CN109142343B - Application of pyridine derivative in preparation of plasma sterilization indicator - Google Patents

Application of pyridine derivative in preparation of plasma sterilization indicator Download PDF

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CN109142343B
CN109142343B CN201811005178.XA CN201811005178A CN109142343B CN 109142343 B CN109142343 B CN 109142343B CN 201811005178 A CN201811005178 A CN 201811005178A CN 109142343 B CN109142343 B CN 109142343B
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CN109142343A (en
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汤百灿
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GUANGZHOU BAOLI BANGDE HIGH POLYMER MATERIAL CO LTD
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Guangzhou Mofu Material Technology Co ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour

Abstract

The patent relates to the field of plasma sterilization indication and discloses application of a pyridine derivative in preparation of a plasma sterilization indicator. The research of the invention discovers the new application of the pyridine derivative for the first time, the pyridine derivative is helpful for promoting the dye to generate obvious color change before and after the hydrogen peroxide plasma sterilization, the color after the sterilization can not be recovered to the original color, the color stability is excellent, and whether the sterilization target object is subjected to the sterilization process or not can be reliably judged; the pyridine derivative can control the color change speed of the dye in hydrogen peroxide plasma, so that whether the sterilization condition of a sterilization target object is proper or not can be judged through the change of the color tone.

Description

Application of pyridine derivative in preparation of plasma sterilization indicator
Technical Field
The patent relates to the field of plasma sterilization indicators, and more particularly to the use of pyridine derivatives in the preparation of plasma sterilization indicators.
Background
With the rapid development of medical health and health care and the continuous improvement of medical technology, various precision instruments and equipment are gradually popularized and applied, and the equipment can not be sterilized at high temperature (mainly high-temperature high-pressure steam and high-temperature dry heat). In order to solve this problem, various low-temperature chemical sterilization methods have been developed, such as ethylene oxide low-temperature sterilization applied to hospital sterilization in the 50 th century, and ethylene oxide sterilizers are widely used by some large-city hospitals in the U.S. and china by the middle of the 90 th century. The epoxy ethane has the function of killing various microorganisms such as bacteria, spores, fungi, viruses and the like; the sterilization mechanism is combined with amino, hydroxyl, carboxyl or sulfydryl in bacterial protein molecules, enzymes and nucleic acid to damage the bacterial cells, thereby achieving the sterilization effect. However, ethylene oxide is toxic and is a suspected carcinogen, and besides extremely strict indoor air concentration control, complicated purification and emission treatment is also needed, so that the operation period is long; the other widely used method is low-temperature steam formaldehyde sterilization, the sterilization mechanism of the method is similar to that of ethylene oxide, and the method also has the defects of gas toxicity, strict concentration control and purification treatment, long sterilization operation period and the like.
In the 90 s of the 20 th century, plasma sterilization began to be a pilot test as a new low temperature sterilization technique. Plasma is generated by gas under the action of heating or strong electromagnetic field, and mainly comprises electrons, ions, atoms, molecules, active free radicals, rays and the like, namely the gas slurry is called as a material aggregation state. The existing plasma sterilization is mainly performed by exciting hydrogen peroxide (H2O2) into 'gas slurry' for sterilization, wherein the hydrogen peroxide (H2O2) is an active oxidant, and the decomposition products of the hydrogen peroxide are water and nascent oxygen. The sterilization mechanism of hydrogen peroxide plasma is mainly caused by the combined action of ultraviolet rays, high-energy particles and active free radicals, wherein active substances such as active free radicals, hydrogen peroxide radicals and hydroxyl radicals are combined with proteins and nucleic acids in bacteria to destroy the metabolism of the bacteria, so that the sterilization effect is achieved. The hydrogen peroxide low-temperature plasma sterilization system has the characteristics that: the sterilization speed is high, only about 55 minutes is needed, and the detoxification time is not needed; no toxic substance is left, and the final decomposition product is water and oxygen which are safe for the environment and medical staff. Therefore, the hydrogen peroxide low-temperature plasma sterilization system (particularly GB/T32309-2015) can be used for sterilizing medical instruments and also used in the industries and works requiring sterilization of sanitary materials, food, tableware and the like.
Important in the application of these sterilization methods are: whether the equipment to be sterilized is subjected to the sterilization process is judged, and whether the sterilization effect on the equipment is proper is checked. On the other hand, indicator compositions that change color tone during sterilization have become a means of determining whether sterilization has been performed or a means of inspecting whether the sterilization effect is appropriate.
Various indicator compositions exist for indicating the presence of hydrogen peroxide based on the principle of acid-base titration. The acid-base indicators each have a different pKa value and therefore a different acid-base indicating color. The method comprises the steps of compounding a suitable acid-base indicator with iodide, metal salt, transition metal salt and the like, and compounding a suitable aqueous polymer solution with hydrogen sulfide, sodium hypochlorite and the like to filter test paper to form the indicator test paper; the hydrogen peroxide forms plasma under the action of a high-frequency electromagnetic field in the sterilizer, active factors such as free radicals HO, perhydroxyl free radicals HO2, excited state H2O2, active oxygen atoms O, active hydrogen atoms H and the like in the plasma react with the acid-base indicator to generate color change, so the prepared test paper can detect the hydrogen peroxide. Also, some products in the form of printing ink are applied to a hydrogen peroxide low-temperature plasma sterilization system based on the chemical action, but the finished indicator product is unstable before and after use, such as the product is influenced by external air moisture and acid and alkali substances of contact products, the indicator changes are not obvious after being stored for a long time, or the indicator fades during the recording period after being processed by the sterilization system, and the like, which all affect the daily management of a hospital supply center.
The pyridine derivatives have unique biological activity, low toxicity and high systemic property, and are often used as structural building blocks of medicines and pesticides. However, there is currently no document disclosing the role of pyridine derivatives in plasma sterilization indications.
Disclosure of Invention
In view of the above, in order to overcome at least one of the deficiencies in the prior art, the present patent finds a substance that promotes the color change of the dye in the hydrogen peroxide plasma and promotes the color fixation of the dye after the color change, and researches find that the pyridine derivative has the characteristics of promoting the color change of the dye in the hydrogen peroxide plasma and effectively fixing the color after the color change, and is suitable for indicating plasma sterilization.
In order to solve the technical problems, the patent adopts the following technical scheme:
use of a pyridine derivative for the preparation of a plasma sterilisation indicator.
Further, the pyridine derivative is one or more of pyridone, pyrithione or a pyrithione salt.
Further, the pyrithione salt is one or more of copper pyrithione, zinc pyrithione, sodium pyrithione, magnesium pyrithione, cadmium pyrithione, and zirconium pyrithione.
Further, the plasma sterilization indicator is a hydrogen peroxide plasma sterilization indicator.
Further, the component which plays a role in changing color in the plasma sterilization indicator is a dye.
Further, the dye which plays a role in changing color in the plasma sterilization indicator is a vat dye or a sulfur vat dye.
The pyridine derivative and the dye generate other colors under the fading or matching action under the action of hydrogen peroxide with strong oxidation effect, and the action of the pyridine derivative is very critical and important, influences and controls the color development speed and the color development stability, and plays a role in controlling the color development speed and the color fixation stably.
The hydrogen peroxide plasma sterilization indicator is substantially the same as the dye used in the ethylene oxide gas sterilization indicator. However, because the sterilization mechanisms of the ethylene oxide gas and the dye are different, the ethylene oxide gas kills the thalli through alkylation, and the hydrogen peroxide plasma kills the thalli through stronger (radio frequency ion) oxidation, so the dye discoloration mechanisms of the ethylene oxide gas and the dye are different, and the ethylene oxide gas and the dye can be stably generated or degenerated into another color after the reaction; however, even if hydrogen peroxide having a strong oxidizing action reacts with a dye after the hydrogen peroxide plasma is generated in the sterilizer, the indicator may not change color, or may change color but may be unstable or may not change color after being left for a long time. It has been found that the incorporation of a pyridine derivative into an indicator for hydrogen peroxide plasma sterilization can more stably prevent discoloration of a dye which has been discolored during hydrogen peroxide plasma sterilization.
The pyridine derivative is preferably a pyridine derivative having an ionizing group, such as copper pyrithione, zinc pyrithione, sodium pyrithione, etc., and particularly, the pyridine derivative is used in the preparation of a plasma sterilization indicator in which the dye serving as a discoloration indicator is a vat dye or a sulfur vat dye. The vat dye and the sulfur vat dye are not dissolved in an aqueous system, although the leuco dye can be dissolved in the aqueous system, a non-aqueous solution can be generated along with the reduction of the pH value of the system, and the introduced copper pyrithione, sodium pyrithione and zinc pyrithione with ionized groups can stabilize the system and play a role in improving the plasma sensitivity.
This patent compares with prior art has following beneficial effect:
the research of the invention discovers the new application of the pyridine derivative for the first time, the pyridine derivative is helpful for promoting the dye to generate obvious color change before and after the hydrogen peroxide plasma sterilization, the color after the sterilization can not be recovered to the original color, the color stability is excellent, and whether the sterilization target object is subjected to the sterilization process or not can be reliably judged; the pyridine derivative can control the color change speed of the dye in hydrogen peroxide plasma, so that whether the sterilization condition of a sterilization target object is proper or not can be judged through the change of the color tone.
Detailed Description
This patent is described in further detail below with reference to specific examples.
Example 1
In this embodiment, the plasma sterilization indicator includes the following components in parts by weight:
dye: 5 parts of reactive red B and 0.5 part of OB dye blue;
pyridine derivatives: 2 parts of sodium pyrithione;
aqueous polymer resin binder: 30 parts of polyurethane emulsion and 30 parts of acrylic emulsion;
auxiliary agent: 2 parts of nano titanium dioxide, 0.5 part of rheological agent, 0.7 part of film forming agent, 0.1 part of defoaming agent and 10 parts of thickening agent;
solvent: deionized water/alcohol 19.2 parts.
Example 2
In this embodiment, the plasma sterilization indicator includes the following components in parts by weight:
dye: active blue BF4R 2.4.4 parts, disperse pink R3L 2 parts;
pyridine derivatives: 2 parts of sodium pyrithione;
aqueous polymer resin binder: 40 parts of polyurethane emulsion and 20 parts of acrylic emulsion;
auxiliary agent: 3 parts of nano titanium dioxide, 0.3 part of rheological agent, 0.7 part of film forming agent, 0.4 part of defoaming agent and 10 parts of thickening agent; solvent: deionized water/alcohol 19.2 parts.
Example 3
In this embodiment, the plasma sterilization indicator includes the following components in parts by weight:
dye: active violet 5R 1 and vat yellow G0.5;
pyridine derivatives: 1 part of zinc pyrithione and 1 part of barium pyrithione;
aqueous polymer resin binder: 35 parts of polyurethane emulsion and 35 parts of acrylic emulsion;
auxiliary agent: 3 parts of nano titanium dioxide, 0.2 part of rheological agent, 1.0 part of film forming agent, 0.3 part of defoaming agent and 10 parts of thickening agent; solvent: deionized water/alcohol 12.5 parts.
Example 4
In this embodiment, the plasma sterilization indicator includes the following components in parts by weight:
dye: 0.4 part of vat black B, 1.0 part of active violet 5R, 0.1 part of disperse blue RRL and 0.2 part of vat yellow G; pyridine derivatives: 1 part of sodium pyrithione and 1 part of copper pyrithione;
aqueous polymer resin binder: 40 parts of polyurethane emulsion and 30 parts of acrylic emulsion;
auxiliary agent: 5 parts of nano titanium dioxide, 0.2 part of rheological agent, 0.8 part of film forming agent, 0.2 part of defoaming agent and 10 parts of thickening agent; solvent: 10.1 parts of deionized water/alcohol.
Example 5
In this embodiment, the plasma sterilization indicator includes the following components in parts by weight:
dye: 3.5 parts of vat blue RS;
pyridine derivatives: 2 parts of sodium pyrithione;
aqueous polymer resin binder: 30 parts of polyurethane emulsion and 30 parts of acrylic emulsion;
auxiliary agent: 4 parts of nano titanium dioxide, 0.5 part of rheological agent, 0.7 part of film forming agent, 0.1 part of defoaming agent and 10 parts of thickening agent; solvent: deionized water/alcohol 19.2 parts.
Example 6
In this embodiment, the plasma sterilization indicator includes the following components in parts by weight:
dye: 4.4 parts of vat yellow WG;
pyridine derivatives: 2 parts of sodium pyrithione;
aqueous polymer resin binder: 40 parts of polyurethane emulsion and 20 parts of acrylic emulsion;
auxiliary agent: 3 parts of nano titanium dioxide, 0.3 part of rheological agent, 0.7 part of film forming agent, 0.4 part of defoaming agent and 10 parts of thickening agent;
solvent: deionized water/alcohol 19.2 parts.
Example 7
In this embodiment, the plasma sterilization indicator includes the following components in parts by weight:
dye: 2 parts of vulcanized reduced indigo and 0.5 part of disperse pink;
pyridine derivatives: 1.5 parts of sodium pyrithione;
aqueous polymer resin binder: 35 parts of polyurethane emulsion and 35 parts of acrylic emulsion;
auxiliary agent: 2 parts of nano titanium dioxide, 0.2 part of rheological agent, 1.0 part of film forming agent, 0.3 part of defoaming agent and 10 parts of thickening agent;
solvent: 10.1 parts of deionized water/alcohol.
Example 8
In this embodiment, the plasma sterilization indicator includes the following components in parts by weight:
dye: 1.5 parts of vulcanized vat yellow 2G and 0.2 part of OB dye blue;
pyridine derivatives: 1.5 parts of sodium pyrithione and 0.5 part of cadmium pyrithione;
aqueous polymer resin binder: 40 parts of polyurethane emulsion and 30 parts of acrylic emulsion;
auxiliary agent: 5 parts of nano titanium dioxide, 0.2 part of rheological agent, 0.8 part of film forming agent, 0.2 part of defoaming agent and 10 parts of thickening agent;
solvent: 10.1 parts of deionized water/alcohol.
Comparative example 1
This comparative example is different from example 1 in that the pyridine derivative is not included in the plasma sterilization indicator, and the other example is the same as example 1.
Comparative example 2
This comparative example is different from example 6 in that the pyridine derivative is not included in the plasma sterilization indicator, and the other example is the same as example 6.
The test method comprises the following steps:
1. the plasma sterilization indicators of the above-described examples and comparative examples were manually coated on a substrate of polypropylene-based synthetic paper (Yupo FGS-250, manufactured by Yupo corporation) using a loop-rod type wet film coater of 0.45m/m to prepare corresponding indicator paper, and the initial color of each indicator paper was recorded in Table 1.
2. The sterilization treatment (2-minute elimination treatment and short-cycle treatment) was performed with a plasma sterilizer (LK/DZK series) of the genu laken medical science and technology ltd, and the discoloration results were recorded in table 1. The 2-minute abatement treatment is a treatment in which the sterilization chamber is depressurized to about 0.5torr, high-frequency energy is applied to the sterilization chamber in this state to produce an air plasma state, the pressure is restored to a first pressure, the sterilization chamber is depressurized to about 0.4torr again, and hydrogen peroxide is injected and diffused for 2 minutes; the short cycle treatment is a treatment in which hydrogen peroxide is diffused for 6 minutes, then slightly decompressed, and then high-frequency energy is applied to produce a low-temperature plasma state of hydrogen peroxide, and then hydrogen peroxide is injected and diffused for 8 minutes to apply high-frequency energy, followed by "2-minute elimination treatment".
3. The color change was recorded in table 1 after placing each indicator paper subjected to hydrogen peroxide plasma sterilization treatment in a constant temperature and humidity chamber at 23 ℃ and 90% RH for 1 month.
TABLE 1
Figure BDA0001783850550000061
As can be seen from the test results in table 1, the above examples exhibited significant color transition before and after the plasma sterilization treatment, and the color after the transition could be stably present. From the test results of example 1 and comparative example 1, and example 6 and comparative example 2, it is understood that the pyridine derivative plays a key role in plasma sterilization indication, in example 1, the pyridine derivative is a key factor for indicating whether or not the indicator undergoes color transition before and after the plasma sterilization treatment, and in example 6, the pyridine derivative affects the color difference of the indicator undergoing color transition before and after the plasma sterilization treatment.
It should be understood that the above examples of the present patent are only examples for clearly illustrating the present patent, and are not intended to limit the embodiments of the present patent. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of this patent shall be included in the protection scope of the claims of this patent.

Claims (1)

1. The application of pyridine derivatives in the preparation of hydrogen peroxide plasma sterilization indicators,
the hydrogen peroxide plasma sterilization indicator comprises the following components in parts by weight: dye: 5 parts of reactive red B, 0.5 part of OB dye blue, and pyridine derivatives: 2 parts of sodium pyrithione, an aqueous polymer resin binder: 30 parts of polyurethane emulsion, 30 parts of acrylic emulsion, and an auxiliary agent: 2 parts of nano titanium dioxide, 0.5 part of rheological agent, 0.7 part of film forming agent, 0.1 part of defoaming agent, 10 parts of thickening agent and solvent: 19.2 parts of deionized water/alcohol; or
The hydrogen peroxide plasma sterilization indicator comprises the following components in parts by weight: dye: vat yellow WG 4.4 parts, pyridine derivative: 2 parts of sodium pyrithione, an aqueous polymer resin binder: 40 parts of polyurethane emulsion, 20 parts of acrylic emulsion, and an auxiliary agent: 3 parts of nano titanium dioxide, 0.3 part of rheological agent, 0.7 part of film forming agent, 0.4 part of defoaming agent, 10 parts of thickening agent and solvent: deionized water/alcohol 19.2 parts.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201182775Y (en) * 2007-12-28 2009-01-21 国家纳米技术与工程研究院 Color-changing printing ink indicating card for indicating disinfection
CN101444632A (en) * 2009-01-15 2009-06-03 杭州三源医疗设备有限公司 Peroxide plasma body sterilizing equipment effect verification device and method and indicator used
CN101486844A (en) * 2009-02-23 2009-07-22 湖北得宝染料工业有限公司 Yellow azo dye mixture, and preparation method and use thereof
CN101618226A (en) * 2009-08-12 2010-01-06 成都老肯科技有限公司 Hydrogen peroxide plasma sterilizer and sterilizing method thereof
CN101965203A (en) * 2008-03-10 2011-02-02 保木医疗股份有限公司 Plasma sterilization indicator

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201182775Y (en) * 2007-12-28 2009-01-21 国家纳米技术与工程研究院 Color-changing printing ink indicating card for indicating disinfection
CN101965203A (en) * 2008-03-10 2011-02-02 保木医疗股份有限公司 Plasma sterilization indicator
CN101444632A (en) * 2009-01-15 2009-06-03 杭州三源医疗设备有限公司 Peroxide plasma body sterilizing equipment effect verification device and method and indicator used
CN101486844A (en) * 2009-02-23 2009-07-22 湖北得宝染料工业有限公司 Yellow azo dye mixture, and preparation method and use thereof
CN101618226A (en) * 2009-08-12 2010-01-06 成都老肯科技有限公司 Hydrogen peroxide plasma sterilizer and sterilizing method thereof

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