WO2022267966A1 - Method for detecting microorganisms, gas components and particulate matter in indoor air - Google Patents

Method for detecting microorganisms, gas components and particulate matter in indoor air Download PDF

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WO2022267966A1
WO2022267966A1 PCT/CN2022/099029 CN2022099029W WO2022267966A1 WO 2022267966 A1 WO2022267966 A1 WO 2022267966A1 CN 2022099029 W CN2022099029 W CN 2022099029W WO 2022267966 A1 WO2022267966 A1 WO 2022267966A1
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electrostatic adsorption
component
assembly
detection
microorganisms
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PCT/CN2022/099029
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French (fr)
Chinese (zh)
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张玉芝
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张玉芝
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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
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/569Immunoassay; Biospecific binding assay; Materials therefor for microorganisms, e.g. protozoa, bacteria, viruses
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/569Immunoassay; Biospecific binding assay; Materials therefor for microorganisms, e.g. protozoa, bacteria, viruses
    • G01N33/56983Viruses

Definitions

  • the invention relates to the field of environmental detection, in particular to a rapid and high-sensitivity detection method for microorganisms such as viruses, and a comprehensive detection method for high-precision composite gas components and concentrations, and particle size and concentration of suspended particles.
  • viruses and other microorganisms in the air such as influenza virus and other microorganisms, SARS virus and other microorganisms, new coronavirus and other microorganisms (COVID-19), etc.
  • the detection and early warning of viruses and other microorganisms in the indoor ambient air is very necessary.
  • the new coronavirus is sweeping the world.
  • the cumulative number of new coronavirus infections in the world is 167 million, and the cumulative number of deaths is 0.035 billion.
  • Asia, Europe, and North America are the cumulative cases most continents.
  • the cumulative number of cases in the United States, India, and Brazil exceeded 10 million, and the number of new cases in Brazil, the United States, Argentina, Colombia, Spain, and Iran exceeded 10,000 on May 24.
  • PCR technology is currently the most common screening method for microorganisms such as the new coronavirus, but it has disadvantages such as limited use environment, long detection time, and low accuracy rate, and cannot be applied to the detection of viruses and other microorganisms in indoor air environments.
  • the present invention provides a detection device for microorganisms such as viruses in the air with high measurement sensitivity, high precision, fast measurement process and strong environmental adaptability, and it can also simultaneously detect gas components and particulate matter Comprehensive testing.
  • the present invention provides a method for detecting microorganisms such as viruses in indoor air, gas components, and particulate matter, which is characterized in that it includes the following steps:
  • the strong electric field is higher than a predetermined value for disinfecting microorganisms and treating particulate matter.
  • the method further includes: before the laser is incident on the electrostatic adsorption component, filtering the laser.
  • an aspherical long-focus filter component (1.2.7) is arranged at the outlet of the adsorption component and in front of the Raman detection component (1.2.8) to perform a filter on the emitted Raman scattered light. Filter to remove background fluorescence and stray light.
  • the method further includes using artificial intelligence image analysis and processing technology to detect microbial aerosols such as viruses based on Raman signals.
  • the method further includes, arranging a multi-pass reflection assembly (1.2.5) on both sides of the electrostatic adsorption assembly, which has at least one reflection surface facing the adsorption assembly, the laser Incident to the reflective surface of the multi-pass reflective component (1.2.5), so that it is irradiated on the electrostatic adsorption component multiple times.
  • it also includes performing gas component detection before or after the microbial detection.
  • an air pump is arranged upstream of the electrostatic adsorption assembly to clean the electrostatic adsorption assembly through a strong air flow
  • the comprehensive gas detection device also includes a temperature-controlled disinfecting assembly (1.3.2) , the temperature-controlled disinfecting component (1.3.2) is used to disinfect the gate-enrichment module.
  • the electrostatic adsorption component is made of nano-metal material, preferably, nano-metal particle material, and more preferably, the electrostatic adsorption component includes nano-gold or nano-silver particles.
  • the invention proposes a detection method that can realize the detection of microorganisms.
  • the present invention can not only detect microorganisms such as viruses in gas, but also detect various gas components and particles.
  • the method of the present invention uses a charging device to recharge microbial aerosol particles such as viruses with a certain charge in the upstream of the gas travel path, and recharges the charged microbial aerosol particles such as viruses under the force of an electrostatic field to the downstream of the gas travel path.
  • the sol particles are separated from the air flow—that is, after the charged micro-viruses and other microbial particles enter the electric field, they are deflected under the action of the electric field force, and thus are adsorbed on the surface of the metal nano-micro-material.
  • Other particulate matter such as PM2.5, PM10, etc. have very little charge and are under the action of an electric field. They are blown out of the gating enrichment module under the action of airflow, thereby achieving the gating effect and greatly reducing the fluorescence of the particulate matter. The impact of the effect on the detection.
  • microbial aerosol particles such as different types of viruses can be realized Efficient and high survival rate collection.
  • the forward multi-pass surface-enhanced Raman effect obtains the Raman spectral information of viruses and other microbial aerosols, and combines artificial intelligence image analysis and processing technology to complete the detection of viruses and other microbial aerosols.
  • the incident light is irradiated on the metal nano-micromaterial, preferably, for example, on the gold nano-micromaterial, and the electrons in the nanoparticles vibrate under the action of an external electric field.
  • the frequency of the incident light is equal to the natural vibration frequency of the electron, Local surface plasmon resonance will occur, and a local enhanced electric field stronger than the excited electric field will be formed on the surface of the metal nanostructure.
  • the free electrons in the metal are greatly increased under the excitation of the strong electric field, so that the electric field intensity on the surface of the metal nanostructure can be an order of magnitude higher than that before the electric field is applied, and the surface-enhanced Raman scattering (SERS ) is proportional to the fourth power of the surface-enhanced electric field. Therefore, the device of the present invention is sufficient to increase the Raman signal by 10 4 times, that is, the signal-to-noise ratio is increased by 40 dB.
  • SERS surface-enhanced Raman scattering
  • the collected Raman spectra were subjected to spectral preprocessing, S-G convolution was used to achieve spectral smoothing, multi-stage low-order polynomial convergence algorithm was used to achieve baseline alignment, and then the maximum normalization method was used for spectral normalization.
  • the obtained spectrum adopts principal component analysis method and SVM support vector machine supervised artificial intelligence pattern recognition method to obtain a deconstruction model, so as to identify different types of microbial aerosols such as viruses.
  • the specific algorithm formula is as follows:
  • the model can achieve a detection rate higher than 95%.
  • the method of the present invention completes the killing and cleaning of the enrichment chip by adopting temperature field inactivation and high-flow airflow scouring technology, and can also achieve the effect of inactivating microorganisms such as viruses by adjusting the intensity of the high-voltage electric field.
  • the detection method of the present invention is fast, highly sensitive and preferably, it can also detect the composition and concentration of composite gas and the particle size and concentration of suspended particles with high precision.
  • the method of the present invention first screens out the particles in the detection sample through the selection process, can greatly reduce the influence of particle fluorescence on the detection, and can increase the service life of the device.
  • the method of the present invention greatly increases the number of free electrons by applying a strong electric field to the metal nanomaterial, so that the electric field intensity on the surface of the metal nanostructure can be an order of magnitude higher than that before the electric field is applied, and then through the side/forward multi-pass Raman
  • the surface-enhanced remultiplication technology increases the Raman signal by 10 4 times, greatly improving the signal-to-noise ratio and detection sensitivity.
  • a detection rate higher than 95% can be achieved.
  • the method of the present invention also proposes the use of temperature field inactivation and high-velocity airflow scouring to complete the killing and cleaning of the enrichment chip, which improves the service life of the detection device and reduces the detection cost.
  • Fig. 1 is the detection conceptual schematic diagram of the inventive method
  • Fig. 2 is the structural representation of the device for carrying out the method of the present invention
  • Example 3 is a schematic diagram of the principle of the gas component detection device in Example 2 of the present invention.
  • the detection method of this embodiment is mainly divided into several steps: gating enrichment of microbial aerosols such as viruses, applying a strong electric field to metal nano-micromaterials so that the number of free electrons contained in them is greatly increased, and based on The multi-pass surface-enhanced Raman effect regulated by strong electric field and artificial intelligence image analysis and processing are used to complete the detection of microbial aerosols, and finally perform airflow washing and microbial disinfecting.
  • the method of the present embodiment includes the following steps:
  • the intensity of the strong electric field can also be set to be higher than a certain value, for example, up to thousands of volts, so as to disinfect microorganisms and treat particulate matter.
  • the laser light is filtered before the laser light is incident on the electrostatic adsorption component.
  • An aspherical long-focus filter component is arranged at the exit of the adsorption component and in front of the Raman detection component to filter the outgoing Raman scattered light and filter out background fluorescence and stray light.
  • a multi-pass reflective assembly is provided on both sides of the electrostatic adsorption assembly, which has at least one reflective surface facing the adsorption assembly, and the laser is incident on the reflective surface of the multi-pass reflective assembly, so that the It is irradiated on the electrostatic adsorption assembly multiple times.
  • a corresponding device for implementing the method of the present invention which includes a microorganism detection module 1 , a gas component detection module 2 (optional) and a processing control communication module 3 .
  • the gas component detection module can be optional, and the gas to be tested can be passed into one detection module for detection, and then the gas can be passed into another detection module for detection.
  • the microbial detection module includes a gating enrichment module, a Raman module, and a disinfecting and cleaning module.
  • the gate-enrichment module includes an air pump 1.1.1, a charging component 1.1.2 and an electrostatic adsorption component 1.1.3.
  • the gating and enrichment module is used for gating and enriching microbial aerosols such as viruses.
  • the charging component is installed in the charging chamber, the cavity is sealed, one end on both sides communicates with the air pump 1.1.1, and the other end communicates with the adsorption chamber of the electrostatic adsorption component 1.1.3.
  • the charging component 1.1.2 has a high-voltage power supply and one or more sets of tungsten wire pairs with a diameter of 40 ⁇ m (other sizes can also be used). The discharge distance of the tungsten wires is set to 8mm, and the charging voltage is +5kV. Aerosol charges.
  • an electrostatic adsorption component 1.1.3 is arranged in the adsorption chamber, and the main material of the electrostatic adsorption component 1.1.3 is formed by stacking three-dimensional flocculated gold nanomaterials.
  • the electrostatic adsorption component is used to adsorb microorganisms in the charged target gas, and a laser path is reserved in the adsorption component. It should be noted that the reserved laser path mentioned in the present invention includes two meanings.
  • the gold nanomaterials in the electrostatic adsorption component are sparse enough for the laser to pass through, or that the nanomaterials in the electrostatic adsorption component are along the A sheet or planar structure is formed along the laser path, and the laser passes through gaps in the sheet structure and is at least partially irradiated on the nanometer material.
  • Raman module includes strong electric field component 1.2.1, laser excitation source 1.2.2, interference filter component 1.2.3, Rayleigh filter 1.2.4, multi-pass reflection component 1.2.5, laser absorption pool 1.2.6, non Spherical long focal depth filter component 1.2.7, Raman detection component 1.2.8.
  • the Raman module applies a strong electric field to the electrostatic adsorption component 1.1.3 through the strong electric field component 1.2.1, which greatly increases the number of free electrons contained in the electrostatic adsorption component 1.1.3, and enhances the Raman effect principle through the side/forward multi-pass surface
  • the strong electric field component 1.2.1 is arranged on the upper, lower or left and right sides of the electrostatic adsorption component, sandwiching the electrostatic adsorption component in the middle.
  • the laser excitation source 1.2.2 is used to emit laser light into the electrostatic adsorption assembly along the laser path.
  • a collection electric field component is added (that is, an additional set of electrode plates is provided on the upper and lower surfaces of the adsorption component).
  • Collecting electric field (1.1.3.1) strength E 3.5kV/cm, composed of silver material, the distance h between parallel electrode plates is 20mm, the width b is 10mm, and the length l is 100mm.
  • the flow rate of the turbo air pump is 10L/min.
  • the working process of the gating enrichment module is as follows: firstly, the gas pump 1.1.1 is started to drive the measured gas into the charged component.
  • the tungsten wire is powered by a high-voltage power supply for high-voltage discharge.
  • Microbial aerosol particles such as viruses with a certain charge are recharged by the charging component.
  • the charged air further enters the electrostatic adsorption component and passes through the electrostatic adsorption component (the electrostatic adsorption component uses nano-particle materials, and the gas can pass through it).
  • the electrostatic adsorption component due to the externally applied electric field, the more charged microorganisms are deflected under the action of the electric field force, and thus are adsorbed on the surface of the metal nano-micro material.
  • Other particles such as PM2.5, PM10, etc. have very little charge, are subjected to little electric field force, and are blown out of the gate enrichment module under the action of airflow.
  • the charging component recharges the microbial aerosol particles such as viruses with a certain charge, and separates the charged microbial aerosol particles such as viruses from the air flow under the force of an electrostatic field—that is, charged micro-viruses and other microbial particles After entering the electric field, it is deflected under the action of the electric field force, and thus is adsorbed on the surface of the metal nano-micro material.
  • Other particles such as PM2.5, PM10, etc. have very little charge and are under the action of the electric field. They are blown to the outside of the gating enrichment module under the action of the airflow, so as to achieve the gating effect.
  • the Raman module applies a strong electric field to the electrostatic adsorption component 1.1.3 through the strong electric field component 1.2.1, the number of free electrons contained in it increases by at least one order of magnitude, thereby increasing the electric field intensity on the surface of the metal nanostructure by at least 10 times, when the microorganisms are adsorbed to the electrostatic adsorption component 1.1.3, the laser light emitted by the laser source 1.2.2 of the Raman module is filtered by the interference filter component 1.2.3 and the Rayleigh filter 1.2.4, and finally irradiated to On the microorganisms adsorbed in the adsorption component.
  • a multi-pass reflective component 1.2.5 on the outside of the adsorption component, with its reflection surface facing the adsorption component 1.1.3.
  • the incident direction of the laser is set as an oblique incident, so that the laser is reflected by the multi-pass reflection component 1.2.5, turns back several times in the adsorption component 1.1.3, and then exits from the other side.
  • the device of the present invention can measure the surface-enhanced Raman spectrum of R6G at 10 -8 M, and the number of molecules irradiated by the laser is: 6.02*10 23 *10 -8 *(0.65*10 -5 )2*3.14*10 - 5 ⁇ 5 R6G molecules/m 3 , the signal-to-noise ratio is increased by 40dB, and the measurement sensitivity of viruses and other microorganisms is also increased by 4 orders of magnitude;
  • the interference filter component is a 532nm interference filter;
  • the Rayleigh filter is a notch filter, Its absorption center is located at 532nm;
  • the multi-pass reflection component is an optical lens coated with a high-reflection film with a wavelength of 532nm;
  • the laser absorption pool is a blackened aluminum alloy light collector;
  • the wavelength is highly transparent;
  • the Raman detection component is a CCD detector; as shown in Figure 2, the components in the Raman module are placed coaxially according to
  • the laser absorption pool is a laser trash can, made of aluminum alloy, the surface is oxidized and blackened, and placed at the end of the main optical path.
  • the disinfecting and cleaning module uses a high-temperature heating rod and a turbo air pump in the gate-enrichment module to disinfect and clean microorganisms such as viruses in the gate-enrichment module.
  • the processing and control communication module adopts artificial intelligence graphic analysis and processing technology, including spectral preprocessing, and then uses the principal component analysis method and SVM support vector machine supervised artificial intelligence pattern recognition method to obtain the spectrum obtained to obtain different viruses. and other unique deconstruction models for microorganisms. During the detection, the collected graphics are compared with the structural model library, so that different types of viruses and other microorganisms can be matched and identified.
  • the metal nanomaterial can be a plurality of two-dimensional flat metal nanoplates placed in parallel, preferably two-dimensional flat gold nanoplates, and combined with other two-dimensional flat gold nanoplates and multiple
  • the reflective optical path is composed of the pass-reflector components, which can reflect the laser light emitted by the laser excitation source between the two-dimensional flat gold nanoplate and the multi-pass reflector components. It can effectively enhance the excitation electric field intensity and improve the detection sensitivity of the device.
  • the comprehensive detection method of the present invention also includes gas component detection before or after the microorganism detection.
  • Gas component detection includes:
  • Step 2-1 Transmit light pulses of multiple wavelengths into the test gas chamber in the form of a pulse sequence with a repetition frequency of R and a pulse width of ⁇ for testing.
  • the dissipation time t of a single pulse of wavelength ⁇ in the gas chamber is
  • the test gas chamber can be a conventional gas chamber, as long as it can allow airflow to pass through and allow light pulses to enter and exit and irradiate the gas inside.
  • Step 2-2 Use the light scattering method to measure the particle size and corresponding concentration of suspended particles, randomly select the test light suitable for the measurement of the scattering spectrometry from the test light of multiple wavelengths, and determine the scattering coefficient of the selected wavelength. If the wavelength of the test light is ⁇ , the outgoing light intensity is I 0 ( ⁇ ), the test optical path length is l, and the forward scattering light intensity I s
  • the homogeneous scattering coefficient equation, ⁇ a , ⁇ b are two kinds of measurement wavelengths. According to this formula, under the condition of the same scattering medium, two pairs of test lights used for infrared spectroscopy measurement are substituted into the formula respectively, and multiple homogeneous scattering coefficient equations are obtained to form a group of homogeneous scattering coefficient equations.
  • the present invention transmits light pulses of several wavelengths into the test gas chamber in the form of a pulse sequence with a repetition frequency of R and a pulse width of ⁇ for testing. This allows a single pulse with a wavelength of ⁇ to have a higher peak power and a higher contrast in the detection process. At the same time, it is only necessary to ensure that the dissipation time t of a single pulse with wavelength ⁇ in the gas chamber satisfies
  • Step 2-3 Use the infrared spectroscopic detection method to measure according to the above formula (8). These measurement lights can be directly transmitted and received in sequence with the light pulses used for spectroscopic measurement in the pulse sequence, or can be transmitted separately. In the infrared spectrum detection, for the gas component 1, gas component 2, gas component 3...
  • the test wavelength at least includes the light wavelength corresponding to the absorption peak of each component), and the corresponding molar molecular absorption coefficients are respectively
  • the corresponding measured concentrations are c 1 , c 2 , c 3 ⁇ c n
  • the test wavelengths ⁇ 1 , ⁇ 2 , ⁇ 3 ⁇ n are only compatible with the corresponding gas components 1, Gas component 3...
  • the detection optical path is L, and the infrared spectrum measurement equations are obtained
  • Step 2-4 Simultaneously combine (5)(7)(8) (bring formula 5 and 7 into formula 8).
  • (5)(7)(8) (bring formula 5 and 7 into formula 8).
  • the gas with a larger molar absorption coefficient is directly obtained from the aforementioned infrared spectrum measurement equation with the scattering item determined, and after the concentration of the gas component with a larger molar molecular absorption coefficient is obtained, it is brought back to the infrared spectrum measurement equation
  • the accurate gas component concentration results can be obtained by using the step difference operation of the infrared spectrum measurement equation group with the size of the scattering item determined, and the operation formula is as follows
  • FIG. 3 it is a detection device for performing the method of this embodiment, which includes a multi-wavelength pulse sequence generation module 301, a first detection unit 302, a second detection unit 303, a gas chamber main body 304, a gas chamber inlet assembly 305 and Air chamber outlet assembly 306 .
  • the measured gas enters the gas chamber from the gas chamber inlet assembly 305 and flows out from the gas chamber outlet assembly 306 .
  • the multi-wavelength pulse sequence generation module 301 is a module composed of a pulse power supply and four QCL laser light source packages with different central wavelengths.
  • the central wavelengths correspond to the fingerprint wavelengths (532nm, 640nm) of PM2.5 and PM10 particles respectively, CO 2 's fingerprint wavelength (4.26 ⁇ m) and formaldehyde's fingerprint wavelength (3.56 ⁇ m).
  • the first detection unit 302 is arranged near the entrance of the air chamber, and adopts a photodiode responsive to the fingerprint wavelength (532nm, 640nm) of PM2.5 and PM10 particles. It is used for measurement by light scattering method, and measures the scattered light intensity and forward scattered light intensity of dual-wavelength pulsed light at a specific scattering angle.
  • the second detection unit 303 is arranged near the outlet of the gas chamber, and adopts a photodiode responsive to the fingerprint wavelength (4.26 ⁇ m) of CO and formaldehyde (3.56 ⁇ m), and is used to measure the multi-wavelength pulsed light by infrared spectroscopic absorption method.

Abstract

Provided in the present invention is a method for comprehensively detecting microorganisms and gas components in air. The method comprises: (1) performing electric discharging on a target gas, so as to load same with an electric charge; (2) driving the target gas to pass through an electrostatic adsorption assembly, wherein an electric field is applied to the outer side of the electrostatic adsorption assembly so as to adsorb target microorganisms, and a metal micro-nano material is provided inside the electrostatic adsorption assembly; (3) emitting, along a laser light path, laser light into the electrostatic adsorption assembly; and (4) detecting a Raman signal that is emitted from the electrostatic adsorption assembly, and performing microorganism detection on the basis of the Raman signal. The method of the present invention has the advantages of high measurement sensitivity, high precision, a fast measurement process, strong environmental adaptability, low costs, etc.

Description

一种室内空气中微生物及气体组分、颗粒物检测方法A method for detecting microorganisms, gas components, and particles in indoor air
相关申请related application
本申请主张于2021年6月25日提交的、名称为“一种室内空气中微生物及气体组分、颗粒物检测方法”的中国发明专利申请:202110710711.8的优先权。This application claims the priority of the Chinese invention patent application: 202110710711.8, filed on June 25, 2021, entitled "A Method for Detection of Microorganisms, Gas Components, and Particulate Matter in Indoor Air".
技术领域technical field
本发明涉及环境检测领域,具体涉及一种快速高灵敏度病毒等微生物检测,高精度复合气体组份、浓度及悬浮颗粒的颗粒度、浓度的综合检测方法。The invention relates to the field of environmental detection, in particular to a rapid and high-sensitivity detection method for microorganisms such as viruses, and a comprehensive detection method for high-precision composite gas components and concentrations, and particle size and concentration of suspended particles.
背景技术Background technique
人类生活的环境,空气中存在各种各样的病毒等微生物如流感病毒等微生物,SARS病毒等微生物,新冠病毒等微生物(COVID-19)等。室内环境空气中病毒等微生物的检测预警是十分必要的。新型冠状病毒席卷全球,全球新型冠状病毒感染累计病例1.67亿人,累计死亡病例0.035亿人,5月24日当天新增病例255104人,新增死亡病例5428人,亚洲、欧洲、北美是累计病例最多的大洲。美国、印度、巴西累计病例超过1000万人,巴西、美国、阿根廷、哥伦比亚、西班牙、伊朗5月24日当天新增数超过1万人。In the environment of human life, there are various viruses and other microorganisms in the air, such as influenza virus and other microorganisms, SARS virus and other microorganisms, new coronavirus and other microorganisms (COVID-19), etc. The detection and early warning of viruses and other microorganisms in the indoor ambient air is very necessary. The new coronavirus is sweeping the world. The cumulative number of new coronavirus infections in the world is 167 million, and the cumulative number of deaths is 0.035 billion. On May 24, there were 255,104 new cases and 5,428 new deaths. Asia, Europe, and North America are the cumulative cases most continents. The cumulative number of cases in the United States, India, and Brazil exceeded 10 million, and the number of new cases in Brazil, the United States, Argentina, Colombia, Spain, and Iran exceeded 10,000 on May 24.
随着新冠疫苗的投入,常态化监测公共场所,如机场,高铁站,会议室等场所中空气中的病毒等微生物,是当下新冠疫情防控的重点和难点。With the introduction of the new crown vaccine, normalized monitoring of viruses and other microorganisms in the air in public places, such as airports, high-speed rail stations, conference rooms, etc., is the focus and difficulty of the current prevention and control of the new crown epidemic.
PCR技术是目前最常见的新冠病毒等微生物筛查方法,但其存在使用环境受限,检测时间长,准确率偏低等缺点,且不能应用于室内空气环境中病毒等微生物的检测。PCR technology is currently the most common screening method for microorganisms such as the new coronavirus, but it has disadvantages such as limited use environment, long detection time, and low accuracy rate, and cannot be applied to the detection of viruses and other microorganisms in indoor air environments.
另外随着社会的发展,人们对于空气质量及安全性的关注度逐年提高。一方面,随着污染的加剧,各种有毒、有害气体,以及颗粒物都使得生活环境中的空气影响到人们的身体健康。因此,对于能够快速、实时、高精度的复合气体组份浓度、颗粒度的综合检测装置的需求也越来越高。In addition, with the development of society, people's attention to air quality and safety is increasing year by year. On the one hand, with the intensification of pollution, various toxic and harmful gases, and particulate matter make the air in the living environment affect people's health. Therefore, there is an increasing demand for a comprehensive detection device capable of fast, real-time, and high-precision detection of compound gas component concentration and particle size.
发明内容Contents of the invention
本发明为了克服现有技术的不足,提供了一种测量灵敏度、精度高,测量过程快速,环境适应性强的空气中病毒等微生物检测装置,并且,其还能够同时对气体组分和颗粒物进行综合检测。In order to overcome the deficiencies of the prior art, the present invention provides a detection device for microorganisms such as viruses in the air with high measurement sensitivity, high precision, fast measurement process and strong environmental adaptability, and it can also simultaneously detect gas components and particulate matter Comprehensive testing.
具体而言,本发明提供一种室内空气中病毒等微生物及气体组分、颗粒物检测方法,其特征在于,包括以下步骤:Specifically, the present invention provides a method for detecting microorganisms such as viruses in indoor air, gas components, and particulate matter, which is characterized in that it includes the following steps:
(1)对目标气体放电以使其负载电荷;(1) Discharge the target gas so that it is charged;
(2)驱动所述目标气体通过静电吸附组件,所述静电吸附组件外侧施加有电场以对目标微生物进行吸附,所述静电吸附组件内具有金属纳米微材料;(2) driving the target gas through the electrostatic adsorption assembly, an electric field is applied to the outside of the electrostatic adsorption assembly to adsorb the target microorganisms, and the electrostatic adsorption assembly has metal nano-micromaterials;
(3)沿着所述激光通路向所述静电吸附组件内发射激光;(3) emitting laser light into the electrostatic adsorption component along the laser path;
(4)探测从所述静电吸附组件出射的拉曼信号基于所述拉曼信号进行 微生物检测。(4) Detecting the Raman signal emitted from the electrostatic adsorption component and performing microorganism detection based on the Raman signal.
在另一种优选实现方式中,所述强电场高于预定值,以进行微生物消杀和颗粒物处理。In another preferred implementation manner, the strong electric field is higher than a predetermined value for disinfecting microorganisms and treating particulate matter.
在另一种优选实现方式中,所述方法还包括:在将所述激光入射至所述静电吸附组件之前,对所述激光进行滤波。In another preferred implementation manner, the method further includes: before the laser is incident on the electrostatic adsorption component, filtering the laser.
在另一种优选实现方式中,在所述吸附组件的出口处、拉曼探测组件(1.2.8)前方设置非球面长焦深滤波组件(1.2.7),对出射的拉曼散射光进行滤波,滤除背景荧光和杂散光。In another preferred implementation, an aspherical long-focus filter component (1.2.7) is arranged at the outlet of the adsorption component and in front of the Raman detection component (1.2.8) to perform a filter on the emitted Raman scattered light. Filter to remove background fluorescence and stray light.
在另一种优选实现方式中,所述方法还包括采用人工智能图像分析处理技术基于拉曼信号完成病毒等微生物气溶胶的检测。In another preferred implementation manner, the method further includes using artificial intelligence image analysis and processing technology to detect microbial aerosols such as viruses based on Raman signals.
在另一种优选实现方式中,所述方法还包括,在所述静电吸附组件两侧设置多通反射组件(1.2.5),其具有朝向所述吸附组件的至少一个反射面、所述激光对向所述多通反射组件(1.2.5)的反射面入射,以使得所述其多次照射在所述静电吸附组件上。In another preferred implementation manner, the method further includes, arranging a multi-pass reflection assembly (1.2.5) on both sides of the electrostatic adsorption assembly, which has at least one reflection surface facing the adsorption assembly, the laser Incident to the reflective surface of the multi-pass reflective component (1.2.5), so that it is irradiated on the electrostatic adsorption component multiple times.
在另一种优选实现方式中,还包括在进行微生物检测之前或之后进行气体组分检测。In another preferred implementation manner, it also includes performing gas component detection before or after the microbial detection.
在另一种优选实现方式中,在所述静电吸附组件上游设置气泵,以通过强气流对所述静电吸附组件进行清洗,所述气体综合检测装置还包括温控消杀组件(1.3.2),所述温控消杀组件(1.3.2)用于对所述选通富集模块进行消杀。In another preferred implementation, an air pump is arranged upstream of the electrostatic adsorption assembly to clean the electrostatic adsorption assembly through a strong air flow, and the comprehensive gas detection device also includes a temperature-controlled disinfecting assembly (1.3.2) , the temperature-controlled disinfecting component (1.3.2) is used to disinfect the gate-enrichment module.
在另一种优选实现方式中,所述静电吸附组件由纳米金属材料,优选,纳米金属颗粒材料构成,更优选地,所述静电吸附组件包括纳米金或纳米 银颗粒。In another preferred implementation manner, the electrostatic adsorption component is made of nano-metal material, preferably, nano-metal particle material, and more preferably, the electrostatic adsorption component includes nano-gold or nano-silver particles.
发明原理Principle of invention
本发明提出了可以实现对微生物进行检测的检测方法。在优选实现方式中,本发明既能够对气体中病毒等微生物进行检测又能对各种气体组分和颗粒物进行检测。The invention proposes a detection method that can realize the detection of microorganisms. In a preferred implementation mode, the present invention can not only detect microorganisms such as viruses in gas, but also detect various gas components and particles.
首先,本发明方法在气体行进路径上游,利用荷电装置使本身带有一定电荷的病毒等微生物气溶胶粒子重新荷电,并气体行进路径下游,在静电场作用力下将带电病毒等微生物气溶胶粒子从气流中分离出——即带电微病毒等微生物粒子进入电场后,在电场力的作用下发生偏转,从而被吸附在金属纳米微材料表面上。而其它颗粒物如PM2.5、PM10等带电量很少,受电场作用力很小,在气流作用下被吹送到选通富集模块外,从而达到选通效果,极大减小了颗粒物的荧光效应给检测带来的影响。First of all, the method of the present invention uses a charging device to recharge microbial aerosol particles such as viruses with a certain charge in the upstream of the gas travel path, and recharges the charged microbial aerosol particles such as viruses under the force of an electrostatic field to the downstream of the gas travel path. The sol particles are separated from the air flow—that is, after the charged micro-viruses and other microbial particles enter the electric field, they are deflected under the action of the electric field force, and thus are adsorbed on the surface of the metal nano-micro-material. Other particulate matter such as PM2.5, PM10, etc. have very little charge and are under the action of an electric field. They are blown out of the gating enrichment module under the action of airflow, thereby achieving the gating effect and greatly reducing the fluorescence of the particulate matter. The impact of the effect on the detection.
采用本发明方法,通过设计不同极板间距(mm),荷电电压(kV),静电场强度(kV/cm),气流流量(L/min),可实现对不同种类病毒等微生物气溶胶粒子的高效、高存活率收集。By adopting the method of the present invention, by designing different plate spacing (mm), charging voltage (kV), electrostatic field strength (kV/cm), and airflow flow rate (L/min), microbial aerosol particles such as different types of viruses can be realized Efficient and high survival rate collection.
然后,通过强电场组件给吸附组件中的金属纳米微材料施加强电场,使其所含自由电子数增加至少一个量级,从而使金属纳米结构表面的电场强度增强至少10倍,并采用侧/前向多通表面增强拉曼效应获得病毒等微生物气溶胶的拉曼光谱信息,结合人工智能图像分析处理技术完成病毒等微生物气溶胶的检测。Then, apply a strong electric field to the metal nano-micromaterial in the adsorption component through the strong electric field component, so that the number of free electrons contained in it increases by at least one order of magnitude, so that the electric field intensity on the surface of the metal nanostructure is enhanced by at least 10 times, and the side/ The forward multi-pass surface-enhanced Raman effect obtains the Raman spectral information of viruses and other microbial aerosols, and combines artificial intelligence image analysis and processing technology to complete the detection of viruses and other microbial aerosols.
具体来说,使入射光照射到金属纳米微材料上,优选的,例如金纳米 微材料上,纳米粒子中的电子在外电场的作用下振动,当入射光的频率与电子固有振动频率相等时,就会发生局域表面等离子体共振,在金属纳米结构表面形成比激发电场更强的局域增强电场。本发明通过给金属纳米结构施加强电场,使金属中自由电子在强电场激发下大大增加,从而使金属纳米结构表面的电场强度可以比施加电场前高一个数量级,而表面增强拉曼散射(SERS)的信号强度正比于表面增强电场的四次方。所以,本发明装置足够将拉曼信号再提高10 4倍,即信噪比提高40dB。 Specifically, the incident light is irradiated on the metal nano-micromaterial, preferably, for example, on the gold nano-micromaterial, and the electrons in the nanoparticles vibrate under the action of an external electric field. When the frequency of the incident light is equal to the natural vibration frequency of the electron, Local surface plasmon resonance will occur, and a local enhanced electric field stronger than the excited electric field will be formed on the surface of the metal nanostructure. In the present invention, by applying a strong electric field to the metal nanostructure, the free electrons in the metal are greatly increased under the excitation of the strong electric field, so that the electric field intensity on the surface of the metal nanostructure can be an order of magnitude higher than that before the electric field is applied, and the surface-enhanced Raman scattering (SERS ) is proportional to the fourth power of the surface-enhanced electric field. Therefore, the device of the present invention is sufficient to increase the Raman signal by 10 4 times, that is, the signal-to-noise ratio is increased by 40 dB.
将采集到的拉曼光谱进行光谱预处理,采用S-G卷积实现光谱平滑,采用多段低阶多项式收敛算法实现基线对准,再采用最大归一化法进行光谱归一化。所得光谱采用主成分分析法和SVM支持向量机有监督的人工智能模式识别法,得到解构模型,从而对不同种类病毒等微生物气溶胶进行识别。具体算法公式如下:The collected Raman spectra were subjected to spectral preprocessing, S-G convolution was used to achieve spectral smoothing, multi-stage low-order polynomial convergence algorithm was used to achieve baseline alignment, and then the maximum normalization method was used for spectral normalization. The obtained spectrum adopts principal component analysis method and SVM support vector machine supervised artificial intelligence pattern recognition method to obtain a deconstruction model, so as to identify different types of microbial aerosols such as viruses. The specific algorithm formula is as follows:
S-G卷积S-G convolution
Figure PCTCN2022099029-appb-000001
Figure PCTCN2022099029-appb-000001
多项式收敛polynomial convergence
BL(n)=min[f(n),S(n)],n=1,2,...,L,    (2)BL(n)=min[f(n), S(n)], n=1, 2,..., L, (2)
归一化Normalized
Figure PCTCN2022099029-appb-000002
Figure PCTCN2022099029-appb-000002
采用主成分分析法选取数个贡献率大于1%的主成分,得到累计贡献率,再以一定数量的样本数据分别作为训练集和预测集,采用SVM有监督的人工智能模式识别法,建立解构模型,可以实现高于95%的检出率。Use the principal component analysis method to select several principal components with a contribution rate greater than 1% to obtain the cumulative contribution rate, and then use a certain number of sample data as the training set and prediction set respectively, and use the SVM supervised artificial intelligence pattern recognition method to establish a deconstruction The model can achieve a detection rate higher than 95%.
SVM的多项式核函数:The polynomial kernel function of SVM:
K(x,y)=[(x·y)+1] d    (4) K(x,y)=[(x·y)+1] d (4)
本发明方法通过采用温度场灭活和大流速气流冲刷技术完成富集芯片的消杀清洗,也可以通过调节高压电场强度达到病毒等微生物灭活的作用。The method of the present invention completes the killing and cleaning of the enrichment chip by adopting temperature field inactivation and high-flow airflow scouring technology, and can also achieve the effect of inactivating microorganisms such as viruses by adjusting the intensity of the high-voltage electric field.
技术效果technical effect
1、本发明的检测方法快速、高灵敏度并且优选地,其还能够高精度检测复合气体组份、浓度及悬浮颗粒的颗粒度、浓度。本发明方法首先通过选通过程,筛除了检测样本中的颗粒物,可以大幅减少颗粒物荧光对检测的影响,且能增加装置使用寿命。1. The detection method of the present invention is fast, highly sensitive and preferably, it can also detect the composition and concentration of composite gas and the particle size and concentration of suspended particles with high precision. The method of the present invention first screens out the particles in the detection sample through the selection process, can greatly reduce the influence of particle fluorescence on the detection, and can increase the service life of the device.
2、本发明方法通过给金属纳米材料施加强电场,使其自由电子数大大增加,从而使金属纳米结构表面的电场强度可以比施加电场前高一个数量级,然后通过侧/前向多通拉曼表面增强再倍增技术,将拉曼信号再提高10 4倍,大大提高了信噪比和探测灵敏度。通过结合人工智能图像处理技术,可以实现高于95%的检出率。 2. The method of the present invention greatly increases the number of free electrons by applying a strong electric field to the metal nanomaterial, so that the electric field intensity on the surface of the metal nanostructure can be an order of magnitude higher than that before the electric field is applied, and then through the side/forward multi-pass Raman The surface-enhanced remultiplication technology increases the Raman signal by 10 4 times, greatly improving the signal-to-noise ratio and detection sensitivity. By combining artificial intelligence image processing technology, a detection rate higher than 95% can be achieved.
3、本发明方法还提出了采用温度场灭活和大流速气流冲刷完成富集芯片的消杀清洗,提高了检测装置的使用寿命,降低了检测成本。3. The method of the present invention also proposes the use of temperature field inactivation and high-velocity airflow scouring to complete the killing and cleaning of the enrichment chip, which improves the service life of the detection device and reduces the detection cost.
附图说明Description of drawings
图1为本发明方法的检测构思示意图;Fig. 1 is the detection conceptual schematic diagram of the inventive method;
图2为用于执行本发明方法的装置的结构示意图;Fig. 2 is the structural representation of the device for carrying out the method of the present invention;
图3为本发明实施例2中的气体组分检测装置的原理示意图;3 is a schematic diagram of the principle of the gas component detection device in Example 2 of the present invention;
具体实施方式detailed description
为使发明装置的目的、技术方案和优点更加清楚,下面将发明中的技术方案进行清楚地描述,显然,所描述的实施例是发明装置的一部分实施例,而不是全部的实施例。基于发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于发明保护的范围。In order to make the purpose, technical solutions and advantages of the inventive device clearer, the technical solutions in the invention will be clearly described below. Apparently, the described embodiments are part of the embodiments of the inventive device, not all of them. Based on the embodiments of the invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the invention.
实施例1:Example 1:
如图1所示,本实施例的检测方法主要分成几个步骤:病毒等微生物气溶胶的选通富集、通过给金属纳米微材料施加强电场使其所含自由电子数目大幅增加,通过基于强电场调控的多通表面增强拉曼效应和人工智能图像分析处理来完成微生物气溶胶的检测,最后进行气流冲刷和微生物消杀。As shown in Figure 1, the detection method of this embodiment is mainly divided into several steps: gating enrichment of microbial aerosols such as viruses, applying a strong electric field to metal nano-micromaterials so that the number of free electrons contained in them is greatly increased, and based on The multi-pass surface-enhanced Raman effect regulated by strong electric field and artificial intelligence image analysis and processing are used to complete the detection of microbial aerosols, and finally perform airflow washing and microbial disinfecting.
就具体的气流走向而言,本实施例的方法包括以下步骤:As far as the specific airflow direction is concerned, the method of the present embodiment includes the following steps:
(1)对目标气体放电以使其负载电荷;(1) Discharge the target gas so that it is charged;
(2)驱动所述目标气体通过静电吸附组件,所述静电吸附组件外侧施加有电场以对目标微生物进行吸附,所述静电吸附组件内具有金属纳米微材料;(2) driving the target gas through the electrostatic adsorption assembly, an electric field is applied to the outside of the electrostatic adsorption assembly to adsorb the target microorganisms, and the electrostatic adsorption assembly has metal nano-micromaterials;
(3)沿着所述激光通路向所述静电吸附组件内发射激光,以使激光至 少部分照射到纳米材料表面,进行电场增强的拉曼检测;探测从所述静电吸附组件出射的拉曼信号基于所述拉曼信号进行微生物检测。(3) emit laser light into the electrostatic adsorption component along the laser path, so that the laser light is at least partially irradiated on the surface of the nanomaterial, and perform electric field enhanced Raman detection; detect the Raman signal emitted from the electrostatic adsorption component Microbial detection is performed based on the Raman signal.
优选地,还可以设置强电场的强度,使其高于一定值,比如,达到上千伏,以进行微生物消杀和颗粒物处理。Preferably, the intensity of the strong electric field can also be set to be higher than a certain value, for example, up to thousands of volts, so as to disinfect microorganisms and treat particulate matter.
此外,在将所述激光入射至所述静电吸附组件之前,对所述激光进行滤波。在所述吸附组件的出口处、拉曼探测组件前方设置非球面长焦深滤波组件,对出射的拉曼散射光进行滤波,滤除背景荧光和杂散光。In addition, before the laser light is incident on the electrostatic adsorption component, the laser light is filtered. An aspherical long-focus filter component is arranged at the exit of the adsorption component and in front of the Raman detection component to filter the outgoing Raman scattered light and filter out background fluorescence and stray light.
优选地,在所述静电吸附组件两侧设置多通反射组件,其具有朝向所述吸附组件的至少一个反射面、所述激光对向所述多通反射组件的反射面入射,以使得所述其多次照射在所述静电吸附组件上。Preferably, a multi-pass reflective assembly is provided on both sides of the electrostatic adsorption assembly, which has at least one reflective surface facing the adsorption assembly, and the laser is incident on the reflective surface of the multi-pass reflective assembly, so that the It is irradiated on the electrostatic adsorption assembly multiple times.
如图2所示,其中介绍了用于执行本发明方法的一种对应装置,其包括微生物检测模块1、气体组分检测模块2(可选)和处理控制通信模块3。气体组分检测模块可以选装,可以将待测气体先通入一种检测模块检测后,再将气体通入另一种检测模块,进行检测。As shown in FIG. 2 , a corresponding device for implementing the method of the present invention is introduced, which includes a microorganism detection module 1 , a gas component detection module 2 (optional) and a processing control communication module 3 . The gas component detection module can be optional, and the gas to be tested can be passed into one detection module for detection, and then the gas can be passed into another detection module for detection.
微生物检测模块包括选通富集模块、拉曼模块、消杀清洗模块。如图2所示,选通富集模块包括气泵1.1.1,荷电组件1.1.2和静电吸附组件1.1.3。选通富集模块用于对病毒等微生物气溶胶进行选通、富集。The microbial detection module includes a gating enrichment module, a Raman module, and a disinfecting and cleaning module. As shown in Figure 2, the gate-enrichment module includes an air pump 1.1.1, a charging component 1.1.2 and an electrostatic adsorption component 1.1.3. The gating and enrichment module is used for gating and enriching microbial aerosols such as viruses.
在本实施例中,荷电组件安装在荷电腔内,该腔体密封、两侧一端与气泵1.1.1相连通,另一端与静电吸附组件1.1.3的吸附腔相连通。荷电组件1.1.2具有高压电源和直径为40μm(也可以采用其他尺寸)的一组或者多组钨丝对,设置钨丝的放电间距为8mm,荷电电压+5kV,对通过其间的进行气溶胶荷电。In this embodiment, the charging component is installed in the charging chamber, the cavity is sealed, one end on both sides communicates with the air pump 1.1.1, and the other end communicates with the adsorption chamber of the electrostatic adsorption component 1.1.3. The charging component 1.1.2 has a high-voltage power supply and one or more sets of tungsten wire pairs with a diameter of 40 μm (other sizes can also be used). The discharge distance of the tungsten wires is set to 8mm, and the charging voltage is +5kV. Aerosol charges.
本实施例中,吸附腔内设置静电吸附组件1.1.3,静电吸附组件1.1.3的主材料为三维絮网状金纳米材料堆积而成。静电吸附组件用于对经荷电处理的目标气体中的微生物进行吸附,吸附组件内预留激光通路。需要说明的是,本发明中所提到的预留激光通路包含两方面含义,一方面指的是静电吸附组件中金纳米材料的稀疏度足够激光通过,或者,静电吸附组件中的纳米材料沿着激光路径形成片层或面状结构,激光从片层结构的间隙通过,并至少部分照射在纳米材料上。In this embodiment, an electrostatic adsorption component 1.1.3 is arranged in the adsorption chamber, and the main material of the electrostatic adsorption component 1.1.3 is formed by stacking three-dimensional flocculated gold nanomaterials. The electrostatic adsorption component is used to adsorb microorganisms in the charged target gas, and a laser path is reserved in the adsorption component. It should be noted that the reserved laser path mentioned in the present invention includes two meanings. On the one hand, it means that the gold nanomaterials in the electrostatic adsorption component are sparse enough for the laser to pass through, or that the nanomaterials in the electrostatic adsorption component are along the A sheet or planar structure is formed along the laser path, and the laser passes through gaps in the sheet structure and is at least partially irradiated on the nanometer material.
拉曼模块包括强电场组件1.2.1,激光激发源1.2.2,干涉滤波组件1.2.3,瑞利滤光片1.2.4,多通反射组件1.2.5,激光吸收池1.2.6,非球面长焦深滤波组件1.2.7,拉曼探测组件1.2.8。Raman module includes strong electric field component 1.2.1, laser excitation source 1.2.2, interference filter component 1.2.3, Rayleigh filter 1.2.4, multi-pass reflection component 1.2.5, laser absorption pool 1.2.6, non Spherical long focal depth filter component 1.2.7, Raman detection component 1.2.8.
拉曼模块通过强电场组件1.2.1给静电吸附组件1.1.3施加强电场,使静电吸附组件1.1.3所含自由电子数大大增加,并通过侧/前向多通表面增强拉曼效应原理利用拉曼探测组件1.2.8获得病毒等微生物气溶胶的拉曼光谱信息。强电场组件1.2.1设置在静电吸附组件的上、下或左、右两侧,将在静电吸附组件夹在中间。所述激光激发源1.2.2用于沿着所述激光通路向所述静电吸附组件内发射激光。The Raman module applies a strong electric field to the electrostatic adsorption component 1.1.3 through the strong electric field component 1.2.1, which greatly increases the number of free electrons contained in the electrostatic adsorption component 1.1.3, and enhances the Raman effect principle through the side/forward multi-pass surface Use the Raman detection component 1.2.8 to obtain the Raman spectrum information of microbial aerosols such as viruses. The strong electric field component 1.2.1 is arranged on the upper, lower or left and right sides of the electrostatic adsorption component, sandwiching the electrostatic adsorption component in the middle. The laser excitation source 1.2.2 is used to emit laser light into the electrostatic adsorption assembly along the laser path.
优选地,为了增加吸附效果,在吸附组件两侧,除了强电长组件1.2.1之外,增设收集电场组件(即,在吸附组件上下表面,额外提供一组电极板)。收集电场(1.1.3.1)强度E=3.5kV/cm,由银材料组成平行电极板间距h为20mm,宽度b为10mm,长度l为100mm。涡轮气泵流量为10L/min。以此模块对病毒等微生物气溶胶进行富集,并筛除颗粒物和达到选通效果。Preferably, in order to increase the adsorption effect, on both sides of the adsorption component, in addition to the strong electric field component 1.2.1, a collection electric field component is added (that is, an additional set of electrode plates is provided on the upper and lower surfaces of the adsorption component). Collecting electric field (1.1.3.1) strength E=3.5kV/cm, composed of silver material, the distance h between parallel electrode plates is 20mm, the width b is 10mm, and the length l is 100mm. The flow rate of the turbo air pump is 10L/min. This module enriches microbial aerosols such as viruses, and screens out particulate matter and achieves a gating effect.
选通富集模块的工作过程为:首先,气泵1.1.1启动,驱动被测气体进 入到荷电组件内。通过高压电源为钨丝供电,进行高压放电。通过该荷电组件使本身带有一定电荷的病毒等微生物气溶胶粒子重新荷电。经荷电处理后的空气进一步进入到静电吸附组件内,并通过静电吸附组件(静电吸附组件采用的是纳米颗粒材料,气体可以通过)。在静电吸附组件内,由于外部施加的电场,带电荷较多的微生物在电场力的作用下发生偏转,从而被吸附在金属纳米微材料表面上。而其它颗粒物如PM2.5、PM10等带电量很少,受电场作用力很小,在气流作用下被吹送到选通富集模块外。The working process of the gating enrichment module is as follows: firstly, the gas pump 1.1.1 is started to drive the measured gas into the charged component. The tungsten wire is powered by a high-voltage power supply for high-voltage discharge. Microbial aerosol particles such as viruses with a certain charge are recharged by the charging component. The charged air further enters the electrostatic adsorption component and passes through the electrostatic adsorption component (the electrostatic adsorption component uses nano-particle materials, and the gas can pass through it). In the electrostatic adsorption component, due to the externally applied electric field, the more charged microorganisms are deflected under the action of the electric field force, and thus are adsorbed on the surface of the metal nano-micro material. Other particles such as PM2.5, PM10, etc. have very little charge, are subjected to little electric field force, and are blown out of the gate enrichment module under the action of airflow.
该荷电组件使本身带有一定电荷的病毒等微生物气溶胶粒子重新荷电,并在静电场作用力下将带电病毒等微生物气溶胶粒子从气流中分离出——即带电微病毒等微生物粒子进入电场后,在电场力的作用下发生偏转,从而被吸附在金属纳米微材料表面上。而其它颗粒物如PM2.5、PM10等带电量很少,受电场作用力很小,在气流作用下被吹送到选通富集模块外,从而达到选通效果。The charging component recharges the microbial aerosol particles such as viruses with a certain charge, and separates the charged microbial aerosol particles such as viruses from the air flow under the force of an electrostatic field—that is, charged micro-viruses and other microbial particles After entering the electric field, it is deflected under the action of the electric field force, and thus is adsorbed on the surface of the metal nano-micro material. Other particles such as PM2.5, PM10, etc. have very little charge and are under the action of the electric field. They are blown to the outside of the gating enrichment module under the action of the airflow, so as to achieve the gating effect.
与此同时,由于拉曼模块通过强电场组件1.2.1给静电吸附组件1.1.3施加强电场,使其所含自由电子数增加至少一个量级,从而使金属纳米结构表面的电场强度增强至少10倍,当微生物吸附到静电吸附组件1.1.3之后,通过拉曼模块的激光源1.2.2发出的激光经由干涉滤波组件1.2.3,瑞利滤光片1.2.4的滤波,最终照射到吸附组件内所吸附的微生物上。本实施例中,为了增加激光与材料的相互作用,优选在吸附组件的外侧设置了多通反射组件1.2.5,其反射面朝向吸附组件1.1.3。并且,将激光的入射方向设置为斜向入射,使得激光在多通反射组件1.2.5的反射下,在吸附组件1.1.3内折返几次,然后从另一侧出射。At the same time, since the Raman module applies a strong electric field to the electrostatic adsorption component 1.1.3 through the strong electric field component 1.2.1, the number of free electrons contained in it increases by at least one order of magnitude, thereby increasing the electric field intensity on the surface of the metal nanostructure by at least 10 times, when the microorganisms are adsorbed to the electrostatic adsorption component 1.1.3, the laser light emitted by the laser source 1.2.2 of the Raman module is filtered by the interference filter component 1.2.3 and the Rayleigh filter 1.2.4, and finally irradiated to On the microorganisms adsorbed in the adsorption component. In this embodiment, in order to increase the interaction between the laser and the material, it is preferable to arrange a multi-pass reflective component 1.2.5 on the outside of the adsorption component, with its reflection surface facing the adsorption component 1.1.3. Moreover, the incident direction of the laser is set as an oblique incident, so that the laser is reflected by the multi-pass reflection component 1.2.5, turns back several times in the adsorption component 1.1.3, and then exits from the other side.
在本实施例中,拉曼模块中强电场组件的电场强度为E=4.3kV/cm,用于给纳米材料表面施加强电场;激光激发源参数为50微瓦、532nm波长,1.3微米直径,1微米焦深,功率密度为5*10 -5/10 -8=500W/cm 2。采用本发明的装置可测得10 -8M的R6G表面增强拉曼光谱,其激光照射的分子数量为:6.02*10 23*10 -8*(0.65*10 -5)2*3.14*10 -5≈5个R6G分子/m 3,信噪比提高40dB,病毒等微生物测量灵敏度也相应提升4个量级;干涉滤波组件为532nm干涉滤波片;瑞利滤光片为陷波滤光片,其吸收中心位于532nm;多通反射组件为镀有532nm波长高反膜的光学镜片;激光吸收池为发黑铝合金光收集器;非球面长焦深滤波组件为熔石英材质,表面镀有532nm波长高透膜;拉曼探测组件为CCD探测器;如图2所示,拉曼模块中各组件按光路同轴放置。 In this embodiment, the electric field strength of the strong electric field component in the Raman module is E=4.3kV/cm, which is used to apply a strong electric field to the surface of the nanomaterial; the laser excitation source parameters are 50 microwatts, 532nm wavelength, 1.3 micron diameter, With a depth of focus of 1 micron, the power density is 5*10 -5 /10 -8 = 500 W/cm 2 . The device of the present invention can measure the surface-enhanced Raman spectrum of R6G at 10 -8 M, and the number of molecules irradiated by the laser is: 6.02*10 23 *10 -8 *(0.65*10 -5 )2*3.14*10 - 5 ≈5 R6G molecules/m 3 , the signal-to-noise ratio is increased by 40dB, and the measurement sensitivity of viruses and other microorganisms is also increased by 4 orders of magnitude; the interference filter component is a 532nm interference filter; the Rayleigh filter is a notch filter, Its absorption center is located at 532nm; the multi-pass reflection component is an optical lens coated with a high-reflection film with a wavelength of 532nm; the laser absorption pool is a blackened aluminum alloy light collector; The wavelength is highly transparent; the Raman detection component is a CCD detector; as shown in Figure 2, the components in the Raman module are placed coaxially according to the optical path.
本实施例中,激光吸收池为激光垃圾桶,铝合金材质,表面氧化发黑处理,放置在主光路末端。In this embodiment, the laser absorption pool is a laser trash can, made of aluminum alloy, the surface is oxidized and blackened, and placed at the end of the main optical path.
在本实施例中,消杀清洗模块采用高温加热棒和选通富集模块中的涡轮气泵,起到对选通富集模块中的病毒等微生物进行消杀和清洗的作用。In this embodiment, the disinfecting and cleaning module uses a high-temperature heating rod and a turbo air pump in the gate-enrichment module to disinfect and clean microorganisms such as viruses in the gate-enrichment module.
在本实施例中,处理控制通信模块,采用人工智能图形分析处理技术,包括光谱预处理,然后将所得光谱采用主成分分析法和SVM支持向量机有监督的人工智能模式识别法,得到不同病毒等微生物独有的解构模型。检测时根据采集到的图形与结构模型库进行对比,从而可以对不同种类病毒等微生物进行匹配识别。In this embodiment, the processing and control communication module adopts artificial intelligence graphic analysis and processing technology, including spectral preprocessing, and then uses the principal component analysis method and SVM support vector machine supervised artificial intelligence pattern recognition method to obtain the spectrum obtained to obtain different viruses. and other unique deconstruction models for microorganisms. During the detection, the collected graphics are compared with the structural model library, so that different types of viruses and other microorganisms can be matched and identified.
在其他一些实施例中,所述金属纳米材料可以为多块平行放置的二维平板状金属纳米板,优选的为二维平板状金纳米板,并与其他二维平板状 金纳米板和多通反射组件一起组成反射光路,可以使激光激发源发出的激光在二维平板状金纳米板和多通反射组件之间反射。其可以有效增强激发电场强度,提高装置的探测灵敏度。In some other embodiments, the metal nanomaterial can be a plurality of two-dimensional flat metal nanoplates placed in parallel, preferably two-dimensional flat gold nanoplates, and combined with other two-dimensional flat gold nanoplates and multiple The reflective optical path is composed of the pass-reflector components, which can reflect the laser light emitted by the laser excitation source between the two-dimensional flat gold nanoplate and the multi-pass reflector components. It can effectively enhance the excitation electric field intensity and improve the detection sensitivity of the device.
实施例2Example 2
在本实施例中,除了上述微生物检测之外,本发明的综合检测方法还包括在进行微生物检测之前或之后进行气体组分检测。In this embodiment, in addition to the above microorganism detection, the comprehensive detection method of the present invention also includes gas component detection before or after the microorganism detection.
气体组分检测包括:Gas component detection includes:
步骤2-1:以重复频率为R,脉冲宽度为τ的脉冲序列的方式,向测试气室中发射多个波长的光脉冲,进行测试。单个波长为λ的脉冲在气室内的耗散时间t满
Figure PCTCN2022099029-appb-000003
测试气室可以采用常规气室,只要能够允许气流通过并且允许光脉冲进出并照射到其内气体即可。
Step 2-1: Transmit light pulses of multiple wavelengths into the test gas chamber in the form of a pulse sequence with a repetition frequency of R and a pulse width of τ for testing. The dissipation time t of a single pulse of wavelength λ in the gas chamber is
Figure PCTCN2022099029-appb-000003
The test gas chamber can be a conventional gas chamber, as long as it can allow airflow to pass through and allow light pulses to enter and exit and irradiate the gas inside.
步骤2-2:使用光散射法进行悬浮颗粒物颗粒度及相应浓度的测量,任意从多个波长的测试光中选取适用于散射光谱法测量的测试光,确定选定波长的散射系数。若测试光波长为λ,出射光强为I 0(λ),测试光程长度为l,并测量前向散射光强I s||(λ),得到多个参考散射系数(每个波长有一个参考散射系数) Step 2-2: Use the light scattering method to measure the particle size and corresponding concentration of suspended particles, randomly select the test light suitable for the measurement of the scattering spectrometry from the test light of multiple wavelengths, and determine the scattering coefficient of the selected wavelength. If the wavelength of the test light is λ, the outgoing light intensity is I 0 (λ), the test optical path length is l, and the forward scattering light intensity I s|| (λ) is measured, multiple reference scattering coefficients (each wavelength has a reference scattering coefficient)
Figure PCTCN2022099029-appb-000004
Figure PCTCN2022099029-appb-000004
将所获得的参考散射系数代入式(5)。Substitute the obtained reference scattering coefficient into formula (5).
Figure PCTCN2022099029-appb-000005
Figure PCTCN2022099029-appb-000005
即为同质散射系数方程,λ a、λ b为两种测量波长。根据此公式,相同散射介质条件下,两两一组,将用于红外光谱法测量的不同波长测试光分别代 入该公式,得到多个同质散射系数方程,构成同质散射系数方程组。 That is, the homogeneous scattering coefficient equation, λ a , λ b are two kinds of measurement wavelengths. According to this formula, under the condition of the same scattering medium, two pairs of test lights used for infrared spectroscopy measurement are substituted into the formula respectively, and multiple homogeneous scattering coefficient equations are obtained to form a group of homogeneous scattering coefficient equations.
本发明为确保各个波长信号间相互无干扰,以重复频率为R,脉冲宽度为τ的脉冲序列的方式,向测试气室中发射若干波长的光脉冲,进行测试。这样使得单个波长为λ的脉冲拥有更高的峰值功率,在探测过程中拥有更高的对比度。同时只要确保单个波长为λ的脉冲在气室内的耗散时间t满足In order to ensure that there is no interference among the signals of various wavelengths, the present invention transmits light pulses of several wavelengths into the test gas chamber in the form of a pulse sequence with a repetition frequency of R and a pulse width of τ for testing. This allows a single pulse with a wavelength of λ to have a higher peak power and a higher contrast in the detection process. At the same time, it is only necessary to ensure that the dissipation time t of a single pulse with wavelength λ in the gas chamber satisfies
Figure PCTCN2022099029-appb-000006
Figure PCTCN2022099029-appb-000006
即可确保多种测试光脉冲,在经过气室后进行测量时相互独立。This ensures that multiple test light pulses are independent of each other when measured after passing through the gas cell.
同时测量特定散射角下所选取的多波长的侧向散射光强I s⊥(λ),按照上述公式(4)使用光散射法分析得到悬浮颗粒物颗粒度及相应浓度。 Simultaneously measure the selected multi-wavelength side scattered light intensity I s⊥ (λ) at a specific scattering angle, and use the light scattering method to analyze the particle size and corresponding concentration of suspended particles according to the above formula (4).
步骤2-3:按照上述公式(8)使用红外光谱检测法进行测量,这些测量光可以直接在脉冲序列内与用于光谱法测量的光脉冲顺序发射接收,也可以单独发射。在红外光谱检测中,对于需要测量的气体组份1、气体组份2、气体组份3···气体组份m,采用对应测试波长λ 1、λ 2、λ 3···λ n(测试波长中至少包含对应每一种组分的吸收峰的光波长),对应摩尔分子吸收系数分别为
Figure PCTCN2022099029-appb-000007
对应所需测得浓度为c 1、c 2、c 3···c n,且测试波长λ 1、λ 2、λ 3···λ n仅与对应气体组份1、气体组份2、气体组份3···气体组份n存在较强吸收,其余组份的吸收可以忽略。检测光程为L,得到红外光谱测量方程组
Step 2-3: Use the infrared spectroscopic detection method to measure according to the above formula (8). These measurement lights can be directly transmitted and received in sequence with the light pulses used for spectroscopic measurement in the pulse sequence, or can be transmitted separately. In the infrared spectrum detection, for the gas component 1, gas component 2, gas component 3... gas component m to be measured, the corresponding test wavelengths λ 1 , λ 2 , λ 3 ···λ n ( The test wavelength at least includes the light wavelength corresponding to the absorption peak of each component), and the corresponding molar molecular absorption coefficients are respectively
Figure PCTCN2022099029-appb-000007
The corresponding measured concentrations are c 1 , c 2 , c 3 ···c n , and the test wavelengths λ 1 , λ 2 , λ 3 ···λ n are only compatible with the corresponding gas components 1, Gas component 3... There is a strong absorption of gas component n, and the absorption of other components is negligible. The detection optical path is L, and the infrared spectrum measurement equations are obtained
Figure PCTCN2022099029-appb-000008
Figure PCTCN2022099029-appb-000008
步骤2-4:将(5)(7)(8)联立(将公式5和7带入公式8),在求解 过程中,由于公式(7)中可以获得多个参考散射系数,在选取时,选择参考散射系数与测试波长相近的波长的参考散射系数,确定散射项大小。Step 2-4: Simultaneously combine (5)(7)(8) (bring formula 5 and 7 into formula 8). During the solution process, since multiple reference scattering coefficients can be obtained in formula (7), when selecting When , select the reference scattering coefficient of the wavelength whose reference scattering coefficient is close to the test wavelength to determine the size of the scattering item.
对于各个气体组分,摩尔分子吸收系数较大的气体由前述确定了散射项的红外光谱测量方程直接得到,得到了摩尔分子吸收系数较大的气体组分浓度之后,带回到红外光谱测量方程组,对摩尔分子吸收系数较小的,由确定了散射项大小的红外光谱测量方程组采用阶梯差分运算得到准确的气体组份浓度结果,其运算公式如下For each gas component, the gas with a larger molar absorption coefficient is directly obtained from the aforementioned infrared spectrum measurement equation with the scattering item determined, and after the concentration of the gas component with a larger molar molecular absorption coefficient is obtained, it is brought back to the infrared spectrum measurement equation For those with small molar molecular absorption coefficients, the accurate gas component concentration results can be obtained by using the step difference operation of the infrared spectrum measurement equation group with the size of the scattering item determined, and the operation formula is as follows
Figure PCTCN2022099029-appb-000009
Figure PCTCN2022099029-appb-000009
如图3所示为用于执行本实施例方法的检测装置,其包括多波长脉冲序列发生模块301,第一探测单元302,第二探测单元303,气室主体304,气室入口组件305以及气室出口组件306。被测气体从气室入口组件305处进入气室内部,从气室出口组件306处流出。As shown in Figure 3, it is a detection device for performing the method of this embodiment, which includes a multi-wavelength pulse sequence generation module 301, a first detection unit 302, a second detection unit 303, a gas chamber main body 304, a gas chamber inlet assembly 305 and Air chamber outlet assembly 306 . The measured gas enters the gas chamber from the gas chamber inlet assembly 305 and flows out from the gas chamber outlet assembly 306 .
本实施例中,多波长脉冲序列发生模块301为由脉冲电源与4个不同中心波长QCL激光光源封装组成的模块,中心波长分别对应PM2.5、PM10颗粒物的指纹波长(532nm,640nm),CO 2的指纹波长(4.26μm)和甲醛的指纹波长(3.56μm)。第一探测单元302设置于气室入口附近,采用对PM2.5、PM10颗粒物的指纹波长(532nm,640nm)响应的光电二极管。用于进行以光散射法进行测量,测量双波长脉冲光特定散射角散射光强及前向散射光强。第二探测单元303设置于气室出口附近,采用对CO 2的指纹波长(4.26μm)和甲醛的指纹波长(3.56μm)响应的光电二极管,用于以红外光谱吸收法测量多波长脉冲光经气室主模块(4)传播后的光强。 In this embodiment, the multi-wavelength pulse sequence generation module 301 is a module composed of a pulse power supply and four QCL laser light source packages with different central wavelengths. The central wavelengths correspond to the fingerprint wavelengths (532nm, 640nm) of PM2.5 and PM10 particles respectively, CO 2 's fingerprint wavelength (4.26μm) and formaldehyde's fingerprint wavelength (3.56μm). The first detection unit 302 is arranged near the entrance of the air chamber, and adopts a photodiode responsive to the fingerprint wavelength (532nm, 640nm) of PM2.5 and PM10 particles. It is used for measurement by light scattering method, and measures the scattered light intensity and forward scattered light intensity of dual-wavelength pulsed light at a specific scattering angle. The second detection unit 303 is arranged near the outlet of the gas chamber, and adopts a photodiode responsive to the fingerprint wavelength (4.26 μm) of CO and formaldehyde (3.56 μm), and is used to measure the multi-wavelength pulsed light by infrared spectroscopic absorption method. The light intensity transmitted by the air chamber main module (4).
虽然上面结合本发明的优选实施例对本发明的原理进行了详细的描述,本领域技术人员应该理解,上述实施例仅仅是对本发明的示意性实现方式的解释,并非对本发明包含范围的限定。实施例中的细节并不构成对本发明范围的限制,在不背离本发明的精神和范围的情况下,任何基于本发明技术方案的等效变换、简单替换等显而易见的改变,均落在本发明保护范围之内。Although the principle of the present invention has been described in detail above in conjunction with the preferred embodiments of the present invention, those skilled in the art should understand that the above embodiments are only explanations for the exemplary implementation of the present invention, and are not intended to limit the scope of the present invention. The details in the embodiments do not constitute a limitation to the scope of the present invention. Without departing from the spirit and scope of the present invention, any obvious changes such as equivalent transformations and simple replacements based on the technical solutions of the present invention fall within the scope of the present invention. within the scope of protection.

Claims (10)

  1. 一种室内空气中微生物及气体组分、颗粒物检测方法,其特征在于,包括以下步骤:A method for detecting microorganisms, gas components, and particles in indoor air, characterized in that it comprises the following steps:
    (1)对目标气体放电以使其负载电荷;(1) Discharge the target gas so that it is charged;
    (2)驱动所述目标气体通过静电吸附组件,所述静电吸附组件外侧施加有电场以对目标微生物进行吸附,所述静电吸附组件内具有金属纳米微材料;(2) driving the target gas through the electrostatic adsorption assembly, an electric field is applied to the outside of the electrostatic adsorption assembly to adsorb the target microorganisms, and the electrostatic adsorption assembly has metal nano-micromaterials;
    (3)向所述静电吸附组件内发射激光;(3) emitting laser light into the electrostatic adsorption component;
    (4)探测从所述静电吸附组件出射的拉曼信号,并基于所述拉曼信号进行微生物检测。(4) Detecting the Raman signal emitted from the electrostatic adsorption component, and performing microorganism detection based on the Raman signal.
  2. 根据权利要求1所述的方法,其特征在于,所述静电吸附组件由纳米金属材料组成。The method according to claim 1, characterized in that the electrostatic adsorption component is made of nano-metal material.
  3. 根据权利要求1所述的方法,其特征在于,所述强电场高于预定值,以进行微生物消杀和颗粒物处理。The method according to claim 1, characterized in that the strong electric field is higher than a predetermined value for disinfecting microorganisms and treating particles.
  4. 根据权利要求1所述的方法,其特征在于,所述方法还包括:在将所述激光入射至所述静电吸附组件之前,对所述激光进行滤波。The method according to claim 1, further comprising: filtering the laser light before the laser light is incident on the electrostatic adsorption component.
  5. 根据权利要求1所述的方法,其特征在于,在所述吸附组件的出口处、拉曼探测组件(1.2.8)前方设置非球面长焦深滤波组件(1.2.7),对出射的拉曼散射光进行滤波,滤除背景荧光和杂散光。The method according to claim 1, characterized in that an aspherical long-focus filter assembly (1.2.7) is set at the outlet of the adsorption assembly and in front of the Raman detection assembly (1.2.8), to prevent the outgoing Raman Mann scattered light is filtered to remove background fluorescence and stray light.
  6. 根据权利要求1所述的方法,其特征在于,所述方法还包括:针对不同的微生物生成不同的微生物拉曼信号图谱,基于微生物拉曼信号图谱采用人工智能图像分析处理技术进行微生物气溶胶的检测。The method according to claim 1, characterized in that, the method also includes: generating different microbial Raman signal spectra for different microorganisms, and using artificial intelligence image analysis and processing technology to detect microbial aerosols based on microbial Raman signal spectra detection.
  7. 根据权利要求1所述的方法,其特征在于,所述方法还包括,在所述静电吸附组件两侧设置多通反射组件(1.2.5),其具有朝向所述吸附组件的至少一个反射面、所述激光对向所述多通反射组件(1.2.5)的反射面入射,以使得所述其多次照射在所述静电吸附组件上。The method according to claim 1, characterized in that the method further comprises, arranging a multi-pass reflection assembly (1.2.5) on both sides of the electrostatic adsorption assembly, which has at least one reflection surface facing the adsorption assembly . The laser is incident on the reflective surface of the multi-pass reflective component (1.2.5), so that it is irradiated on the electrostatic adsorption component multiple times.
  8. 根据权利要求1所述的方法,其特征在于,还包括在进行微生物检测之前或之后进行气体组分检测。The method according to claim 1, further comprising detecting gas components before or after performing microbial detection.
  9. 根据权利要求1所述的方法,其特征在于,在所述静电吸附组件上游设置气泵,以通过强气流对所述静电吸附组件进行清洗,所述气体综合检测装置还包括温控消杀组件(1.3.2),所述温控消杀组件(1.3.2)用于对所述选通富集模块进行消杀。The method according to claim 1, wherein an air pump is arranged upstream of the electrostatic adsorption assembly to clean the electrostatic adsorption assembly through a strong air flow, and the comprehensive gas detection device also includes a temperature-controlled disinfecting assembly ( 1.3.2), the temperature control disinfecting component (1.3.2) is used for disinfecting the gate enrichment module.
  10. 根据权利要求1所述的方法,其特征在于,所述静电吸附组件包括纳米金或纳米银颗粒。The method according to claim 1, characterized in that, the electrostatic adsorption component comprises nano-gold or nano-silver particles.
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