisms present on a surface of a living body or in a vicinity of the surface includes a step of applying a liquid having a pH value of 4.8 or lower to the surface of the living body, and exposing the liquid present on the surface of the living body to low-temperature plasma.
In the methods described above, the liquid is applied in a form of a gelatin sheet to the surface of the living body.
A sterilization apparatus, for sterilizing microorganisms present in a liquid or on a surface thereof, includes a pH adjustment device that adjusts a pH value of the liquid at 4.8 or lower, and a plasma generation device that emits plasma to the liquid.
A sterilization apparatus, for sterilizing microorganisms present in an object or on a surface thereof, includes a housing capable of surrounding and hermetically enclosing at least a part of the object, a pH adjustment device that supplies a pH adjusting substance such that a pH value of said at least the part of the object becomes 4.8 or lower, a plasma generation device that generates plasma inside the housing, an introduction portion that introduces an atmospheric gas containing nitrogen gas into the housing, and an exhaust portion that draws out the atmospheric gas.
It is preferable that the pH value be adjusted to become 4.5 or lower. It is more preferably that the pH value be adjusted to become 2 or higher but 3.5 or lower.
It should be noted that “complete sterilization” means annihilating or completely inactivating bacteria, fungi, viruses, and the like, and generally requires more strict conditions than in the case of “sterilization”. To be specific, the sterilization means a state in which the number of microorganisms is reduced to 1/103 or less of the original microorganisms concentration. However, the complete sterilization means a case in which the survival probability of microorganisms is reduced to 1×10−6 or less. To put it differently, in the case of sterilization, although the number of microorganisms is temporarily reduced to a harmless level, the microorganisms may increase in numbers depending on the conditions provided thereafter. On the other hand, since the microorganisms have been entirely annihilated in the case of complete sterilization, the microorganisms will never grow, for example, in retort-packed foods or canned foods unless they are opened.
In the description hereinafter, decreasing the density in number of microorganisms is referred to as “sterilization”.
Hereinafter, various embodiments will be described.
As illustrated in
Next, the liquid LQ is adjusted to have a pH value of 4.8 or lower. Preferably, the pH value is adjusted to become 4.5 or lower, or more preferably 3.5 or lower. At the same time, it is also preferable that the pH value be adjusted to be 1 or higher, more preferably 2 or higher to lessen the influence on human body and make the post processing of the liquid LQ easier.
In order to adjust the pH as described above, there are provided such methods as charging acid, or salt that indicates acidity, such as, for example, citric acid (C6H8O7) or phosphate (e.g., KH2PO4) from a charging container TY into the liquid LQ, or blowing a carbonic acid gas (CO2) into the liquid LQ. In this way, when the pH is adjusted and the liquid LQ turns into acidic, protons (hydrogen ions) H+ in the liquid LQ increase as illustrated in
It is to be noted that, although the drawings do not illustrate, such a charging device that charges the acid or salt by means of the charging container TY or a blowing device that blows the carbonic acid gas into the liquid LQ corresponds to a pH adjustment device 11.
Thereafter, the liquid LQ is brought into contact with plasma PM in the air. As a method for bringing the liquid LQ into contact with the plasma PM,
Alternatively, as illustrated in
Although it is not illustrated, it is also possible to generate the plasma PM in an atmosphere containing a mixed gas including nitrogen gas and oxygen gas at an appropriate ratio. Still alternatively, in the case where the oxygen can be obtained from the components of the liquid, for example, when the liquid is water, it is also possible to generate the plasma in an atmosphere containing the nitrogen gas but excluding the oxygen gas. In this case, it is deemed that oxygen radicals are supplied by means of decomposition of the water.
Nitrogen may be fed into the liquid instead of using an atmosphere containing the nitrogen gas to generate the plasma. For example, this is achieved by putting nitric acid or powders of nitrate salt into the liquid and making them dissolve therein. Instead, various substances including nitrogen may be put into the liquid.
It is also possible to generate the plasma PM in the vicinity of the liquid LQ instead of bringing the liquid LQ into contact with the plasma PM.
Active species such as radicals are supplied primarily from a gas phase kept in contact with the plasma, and therefore the plasma is not necessarily brought into contact with the liquid for performing sterilization of the liquid. It is possible to emit the plasma into an atmosphere of air, or a mixed gas containing nitrogen and oxygen to thereby generate radicals in a large amount and supply the radicals thus generated to the target liquid. In this way, it is possible to attain biocidal activities similar to the case where the plasma is made contact with the liquid.
As illustrated in
As illustrated in
The plasma PM may also be generated, as illustrated in
In this way, it is possible to perform sterilization of the surface of the liquid LQ or in the liquid LQ by generating the plasma PM in the vicinity of or in a manner to make contact with the liquid LQ that is adjusted to have a pH value of 4.8 or lower.
The following is considered to be a principle of the sterilization according to the present embodiment.
Superoxide anion radicals (O2−.), which are generated by the plasma PM when the plasma PM makes contact with the liquid LQ, diffuse into the liquid LQ. The diffused superoxide anion radicals (O2−.) react with protons (H+) in the liquid LQ to thereby form hydroperoxy radicals (HOO.).
[Chemical Formula 1]
[O2−.]+[H+]⇄[HOO.] (1)
The right-hand and left-hand sides of the above-mentioned chemical formula are in an equilibrium relationship. The reaction progresses either from the right-hand side to the left-hand side or from the left-hand side to the right-hand side depending on the concentration. The hydroperoxy radicals (HOO.) formed in this way have a powerful antimicrobial effect which sterilize the microorganisms in the liquid LQ.
A value representing the equilibrium constant of this equilibrium reaction (acid dissociation constant), i.e., pKa, is “4.8”, which means that the superoxide anion radicals (O2−.) and the hydroperoxy radicals (HOO.) are present in equal densities when the pH is at 4.8. This also indicates that, in a state in which the pH value is higher than 4.8, the amount of the hydroperoxy radicals (HOO.) reduces extremely, and that, contrary, in a state in which the pH value is lower than 4.8, the amount of the hydroperoxy radicals (HOO.) increases rapidly.
Based on this principle, the pH value of the liquid LQ is adjusted to be 4.8 or lower, and the liquid LQ is made contact with the plasma PM to thereby generate the hydroperoxy radicals (HOO.) with which the microorganisms in the liquid LQ are sterilized. When the pH value of the liquid LQ is adjusted at 4.8 or lower, preferably 4.5 or lower and the liquid LQ is made contact with the plasma PM, it is possible to attain a significantly increased microbiocidal activity.
Hydroxyl radicals (OH.), hydroperoxy radicals (HOO.), superoxide anion radicals (O2−.), and the like are known as active species having oxidative potential. Sterilization is performed by generating such active species by the plasma that makes contact with the liquid and infiltrating the active species into the liquid. In doing so, it is possible to dramatically enhance the microbiocidal activity by adjusting the pH value of the liquid toward an acidity side, i.e., 4.8 or lower.
The superoxide anion radicals have a relatively long life time but are weak in oxidizability, and are in an equilibrium relationship expressed in Formula (1) with protons (H+) in the liquid. Accordingly, in an acidic environment with a lot of protons (Hi), the hydroperoxy radicals (HOO.) having high oxidative potential are prone to be formed. Particularly, at a pH value of 4.8 or lower, which corresponds to the pKa, the ratio of presence of the hydroperoxy radicals (HOO.) increases significantly.
Furthermore, nitrogen and oxygen included in the air are combined together by the action of plasma to thereby form nitrogen oxide, which is a radical of oxygen and nitrogen, such as nitric oxide (NO.) or nitrogen dioxide (NO2.). The nitric oxide (NO.) combines with the hydroperoxy radicals (HOO.) to become peroxynitrite (ONOOH(ONOO−)) having a high microbiocidal activity, which, as a result, provides further high microbiocidal activities. It is considered that various active species formed from oxygen and nitrogen generate a synergistic effect to provide a high microbiocidal activity.
[Chemical Formula 2]
[OONO2−]+[H+]⇄[ONOOH(ONOO−)] (2)
It is deemed that, the microbiocidal activity is attained by the hydroperoxy radicals (HOO.) generated by the liquid LQ having a pH value of 4.8 or lower and the plasma PM, and further the peroxynitrite (ONOOH(ONOO−)) is generated because of the presence of nitrogen, which helps attain a further enhanced microbiocidal activity.
Biological materials constituting the microorganisms are altered in properties by the radicals in the liquid, which prevents the microorganisms from further growing or sterilization progresses. This method is applicable to inactivate protein such as pathogenic viruses and prions which are not contained in the microorganisms, and also applicable to chemical modification of biological macromolecules such as protein.
It is possible to generate radicals in the liquid by a chemical method using chemical agents. However, it is also possible to produce radicals in a large amount highly efficiently under a chemically clean environment by using plasma generated mainly with a rare gas. In addition, when the pH value is adjusted at 3.5 or lower, efficient sterilization effect is further secured. When the pH value is adjusted at 2 or higher, the chemical agents used for adjusting the pH do not cause problems, which makes it possible to apply the method to human bodies, odontotherapy, foods, medical equipment, and so on.
As illustrated in
As illustrated in
In this way, according to the present embodiment, active species are produced by making the plasma contact with a surface of the liquid or generating the plasma in the vicinity of the liquid in the air, a nitrogen gas atmosphere, or an atmosphere containing nitrogen gas and oxygen gas. Then, the action of the active species thus produced are strengthened by adjusting the pH in the liquid to thereby effectively perform sterilization of the liquid itself or various articles such as equipment immersed in the liquid.
When the low-temperature plasma is used, it causes less chemical and mechanical damages because the temperature is low and no special chemical agents are required, and does not cause problems by residual gas. This means that it is possible to sterilize, without adverse effects, plastic products and medical equipment having a precision structure such as the one represented by a gastrocamera.
Since the sterilization is performed effectively under two conditions which overlap with each other, i.e., a region with a lowered pH value and a region where radicals produced by the plasma can reach, it becomes possible to perform local sterilization by adjusting each of the regions appropriately. For example, it becomes possible to sterilize a surface layer of wounds of human body.
As described above, in the present embodiment, the charging device for charging acid or salt by means of the charging container TY, or the blowing device that blows the carbonic acid gas into the liquid LQ corresponds to the pH adjustment device 11. The pH adjustment device 11 may also include the container YK, a pH sensor, an adjustment device for adjusting the pH at a predetermined value, and the like. It is also possible to use, as the charging device, a manipulator that, for example, holds and moves the charging container TY, or a spewing device that spews out acid or salt.
Further, the plasma generation device 12 corresponds to the plasma generation device according to the present invention. An entirety including the plasma generation device 12 and the pH adjustment device 11 corresponds to the sterilization apparatus 1 according to the present invention. However, the pH adjustment device 11 and the plasma generation device 12 are not limited to the examples described above, and the pH adjustment device 11 and the plasma generation device having various structures, shapes, or principles may be used.
Next, examples are described hereinafter by incorporating demonstration experiments and the results thereof about the adjustment of pH of the liquid LQ and the case where the liquid is made contact with the plasma PM.
Prior to the description of the examples, a description will be given of a method for evaluating the sterilization.
The evaluation of the number of microorganisms is usually performed by counting the number of colonies formed on the agar plate medium and is expressed in colony forming unit (CFU). The colony is a state in which microbial bodies of a single kind are sufficiently distributed and grown to an extent that can be visible. The CFU is equal to the number of living microorganisms included in an object to be evaluated.
As an index indicating the microbiocidal activity, D value, a time period for the CFU to decrease to 1/10 of the original value is provided. It is determined that, the smaller the D value is, the greater the microbiocidal 1 activity is. A sterility assurance level (SAL) indicates a state in which the survival probability of microorganisms is reduced to, as low as 1×10−6, and the time required to reach the state is referred to as a sterility assurance time. Usually, the initial concentration is assumed to be 1.0×106 CFU/ml, and the time required to reach the SAL is calculated by multiplying the D value by 12. For example, the time required to reach the SAL is 15 minutes in a complete sterilization operation by autoclave at a temperature of 121° C. Such a case indicates that the D value is 75 seconds. In actual cases, since it takes an extra time for the temperature to increase to 121° C. and an extra time for cooling, the entire complete sterilization operation takes about 1 to 1.5 hours.
In Example 1, the sterilization effects are examined for each of the cases where the liquids having different pH values are exposed to the plasma PM and where they are not exposed.
Specifically, two sets of microbial suspension containing Escherichia coli are prepared. Each set is made up of two types of pH values individually adjusted at “6.0” and “3.5”. One of the sets is exposed to the plasma PM for two minutes, and the other is not exposed. The result of counting the number of bacteria by a colony counting method is illustrated in
As illustrated in
In contrast, when the pH value is “3.5” and the set is exposed to the plasma PM, the number of bacteria is decreased to about a millionth. This means a significantly strong microbiocidal activity. To put it differently, the result shows that, when the pH value is adjusted at “3.5” and the set is exposed to the plasma PM, a drastic microbiocidal activity of such an extent that it can be called completely sterilized with respect to the original bacteria concentration of 7,000,000 CFU/ml is attained. This kind of microbiocidal activity in such a short time period is equivalent to relatively strong bactericide and, at the same time, has a very wide applicability because it utilizes the plasma PM whose strength and reaction time can be controlled by parameters externally supplied.
For example, a sterilization target is indirectly sterilized by immersing the target in a liquid whose pH is adjusted or by spraying a liquid whose pH is adjusted onto the target, and thereafter the liquid or the target is exposed to the atmospheric plasma.
In Example 2, the sterilization effect is examined according to the exposure time during which the liquids having different pH values are exposed to the plasma PM.
(I) Conditions of Experiment
(1) Preparation of Bacteria and Evaluation Method of Sterilization
Escherichia coli or lactic acid bacteria shaking-cultured using a liquid culture medium for over 18 hours at 30° C. are diluted with sterilized water and adjusted to have a concentration of about 7.0×107 CFU/ml, which is used as microbial suspension.
Usually, turbidity and concentration (CFU/ml) of microorganisms are in a proportional relationship. It is known that, in the case of Escherichia coli, when the optical density for light having a wavelength of 600 nm (OD600) is 1.0, the bacteria concentration becomes about 7.0×108 CFU/ml. Therefore, it is possible to obtain microbial suspension having the aforementioned concentration of 7.0×107 CFU/ml by recovering the cultured Escherichia coil through centrifugal separation, diluting the suspension by adding thereafter sterilized water so that OD600 becomes 0.1. The relationship between the turbidity (OD600) and concentration (CFU/ml) is about the same for lactic acid.
The microbial suspension is added to 0.45 ml of sterilized water or to 2.0 mM (or 10 mM) or citric acid-NaOH buffer solution whose pH value has been adjusted at a predetermined value, and the mixture is put into a well of a microplate made of polystyrene and having 24 wells. The mixture is exposed to an LF plasma jet (3.0 litters /min, He gas , and a primary voltage of 70V) for a predetermined period of time. The LF plasma jet will be described later.
After being exposed to the plasma, the mixture is recovered, serially diluted, applied onto the agar plate medium, and measured for the number of colonies after sixteen-hour cultivation. To be specific, the recovered microbial suspension is diluted to 1/10 of concentration by sterilized water, and further diluted to 1/10 of concentration to thereby produce a diluent having 1/102 of the original concentration. This way, diluents down to 1/104 of the original concentration are prepared, and 0.1 ml each of individual diluents are dispersed on the agar plate medium for overnight cultivation at 30° C.
Eventually, data for 50-500 colonies/plate, which can be considered the most reliable among others, is chosen. Just for reference, when 0.1 ml of the non-diluted mixture, which has the highest concentration, are dispersed, no colonies are detected. In this case, the bacteria concentration is 10 CFU/ml or lower, which is a limit for detection. Since this figure is smaller than 10 CFU/ml, it is considered that this state substantially represents a complete sterilization state. It should be noted, however, that there are some cases in which actual measurements are performed only for the case where the diluent diluted down to 1/102 of the original concentration is dispersed. In such a case, the bacteria concentration of 1.0×103 CFU/ml is regarded as the detection limit.
(2) Exposure to Plasma
The plasma used in Example 2 is called an LF plasma jet. The LF plasma jet was invented by Kitano et al, who are also inventors of the present invention, and is disclosed in International Application PCT/JP2007/061837.
According to the LF plasma jet, it is possible to generate a low-temperature atmospheric plasma jet easily. By exposing a liquid to such plasma to thereby supply various types of active species (electrons, ions, radicals, electric field, etc.) into the liquid, plasma processing in the liquid conventionally unachieved is aimed. Since the LF plasma jet is in a stable state as compared with arc discharges or spark discharges, it is possible to perform plasma processing without physically destroying the liquid itself and substances present in the liquid by heat or shock waves. One example of which is the plasma sterilization according to the present embodiment.
The LF plasma jet uses helium gas. When the LF plasma is jetted into air, oxygen and nitrogen are respectively energized and thereby excited to possibly become reactive species. For example, only jetting the plasma in the air causes ozone to be generated and accompanying smell of ozone as well. In order to evaluate what is described above, evaluation is performed on the influence of the atmospheric gas by not only emitting the plasma in a jet form but also arranging an atmospheric gas with the helium gas alone or the helium gas mixed with air. In the drawings, the results of sterilization experiments illustrated in the same drawing indicate that the experiment is conducted under the same plasma generation condition. However, the results of experiments illustrated in different drawings do not necessarily mean that the same plasma generation condition is used.
Example 2 is implemented by using the LF plasma jet having a variety of characteristics as described above. When the reaction mechanism is verified scientifically, it is finally found that any type can be used as long as it is plasma.
Detailed description of the LF plasma jet will be given later.
(3) Other Types of Plasma Can be Used
An evaluation of biocidal activity can be performed through a similar operation even when mixture is prepared according to the conditions described above and the liquid is processed using a plasma source other than the LF plasma jet (e.g., a chamber-type plasma emitting device).
However, when the influence of the pH described later is taken into account, such a powerful microbiocidal effect can not be expected from the exposure to plasma in a non oxygen-containing atmosphere. Accordingly, a system for supplying oxygen in some form or another is necessary. In an experiment using the chamber-type plasma emitting device and when plasma with only a helium gas is emitted, the microbiocidal activity is relatively low even in the case where the pH is adjusted. On the contrary, when air is mixed therewith, extremely high biocidal activities are obtained. From this result, it is found that nitrogen included in the air also plays a role in providing the biocidal activities.
However, how the oxygen is supplied is not restricted to a method in which the oxygen gas is simply mixed with the plasma gas. It is also considered effective, for example, to increase in advance dissolved oxygen in a liquid by means of microbubbles, add a reagent which is supposed to supply oxygen into the liquid by chemical reaction, or the like. By using such a method, an increase in microbiocidal activity by way of adjusting the pH value is expected even when a plasma source that discharges directly in the liquid is used.
(II) Change in Sterilization Performance According to a Change in pH
According to a result of evaluating the microbiocidal activity on Escherichia coli at various pH values (7.8 to 3.5), it is observed that the lower the pH value is, the stronger the microbiocidal activity tends to become, and the effect of which is found to be noticeable at a pH value of about 4.5. This value is slightly toward the acidity side from the pKa of 4.8 in the equilibrium reaction between the superoxide anion radicals (O2−.) and the hydroperoxy radicals (HOO.) shown in Formula 1 presented above.
As illustrated in
According to
The above-mentioned results indicate that the microbiocidal activity by the plasma does not depend on the pH values at least under the condition in which the pH value is 7.8-4.77. However, the change in pH sharply contributes to the enhancement of the microbiocidal activity when the pH value is 4.5 or less. This means that the sterilization effect by the plasma can be significantly increased by adjusting the pH value of a liquid to be sterilized to become 4.5 or lower.
Further, as shown in
In
As described above, enhancement in microbiocidal activity is confirmed not only on Escherichia coli but also on lactic acid bacteria and spores of Bacillus subtilis by adjusting the pH value.
(III) Sterilization by Radicals
(1) Hydroperoxy Radicals Formed from Superoxide
Although various factors are pointed out about sterilization in liquid by plasma, active species such as radicals or the like that are secondarily-generated from the plasma are deemed to have a large part of the microbiocidal activity because the plasma (ions and electrons), per se, can not penetrate into the liquid.
Hydroxyl radicals (OH.) are radicals that are highly reactive but can barely move in a solution because the hydroxyl radicals have a shorter life time. For this reason, it is considered that the hydroxyl radicals (OH.) are produced only in the vicinity of a surface of the liquid where the plasma makes contact with the liquid. It is found, from a result of the experiment, that the biocidal activity penetrates in a depth direction by 1.0 cm or more. Accordingly, another type of active species having a longer life time is supposed to be involved.
Contrary to the hydroxyl radicals (OH.), superoxide anion radicals (O2−.) have a relatively longer life time and it is considered that they can exist even in water for a few seconds. Although the superoxide anion radicals (O2−.) can be produced easily when oxygen in the air is excited by the plasma, the superoxide anion radicals, per se, have low reactivity and a fairly low microbiocidal activity. However, the superoxide anion radicals (O2−.) are considered to react with hydrogen ions (H+) in the water and maintain the equilibrium state shown by Formula (1) discussed above.
To be specific, the superoxide anion radicals (O2−.) react with the hydrogen ions (H+) in the liquid to form hydroperoxy radicals (HOO.). The hydroperoxy radicals (HOO.) are known to have an extremely strong microbiocidal activity. According to one theory, the hydroperoxy radicals (HOO.) are said to have microbiocidal activity 100,000 times strong as that of the superoxide anion radicals (O2−.). Moreover, the equilibrium state shown in Formula (1) indicates that the higher the concentration of the hydrogen ions (H+) becomes, i.e., the lower the pH value becomes, the greater the amount of the hydroperoxy radicals (HOO.) increases.
Since the value representing the equilibrium constant of the equilibrium reaction shown in Formula (1) above, i.e., pKa, is 4.8, such an effect is expected to dramatically increase at a pH value equal to or lower than 4.8, which truly coincides with a result of the experiment where the microbiocidal activity sharply increases at a pH value of 4.5 or lower. To put it differently, as long as the pH is 4.8 or higher, a majority part of the superoxide anion radicals (O2−.) is dissociated from hydrogen, and a majority part of the superoxide anion radicals (O2−.) is combined with the hydrogen, which forms the hydroperoxy radicals (HOO.) when the pH becomes 4.8 or lower.
The improvement of the microbiocidal activity by the plasma depending on the decrease in pH is considered to be attributable to such a mechanism. To verify this, a sterilization experiment is conducted by adding superoxide dismutase (SOD), an enzyme having a function of causing a reaction between the superoxide anion radicals (O2−.) and water and converting them into hydrogen peroxide. In other words, by conducting an experiment using the SOD, it is possible to evaluate the microbiocidal activity of the superoxide anion radicals (O2−.). The result of the experiment is illustrated in
In
It should be noted, however, that, since the limit for detection is 1.0×103 CFU/ml, the number of bacteria is actually reduced more when the SOD is not added but the plasma is emitted. For this reason, the improvement in survival rate of bacteria is expected to be 10,000 times or more when the SOD is added.
This indicates that the superoxide anion radicals (O2−.) exert a great influence on biocidal activity, and suggests the involvement of the hydroperoxy radicals (HOO.).
From the foregoing discussion, it is considered that, in the sterilization in liquid by plasma, the superoxide anion radicals (O2−.), one type of oxygen radical, are combined with the hydrogen ions (H+) in the liquid to form the hydroperoxy radicals (HOO.) to thereby show the microbiocidal effect. The effect is considered to be dramatically enhanced by raising the concentration of the hydrogen ions (H+), i.e., lowering the pH. It is important that such a pH should be lower than 4.8 which is a value of pKa in the equilibrium reaction represented by Formula (1) described above. From the results of the experiment illustrated in
(IV) Evaluation of NOx and H2O2
When the LF plasma jet is emitted in the air, the nitrogen in the air is oxidized by the plasma to become NO2. The NO2, by dissolving in water, turns to HNO2 or HNO3, which reduces the pH value as a result. In addition, since dissolved nitrogen included in the water is also oxidized under the influence of the plasma, a slight reduction in pH is caused even with the plasma exposure in an atmosphere that does not contain nitrogen. However, the reduction in pH from this kind of cause is not constant due to a change in the environment in which the plasma is used or a change in volume of an object to be sterilized. Therefore, it is difficult to define the sterilization time. Further, when compared with the case in which the pH is adjusted at 3.5 in advance, it is confirmed by the experiment that it takes longer time for achieving sterilization. Above all, the reduction in pH caused by NOx− does not influence the effect of enhancement in microbiocidal activity of a buffer solution having a pH value adjusted at 4.8 or lower in advance.
Other than what is described above, it is found that H2O2 is also generated as a result of a reaction between oxygen and water with plasma exposure. However, the amount of H2O2 thus generated under the condition of the sterilization experiment is merely 50 mg/1 at the maximum, which is not such a concentration that affects the sterilization effect. In addition, the amount of produced H202 is constant regardless of the pH value.
(V) Conclusion
(1) Synergistic Effect Between pH Adjustment and Sterilization by Plasma
Sterilization by plasma can be divided into two cases, i.e., (a) the plasma directly exerts influences on microorganisms, and (b) active species such as radicals that are generated secondarily exert influences.
In the case of (a), the plasma barely works in the liquid and on a target that has a complicated structure. On the other hand, the active species generated secondarily can act upon the microorganisms in the liquid by dissolving therein. The superoxide anion radicals (O2−.) having a relatively longer life time in the aqueous solution are combined with the hydrogen ions (H+) to turn into the hydroperoxy radicals (HOO.) having an extremely powerful microbiocidal activity, and the concentration of which depends on the concentration of the hydrogen ions (H+), that is, pH.
Particularly, since pKa of the equilibrium reaction expressed in Formula (1) above is 4.8, a proportion of the hydroperoxy radicals (HOO.) is expected to increase in a case where pH is lower than that value. For example, in the case where the pH is 4.8, the abundance ratio of the hydroperoxy radicals (HOO.) to the superoxide anion radicals (O2−.) is 1 to 1. However, the ratio becomes 2 to 1 at a pH value of 4.5 and 20 to 1 at a pH value of 3.5. In this way, the abundance ratio of the hydroperoxy radicals (HOO.) having a strong microbiocidal activity increases depending on the pH value.
Accordingly, it is possible to significantly increase the microbiocidal activity by plasma by adjusting pH of a liquid at 4.8 or lower (ideally at 3.5 or lower) when the liquid or a target in the liquid is sterilized by bringing the plasma into contact with the liquid. Further, the chemical agents used for adjusting the pH are not particularly limited, and such chemical agents are not required at all to have a microbiocidal activity or oxidizability.
In the Second Embodiment described hereinafter, a description will be given of an example in which the sterilization method is applied to a living body.
Here, microorganisms present on a surface of a living body or in the vicinity thereof are sterilized. Such a sterilization method is implemented by a step of applying a liquid having a pH value of 4.8 or lower to the surface of the living body and a step of exposing a liquid present on the surface of the living body to low-temperature plasma. Hereinafter, a description will be given of a method for sterilizing wounds of a human body by using a gel-patch.
More often than not, a wound with seriously damaged skin by burn or bedsore is accompanied by infection. It is possible to sterilize such a wound, without using a bactericide or an antibiotic, by exposing the wound to the LF plasma jet. In doing so, by applying an acidic liquid to the human body beforehand, effective sterilization is expected, and a sterilization effect not only on the surface of the skin but also inside is expected. The following method is used to prevent the human body from the influence exerted by the plasma.
As illustrated in
The gelatin sheet 21 is produced by, for example, dissolving gelatin in an acidic aqueous solution having a pH value of about 2-4.5 and molding the resultant into a sheet having a thickness of about one to a few millimeters. With this gelatin sheet 21, a liquid having a adjusted pH value is applied to the surface of the living body ST. It is also possible to use such a gelatin sheet available on the market for medical use.
When the gelatin sheet 21 is exposed to the plasma PM, superoxide anion radicals (O2−.) are supplied and accompanied by the reaction expressed in Formula (1) in the gelatin sheet 21. As a result, hydroperoxy radicals (HOO.) are produced with which the microorganisms in the wound KS are sterilized efficiently. The plasma exposure may be performed, for example, for a period of about one to a few minutes, which enables the sterilization of the wound within a short period of time.
Alternatively, as a method for applying an acidic liquid to the wound KS, an acidic aqueous solution having a pH value of about 2 to 4.5 may be applied to the wound KS by a brush in lieu of or together with the gelatin sheet 21.
Although the acidic aqueous solution may be applied in advance, an acidic material may be gradually applied in a form of a liquid or a gas though a tip of a pen or the like during the operation.
Alternatively, a rolled sheet moistened with an acidic liquid is applied to the wound KS, and the wound KS is exposed to the plasma indirectly through the rolled sheet. Here, the rolled sheet is arranged to be sequentially fed so that a fresh sheet is used at any time.
In the third embodiment, a description will be given of a method for performing sterilization after turning a tooth, dental pulp, or gum acidic.
The sterilization method adopting adjustment of pH and the plasma PM is applicable not only to simple sterilization of the skin surface but also a dental treatment. It is recognized that what is required is complete sterilization but not normal microbiocidal treatment of a tooth, dental pulp, or gum. Conventionally, sterilization is performed using chemical agents, which causes a postoperative infectious disease due to insufficient sterilization. In contrast, a new completely sterilizing effect is expected from the sterilization using the pH adjustment and the plasma PM.
Specifically, the pH value of the tooth, dental pulp, or gum is adjusted to become acidic, and the plasma is emitted thereto. For example, an acidic aqueous solution having a pH value of about 2-4.5 is coated or injected to or around the tooth, dental pulp, or gum, or the acidic aqueous solution is used for gargling to turn these areas acidic.
When the tooth, dental pulp, or gum is exposed to the plasma PM, hydroperoxy radicals (HOO.) are produced on or around the tooth, dental pulp, or gum, which performs complete sterilization.
If necessary, sterilized water is used for rinsing, and thereafter the tooth, the dental pulp, or the like is sealed to complete the treatment.
Next, a sterilization apparatus 1B used for dental treatment will be described.
When the plasma generation device 12 is used to perform sterilization, there is a possibility that a toxic gas such as ozone or NOx is generated as a byproduct along with generation of the plasma PM. This means that, when the sterilization method according to the present embodiment is applied near someone's presence, it is necessary to provide a device for exhausting such gases. Particularly, when the method is applied to the dental treatment or the like, plasma processing is performed in the oral cavity of a patient. Therefore, it is necessary to enclose a portion subjected to the plasma processing so that the toxic gas does not leak into the oral cavity.
With reference to
The plasma generation device 12 generates the plasma PM within the housing 15. The timing at which the plasma PM is generated is controlled by means of an unillustrated control mechanism automatically or based on the instructions of the operator.
The housing 15 has a container-like shape having, at one portion thereof, an opening 15a so that a surface of a part of a tooth HA to be targeted is surrounded and hermetically enclosed. Although the opening 15a should be shaped in accordance with a shape of the tooth HA, a periphery of a body portion 15b may be arranged in a cylindrical shape, a rectangular envelope shape, a spherical shape, or the like. The housing 15 may be formed by molding using such a material as a synthetic resin or glass.
The seal member 16 is provided in the opening 15a of the housing 15 and seals a gap between the opening 15a and the tooth HA to maintain airtightness of the housing 15. The seal member 16 may be produced using silicon rubber, other synthetic rubber, synthetic resin, or the like. An O-ring, another type of sealing member, or a gasket may be used as the seal member 16. It is also possible to form the housing 15 integrally with the seal member 16.
The atmospheric gas introduction pipe line 17a is a pipe line for introducing an atmospheric gas containing nitrogen gas into the housing 15. An amount of the atmospheric gas, timing at which the gas is introduced, or the like through the atmospheric gas introduction pipe line 17a is controlled by means of an unillustrated atmospheric gas control mechanism automatically or based on the instructions of the operator.
The gas exhausting pipe line 17b is a pipe line for exhausting the atmospheric gas inside the housing 15 to outside. It is possible to use a flexible tube made of a synthetic resin or a synthetic rubber for the atmospheric gas introduction pipe line 17a and the gas exhausting pipe line 17b.
The pH adjustment pipe line 18 is a pipe line for feeding a pH adjustment substance so that at least a part of the tooth HA as a target is adjusted to have a pH value of 4.8 or lower. The opening at a tip end of the pH adjustment pipe line 18 is directed toward the surface of the tooth HA to be treated. A liquid containing acid or salt, a gas such as carbonic acid gas, and other chemical agents can be used as the substance that is fed through the pH adjustment pipe line 18. If the substance used for adjusting the pH is a gas, it is preferable that the surface of the tooth HA be moistened in advance. An amount of the substance to be fed through, timing at which the gas is introduced, or the like is controlled by means of an unillustrated substance control mechanism automatically or based on the instructions of the operator.
A description will be given of how to operate the sterilization apparatus 1B and how the apparatus 1B operates.
First, while the patient keeps his/her mouth opened, the operator places the housing 15 of the sterilization apparatus 1B over the tooth HA which is a target for treatment. Then, the substance is supplied through the pH adjustment pipe line 18 and decreases the pH value of the surface of the tooth HA to 4.8 or lower. An atmospheric gas containing nitrogen gas, for example, the air, is fed into the housing 15. Along with this, the plasma PM is generated by the plasma generation device 12. The atmospheric gas, and toxic gases etc. produced by plasma processing are exhausted to outside through the gas exhausting pipe line 17b so as not to leak into the oral cavity.
Radicals produced by the plasma PM make contact with the surface of the tooth HA, and the hydroperoxy radicals (HOO.) and the peroxynitrite (ONOOH(ONOO−)) as described above are generated, which sterilize the tooth HA.
Since the plasma processing by the plasma generation device 12 is carried out in a space hermetically enclosed by the housing 15 and the seal member 16, a toxic gas, even if generated, is exhausted to outside through the gas exhausting pipe line 17b and does not leak into the oral cavity. Consequently, there is no chance of the patient to inhale the toxic gas, and, as a result, unnecessary damage caused to the respiratory system can be avoided.
In this way, by using the sterilization apparatus 1B having an airtight structure, it becomes possible to perform sterilization only on a specific part.
In the sterilization apparatus 1B described above, the pH adjustment pipe line 18 is provided, through which a substance for decreasing the pH is also supplied. However, it is also possible to provide a pipe line that can be opened and closed or merely a hole as the pH adjustment pipe line 18. Then, the operator inserts a nozzle of an injector or an atomizer into the pipe line or the hole and manually operates the injector or the atomizer to thereby feed the substance.
Alternatively, instead of providing such a dedicated pH adjustment pipe line 18 in the housing 15, a gas supply pipe 31 may be used for feeding the substance as well.
For example, in a plasma generation device 12B illustrated in
It is to be noted that how the pH adjustment pipe line 18B branches off from the gas supply pipe 31, a position and an angle of the branch, sizes of individual pipes, and so on may be decided in a diversifying manner differently from what are illustrated in
When such a plasma generation device 12B is used, the sterilization apparatus 1B is placed over the tooth HA, thereafter a substance for adjusting the pH value is supplied through the pH adjustment pipe line 18B, and then helium gas is supplied to the gas supply pipe 31 to generate the plasma PM.
It is also possible for the operator to supply the substance for adjusting the pH value without providing such pH adjustment pipe lines 18 or 18B. For example, a liquid having a pH value of 4.5 or lower is infiltrated in absorbent cotton and applied to the tooth HA. Alternatively, a liquid or a gas for adjusting the pH is sprayed onto the tooth HA using an atomizer or the like. Thereafter, the sterilization apparatus 1B is placed over the tooth HA, and plasma processing is performed.
Hereinbefore, the description has been given of a case in which the target of the sterilization apparatus 1B is the tooth HA. It is also possible to arrange a biological part other than the tooth HA or a non-biological object as the target.
In the fourth embodiment, a description will be given of a method for performing sterilization by applying an acidic liquid to medical devices.
As illustrated in
With this arrangement, hydroperoxy radicals (HOO.) are produced on a surface of the device KK to thereby sterilize the device KK.
It is also possible to mix polymers into an acidic liquid to increase the viscosity thereof and pectize it so as to prevent the acidic liquid from diffusing from the device KK. The resultant can also be applied. Alternatively, in order to generate an acidity state on the surface of the device KK, the acidic liquid may be sprayed thereto using an atomizer, or the device KK may be immersed in the acidic liquid for a predetermined period of time.
In the fifth embodiment, a description will be given of a method for performing sterilization while a medical device is immersed in an acidic liquid.
As illustrated in
With this arrangement, hydroperoxy radicals (HOO.) are produced in the liquid LQ, and sterilization of the device KK is performed.
The plasma generation device 12E is filled with helium gas and a mixed gas containing small amounts of nitrogen and oxygen. Therefore, the plasma PM with helium gas serving as a medium gas is generated. However, other gasses than the helium gas may be used. It is preferable that the depth of the container YK be shallow so that the hydroperoxy radicals (HOO.) produced in the liquid LQ by the action of plasma PM can sufficiently reach the surface of the device KK. However, even with a substantial depth, sufficient agitation compensates it.
Hereinbefore, the first to fifth embodiments have been described. Hereinafter, various variation examples of the elements or examples of applications that can be applied to these embodiments or other types of embodiments will be described.
[Sterilization Utilizing Neutral Helium Metastable to Prevent Electric Current from Being Caused by Charged Particles]
Instead of directly exposing an acidic liquid to plasma, the liquid is exposed to metastable atoms that are in a metastable state of a noble gas such as helium to thereby promote generation of radicals in the liquid. When the LF plasma jet is used, charged plasma particles themselves are prevented from being emitted by using an electrode arrangement adopted for a so-called reverse jet so that unnecessary damage caused to human cells is reduced. The reverse jet is produced by arranging a ground electrode in the vicinity of a plasma jetting port so that an electric field does not leak outside. By this arrangement, unnecessary emission of charged particles can be controlled.
Oxygen-based radicals exerting sterilization ability are generated when the metastable collides with oxygen molecules or water molecules in the air.
Further, by mixing a small amount of oxygen gas or nitrogen gas into a plasma-generating gas in the reverse jet, various types of radicals are generated in a plasma discharging portion. The liquid is exposed to only these radicals to make it a safer type of discharge.
[Shape of a Chamber of a Plasma Generation Device]
A chamber of a plasma generation device 12F has a shape as illustrated in
Referring to
Such a structure using the three pipes provides relatively a better efficiency. Since the helium having a low concentration tends to stay in an upper portion of the chamber 41, it is possible to reduce the consumption of the relatively expensive helium. When an application to a human body is taken into account, the interface portion of the chamber 41, i.e., a contact portion located in the lowest position thereof, is made to have a soft structure using a silicone resin or the like so that air tightness is also maintained.
[Surgical Instruments]
There is a method to perform sterilization by drawing a vacuum and generating the plasma. In implementing such a method, an enhanced sterilization effect is expected when an acidic solution is applied. However, the pressure should be kept at a saturated vapor pressure of water or higher.
[Liquid Sterilization]
In each embodiment, sterilization is performed by bringing the plasma PM into contact with a liquid having a adjusted pH value.
When liquid sterilization is performed, the liquid is treated to become acid, and then discharges made available at a low cost such as spark discharges, arc discharges, or impulse discharges are performed. Through this process, an enhanced liquid sterilization performance is expected. This type of sterilization method is applicable to sewage treatment or the like.
[pH Adjustment by Carbonic Acid Gas]
The carbonic acid gas (carbon dioxide) is harmless to human body. Therefore, it is possible to perform neutralization treatment on a liquid, which has been subjected to a pH adjustment process, by using the carbonic acid gas dissolved in a liquid and merely leaving the liquid as is.
Usually, distilled water turns into an equilibrium state when the carbonic acid gas in the air dissolves thereinto, and maintains a pH value of approximately 5.6. However, it is possible to temporarily lower the pH value of the solution by actively dissolving the carbonic acid gas thereinto.
It is also possible to maintain the concentration of carbonate ions in the solution at a high level by generating the plasma under an atmosphere of a high carbonic acid gas concentration (a few percent to a few dozen percent of the carbonic acid gas concentration). In this case, it is not necessary to use a pressurized container because the partial pressure of the carbonic acid gas can be simply raised.
When the pH value is lowered by the carbonic acid gas, the pH value of the liquid that has been subjected to the sterilization process rises by itself to a pH value of 5.6 by allowing the liquid to make contact with the air. This method provides an advantage in that an object that has been sterilized in the liquid does not require a cleaning process again because chemical agents will never stay even after drying.
[pH Adjustment Method]
The form of a chemical agent for adjusting the pH is not particularly important. For example, if it is solid such as citric acid, it may be charged into the liquid as is and dissolved. Alternatively, it is also possible to add such a solution that has been prepared by adjusting the pH. Further, it is also possible to use a gas such as the carbonic acid gas which can dissolve in the water and function to lower the pH, and it is possible to lower the pH by actively dissolving the chemical agent or placing the liquid in the high concentration gas atmosphere.
If the object to be sterilized is not a liquid (or in a liquid), the pH value on the surface of the object is adjusted by applying or spraying a liquid having a adjusted pH value onto the surface.
When the acidic liquid is sprayed, spraying can be divided and performed in multiple times so as to prevent the acidic liquid from evaporating. When the object is made contact with the plasma PM in the chamber, the acidic liquid is supplied by spraying in a form of droplets while the plasma PM is generated. Additional spraying is performed as required while the plasma PM is generated.
Although an acidic liquid having a adjusted pH value is used in each embodiment, it is also possible to generate the plasma PM to perform sterilization and, at the same time, increase the pH of the liquid by decomposing the acidic substances.
For example, it can be arranged to increase the pH value to an appropriate value, e.g., 5.0 or higher when a liquid having a pH value of 3.0 is used, sterilization is performed by emitting the plasma PM for a predetermined period of time, and the sterilization is completed as the predetermined period has elapsed. In this way, by the time the sterilization is completed, the liquid has turned almost neutral and can be disposed of as is.
[LF Plasma Jet]
A description will be given of the LF plasma jet that is used throughout the present embodiment.
In
The gas supply pipe 31 is formed of a dielectric such as a quartz pipe or a plastic tube and has a rear end thereof to which the gas tube 32 is connected. For example, helium (He) gas is supplied from an unillustrated medium gas source. The helium gas that has passed through a bore of the gas supply pipe 31 is jetted out from a jet port 31a to constitute a gas stream generating portion for forming a gas stream of a medium gas. A pipe having, for example, an inner diameter of 50 μm to 50 mm can be used as the gas supply pipe 31.
A coaxial single high-potential electrode 33 for generating plasma is provided on an outer circumference of an end portion on a side of the jet port 31a of the gas supply pipe 31. A voltage applying device 34 is connected to the high-potential electrode 33 to which a positive voltage in a form of pulse train having a predetermined frequency is applied. The voltage value to be applied by the voltage applying device 34 is set, for example, at 10 kV, and the frequency is set, for example, at about 10 kHz. With this arrangement, a non-equilibrium plasma jet PMJ that extends in an elongated shape from the jet port 31a is generated. This plasma jet PMJ is the LF plasma jet.
Thus, as represented by a broken line in
In order to generate a plasma stream limited in a medium only by partial discharge, the gas supply pipe 31 and the gas tube 32 function as a gas stream generating portion that generates a medium gas flux, and the high-potential electrode 33 and the voltage applying device 34 function as an electric field forming portion that forms an electric field corresponding to each medium gas stream.
It is also possible to provide an on-off valve that allows or prohibits passage of the helium gas in a junction portion between the gas supply pipe 31 and the gas tube 32 or in other portions. In addition, as described previously, it is also possible to provide a branch-off pipe line or a passage changeover valve to the gas supply pipe 31 in order to supply a plurality of types of fluids to the object by using the gas supply pipe 31.
The voltage applying device 34 applies a positive voltage in a form of pulse train having a predetermined frequency to the high-potential electrode 33. The voltage applying device 34 outputs, for example, a voltage having a waveform as illustrated in
Although helium gas is preferred as a medium gas, another gas may also be used as long as conditions are set appropriately. For example, a mixed gas of argon and ketone also can be used. Further, various processes can be performed by supplying vapor of a chemical agent such as a monomer, or an aerosol such as sprayed mist or fine particles.
The LF plasma jet is a thermally non-equilibrium low-temperature plasma, which can be emitted to a base material such as thin nylon without causing any damage thereto but has energy sufficient for effecting a surface treatment, ozone generation, and a plasma polymerization.
It is also possible to provide a plurality of the high-potential electrodes 33 arranged for a single medium gas flow. By providing an arrangement for generating only a partial discharge, an increase in power consumption resulted from short-circuit discharges can be suppressed, and energy conversion efficiency can be improved, as compared with a conventional coaxial bi-electrode system. Furthermore, it is possible to eliminate an electrode on the ground side whose contribution to the generation of a plasma jet is small and therefore simplify the device. Even with a single high-potential electrode, it is easy to start the generation of the plasma jet PMJ.
Furthermore, according to a method for generating plasma in a space region limited in a medium by a medium gas flux, any medium gas flux is ionized to become plasma stably by causing only a partial discharge. The ignition of plasma can be realized on a wide scale of about 50 μm to 50 mm, and an increase in an aperture size is also possible in principle, using the above procedure.
According to the plasma generation device 12, only a high voltage in a form of pulse train is applied to the high-potential electrode 33 connected to the gas supply pipe 31 through which the medium gas flows, whereby a partial discharge is allowed to occur along the medium gas stream diffused from the gas supply pipe 31 to the atmosphere, which can generate a plasma stream. An example of configuring various conditions for the generation of a plasma stream is described hereinafter.
Medium gas: helium gas
Furthermore, even using an electrode, e.g., width of 2 mm and length of 50 mm, having no plane closed in a rotation angle direction with respect to a medium gas flux, i.e., electrode covering only a part, plasma can be generated by partial discharge.
The LF plasma jet has two characteristics: “generation of a gas flux in the atmosphere” and “partial discharge in the vicinity of a high-potential electrode”. Although discharge is allowed to occur by applying a periodic high voltage, plasma parameters can be controlled not only by the applied voltage but also by the applied frequency. In addition to these, the parameters of plasma to be generated can be also controlled by controlling the waveform (polarity) of a high voltage to be applied.
The polarity of the high voltage that is being applied determines the densities and temperature distribution of ions, electrons, metastable atoms, and the like which are all generated from the plasma, and the plasma itself. Positive corona discharge occurs in the case of a positive voltage, and negative corona discharge occurs in the case of a negative voltage. The positive corona discharge and the negative corona discharge have different physical discharge mechanisms, so that the plasma production state varies. Thus, using the plasma while individual polarities are controlled makes it possible to control the effect of plasma on an object which is exposed to the plasma. On the other hand, in the case of
By controlling the applied waveforms of positive and negative high voltages in combination and thereby generating the plasma jets with different parameters, it is expected that selective promotion of chemical reactions can be performed.
It is desired that the voltage applying device 34 be configured so as to change the peak value of an applied voltage at a time of the ignition of plasma and the peak value of an applied voltage at a time of maintaining generation of plasma, as shown in
Furthermore, the high-potential electrode 33 is not always required to be provided coaxially on the outer circumferential surface of the gas supply pipe 31. The LF plasma jet can be generated even with an electrode attached to a part of the outer circumferential surface or inner circumferential surface of the gas supply pipe 31. More specifically, it is preferred that an electrode be attached to the inner surface or the outer surface of a member made of a dielectric for forming a medium gas stream, and that the dielectric and the electrode be integrally structured. When an electrode is attached to the inner surface of a member made of a dielectric, medium gas comes into contact with both the dielectric and the electrode.
Furthermore, the medium gas does not necessarily form a stream. This means that it is also possible to configure a plasma generation device so as to generate plasma from a medium gas mass. In this case, an electric field forming portion that forms an electric field in a medium gas mass is provided. If the medium gas mass has an elongated shape, an electric field is formed so as to cause partial discharges from the electric field forming portion toward both directions in the longitudinal direction of the medium gas mass. The medium gas mass may be arranged in such a manner that the medium gas is sealed in a tube provided with an electrode. Even in this case, the electrode may be provided either on the inner surface or the outer surface of the tube.
Alternatively, a needle may be fitted to the vicinity of the nozzle aperture for the j et and used as an electrode. In addition, when the plasma PM is generated in the liquid LQ, the plasma PM can be generated while the electrolysis of a liquid is performed at the same time by applying, to the electrode provided in the liquid LQ, a voltage resulted from superimposing a voltage required for generation of the plasma PM on a DC voltage required for performing electrolysis.
Sterilization is performed by exposing microorganisms to plasma in the gas phase according to the conventional sterilization by plasma. However, according to the sterilization in the liquid, it is difficult for active species of the plasma to penetrate into the liquid, resulting in an extremely low sterilization effect. Against this kind of problem, according to each embodiment described above, it is possible to significantly increase the microbiocidal activity by merely adjusting the pH value without involving use of particular chemical agents.
The embodiments provide significantly high practicality because, particularly, it is not necessary to exhaust gas for arranging a vacuum environment as conventionally required, but the atmospheric pressure serves for the purpose.
For example, each embodiment is expected to be applied not only to the sterilization of the medical equipment immediately before the surgical operation but also as a surgical tool for disinfecting human body. In surgical operations, complete sterilization of human organs is practically impossible, and overall sterilization is performed by such measures as administrating antibiotics. In contrast, since the sterilization performed by emitting the plasma jet works only on a part exposed to air, it is possible to perform sterilization in an appropriate area.
As described above, the sterilization of a liquid using the chamber can not be applied in a conventional method, whereas, in this embodiment, it becomes possible.
Finally, in each embodiment described above, the configurations of all or part of the plasma generation devices 12, 12B, 12E, and 12F, the container YK, the liquid LQ, the gelatin sheet 21, the sterilization apparatuses 1 and 1B, and other elements, shapes, dimensions, quantities, materials, voltage waveforms, periods, temperatures, types of gasses, and so on can be arbitrarily modified in various ways within the spirit of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2007-251194 | Sep 2007 | JP | national |
This application is a continuation of U.S. application Ser. No. 12/680,018 filed on Mar. 25, 2010, which is a U.S. national stage application of International Application No. PCT/JP2008/002670 filed on Sep. 25, 2008 and which claims priority to Japanese Application No. 2007-251194 filed on Sep. 27, 2007, the entire contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12680018 | Mar 2010 | US |
| Child | 12771088 | US |
