Background
With the improvement of living standard and the change of living style, people have longer and longer working and living time in a closed environment, and the interiors of hospitals, schools, theaters and other places, vehicles such as automobiles, airplanes, high-speed rails and the like all belong to serious disaster areas with virus propagation and cross infection. It has been considered that the outside environment is serious in air pollution. In fact, the indoor environment of buildings such as offices, living rooms, restaurants, movie theaters, dance halls, etc. has far greater impact on people's health than the outdoor environment.
Such as indoor pollutants, mainly originate from the following 5 aspects: firstly, human breath and smoke; second, the finishing material, daily necessities; thirdly, microorganisms, viruses and bacteria; fourthly, kitchen oil smoke; and fifthly, air conditioning syndrome. More than 500 volatile organic compounds exist in indoor air, more than 20 carcinogenic substances exist in the indoor air, and more than 200 pathogenic viruses exist in the indoor air. The major hazards are: formaldehyde, benzene, toluene, xylene, TVOC, ammonia, etc., and various harmful bacteria and microorganisms, etc. The pollutants enter the human body along with respiration, and are accumulated for a long time, so that the health of people is seriously harmed.
Furthermore, like automobiles or airplanes and the like, the enclosed traffic fear that the space is narrow and closed, pollutants are not easy to volatilize, and especially, when sunshine is irradiated in summer and the heating is started in winter, a large amount of pollutants in the automobiles can be gathered. The 8 carcinogens in air, benzene, toluene, xylene, styrene, ethylbenzene, formaldehyde, acetaldehyde and acrolein, come from three aspects: first, accessories such as seat covers, head rests, etc. The other is the interior decoration of the automobile, such as a genuine leather seat, floor glue and the like. And thirdly, the thinner, glue, paint, coating and the like required by production. In addition, harmful exhaust gases, such as carbon monoxide, carbon dioxide, etc., emitted from the engine may also be harmful to health. The pollutants in the train such as a high-speed rail train mainly come from two sources: one is foreign, including outdoor air entering through a standing door, contaminants brought in by a large number of passengers getting on the bus, etc.; the other is generated in the interior of the locomotive, and comprises locomotive parts and interior decoration materials, paint, glue, adhesives, seat decorations and the like. The pollutants released by parts and interior materials of the locomotive mainly comprise benzene, toluene, formaldehyde, olefin, aromatic hydrocarbon and the like, and the pollutants entering a carriage from the outside mainly comprise haze pollution, harmful bacteria, viruses and the like such as PM2.5 and the like. These harmful substances can cause discomfort symptoms such as dizziness, nausea, drowsiness, cough, asthma, sneeze, etc. to passengers. Besides acute stimulation effect, the formaldehyde, ammonia, benzene, xylene and other volatile organic compounds in the medicine can cause damage to respiratory system, liver, kidney and hematopoietic organs, change of immune function and even risk of inducing cancer if a person is in a high-concentration environment for a long time.
The protection mode that people used commonly at present has gauze mask, air purifier etc. and general gauze mask comprises gauze mask portion and gauze area, and gauze mask portion is for being used for filterable fibrous layer, generally adopts non-woven fabrics or gauze, blocks the particle through the commodity circulation separation mode of the main part of gauze mask. This may work for larger sized dust particles but is not effective for many smaller sized viruses, bacteria, allergenic substances, etc. For example, the commonly used N95 mask is not effective in preventing the spread of influenza virus.
For this reason, charged guards and activated carbon devices have been developed to adsorb viruses and toxins by charged electrons and activated carbon filtration. However, experiments and practices show that the former can play a certain role under the condition of carrying electric charge or only can have the adsorption effect on a small amount of non-specific particles. Therefore, the two methods still cannot effectively and specifically adsorb viruses and bacteria, and allergen molecules with smaller particle size are more difficult to adsorb and intercept. It has no effect on diseases transmitted through respiratory tract by pathogenic microorganisms such as bacteria and viruses.
Similarly, the air purifier generally adopts a similar principle, and can play a certain role in intercepting substances with large particle sizes, but cannot play an effective role in viruses, bacteria, allergen molecules and the like.
Disclosure of Invention
Based on the problems, the invention combines rich experience and professional knowledge and combines with theory from the aspect of practice and theory to invent the protein virus protection and obstruction biological agent and the preparation method thereof, which can be widely applied to various fields and environments to prevent various toxic and harmful substances such as viruses, bacteria, allergen substances and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the protein virus protection and barrier biological agent comprises the following steps:
preparing a biological nano mesoporous material which comprises a one-dimensional nano material, a two-dimensional nano material and a porous nano material, wherein the preparation comprises the steps of raw material preparation, purification and extraction, structure and appearance characterization, photocatalysis, stirring and extraction and the like to obtain a nano adsorptive material;
step two, preparing a specific binding receptor or ligand, and mixing one or more of the specific binding receptor or ligand according to the requirement to prepare a solution, wherein the solution is prepared from an aqueous solution, and the weight percentage concentration is 1-10%;
step three, preparing protective filtrate, mixing and reacting the solutions with certain proportional concentrations obtained in the step one and the step two, and carrying out reduced pressure distillation to obtain the protective filtrate;
step four, manufacturing a multi-layer film structure medium, synthesizing a film polymer through solvent casting, semi-solid casting, Hot Melt Extrusion (HME), solid dispersion extrusion or rolling, and then forming a film through forming and/or evaporating part of added liquid;
and step five, preparing a protein virus protection and barrier biological preparation, and soaking the protection filtrate obtained in the step three at normal temperature or spraying the protection filtrate at high pressure on two sides of the membrane prepared in the step four.
Preferably, the nanomaterial in the first step is a titanium oxide precursor selected from one or more of ethyl titanate, butyl titanate and propyl titanate; the preparation of the nano material comprises one or more of a hydrothermal/solvothermal method, a sol-gel method, a template method, an electrostatic spinning method or a coprecipitation method.
Preferably, the purification and extraction in the first step are completed by the following steps:
step 1.1, taking 0.1g of sample, pretreating for 60 minutes in the atmosphere of nitrogen or argon (the flow is 30mL/min), and naturally cooling to 100 ℃;
step 1.2, introducing NH into the sample3-Ar(5%NH3) Adsorbing the equilibrium gas for 60 minutes to saturation;
step 1.3, after the adsorption is finished, purging the physically adsorbed NH by He3;
And step 1.4, raising the temperature to 700 ℃ at a heating rate of 10 ℃/min, allowing the desorbed ammonia gas to enter a gas chromatograph for on-line analysis, and determining the acid amount and the acid strength according to the peak area and the peak position.
Preferably, the photocatalyst in the first step specifically includes: accurately measuring 2L of distilled water, loading the distilled water into a reactor, starting a constant flow pump to circulate the distilled water in the reactor, and simultaneously starting an air pump; accurately measuring 10mL of methylene blue solution, placing the methylene blue solution in a reactor, and taking an initial sample after the mixture is mixed for 10 minutes; accurately weighing 0.2000g of catalyst sample, adding the catalyst sample into a reactor, and taking an adsorbed initial sample after adsorbing for 30 minutes.
Preferably, the third step specifically includes:
step 3.1, stirring different solutions according to the proportion for 1-10 hours to obtain a mixed solution;
step 3.2, adding an alcohol solution into the mixed solution for mixing, and stirring for 1-12 hours to obtain an alcohol dispersion solution containing the nano active material;
and 3.3, performing acid hydrolysis on the alcohol dispersion solution, wherein the acid is one or more of formic acid, acetic acid, oxalic acid, hydrochloric acid and nitric acid.
Preferably, the acid solution is a 20-40% hydrochloric acid aqueous solution.
Preferably, the UV lamp is turned on after the above photocatalysis and a stopwatch is started, samples are taken every 5 minutes and the samples are stopped after 3 hours.
Preferably, the UV lamp is turned on after the sampling is stopped and a stopwatch is started, the sampling is performed every 5 minutes and the sampling is stopped after 3 hours. Each sample was filtered through a water-based membrane (pore size: 0.22 μm) and placed in a cuvette, and absorbance was measured at a measurement wavelength of 664nm with distilled water as a reference.
Preferably, the membrane of the fifth step comprises a multilayer structure, and the pore diameter decreases from the outside to the inside.
Preferably, the medium is an aqueous solution formed by diluting the protection filtrate prepared according to the third step in a certain proportion.
The invention also provides a protein virus protective and blocking biological protective filter mask which comprises a mask body with a multilayer structure, wherein a filter layer, an adsorption layer and a secondary filter layer are sequentially arranged from outside to inside, and the filter layer, the adsorption layer and the secondary filter layer are all soaked in the filter medium.
The invention also provides a protein virus protection and barrier biological protection filter screen which is made of a material with a certain aperture and is formed by soaking at normal temperature or spraying at high pressure on the filter medium.
The invention also provides a protein virus protection and barrier biological protection filter, which comprises the protein virus protection and barrier biological protection filter screen, a shell, a filter tip, an air guide port, an air exhaust port and a power supply device.
The invention also provides an air purifier, which comprises the protein virus protection and separation biological protection filter screen, a motor, a fan, an intelligent monitoring system, external parts, a filter part, an air channel, a motor and a power supply.
The invention also provides an air purification fresh air system which comprises a fan, an air inlet, an air outlet, various pipelines and joints, wherein the air inlet is provided with the protein virus protection and separation biological protection filter screen.
The high-activity small-particle-size nano material prepared by the invention can effectively filter and block large-particle pollutants and effectively adsorb small-particle-size toxic and harmful substances such as viruses, bacteria or allergens and the like by adding a special process, thereby providing all-round protection for people, firstly promoting the function of preventing infectious diseases with all-round high efficiency in the world and protecting the health of people.
Detailed Description
Features and exemplary embodiments of various aspects of the present invention will be described in detail below, and in order to make objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention. It will be apparent to one skilled in the art that the present invention may be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the present invention by illustrating examples of the present invention.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The invention provides a preparation method of a protein virus protection and barrier biological agent, which comprises the following steps:
preparing a biological nano mesoporous material which comprises a one-dimensional nano material, a two-dimensional nano material and a porous nano material, wherein the preparation comprises the steps of raw material preparation, purification and extraction, structure and appearance characterization, photocatalysis, stirring and extraction and the like to obtain a nano adsorptive material;
step two, preparing a specific binding receptor or ligand, mixing one or more of the specific binding receptor or ligand according to the requirement to prepare a solution, wherein the solution is prepared by water, and the weight percentage concentration is 1-10%;
step three, preparing protective filtrate, mixing and reacting the solutions with certain proportional concentrations obtained in the step one and the step two, and carrying out reduced pressure distillation to obtain the protective filtrate;
step four, manufacturing a multi-layer film structure medium, synthesizing a film polymer through solvent casting, semi-solid casting, Hot Melt Extrusion (HME), solid dispersion extrusion or rolling, and then forming a film through forming and/or evaporating part of added liquid;
and step five, preparing a protein virus protection and barrier biological preparation, and carrying out normal-temperature soaking or high-pressure spraying atomization treatment on the protection filtrate obtained in the step three on two sides of the membrane prepared in the step four.
The nano material in the first step is a titanium oxide precursor selected from one or more of ethyl titanate, butyl titanate and propyl titanate; the preparation of the nano material comprises one or more of a hydrothermal/solvothermal method, a sol-gel method, a template method, an electrostatic spinning method or a coprecipitation method.
Wherein, the purification and extraction in the first step are completed by the following steps:
step 1.1, taking 0.1g of sample, pretreating for 60 minutes in the atmosphere of nitrogen or argon (the flow is 30mL/min), and naturally cooling to 100 ℃;
step 1.2, introducing NH into the sample3-Ar(5%NH3) Adsorbing the equilibrium gas for 60 minutes to saturation;
step 1.3, after the adsorption is finished, purging the physically adsorbed NH by He3;
And step 1.4, raising the temperature to 700 ℃ at a heating rate of 10 ℃/min, allowing the desorbed ammonia gas to enter a gas chromatograph for on-line analysis, and determining the acid amount and the acid strength according to the peak area and the peak position.
Wherein, the photocatalysis in the step one specifically comprises: accurately measuring 2L of distilled water, loading the distilled water into a reactor, starting a constant flow pump to circulate the distilled water in the reactor, and simultaneously starting an air pump; accurately measuring 10mL of methylene blue solution, placing the methylene blue solution in a reactor, and taking an initial sample after the mixture is mixed for 10 minutes; accurately weighing 0.2000g of catalyst sample, adding the catalyst sample into a reactor, and taking an adsorbed initial sample after adsorbing for 30 minutes.
Wherein, step three specifically includes:
step 3.1, stirring different solutions according to the proportion for 1-10 hours to obtain a mixed solution;
step 3.2, adding an alcohol solution into the mixed solution for mixing, and stirring for 1-12 hours to obtain an alcohol dispersion solution containing the nano active material;
and 3.3, performing acid hydrolysis on the alcohol dispersion solution, wherein the acid is one or more of formic acid, acetic acid, oxalic acid, hydrochloric acid and nitric acid.
Wherein the acid solution is 20-40% hydrochloric acid aqueous solution.
After photocatalysis, the ultraviolet lamp is turned on, a stopwatch is started to time, samples are taken every 5 minutes, and the samples are stopped after 3 hours. After stopping sampling, the ultraviolet lamp was turned on and a stopwatch was started to time, samples were taken every 5 minutes, and sampling was stopped after 3 hours. Each sample was filtered through a water-based membrane (pore size: 0.22 μm) and placed in a cuvette, and absorbance was measured at a measurement wavelength of 664nm with distilled water as a reference.
Wherein the membrane of the fifth step comprises a multilayer structure, and the pore diameters are reduced from outside to inside in sequence.
The invention also provides a protein virus protection and barrier biological protection filter medium prepared according to the method, wherein the medium is an aqueous solution formed by diluting the protection filtrate prepared according to the third step in a certain proportion.
The invention also provides a protein virus protective and blocking biological protective filter mask which comprises a mask body with a multilayer structure, wherein a filter layer, an adsorption layer and a secondary filter layer are sequentially arranged from outside to inside, and the filter layer, the adsorption layer and the secondary filter layer are all soaked in the filter medium.
The invention also provides a protein virus protection and barrier biological protection filter screen which is made of a material with a certain aperture and is formed by soaking at normal temperature or spraying and atomizing at high pressure on the filter medium.
The invention also provides a protein virus protection and blocking biological protection filter which comprises the protein virus protection and blocking biological protection filter screen, a shell, a filter tip, an air guide port, an air exhaust port and a power supply device.
The invention also provides an air purifier which comprises the protein virus protection and blocking biological protection filter screen, a motor, a fan, an intelligent monitoring system, an external component, a filter component, an air duct, a motor and a power supply.
The invention also provides an air purification fresh air system which comprises a fan, an air inlet, an air outlet, various pipelines and joints, wherein the air inlet is provided with the protein virus protection and separation biological protection filter screen.
In some embodiments, a gas chromatography apparatus is provided as shown in fig. 1, comprising a-absorption, AIC analysis control, CV check valve, F-filter, FV flow stabilizer valve, FIC flow display control, H-heater, HV shutoff valve, MF mass flow meter, RV pressure regulating valve, RF rotameter, TI temperature display, TIC temperature display control, TCD thermal conductivity detector, and 6V six-way valve.
In some embodiments, as shown in fig. 2, the photocatalysis of the present invention employs a homemade batch circulating slurry photocatalytic reactor, and the photocatalytic evaluation of nanopowder is performed with methylene blue solution as a simulated pollutant. The photocatalysis device consists of a reactor, an ultraviolet lamp, a constant flow pump, an air pump and the like. Air is introduced from a gas inlet at the bottom, and reaction liquid in the reactor is led out from the bottom in a swirling flow mode and is pumped to the top of the reactor by a water pump, so that the catalyst can be prevented from being deposited at the bottom, the reaction liquid is fully mixed, and the circulation of the reaction liquid can be ensured.
In some embodiments, the specific steps of photocatalysis are accurately measuring 2L of distilled water, filling the distilled water into a reactor, starting a constant flow pump to circulate the distilled water in the reactor, and simultaneously starting an air pump; accurately measuring 10mL of methylene blue solution, placing the methylene blue solution in a reactor, and taking an initial sample after the mixture is mixed for 10 minutes; accurately weighing 0.2000g of catalyst sample, adding the catalyst sample into a reactor, and taking an adsorbed initial sample after adsorbing for 30 minutes. The UV lamp was turned on and a stopwatch was started, samples were taken every 5 minutes and after 3 hours the samples were stopped. Each sample was filtered through a water-based membrane (pore size: 0.22 μm) and placed in a cuvette, and absorbance was measured at a measurement wavelength of 664nm with distilled water as a reference. The photocatalytic activity of the sample was evaluated by the residual rate of the methylene blue solution after the reaction. According to the formula: calculating the concentration of the residual liquid at each sampling point when A is-0.0258 +0.1973C, and further calculating the residual rate C of methylene blue at each sampling pointt/C0。
In some examples, as shown in fig. 3 and 4, XRD and TEM patterns of the nano-material obtained by the reaction under the hydrothermal condition of 180 ℃ for 10 hours show that the nano-material prepared in this system has a quasi-hexagonal structure.
Adding 31mL of benzyl alcohol into a proper amount of titanium oxide precursor solution, then placing the mixture into a reaction kettle with a tetrafluoroethylene lining, reacting for 10 hours in a rotary kettle at 180 ℃, taking out and quenching, washing for 4 times by ethanol through low-speed centrifugation (4500 r/min), drying for 2 hours at 80 ℃ to obtain white powder, grinding the white powder, raising the temperature to 580 ℃ at the heating rate of 2 ℃/min, and roasting for 1 hour to obtain the final product, namely the rod-shaped nano titanium dioxide.
During the preparation, the following characteristics were found:
(1) with the increase of the amount of the benzyl alcohol, the crystallinity of the product is increased firstly and then reduced, and the rod length also shows the trend of increasing firstly and then reducing;
(2) with the prolonging of the reaction time, the crystallinity of the obtained product is not obviously changed, the shape of the product gradually grows into a rod shape from a random state, and the whole rod-shaped structure can be obtained after the reaction time is 10 hours;
(3) with the increase of the reaction temperature, the crystallinity of the obtained product gradually increases, and the rod-like structure becomes uniform.
Comparing the different raw material ratios to obtain the photocatalytic and acid catalytic activities of the samples, the following conclusions can be obtained:
(1) the larger the rod length, the stronger the photocatalytic activity and the weaker the acid catalytic activity; the photocatalytic activity of the sample is mainly determined by the factors such as the crystallization strength, the specific surface area, the acid amount, the acid position and the like of the sample; the acid catalytic activity is mainly determined by the type of acid on the surface of the catalyst, the acid strength and the acid amount;
(2) the sample with the molar ratio of 1:21 has the highest photoreaction activity, the degradation rate of methylene blue is about 65% in 180 minutes, and the activities of the 1:86 and 1:200 prepared samples are about the same as 46%;
(3) the sample with the molar ratio of 1:43 has the highest acid catalytic activity, the highest yield of dimethyl ether is 50%, the highest yield of the sample obtained with the ratio of 1:200 is about 40%, and the acid catalytic activity of the sample with the molar ratio of 1:21 is the lowest and is only about 30%.
In some embodiments, Surface Plasmon Resonance (SPR) is one of the important enhancement mechanisms for surface enhanced raman, due to the size effect and quantum effect of noble metal ions to induce resonance of free electrons of the metal by irradiation of excitation light. Valence electrons on the surface of the metal are considered as moving electron gas under the background of uniform positive charges, and when the plasma gas is subjected to electromagnetic interference, the electron density distribution inside the metal becomes nonuniform. As the electrons that have collected leave this region again due to the coulomb force, a collective oscillation of the electronic system is formed, which is called plasma oscillation and is represented in the form of a wave, called ion wave. When light is irradiated onto a metal surface, a total reflection phenomenon occurs due to a difference in refractive index, and an evanescent wave is generated at an interface between air and metal. When evanescent waves meet ion waves in a metal body, resonance can be generated, energy is transferred to surface plasma from photons when resonance is generated, most of incident light is absorbed, and the reflected light intensity is greatly reduced. In the case of metal nanoparticles, the electrons undergo a collective oscillation in the presence of electromagnetic waves, and this resonance occurs only at a specific frequency, and is therefore called Localized Surface Plasmon Resonance (LSPR). From a microscopic view, Localized Surface Plasmon Resonance (LSPR) confines photons in a small-scale nanostructure, causing a sharp increase in the surrounding electric field; from a macroscopic perspective, Localized Surface Plasmon Resonance (LSPR) dramatically attenuates reflected light, with incident and scattered light dramatically increasing.
In some embodiments, the localized surface plasmon resonance frequency (ω) of the nanomaterial is studiedsp) Is determined by its complex dielectric constant.
A nanocrystalline particle may be similar to an electrode, and when a cluster of metal clusters is placed in an electric field, positive and negative charges are separated under the action of the electric field force and generate polarity
Define the polarity of the sphere as
Is the dielectric constant of the metal particles1(ω)+i2(ω),1(ω)、2(ω) is the real and imaginary parts of the dielectric constant of the metal particles, respectively.
To enhance the generation of resonance, i.e. to satisfy the condition1(ω)+22|=minimum————①
Wherein1(ω) the real part of the dielectric constant of the metal particles.
Model by Druder=1-ωp2/(ω2+γ2)————②
ωspFor Localized Surface Plasmon Resonance (LSPR) energy, γ is the half-peak width of the plasmon resonance band, a parameter that can be read from the absorption spectrum.
From (r) and (b) can deduce omegap=(Nhe2/0mh)1/2,NhIs the concentration of free carriers (holes), mhIs the effective mass of the hole.
The nano flaky material is prepared by adopting solvothermal method, the proportion of raw materials and solvent, reaction temperature and reaction time are examined, the influence on the structure and the appearance of the material is examined, and the relationship between the structure and the performance is examined, so that the following conclusion can be obtained:
(1) under the condition of the same temperature and solvent system, the extension of the reaction time has certain influence on the structure and the appearance of the nano material, and only the reaction time is about 24 hours, so that a sheet with relatively uniform appearance can be obtained; the reaction time is more than 60 hours to obtain a long sheet shape;
(2) the reaction temperature has great influence on the structure of the product, the higher the temperature is, the higher the crystallinity is, but the influence on the appearance is not great, and a sheet structure with uniform appearance can be obtained as long as the temperature reaches 180 ℃;
(3) the catalytic activity of the sample is determined by the crystallization strength, the specific surface area, the acid amount, the acid position and other factors, and the acid catalytic activity is higher when the specific surface area is larger and the acid amount is larger; the stronger the acid strength, the higher the acid catalytic activity; the higher the crystallinity, the higher the acid catalytic activity.
The high-activity small-particle-size nano material prepared by the invention can effectively filter and block large-particle pollutants and effectively adsorb small-particle-size toxic and harmful substances such as viruses, bacteria or allergens and the like by adding a special process, thereby providing all-round protection for people, firstly promoting the function of preventing infectious diseases with all-round high efficiency in the world and protecting the health of people.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments. In particular, for the system embodiment, since it is substantially similar to the method embodiment, the description is simple, and for the relevant points, reference may be made to the partial description of the method embodiment.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.