阅读说明：本技术 一种恢复/增强等离子体活化溶液化学活性的方法 (Method for restoring/enhancing chemical activity of plasma activation solution ) 是由 刘志杰 王思韬 庞波伦 高钰婷 孔刚玉 于 2020-12-10 设计创作，主要内容包括：本发明提出一种恢复/增强等离子体活化溶液化学活性的方法。该方法是取保存的活性已出现衰减的等离子体活化液,进行二次活化处理,使其理化特性和活性氧氮粒子浓度恢复或超过保存前的水平；其中,二次活化处理时所取的待处理活化液,其已存储时间最好不要超过7天。本发明不仅提升了等离子体活化液的实用性和有效性,而且有利于等离子体技术领域的产品商业化,在等离子体生物医学临床应用领域有着重大意义。(The invention provides a method for restoring/enhancing the chemical activity of a plasma activation solution. The method comprises the steps of taking a plasma activating solution with attenuated preserved activity, and carrying out secondary activation treatment to restore or exceed the physical and chemical properties and the concentration of active oxygen nitrogen particles to the level before preservation; wherein, the activating solution to be treated taken in the second activating treatment is stored for a period of time preferably not longer than 7 days. The invention not only improves the practicability and effectiveness of the plasma activating liquid, but also is beneficial to the commercialization of products in the technical field of plasma, and has great significance in the field of plasma biomedical clinical application.)

1. A method for restoring/enhancing the chemical activity of a plasma activation solution, characterized in that a plasma activation solution in which the activity of the plasma activation solution has been reduced is taken out and subjected to a secondary activation treatment to restore or exceed the physicochemical properties and the concentration of active oxygen nitrogen particles to the level before the plasma activation solution is stored.

2. The method according to claim 1, wherein if the plasma activation solution is stored under a sealed condition at room temperature after the primary activation treatment, the interval between the primary activation treatment and the secondary activation treatment is more than half an hour and less than 7 days.

3. The method of claim 2, wherein the plasma activating solution with a decreased activity is stored under a normal temperature and sealed condition for 1 day after one activation treatment.

4. A method of restoring/enhancing chemical activity to a plasma activated solution as recited in claim 1, wherein the stored plasma activated solution has a decaying ORP value of 550mV or greater.

5. A method of restoring/enhancing chemical activity of a plasma activating solution as claimed in claim 1, wherein the secondary activating treatment is performed under a lower condition than the previous activating treatment of the plasma activating solution to be treated, the lower condition including a lower discharge voltage, a shorter discharge time, a cheaper working gas and/or a more simply structured cold plasma generating device.

6. A method for restoring/enhancing chemical activity of a plasma activating solution as claimed in claim 5, wherein said more simply constructed cold plasma generating device is a creeping discharge device, a fluidic device or a liquid phase discharge plasma generating device.

7. A method for restoring/enhancing chemical activity of a plasma activating solution as claimed in claim 5, wherein the same cold plasma generating device is used, and the secondary activating discharge time is 3/4 times of the primary activating discharge time under the discharge voltage of 13 kV.

8. A preparation method of a plasma activating liquid is characterized by comprising the following steps:

step 1) carrying out primary activation treatment on a solution to be treated by using a cold plasma generating device;

step 2) after the primary activation is stopped, sealing and storing the obtained activation liquid; if the product is stored at normal temperature, the storage time is not more than 7 days;

and 3) carrying out secondary activation treatment on the stored activation solution by using a cold plasma generating device to obtain the activation solution with better physicochemical properties and active oxygen nitrogen particle concentration than those of the activation solution subjected to the primary activation treatment.

9. A control apparatus for preparing a plasma activating liquid, comprising a processor and a memory, the memory storing a program, wherein the program when loaded and executed by the processor implements the steps of:

step 1) controlling a cold plasma generating device to perform primary activation treatment on a solution to be treated;

step 2) controlling the cold plasma generating device to stop working and waiting for a set interval time;

and 3) controlling the cold plasma generating device to perform secondary activation treatment on the solution after the primary activation treatment after the set interval time is up, so as to obtain an activated solution with better physicochemical properties and active oxygen nitrogen particle concentration than those after the primary activation treatment.

10. The control device as claimed in claim 8, wherein the time for the primary activation treatment in step 1) is 100-200 seconds, the time interval set in step 2) is 1-6 days, and the time for the secondary activation treatment in step 3) is 90-150 seconds.

Technical Field

The invention relates to the technical field of plasmas, in particular to a method for restoring/enhancing chemical activity of a plasma activation solution.

Background

The plasma activating solution is a green disinfectant prepared by processing liquid solution (such as deionized water, physiological saline and PBS solution) with atmospheric pressure cold plasma, and has low pH value and high oxidation-reduction potential. The generation of the plasma activating liquid is a complex chemical process under the coupling of multiple physical fields. On one hand, a plurality of physical fields including an electromagnetic field, a temperature field, a density field and an air flow field generated by the plasma act on the treated aqueous solution; on the other hand, plasma generationProducts such as sex particles and the like undergo a complicated chemical reaction with the aqueous solution to be treated, thereby generating a large amount of liquid phase active oxygen nitrogen particles (RONS) in the solution, such as: OH, O₂ ^-、O₃、H₂O₂、NO₂ ^-、NO₃ ^-And ONOO^-And the like. The antimicrobial effect of the plasma activation fluid may be attributed to the synergistic effect of the acidified solution environment and the concentration of active oxygen nitrogen particles. The active oxygen-nitrogen particles play an important role in the biological effect of the plasma activation liquid, and can interact with main targets such as DNA, RNA, protein, lipid and the like to induce the increase of the intracellular active oxygen level of bacteria, generate oxidative stress and finally cause the death of the bacteria cells.

However, since the active oxygen-nitrogen particles have the characteristics of short life and rapid reaction, and the concentration of the active particles rapidly decreases in a short storage time, the chemical activity of the plasma activation liquid rapidly decreases with time, and even after a certain period of storage and application, the plasma activation liquid degrades back to pure water, and the application effect thereof in the biomedical field is lost.

At present, aiming at the activity of the plasma activating solution, a plurality of researchers propose to improve the chemical activity of the plasma activating solution and slow down the decay rate of active particles by changing the conductivity of the solution, regulating and controlling discharge parameters, reducing the temperature and the like. However, the conventional means cannot maintain the chemical activity of the plasma activating liquid at all, and cannot prolong the effective time of the activating liquid. In clinical application, the plasma activating solution may not meet the use requirement of the application due to the attenuation of chemical activity, thereby limiting the practical application of the plasma activating solution in the biomedical field.

Disclosure of Invention

The invention aims to solve the problem that the plasma activation solution cannot meet the use requirement of application due to the attenuation of chemical activity in the storage process in the clinical application process, and provides a method for recovering/enhancing the chemical activity of the plasma activation solution.

The inventive concept of the present application is as follows:

the current research shows that the chemical activity of the plasma activating liquid is rapidly reduced along with the increase of the storage time. The conventional method is to enhance the chemical activity of the plasma by regulating the conditions during plasma treatment (increasing the discharge power and the discharge time) or to prolong the effectiveness of the chemical activity by changing the storage conditions (reducing the storage temperature, alkaline solution environment). However, the applicant realizes that the activity of the plasma activating liquid still shows a rapid descending trend, and the plasma activating liquid is finally abandoned due to the loss of the original chemical activity and biological effect, thereby limiting the effectiveness and the practicability in clinical application. By carrying out secondary activation treatment on the plasma activation liquid with the activity already attenuated and carrying out experimental analysis, the applicant finds and defines that: by the secondary activation method, the chemical activity of the plasma activating liquid can be quickly restored to the level before storage under lower processing conditions (lower discharge voltage, shorter discharge time and the like), and the plasma activating liquid can also have higher chemical activity and RONS concentration.

The technical scheme of the application is as follows:

a method for restoring/enhancing the chemical activity of a plasma activation solution is characterized in that a plasma activation solution, the activity of which has been reduced, is taken out and subjected to secondary activation treatment to restore or exceed the physical and chemical properties and the concentration of active oxygen nitrogen particles to the level before storage.

Here, "secondary activation treatment" is intended to emphasize that the solution to be treated is a plasma activation liquid whose preserved activity has been attenuated, and the solution to be treated is not limited to a plasma activation liquid that has been subjected to only one treatment, but may be a plasma activation liquid that has been subjected to a plurality of activation treatments. The phrase "exceeding the level before preservation" as used herein mainly refers to the achievement of a lower pH (acidified environment), a higher ORP (oxidation-reduction potential), and a higher concentration of liquid-phase active oxygen nitrogen particles (RONS). The cold plasma generation apparatus and the treatment conditions in the secondary activation treatment may be the same as or different from those used in the previous treatment.

In the process from the first activation treatment to the second activation treatment, the plasma activation liquid may be transferred, or the plasma activation liquid may be left standing in situ.

Alternatively, if the plasma activation solution is stored under a normal temperature sealing condition after the primary activation treatment, the interval time between the primary activation treatment and the secondary activation treatment is half an hour or more and not more than 7 days. That is, if the storage is performed at a lower temperature, the allowable interval time can be longer. It is recommended to perform the secondary activation treatment when the ORP value of the plasma activation liquid is 550mV or more.

Further optionally, the plasma activating solution may be selected to be stored for 1 day under a normal temperature sealing condition after one activation treatment.

Optionally, the treatment conditions of the secondary activation treatment are lower than those of the plasma activation liquid to be treated, and the lower treatment conditions comprise lower discharge voltage, shorter discharge time, cheaper working gas and/or a cold plasma generating device with simpler structure.

Optionally, the cold plasma generating device with a simpler structure adopts a creeping discharge device, a jet device or a liquid phase discharge plasma generating device.

Illustratively, the secondary activation discharge time is 3/4 of the primary activation discharge time at a discharge voltage of 13kV using the same cold plasma generating device.

Correspondingly, the application also provides a preparation method of the plasma activating liquid, which comprises the following steps:

step 1) carrying out primary activation treatment on a solution to be treated by using a cold plasma generating device;

step 2) after the primary activation is stopped, sealing and storing the obtained activation liquid; if the product is stored at normal temperature, the storage time is not more than 7 days;

and 3) carrying out secondary activation treatment on the stored activation solution by using a cold plasma generating device to obtain the activation solution with better physicochemical properties and active oxygen nitrogen particle concentration than those of the activation solution subjected to the primary activation treatment.

Correspondingly, the present application also proposes a control device for preparing a plasma activating liquid, comprising a processor and a memory, wherein the memory stores a program, and is characterized in that the program implements the following steps when the program is loaded and run by the processor:

step 1) controlling a cold plasma generating device to perform primary activation treatment on a solution to be treated;

step 2) controlling the cold plasma generating device to stop working and waiting for a set interval time;

and 3) controlling the cold plasma generating device to perform secondary activation treatment on the solution after the primary activation treatment after the set interval time is up, so as to obtain an activated solution with better physicochemical properties and active oxygen nitrogen particle concentration than those after the primary activation treatment.

Illustratively, the time of the primary activation treatment in the step 1) is 100-200 seconds, the time interval set in the step 2) is 1-6 days, and the time of the secondary activation treatment in the step 3) is 90-150 seconds.

The invention has the following advantages:

(1) by adopting the method and the device, the chemical activity of the plasma activating liquid with attenuated activity can be quickly recovered/enhanced.

(2) Based on the invention, the plasma activating solution can be produced in a large scale and in a centralized way, and is subpackaged, stored and transported; then, in a specific clinical application occasion, according to the actual application needs, a simpler cold plasma generation module is adopted to carry out secondary activation treatment so as to achieve the required clinical application effect. The method not only improves the practicability and effectiveness of the plasma activating solution, but also is beneficial to the commercialization of products in the technical field of plasma, and has great significance in the field of plasma biomedical clinical application.

(3) The method is simple and easy to operate, and correspondingly reduces the cost of the preparation and transportation process of the plasma activating solution.

(4) The present invention also enables to industrially produce a plasma activation solution having excellent physicochemical properties and active oxygen and nitrogen particle concentration with high efficiency in a production control mode of secondary activation.

Drawings

FIG. 1 is a schematic view showing an embodiment of a method for preparing a plasma activation liquid by secondary activation according to the present invention; 100-plasma generation module for first plasma treatment by using creeping discharge structure; 200-a solution to be treated; 300-storage container (15mL centrifuge tube); 400-plasma generation module for secondary activation using creeping discharge structure; 500-plasma activating liquid to be processed after storage.

FIG. 2 shows the physical and chemical parameters and the growth range of the solution to be treated after 120 seconds of treatment, 24 hours of storage at room temperature after one treatment, 300 seconds of continuous treatment (after 120 seconds of treatment and 24 hours of storage), at different times of secondary activation treatment, wherein FIG. 2(a) corresponds to the pH value and FIG. 2(b) corresponds to the ORP value.

FIG. 3 is a graph showing the concentration and growth of active oxygen and nitrogen particles in liquid phase at different time periods of the second activation treatment (after 120 seconds of treatment and 24 hours of storage) after 120 seconds of the first treatment, 24 hours of storage at room temperature after the first treatment, 300 seconds of continuous treatment, and FIG. 3(a) is a graph showing the concentration and growth of active oxygen and nitrogen particles in liquid phase corresponding to ONOO^-And O₂ ^-The concentration of (b) in FIG. 3 corresponds to H₂O₂The concentration of (c) in FIG. 3 corresponds to NO₂ ^-The concentration of (2).

FIG. 4 shows the magnitude of the physicochemical parameters and the magnitude of the increase of the solution after the secondary activation treatment with a voltage of 13kV for 90 seconds, wherein FIG. 4(a) corresponds to the magnitude of pH value, and FIG. 4(b) corresponds to the magnitude of ORP, for the solution stored at room temperature for different days.

FIG. 5 is a graph showing the concentration and growth of active oxygen and nitrogen particles in different liquid phases of the solution after the solution stored at room temperature for 90 seconds is subjected to secondary activation treatment at a voltage of 13kV, wherein FIG. 5(a) corresponds to the concentration of ONOO-and O2-, FIG. 5(b) corresponds to the concentration of H2O2, and FIG. 5(c) corresponds to the concentration of NO 2-.

Detailed Description

The present application will be described in further detail below by way of examples with reference to the accompanying drawings. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention, nor are the inventors' specific development procedures limited thereto.

As shown in fig. 1, the system for preparing the plasma activating solution mainly comprises a cold plasma generating module with a surface discharge structure and a container containing a solution to be treated, wherein a high-voltage electrode and a ground electrode are respectively connected to two sides of an insulating dielectric plate to form the cold plasma generating module for dielectric barrier discharge. Under the action of high-voltage discharge, cold plasma is generated in the air gap and then enters the solution to be treated, so that the solution is subjected to change of physical and chemical parameters and a large amount of active oxygen and nitrogen particles are generated.

The atmospheric pressure cold plasma generation module can be formed by connecting one or more discharge devices in parallel, and is favorable for carrying out large-volume treatment on the solution to be treated. The power supply of the atmospheric pressure cold plasma generation module can select a high-voltage sine power supply or a high-voltage pulse power supply. The specific operation of activating the solution by using the cold plasma generation module can follow the conventional operation method. The solution to be treated for the first treatment can be selected from deionized water, ultrapure water, double distilled water, NaOH solution, ultrapure water containing ethanol and the like.

The obtained plasma activated solution can be moved into a storage container for storage and transportation. For example, a simple centrifuge tube is used for storage, other storage containers can be selected, and even the storage container can be connected with a container containing a solution to be treated, and the generated solution automatically flows into the storage container for storage. The storage container can be stored and transported under the environment of keeping out light or low temperature.

For those skilled in the art, the specific operations of performing the plasma activation treatment and the preservation on the solution by using the cold plasma generation module belong to the conventional technical means, and therefore, the detailed description thereof is omitted.

In this embodiment, the plasma activating solution stored for a certain period of time is transferred into the activating solution container again, and the secondary activating treatment of the plasma activating solution is performed by using the cold plasma generating device to recover and enhance the chemical activity thereof.

The cold plasma generation module, the activating liquid container and the mounting structure thereof adopted in the secondary activation can be the same as or different from those in the primary activation.

The secondary activation is carried out under the following treatment conditions, for example: the volume of the solution to be treated, the discharge voltage, the discharge time, the working gas and the like can be selected differently according to application requirements and actual conditions so as to meet different clinical applications.

The second activation is to be understood in a broad sense (or, in other words, in a relative sense), that is, the activation treatment may be performed twice or more for the initial solution to be treated. Accordingly, one activation (first activation) is not necessarily the first activation in an absolute sense.

In the experiments related to fig. 2 and 3, the discharge voltage was 13kV, the discharge working gas was pure air, the solution to be treated was 5mL of deionized water, and the storage ambient temperature was room temperature.

In the bar charts shown in fig. 2 and fig. 3, the first column corresponds to the detection result of the solution to be processed after 120 seconds of primary processing, the second column corresponds to the detection result of the solution to be processed after 120 seconds of primary processing and after 24 hours of storage at room temperature, and the fourth, fifth, sixth and seventh columns respectively correspond to the detection results of the activating solution after 24 hours of storage after 60 seconds, 90 seconds, 120 seconds and 150 seconds of further processing; the third column corresponds to the test results after one continuous treatment for 300 seconds. The graph also counts the relative increase amplitude of the detection result in each case.

As can be seen from fig. 2 and 3, the plasma activated solution obtained by the primary activation treatment was allowed to stand and stored at room temperature for 24 hours, and the indices such as the pH, the ORP value (oxidation reduction potential), and the concentration of liquid-phase active oxygen nitrogen particles (RONS) were attenuated to different degrees. The secondary activation is carried out on the plasma activation liquid, the pH value of the plasma activation liquid can be further reduced, the ORP value of the plasma activation liquid can be further improved, and the longer the secondary activation time is, the stronger the chemical activity is; meanwhile, the concentration of active particles can be rapidly increased, and when the treatment time of secondary activation is longer than 1/2 of the first treatment time, the concentration of the active particles is close to the concentration before storage; when the treatment time of the secondary activation is greater than 3/4 of the first treatment time, the active particle concentration has already exceeded the pre-storage concentration and has increased substantially as the treatment time of the secondary activation increases.

As shown in the experiments, even if the first activation treatment time is longer, the concentration of liquid phase active oxygen nitrogen particles (RONS) is basically stable and reaches the same level after being stored for 24 hours at room temperature. Therefore, the scheme of the secondary activation proposed in the embodiment not only helps to quickly restore the activation solution even beyond the activity before preservation in clinic, but also can allow the activation treatment time (time of primary activation) to be shortened to some extent when the activation solution is prepared in a production line.

It is also noted that the treatment mode of the primary activation (120 seconds) + the secondary activation (150 seconds) is higher in the ORP value (oxidation reduction potential) and the concentration of liquid-phase active oxygen nitrogen particles (RONS) with a shorter total time than the treatment mode of the primary continuous treatment for 300 seconds. We analyzed that the cause (mechanism) of this phenomenon is:

(1) the solution to be treated changes from deionized water (primary activation) to plasma activated water (secondary activation), wherein the physicochemical properties of the solution have changed, for example: the more acidic liquid environment and the solution have higher oxidation-reduction potential, and the liquid environment is possibly more favorable for improving the chemical activity of the activated liquid;

(2) part of the residual active oxygen nitrogen particles still exist in the plasma activated water after storage, and the part of the residual particles is more likely to trigger chain chemical reaction when in collision contact with the low-temperature plasma.

Experiments show that the secondary activation treatment can be carried out after the primary activation treatment is placed for a short time, for example, half an hour is needed, so that the better effect of the primary continuous activation treatment can be achieved.

As can be seen from FIG. 4, the physicochemical properties of the solution after the second activation treatment were not significantly affected by standing at room temperature for different days. As can be seen from fig. 5, the standing time for 1, 3, and 5 days at room temperature does not greatly affect the concentration of active oxygen nitrogen particles in different liquid phases in the solution after the second activation treatment; however, when the standing time reaches 7 days, the increase degree of the concentration of the active oxygen nitrogen particles in different liquid phases in the solution by the secondary activation treatment is reduced. Therefore, it is recommended that the activating solution to be treated, which is taken at the time of the second activation treatment, be stored for a period of time not exceeding 7 days.

Of course, the time allowed for the interval may be longer if kept at a lower temperature. During the process from the first activation treatment to the second activation treatment, the plasma activation liquid (as shown in fig. 1) may be transferred, or the plasma activation liquid may be left standing in situ. From the parameter index of the plasma activation liquid, the secondary activation treatment is recommended when the ORP value is above 550 mV.

Based on the above conclusion, on a fully automatic or semi-automatic production line, the plasma activating solution can be prepared according to the following steps:

step 1) carrying out primary activation treatment on a solution to be treated by using a cold plasma generating device;

step 2) after the primary activation is stopped, sealing and storing the obtained activation liquid; if the product is stored at normal temperature, the storage time is not more than 7 days;

and 3) carrying out secondary activation treatment on the stored activation solution by using a cold plasma generating device to obtain the activation solution with better physicochemical properties and active oxygen nitrogen particle concentration than those of the activation solution subjected to the primary activation treatment.

Correspondingly, for a fully automatic production line, the control device for preparing the plasma activating liquid comprises a processor and a memory, wherein the memory stores a program, and the program realizes the following steps when being loaded and executed by the processor:

step 1) controlling a cold plasma generating device to perform primary activation treatment on a solution to be treated;

step 2) controlling the cold plasma generating device to stop working and waiting for a set interval time;

and 3) controlling the cold plasma generating device to perform secondary activation treatment on the solution after the primary activation treatment after the set interval time is up, so as to obtain an activated solution with better physicochemical properties and active oxygen nitrogen particle concentration than those after the primary activation treatment.

Illustratively, the time of the primary activation treatment in the step 1) is 100-200 seconds, the time interval set in the step 2) is 1-6 days, and the time of the secondary activation treatment in the step 3) is 90-150 seconds.