DISINFECTION METHOD COMPRISING A DISINFECTANT FORMED BY REACTION OF H.SUB.2.O.SUB.2 AND NO.SUB.2 IN SITU WITH RETARDED RELEASE OF THE ACTIVE SUBSTANCE
20230293751 · 2023-09-21
Assignee
Inventors
- Ansgar Schmidt-Bleker (Bielefeld, DE)
- Jörn Winter (Greifswald, DE)
- Klaus-Dieter Weltmann (Ostseebad Binz, DE)
Cpc classification
International classification
Abstract
The invention relates to a method for disinfecting surfaces comprising providing an active solution comprising the reactants H.sub.2O.sub.2 and NO.sub.2.sup.-, wherein the active solution comprises at least one stopping agent, wherein the stopping agent is a solvent having a boiling temperature below 100° C. Furthermore, the invention relates to a device for the application of this process.
Claims
1. A disinfection method for surfaces, comprising providing an active solution comprising educts H.sub.2O.sub.2 and NO.sub.2.sup.-, characterized in that the active solution comprises at least one stopping agent for reducing the reaction rate of H.sub.2O.sub.2 and NO.sub.2.sup.-, wherein the stopping agent is a solvent having a boiling temperature below 100° C.
2. The method of claim 1, wherein the stopping agent is selected from an alcohol, a ketone and an ester, in particular methanol, ethanol, isopropanol, acetone, ethyl acetate and n-propanol, further in particular ethanol, isopropanol and acetone.
3. The method according to claim 1, wherein the active solution is obtained by mixing the educts H.sub.2O.sub.2 and NO.sub.2.sup.- and the stopping agent at time t.sub.0.
4. The method according to claim 1, wherein the active solution is distributed on a surface to be disinfected until complete wetting at time t.sub.1.
5. The method according to claim 1, wherein the time period between t.sub.0 and t.sub.1 is at least 5 seconds, in particular at least 10 seconds, further in particular at least 15 seconds.
6. The method according to claim 1, wherein the active solution acts until time t.sub.2 to obtain a disinfected surface.
7. The method according to claim 1, wherein the minimum concentration of the stopping agent in the active solution at time t.sub.0 is at least 2.5 % (v/v) and/or the maximum concentration of the stopping agent in the active solution is < 90% (v/v), in particular < 60% (v/v), further in particular < 40% (v/v).
8. The method according to claim 1, wherein the pH-value of the active solution at time t.sub.0 is between 1 and 7, in particular between 2 and 6, in particular between 3 and 5.
9. The method according to claim 1, wherein the initial concentration [H.sub.2O.sub.2].sub.0 at time t.sub.0 is between 1 mM and 1000 mM, in particularly between 10 mM and 500 mM, in particular between 15 and 300 mM.
10. The method according to claim 1, wherein the initial concentration [NO.sub.2.sup.-].sub.0 at time t.sub.0 is between 1 mM and 1000 mM, in particular between 10 mM and 500 mM, in particular between 15 and 300 mM.
11. Device 1 for the simultaneous delivery of at least two volume flows 10, 11 of H.sub.2O.sub.2 and NO.sub.2 solutions, in particular of at least two volume flows 10, 11 of the same size, comprising at least two reservoirs 20, 21 for receiving H.sub.2O.sub.2 and for receiving NO.sub.2, and, arranged in a respective reservoir 20, 21, a displaceable piston 30, 31 for conveying a fluid from the respective reservoir, the pistons 30, 31 being coupled to one another via a force transmission apparatus in such a way that they can be displaced synchronously parallel to one another, so that the fluids can be discharged from the reservoirs 20, 21 at the same time, in particular with same volume flows 10, 11.
12. Device 1 for simultaneous delivery of at least two volume flows 10, 11 of H.sub.2O.sub.2 and NO.sub.2.sup.- according to claim 11, characterized in that the two reservoirs 20, 21 are separated from each other by at least one common partition wall 25, wherein this partition wall 25 has a lower bending strength than the sides of the pistons 30, 31 sliding on the partition wall 25, and wherein a first piston 30 has a projection 33 projecting in the direction of a second piston 31 and the second piston 31 has a recess 34 which is essentially complementary with respect to the shape and size of the projection 33, so that when one piston is displaced, the respective other piston is entrained in the recess 34 whilst deforming the partition wall 25 via an indirect mechanical engagement of the projection 33.
13. Device 1 for simultaneous delivery of at least two volume flows 10, 11 of H.sub.2O.sub.2 and NO.sub.2.sup.- according to claim 12, characterized in that the reservoirs 20, 21 are separated from one another by at least one common partition wall 25, wherein the pistons 30, 31 are connected via at least one connecting member 50, which is configured to cut the partition wall 25 located therebetween at least sectionwise upon displacement of the pistons 30, 31.
14. Device 1 for simultaneous delivery of at least two volume flows of H.sub.2O.sub.2 and NO.sub.2.sup.- according to claim 11, characterized in that the device comprises three reservoirs 20, 21, 22, wherein in the third reservoir 22 a displaceable third piston 32 is arranged for conveying a fluid from the third reservoir 22, wherein the three pistons 30, 31, 32 are coupled to each other via a force transmission apparatus in such a way that they are synchronously displaceable parallel to one another, so that the fluids can be discharged from the reservoirs 20, 21, 22 with the same volume flows.
15. Device for simultaneous delivery of at least two volume flows of H.sub.2O.sub.2 and NO.sub.2.sup.- according to claim 11, characterized in that at least a first reservoir 20 is neighboring on at least two sides of at least a further reservoir 21, 22, wherein in the further reservoir 21, 21 the fluid comprises a lower translucency than the fluid in the first reservoir 20 for the purpose of reducing light irradiation into the fluid in the first reservoir 20.
Description
BRIEF DESCRIPTION OF THE FIGURES
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(bottom). The dashed line indicates the ratio
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DETAILED DESCRIPTION OF FIGS. 8 TO 19
[0155] A cartridge 2 as part of the device 1 according to the invention is shown in
[0156] The movement of the two pistons 30, 31 cannot occur independently of each other in this case. The device 1 is designed in such a way that the pistons 31, 31 can only move synchronously so that they always generate a respective volume flow 10, 11 of fluid to the same extent. In particular, both reservoirs 20, 21 can comprise the same size and both pistons 30,31 can comprise the same cross-section, so that the two volume flows 10,11 are also equal.
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[0160] The mixture of fluids may be dispensed, nebulized, or sprayed from the nozzle 63 for further use as a liquid.
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EXAMPLES
Disinfection Process Without Retarding Solvent
[0166] The pH-dependent rate constant k = k.sub.0 can be calculated as follows:
with
and the unitless quantity
with an effective activation energy E.sub.A = 70 kJ/mol and the temperature T.
[0167] As an example, by solving the differential equations resulting from (2) for the concentrations [H.sub.2O.sub.2] and [NO.sub.2.sup.-] at the same starting concentrations at time t.sub.0 of [H.sub.2O.sub.2].sub.0 = [NO.sub.2.sup.-]0 = 20 mM as well as a pH value of 3.2 and a temperature of 37° C., the concentration curves shown in
EXPERIMENTS PERFORMED
Influence of Isopropanol on the Rate Constant
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Temporal Change of Isopropanol Concentration on Surfaces
[0169] If a solution of water and a solvent with a higher vapor pressure than water is applied to a surface, the solvent evaporates more quickly, reducing its proportion in the solution. The following experiment was performed for this purpose: A metal plate with an area of 567 cm.sup.2 was heated to a temperature of (37 ± 2)°C. 3 mL of an isopropanol solution was spread on the plate. After waiting for 30 s or 60 s, the liquid remaining on the surface was collected in a vessel and the density of the liquid was determined. For this purpose, the weight of 100 .Math.L of the collected liquid was measured. From the data presented in Chu, Kwang-Yu, and A. Ralph Thompson. Journal of chemical and engineering data 7.3 (1962): 358-360 regarding the concentration dependence of the density of isopropanol solutions, the isopropanol concentration of the collected liquid was determined. Furthermore, for verification of the method, the density of the isopropanol solution was determined before it was applied to the metal plate (designated “0 s” in
Temporal Change of the Reaction Rate (3) on Surfaces
[0170] The concentration dependence (90) together with the time variation of the isopropanol concentration shown in
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Microbiological Examinations
[0172] In order to verify the retarded microbiological effect when using a stopping solution, the effect of the active solution on spores of the species Bacillus atrophaeus was investigated in two experiments.
[0173] In the first experiment, 10 .Math.L of a spore solution (containing spores of the bacterium of species Bacillus atrophaeus ) was placed in a reaction vessel. Then, 495 .Math.L of a 50 mM NaNO.sub.2 solution was added, followed by 495 .Math.L of a 50 mM H.sub.2O.sub.2 solution to obtain an active solution. Here, the NaNO.sub.2 solution and the H.sub.2O.sub.2 solution respectively contained the same concentration of isopropanol selected from 0%, 5%, 10%, 15% or 20%, wherein the percentages refer to percent by volume. In addition, the H.sub.2O.sub.2 solution was acidified using 25 mM H.sub.3PO.sub.4. The reaction was stopped after an incubation time of 60 s by dilution in a neutralization solution and then plated out on agar. After an incubation period of 24 h, the colony forming units were quantified on the respective agar plate.
[0174] The results of this test are shown in
[0175] In the second experiment, 10 .Math.L of a spore solution (B. atrophaseus ) was introduced analogously to the first experiment. In a separate reaction vessel, 1 mL of a 75 mM NaNO.sub.2 solution was added and reacted with 1 mL of a 75 mM H.sub.2O.sub.2 solution to obtain an active solution. After 15 s of reaction time, 990 .Math.L of this active solution was added to the spore solution. Analogous to the first experiment, the NaNO.sub.2 solution and the H.sub.2O.sub.2 solution respectively contained the same concentration of isopropanol selected from 0%, 5%, 10%, 15% or 20%. In addition, the H.sub.2O.sub.2 solution was acidified using 37.5 mM H.sub.3PO.sub.4. The higher concentrations of the educts compared to the first experiment were chosen here to approximately compensate for the loss of these educts during the 15 s reaction time. Analogous to the first experiment, the solution was diluted in neutralization solution after 60 s of reaction time and plated out.
[0176] The results of this experiment are shown in
EXAMPLE OF DETERMINING THE MINIMUM SOLVENT CONCENTRATION THAT CAN BE USED
Definitions
[0177] The total process time is the distribution time + drying time. The distribution time ends at time t.sub.1.
[0178] • Drying time = time until wetted surface is completely dry, ends at time t.sub.2.
[0179] •
where x is the concentration of the stopping agent in volume percent relative to the volume of the active solution at time t=t.sub.0.
[0180] The function min(a,b) is equal to a if a < b, b if b ≤ a.
refers to an active solution without stopping agent.
corresponds to the maximum achievable efficacy W=
wherein k denotes the rate constant of the reaction between H.sub.2O.sub.2 and NO.sub.2.sup.-. It is advantageous if the total process time is as short as possible. It is also advantageous if the efficacy is as high as possible during the drying time. The drying time can always be shortened by adding an alcohol with a lower boiling temperature than water.
[0181] In addition, the efficacy is increased by adding alcohol in the drying time. The following points must be taken into account when designing the alcohol concentration: [0182] a) Minimum alcohol addition: The alcohol concentration must be chosen so that the condition is satisfied. [0183] b) Maximum alcohol addition: Too high an alcohol concentration can lead to unwanted changes in the treated surfaces or, in the case of application to the skin, to skin irritation, so the alcohol concentration should be chosen as low as possible. In particular, the alcohol concentration should be less than 90%, in particular less than 60%, in particular less than 40%.
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In addition, the dashed line indicates the required 20% improvement, so that the region to be selected according to the invention can be read off from equation (X).
Determination of the Minimum Applicable Solvent Concentration
[0185] A disinfectant is required which permits a distribution time of at least 15 s, comprises a pH value of 3.2 and wherein isopropanol is used as the retarding solvent. The following steps are to be carried out: [0186] 1. The concentration of H.sub.2O.sub.2 and NO.sub.2.sup.- are to be measured time-resolved at a given pH value after mixing the components for different isopropanol concentrations. This can be carried our, for example, using UV spectroscopy as indicated in PCT/EP2019/062897 and above (see
[0188] For other solvents and pH values, analogous steps must be taken.
LITERATURE LIST
[0189] Zhu, Ling, Christopher Gunn, and Joseph S. Beckman. “Bactericidal activity of peroxynitrite.” Archives of biochemistry and biophysics 298.2 (1992): 452-457 . [0190] Chu, Kwang-Yu, and A. Ralph Thompson. “Densities and Refractive Indices of Alcohol-Water Solutions of n-Propyl, Isopropyl, and Methyl Alcohols.” Journal of chemical and engineering data 7.3 (1962): 358-360 .