CN117035812B - Product coding and quick anti-counterfeiting identification method based on magnetic nanoparticles with different concentrations - Google Patents
Product coding and quick anti-counterfeiting identification method based on magnetic nanoparticles with different concentrations Download PDFInfo
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- G06K19/06009—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking
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- G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
- G06K2019/06215—Aspects not covered by other subgroups
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Abstract
A product coding and quick anti-counterfeiting identification method based on magnetic nanoparticles with different concentrations belongs to the technical field of product traceability detection, and solves the problems that a traditional detection mode is long in detection time, complex in detection process, high in detection cost, incapable of being scaled and difficult to popularize. The method is based on the magnetic property and the targeting coupling property of the superparamagnetic nano particles, adopts a multi-bit coding and fusion integrated technology by utilizing a high-sensitivity weak magnetic sensor, and creatively realizes the anti-counterfeiting tracing of the product; the product coding mode and the coded data have uniqueness, can be used for anti-counterfeiting coding for products with high added values, effectively improve the working efficiency by utilizing the stability and the stronger safety of magnetic nanoparticles, are strong in decoding reliability, are convenient to query, and improve the counterfeiting difficulty. Has important scientific and application values in the aspects of detection speed, detected variety, operation convenience and the like.
Description
Technical Field
The invention belongs to the technical field of product traceability detection, and particularly relates to a product coding and quick anti-counterfeiting identification method based on magnetic nanoparticles with different concentrations, which adopts a multi-bit coding integration integrated technology, can be used for anti-counterfeiting coding for products with high added values, can effectively improve the working efficiency, has strong decoding reliability, is convenient for inquiring coded products, and improves the counterfeiting difficulty.
Background
The product tracing can ensure the product safety and improve the product quality and the market competitiveness. By recording the information of links such as production, processing, circulation and sales of the product, the comprehensive supervision of the quality and safety of the product can be realized, thereby guaranteeing the health and safety of consumers. In addition, the product tracing can also improve the product quality, meet the requirements of consumers on high-quality products, and enhance the market competitiveness of the products. The tracing method of the product can be divided into: the physical method is mainly a label tracing technology, such as two-dimensional codes and the like; the biological method mainly comprises a DNA tracing technology; the chemical method mainly comprises a stable isotope tracing technology, a mineral element fingerprint tracing technology and the like.
In the physical method, the two-dimensional code technology is one of two-dimensional bar code technology, and the literal numerical information is represented by a plurality of geometric shapes corresponding to binary system. By applying the two-dimensional code technology, data encoding is carried out from two dimensions of the horizontal direction and the vertical direction, and through a corresponding encoding algorithm, information such as characters, pictures, websites and the like can be compiled into a square geometric pattern, a user can decode and view related information through a camera or decoding software, and the two-dimensional code has higher data storage capacity than the bar code. From the aspect of the formation, two-dimensional codes can be divided into two types: stacked (row-by-row) two-dimensional codes and matrix two-dimensional codes. From the aspect of morphology, the stacked two-dimensional code is formed by stacking two or more rows of relatively short-cut one-dimensional codes, the matrix two-dimensional code is in a matrix form, black and white squares are used for representing information on corresponding element positions of the matrix, the black squares represent binary '1', the white squares represent binary '0', and the common coding standard is QR codes.
DNA traceability technology is the most convenient and accurate biological method currently applied in biological methods. The DNA tracing technology is derived from the inheritance and variation of DNA, the DNA sequence of each product is unique, and the DNA pattern displayed by the molecular biological method is also unique. Therefore, the DNA traceability technology can also be used as one of the product traceability technologies, and has the advantages of easiness in typing, good repeatability and the like.
In the stable isotope tracing technology and the mineral element fingerprint tracing technology, the influence of the equipment change on the stable isotope ratio and the measurement of the mineral element is less, so the technology has the advantages of high accuracy, high sensitivity, no pollution, good precision, simple experimental operation, capability of better distinguishing whether the tracked substance is newly added or fixed in the experimental system, and the like. Secondly, isotopes and mineral elements do not change with the change of physical properties of the organism, which is a natural attribute of the organism.
However, at present, most of related researches in physical methods are carried out on a certain link in a product circulation chain, and the related researches lack of comprehensive agricultural product tracing based on a map. In addition, the DNA tracing technology needs to optimize the detection method in a further step to meet the requirement of large-scale detection due to the defects of long detection time, complex detection process, high detection cost, incapability of large-scale popularization, and the like. The agricultural product production area is identified by utilizing a stable isotope tracing technology and a mineral element fingerprint tracing technology in a chemical method, so that the agricultural product production area is easily comprehensively influenced by a continental effect, a latitude effect and an altitude effect, and the agricultural product production area is changed along with the change of a geographic position; in addition, the stable isotope technology needs a reliable database support, the technology has relatively large laboratory one-time investment, and the requirement on detection equipment is relatively high. The above factors limit the application of these prior arts in tracing agricultural product origin, so that improvements in the existing fast anti-counterfeit authentication method are necessary.
Disclosure of Invention
The invention aims at the problems and provides a product coding and quick anti-counterfeiting identification method based on magnetic nanoparticles with different concentrations, which adopts a multi-bit coding integration integrated technology, can perform anti-counterfeiting coding on products with high added values, can effectively improve working efficiency, has strong decoding reliability, is convenient for inquiring coded products, and improves counterfeiting difficulty.
The technical scheme adopted by the invention is as follows: the product coding and quick anti-counterfeiting identification method based on the magnetic nanoparticles with different concentrations comprises the following steps:
firstly, respectively selecting two different kinds of magnetic nanoparticle solutions, mixing according to a certain proportion, wherein the mixed magnetic nanoparticle solutions are agglomerated to cause the difference of magnetic response signals of the two unmixed magnetic nanoparticle solutions and the mixed magnetic nanoparticle solution under the same concentration and the same dosage, encoding a product by utilizing the difference, sealing the mixed magnetic nanoparticle with different proportions in a bag by using an anti-counterfeiting sealing bag, adhering the sealing bag on the surface of the product, attaching the magnetic nanoparticle on the surface of the product, and further marking the product for the first time;
sealing the magnetic nano particles with the surface coating modified by functionalization in the anti-counterfeiting sealing bag, adhering the sealing bag on the surface of a product, and marking the product for the second time;
step three, placing the marked product in a detection hole of a product coding traceability detection device;
step four, respectively setting harmonic parameters as 2 times, 4 times, 6 times and 8 times of harmonic by adjusting harmonic components of the lock-in amplifier, and recording voltage amplitude values under the harmonic components;
step five, calculating the ratio of voltage amplitude values under every two harmonic components, and recording the ratio of the two corresponding harmonic components;
step six, adjusting harmonic components into 3 rd harmonic components by adjusting parameters of the lock-in amplifier, detecting secondary coding information of the product, and recording the secondary coding information;
step seven, the information in the step four, the step five and the step six is encoded into independent data bits, the maximum 12 coding bits are set according to the coding principle and the coding mode, each bit represents one coding information, and the coding data of the product is imported into a coding database;
step eight, repeating the steps one to seven, and respectively importing the coded data of the product to be coded into a coded database to form a complete coded data set;
and step nine, carrying out data reduction test on the encoded product to be tested, and verifying the authenticity of the product.
The relaxation phenomenon is the dynamic response characteristic of the magnetic nano particles, and the response of the magnetic nano particles always lags behind the excitation magnetic field under the changed excitation magnetic field, and is called as the relaxation phenomenon of the magnetic nano particles; the relaxation time is a very important detection characteristic value, and the microscopic structural change of the nano-scale superparamagnetic particles can be reflected on a macroscopic magnetic signal through the change of the relaxation time; relaxation phenomena are classified into niere relaxation and brown relaxation; the Neille relaxation is the magnetic relaxation caused by the change of the direction of the unpaired electrons of the outermost layer of each molecular structure in the magnetic core under the state of the magnetic moment of the single magnetic domain, and the relaxation time is generally that ofTo express:
wherein:
wherein:for characteristic times, it is generally advisable to take +.>，/>The inner diameter of the magnetic core is the magnetic anisotropy constant;
the Brownian relaxation is the magnetic relaxation driven by the rotation of magnetic particles in liquid phase and coating layer under the action of external magnetic field and its relaxation time isTo express:
wherein:taking 1mPa of pure water for viscosity of carrier solution>Is the hydrodynamic volume of MNPs after surface modification,d is the hydrodynamic diameter after surface modification, < >>For heat energy>Is Boltzmann constant, T is absolute temperature; from the above, it can be seen that the Brownian relaxation time is related to the viscosity of the carrier solution, the diameter of the MNPs and the temperature;
under the action of an externally applied magnetic field, the two kinds of relaxation exist simultaneously, and the effective relaxation time can be expressed as:
。
the product coding traceability detection device comprises a signal generator, wherein a reference frequency output end of the signal generator is electrically connected with a reference frequency input end of an isolation amplifier, an excitation signal output end of the signal generator is electrically connected with an excitation signal input end of an excitation power amplifier, an excitation signal output end of the excitation power amplifier is connected with an excitation resonance circuit electrode, and the excitation resonance circuit electrode is electrically connected with an excitation coil arranged on the excitation coil so as to generate an alternating magnetic field, so that a sample in a detection hole in the middle of the upper end of the detection coil is excited, and a detected magnetic signal is generated; the magnetic signal generated by exciting the sample is detected by a detection coil connected in parallel with a detection resonant circuit, the detected electric signal is transmitted to an isolation amplifier connected with the detection coil, and then the electric signal is transmitted to a computer through the isolation amplifier by a phase-locked amplifier; and then, comparing the tested sample with the coded data of the coded database by a computer, and verifying the authenticity of the tested product.
Step four, because the magnetic core of the magnetic nano particle has superparamagnetism, when the excitation frequency is low, the magnetization response is thatMeets Langmuir classical paramagnetic theory:
wherein:for exciting the magnetic field strength>Is magnetic core magnetic moment>Is Boltzmann constant, T is absolute temperature, < ->Is vacuum magnetic permeability;
the static magnetization response intensity described by the langerhans equation is developed into the form of a fourier series:
where an and bn are time-varying fourier coefficients, an and bn can be expressed as:
by extending the right side of equation (6) in one fourier series, the kth, even harmonic signal from the magnetic nanoparticle can be obtained:
from the above, if the volume of the magnetic particles is artificially changed, the relaxation time is changed relatively greatly, and the magnetic susceptibility, magnetization, and the like are affected.
Magnetic nanoparticle pair excitation fieldResponsive to->，/>Is the angular frequency of the excitation field; conversely, at high frequencies +.>The magnetic nanoparticles are not magnetically responsive to the excitation field; thus when the following are satisfied:，/>at this time, a harmonic signal can be obtained.
The step six, the encoding mode takes the magnitude of magnetic response signals of harmonic components of mixed solutions introduced with different magnetic nanoparticles as encoding data, takes 2, 4, 6 and 8 even harmonic signals of the magnetic nanoparticles as 4 encoding data bits of product encoding, and the magnetic response signals of all even harmonic components are different and have unique signal values; second, the even harmonic signal ratios are 8/2,6/2, 4/2, 6/4, 8/6, respectively, with the percentages of these 6 ratios being taken as the other 6 individual encoded data bits.
The coding principle is that 12 variables, namely a 2-order harmonic signal value, a 4-order harmonic signal value, a 6-order harmonic signal value, an 8-order harmonic signal value, a 4/2 signal ratio, a 6/2 signal ratio, an 8/2 signal ratio, a 6/4 signal ratio, an 8/6 signal ratio, magnetic response signals of two or more different kinds of magnetic nanoparticles after mixing according to a certain proportion, and magnetic response signals of the magnetic nanoparticles with the surface coatings modified by functionalization, are set as 12 coding variable parameters in total, each variable parameter corresponds to a single coding bit, and each product can comprise one coding bit or several coding bits in parallel; each product is designed as separate coded data, and the coded data unique to each product is listed in a product code database.
Step eight, further comprising a verification process, namely: selecting the coded product, repeatedly repeating the third, fourth, fifth and sixth steps, and verifying whether the data are accurate and whether the error is within the allowable range when the coded information of the single product is detected; and after the coded product is placed for a week, whether the parameter value of each data bit in the product to be tested is consistent with the data in the product coding database or the deviation is within the allowable range is measured, so that whether the product to be tested is a marked product can be determined, and the authenticity of the product can be verified.
Step nine, in the process of tracing the product, measuring the signal values of 2, 4, 6 and 8 harmonic waves of the tested product, calculating the ratio of the signal values of different harmonic waves, mixing two or more different types of magnetic nanoparticles according to a certain proportion, then mixing the magnetic response signals of the solution, and the magnetic response signal values of the magnetic nanoparticles with the surface coating functionally modified, comparing the measured data with the data of a database of the tested product, and determining whether the parameter values of each data bit and the database are consistent, if deviation exists, determining whether the deviation range is within an allowable range; thus, it can be verified whether the tested product is the product which has been encoded.
The invention has the beneficial effects that: the product coding and quick anti-counterfeiting identification method based on the magnetic nanoparticles with different concentrations is based on the magnetic characteristics and the targeting coupling characteristics of the superparamagnetic nanoparticles, adopts a multi-bit coding integration technology by utilizing a high-sensitivity weak magnetic sensor, and creatively realizes the anti-counterfeiting tracing of agricultural products; the product coding mode and the coded data have uniqueness, and the magnetic nano particles have strong safety and stability, are suitable for long-term storage in various different environments, and have important scientific and application values in the aspects of detection speed, detected variety, operation convenience and the like. A 12-bit encoding scheme is implemented, with each bit in the sequence representing a piece of magnetic information. The anti-counterfeiting coding is carried out on products with high added values, the number of coded products is thousands, the stability and the stronger safety of the magnetic nanoparticles are utilized, the working efficiency is effectively improved, the decoding reliability is strong, the coded products are convenient to inquire, and the counterfeiting difficulty is improved. And the agricultural product traceability database is established according to an independently developed coding mode, the technology can be applied to large-scale logistics distribution sites, the authenticity of agricultural products can be ensured during inspection by market supervision, the rights and interests of consumers are ensured, and the market environment in China and abroad is optimized.
Drawings
Fig. 1 is a schematic block diagram of a product code traceability detection device in the method of the present invention.
Fig. 2 is a schematic illustration of the excitation magnetic field of the present invention.
Fig. 3 is a schematic diagram of the detection magnetic field of the present invention.
FIG. 4 is a schematic diagram of the relaxation time versus particle size of a magnetic particle according to the present invention.
FIG. 5 is a schematic diagram of the harmonic signals of the A magnetic ball of the present invention.
Fig. 6 is a schematic diagram of the coding scheme of the present invention.
Fig. 7 is a graph comparing strawberry encoded data of the present invention with strawberry sample measurement data (ABCD four-bit encoding).
Fig. 8 is a graph comparing strawberry encoded data with strawberry sample measurement data (EFGHIJ six-bit encoding) of the present invention.
Fig. 9 is a graph comparing strawberry encoded data of the present invention with strawberry sample measurement data (K-bit encoding).
Fig. 10 is a graph comparing strawberry encoded data with strawberry sample measurement data (L-bit encoding) of the present invention.
Detailed Description
The method is based on the magnetic property and the targeting coupling property of the superparamagnetic nano particles, adopts a multi-bit coding and fusion integrated technology by utilizing the high-sensitivity weak magnetic sensor, and creatively realizes the anti-counterfeiting tracing of agricultural products.
Specific steps of the invention will be described in detail. The product coding and quick anti-counterfeiting identification method based on the magnetic nanoparticles with different concentrations comprises the following steps:
step one, two different kinds of magnetic nanoparticle solutions are selected respectively, mixing is carried out according to a certain proportion (for example, 1:1, 1:3, 1:9 and the like), agglomeration can occur among mixed magnetic nanoparticle particles, two unmixed magnetic nanoparticle solutions and mixed magnetic nanoparticle solutions are caused to have differences in magnetic response signals under the same concentration and the same dosage, products are encoded by the differences, the mixed magnetic nanoparticle with different proportions is sealed in a bag by using an anti-counterfeiting sealing bag, the sealing bag is adhered to the surface of the products, the magnetic nanoparticle is adhered to the surface of the products, and the products are marked for the first time.
When the magnetic nanoparticles of two different kinds or different coating layers are mixed according to different proportions, the equivalent particle diameter of the magnetic nanoparticles in the mixed solution is increased, so that the relaxation time is increased. When two different kinds of magnetic nanoparticle solutions are used, after being mixed according to a certain proportion, magnetic nanoparticles in the solutions are agglomerated due to the mutual repulsive force and the mutual attraction force, so that the magnetic response signals generated by the two different kinds of magnetic nanoparticle solutions are different from those generated by the two different kinds of magnetic nanoparticle solutions, and therefore, products can be encoded by using more than 2 kinds of magnetic nanoparticles mixed according to different proportions as harmonic signals of encoding materials.
In addition, the particle size of the magnetic nano particles spans 3 orders of magnitude, from 5nm to more than 10um, the superparamagnetic nano particles adopt hydrophilic flexible polymers such as PEG, dextran and the like, and the polymers have no toxic or harmful effects on human bodies, can carry out surface modification on small-size magnetic nano materials (generally with the diameter smaller than 50 nm), can improve the water solubility and biocompatibility of the particles, can be used as materials for long-term storage, are not easily influenced by natural environment, and have good dispersibility and operability. The superparamagnetism nanometer particle has stable physical property, and the magnetic nanometer particle has random magnetic moment orientation and no magnetism. When an external magnetic field acts, the magnetic nano particles tend to rotate in the direction of the magnetic field, and have magnetization response quantity macroscopically outwards; when the external magnetic field is removed, the magnetization response of the magnetic nanoparticles is lost, and almost no residual magnetism exists. This is the response law of magnetic nano particles with superparamagnetism under the action of magnetic field. And the magnetic nano particles have larger magnetization response compared with other magnetic marking materials, so that the characteristic value extraction of the measured object is facilitated, and the magnetic nano particles are ideal materials for archiving and recording. The linear characteristic of the magnetic nano material detection data ensures high sensitivity and accuracy of analysis and wide detection interval. Therefore, in the product traceability detection of the invention, most magnetic labels are magnetic nano particles with superparamagnetism.
In addition, the relaxation phenomenon is the dynamic response characteristic of magnetic nanoparticles, which, under a changing excitation magnetic field,the response of the magnetic nanoparticles always lags behind the excitation magnetic field, a phenomenon known as relaxation of the magnetic nanoparticles. The relaxation time is a very important detection characteristic value, and the microscopic structural change of the nano-scale superparamagnetic particles can be reflected on the macroscopic magnetic signal through the change of the relaxation time. Relaxation phenomena are classified into the Neel relaxation and Brownian relaxation. The Neille relaxation is the magnetic relaxation caused by the change of the direction of the unpaired electrons of the outermost layer of each molecular structure in the magnetic core under the state of the magnetic moment of the single magnetic domain, and the relaxation time is generally that ofTo express:
wherein:
wherein:for characteristic times, it is generally advisable to take +.>，/>The inner diameter of the magnetic core, K is the magnetic anisotropy constant.
The Brownian relaxation is the magnetic relaxation driven by the rotation of magnetic particles in liquid phase and coating layer under the action of external magnetic field and its relaxation time isTo express:
wherein:taking 1mPa of pure water for viscosity of carrier solution>Is the hydrodynamic volume of MNPs after surface modification,d is the hydrodynamic diameter after surface modification, < >>For heat energy>Is Boltzmann constant, T is absolute temperature; from the above formula, it can be seen that the Brownian relaxation time is related to the viscosity of the carrier solution, the diameter of the MNPs and the temperature.
Under the action of an externally applied magnetic field, the two kinds of relaxation exist simultaneously, and the effective relaxation time can be expressed as:
FIG. 4 shows the relaxation time of magnetic nanoparticles versus particle size, it can be seen that with smaller magnetic particle sizes, mainly the relaxation of the denier dominates; when the particle size of the magnetic particles is large, mainly the Brownian relaxation plays a dominant role.
And secondly, sealing the magnetic nano particles with the surface coating modified by functionalization in the bag by using an anti-counterfeiting sealing bag, adhering the sealing bag on the surface of a product, and carrying out secondary marking on the product.
The magnetic nano particles with the surface coating modified by the functionalization are coated on the surface of the magnetic core by hydrophilic materials (such as oleic acid and the like), so that the magnetic core is prevented from magnetic aggregation and the magnetic particles are hydrophilic. The outer layer of the hydrophilic coating layer is modified by using chemical bonds or biological proteins with coupling functions, so that the hydrophilic coating layer can be further coupled with various functional targeting proteins or molecules and the like to form superparamagnetic nanoparticles with different magnetic response signals.
The magnetic response signals of the magnetic nanoparticles are different from each other due to the fact that the magnetic response signals of the magnetic nanoparticles are unique and the magnetic response signals of the magnetic nanoparticles are different from each other due to the fact that the magnetic response signals of the magnetic nanoparticles are different from the magnetic response signals of the magnetic nanoparticles before coupling, relaxation time of the magnetic nanoparticles is changed, magnetic response signals of the magnetic nanoparticles are finally affected, and products are coded by taking the magnetic response signals of the magnetic nanoparticles coupled with specific target proteins as variable parameters.
And thirdly, placing the marked product in a detection hole of the product coding traceability detection device.
The product coding tracing detection device comprises a signal generator, wherein a reference frequency output end of the signal generator is electrically connected with a reference frequency input end of an isolation amplifier, an excitation signal output end of the signal generator is electrically connected with an excitation signal input end of the excitation power amplifier, an excitation signal output end of the excitation power amplifier is connected with an excitation resonance circuit electrode, the excitation resonance circuit electrode is electrically connected with an excitation coil arranged on the excitation coil to generate an alternating magnetic field, and then a sample in a detection hole in the middle of the upper end of the detection coil is excited to generate a detected magnetic signal; the magnetic signal generated by exciting the sample is detected by a detection coil connected in parallel with a detection resonant circuit, the detected electric signal is transmitted to an isolation amplifier connected with the detection coil, and then the electric signal is transmitted to a computer through the isolation amplifier by a phase-locked amplifier; and then, comparing the tested sample with the coded data of the coded database by a computer, and verifying the authenticity of the tested product.
And fourthly, respectively setting harmonic parameters to be 2 times, 4 times, 6 times and 8 times of harmonic by adjusting harmonic components of the lock-in amplifier, and recording voltage amplitude values under the harmonic components.
Uniqueness of even harmonic signals. The magnetic characteristic of the superparamagnetism nanometer particle is mainly nonlinear magnetization with ultralow remanence and coercive force, and has extremely high nonlinear alternating-current magnetic susceptibility. In the ac magnetization method (ac detection method), superparamagnetic particles are excited by an alternating magnetic field. The intensity of the alternating current magnetic field needs to meet the requirement of nonlinear magnetization of the superparamagnetic particles, harmonic signals of the superparamagnetic nanoparticles can be obtained in various modes, the mode of collecting even harmonic signals by direct current superposition alternating current excitation is adopted, the harmonic signals are stable, and the harmonic signals cannot change along with the change of an external environment, so that the measured harmonic signals change.
Since the magnetic core of the magnetic nanoparticle has superparamagnetism, when the excitation frequency is low, the magnetization response isMeets Langmuir classical paramagnetic theory:
wherein:for exciting the magnetic field strength>Is magnetic core magnetic moment>Is Boltzmann constant, T is absolute temperature, < ->Is vacuum magnetic permeability.
The static magnetization response intensity described by the langerhans equation is developed into the form of a fourier series:
where an and bn are time-varying fourier coefficients, an and bn can be expressed as:
by extending the right side of equation (6) in one fourier series, the kth, even harmonic signal from the magnetic nanoparticle can be obtained:
from the above, if the volume of the magnetic particles is artificially changed, the relaxation time is changed relatively greatly, and the magnetic susceptibility, magnetization, and the like are affected.
Research shows that magnetic nano particles are opposite to excitation fieldResponsive to->，/>Is the angular frequency of the excitation field; conversely, at high frequencies +.>The magnetic nanoparticles are not magnetically responsive to the excitation field; thus when the following are satisfied:，/>at this time, a harmonic signal can be obtained.
And (3) applying an excitation magnetic field of 26mT to the A magnetic nanoparticles, and analyzing the characteristics of harmonic signals generated by the A magnetic nanoparticles. The amplitude of each subharmonic is reflected by fig. 5 and equation (9) to decrease in order with the harmonic decomposition order; however, as the sample amount increases, the amplitude of each subharmonic tends to increase, and the value exhibits uniqueness. Assuming that the magnetic field strength H is 26mT, the magnetic response signal value of the 4 th harmonic is smaller than that of the 2 nd harmonic according to the formula. Thus, the magnetic properties of superparamagnetic nanoparticles can be used to encode products with magnetic response signals in harmonic components. Regardless of the environment, the even harmonic signal of the magnetic nanoparticle is the only specific value, so that the superparamagnetic nanoparticle material can be used as the only encoding material, and even harmonic components can be used as the unique encoding data of the product.
And fifthly, calculating the ratio of the voltage amplitude values under every two harmonic components, and recording the ratio of the two corresponding harmonic components.
And step six, adjusting the harmonic component into a 3 rd harmonic component by adjusting parameters of the lock-in amplifier, detecting the secondary coding information of the product, and recording the secondary coding information.
As described above, the encoding mode takes the magnitude of the magnetic response signal of the harmonic component of the mixed solution introduced with different magnetic nanoparticles as encoding data, uses 2, 4, 6, 8 even harmonic signals of the magnetic nanoparticles as 4 encoding data bits of product encoding, and the magnetic response signals of the even harmonic components are different and have unique signal values; second, the even harmonic signal ratios are 8/2,6/2, 4/2, 6/4, 8/6, respectively, with the percentages of these 6 ratios being taken as the other 6 individual encoded data bits.
And step seven, encoding the information in the step four, the step five and the step six into independent data bits, setting the data into at most 12 coding bits according to the coding principle and the coding mode, wherein each bit represents one coding information, and importing the coding data of the product into a coding database.
Coding principle: the method comprises the steps of setting 12 variables of a 2 nd harmonic signal value, a 4 th harmonic signal value, a 6 th harmonic signal value, an 8 th harmonic signal value, a 4/2 signal ratio, a 6/2 signal ratio, an 8/2 signal ratio, a 6/4 signal ratio, an 8/6 signal ratio, a magnetic response signal of a solution after mixing two or more different kinds of magnetic nanoparticles according to a certain proportion, and a magnetic response signal of the magnetic nanoparticles with the surface coating modified by functionalization as 12 coding variable parameters, wherein each variable parameter corresponds to a single coding bit, and each product can comprise one coding bit or several coding bits in parallel. And the parameter value of each product coding bit can be designed into a fixed value or within a range according to the different products to be coded, and the range can be designed into a range of one coding bit or a range of several coding bits according to the different products. And finally, designing each product into independent coded data, and listing the coded data unique to each product into a product coding database.
And step eight, repeating the steps one to seven, and respectively importing the coded data of the product to be coded into a coded database to form a complete coded data set.
Step eight also includes a verification process, namely: selecting the coded product, repeatedly repeating the third, fourth, fifth and sixth steps, and verifying whether the data are accurate and the error is within 3% when the coded information of the single product is detected; and after the coded product is placed for a week, whether the parameter value of each data bit in the product to be tested is consistent with the data in the product coding database or the deviation is within 3% is measured, so that whether the product to be tested is a marked product can be determined, and the authenticity of the product can be verified.
And step nine, carrying out data reduction test on the encoded product to be tested, and verifying the authenticity of the product.
In the process of tracing the source of the product, measuring the signal values of 2, 4, 6 and 8 harmonic waves of the product to be measured, calculating the ratio of the signal values of different harmonic waves, mixing two or more different types of magnetic nanoparticles according to a certain ratio, then mixing the magnetic response signals of the solution, and the magnetic response signal values of the magnetic nanoparticles with the surface coating modified by functionalization, comparing the measured data with the data of a database of the product to be measured, and determining whether the parameter value of each data bit and the database is consistent, and if the deviation exists, determining whether the deviation range is within 3%. Thus, it can be verified whether the tested product is the product which has been encoded.
Examples:
the agricultural product code information is set in A, B, C, D, E, F, G, H, I, J, K, L form. A is defined as a 2 nd harmonic signal value, B is defined as a 4 th harmonic signal value, C is defined as a 6 th harmonic signal value, D is defined as an 8 th harmonic signal value, E is defined as a 4/2 signal ratio, F is defined as a 6/2 signal ratio, G is defined as an 8/2 signal ratio, H is defined as a 6/4 signal ratio, I is defined as an 8/4 signal ratio, J is defined as an 8/6 signal ratio, K is defined as a signal value under a mixed solution of two magnetic nanoparticles, and L is defined as a signal value of a magnetic nanoparticle whose surface coating is functionally modified; each letter represents a coded bit, and each bit may be assigned a different product code information by a change in the corresponding value.
Coded bits-type of magnetic nanoparticles
Under the conditions of 26mT of excitation magnetic field intensity and 1500Hz of excitation frequency, the strawberries sprayed with 10ul of A magnetic balls, B magnetic balls, C magnetic balls and D magnetic balls are used for repeatedly measuring the amplitude of the magnetic signals under the third 2-order harmonic. The above experiment was repeated three times, and the average value of the three experimental data was taken. As proved by experiments, the signal values of the 4 magnetic balls are different, and the average value of the magnetic balls is taken as one of the coding bits.
TABLE 1 different kinds of magnetic nanoparticle encoding information table
| Kind of magnetic ball | Base noise | Signal value (mV) | Signal value (mV) | Signal value (mV) | Average value (mV) |
| A magnetic ball (30 nm) | 0.0075 | 0.0999 | 0.1 | 0.1001 | 0.0925 |
| B magnetic ball (30 nm) | 0.0075 | 0.1375 | 0.1363 | 0.1365 | 0.1292 |
| C magnetic ball (25 nm) | 0.0075 | 0.2594 | 0.2588 | 0.2589 | 0.251 |
| D magnetic ball (30 nm) | 0.0075 | 0.335 | 0.331 | 0.332 | 0.3251 |
Code bit-even harmonic signal ratio
And under the conditions of the excitation magnetic field strength of 26mT and the excitation frequency of 1500Hz, the amplitude values of the magnetic signals of the strawberries sprayed with the magnetic nano particles under 2 times, 4 times, 6 times and 8 times of harmonic waves are respectively measured. And respectively calculating the ratio of the amplitude of each harmonic signal, repeating the experiment for three times, taking the average value of three groups of experimental data, and taking the calculated average value ratio as one of the coding bits.
Table 22, 4, 6, 8 amplitude table of A magnetic ball magnetic signal under harmonic wave
| Magnetic ball | Harmonic order | Base noise | Signal value (mV) | Signal value (mV) | Signal value (mV) | Average value (mV) | Signal ratio | Signal ratio | Signal ratio |
| A magnetic ball (30 nm) | 2 | 0.0075 | 0.0999 | 0.1 | 0.1001 | 0.0925 | 4/2 6/2 8/2 | 6/4 8/4 | 8/6 |
| A magnetic ball (30 nm) | 4 | 0.0028 | 0.0432 | 0.0432 | 0.0432 | 0.0404 | 43.78％ | 51.49％ | 71.63％ |
| A magnetic ball (30 nm) | 6 | 0.0016 | 0.0224 | 0.0224 | 0.0224 | 0.0208 | 22.49％ | 36.88％ | |
| A magnetic ball (30 nm) | 8 | 0.0006 | 0.0156 | 0.0154 | 0.0155 | 0.0149 | 16.11％ |
Coded bits-solution of mixed magnetic nano particles of different kinds according to a certain proportion
Under the condition of excitation magnetic field intensity 26mT and excitation frequency 1500Hz, mixing ratios of the magnetic ball A and the magnetic ball B (30 nm) are respectively 1: 1. 1: 3. 1: 6. 1: and 9, measuring the amplitude of the magnetic signal under the 2 nd harmonic wave, repeating the experiment three times, taking the average value of three groups of experimental data, and taking the average value as one coding bit.
TABLE 3 coding information table of different kinds of magnetic nanoparticle mixed solutions
| Mixing ratio | Base noise | Signal value (mV) | Signal value (mV) | Signal value (mV) | Average value (mV) |
| 1：1 | 0.0075 | 0.0549 | 0.0555 | 0.0545 | 0.0474 |
| 1：3 | 0.0075 | 0.0748 | 0.0748 | 0.0748 | 0.0673 |
| 1：6 | 0.0075 | 0.0999 | 0.0989 | 0.0990 | 0.0917 |
| 1：9 | 0.0075 | 0.1322 | 0.1322 | 0.1322 | 0.1247 |
Magnetic nano particle with coded bits and surface coating functionally modified
And under the conditions of excitation magnetic field intensity of 26mT and excitation frequency of 1500Hz, performing functional modification on the magnetic nano particles, spraying the modified magnetic nano particles on the surface of the strawberry, and measuring the amplitude of a magnetic signal under harmonic waves. Repeating the experiment for three times, and taking the average value of three groups of experimental data to obtain one bit of encoded data.
Table 4 magnetic nanoparticle encoded information table with surface coatings modified by functionalization
| Species of coupled targeting materials | Base noise | Signal value (mV) | Signal value (mV) | Signal value (mV) | Average value (mV) |
| 0.9% physiological saline | 0.0075 | 1.4152 | 1.4157 | 1.415 | 1.4078 |
| Lipase enzyme | 0.0028 | 0.5 | 0.4999 | 0.4996 | 0.497 |
In practical application, the encoded agricultural product to be tested is subjected to data reduction test, and authenticity of the agricultural product is verified.
First, unique coded data is set for the strawberry according to the developed coding mode. For example: the encoded information of product a may be set as the magnetic signal of magnetic sphere a, a=0.0925, b=0.0404, c=0.0208, d=0.0149, e=43.78, f=22.49, g=16.11, h=51.49, i=36.88, j=71.63, k=0.0663, l= 1.4078, i.e. A, B, C, D, E, F, G, H, I, J, K, L is defined as the encoded information number of strawberries. Under the condition of 1500Hz and 7mT excitation magnetic field, 3 strawberries are respectively measured for 3 times, and whether the coded data of the strawberries are correct or not is verified. And respectively measuring the signal values of 2 times, 4 times, 6 times and 8 times of harmonic waves, respectively calculating the proportion of the signal values of each harmonic wave, and verifying whether the data of each bit of the strawberry coding information is correct. Selecting 3 nine strawberries which are often crowned with genuine products in the current market, firstly taking 10uL of A magnetic ball stock solution, adding 100uL of pure water for dilution, uniformly spraying 20uL of diluted solution on the surfaces of 3 strawberries with basically consistent shapes and weights, sequentially measuring the data of each code, assuming that the 3 strawberries are not determined to be genuine products, and verifying that the strawberries sprayed with the magnetic nanoparticles belong to the genuine products by measuring the four coding parameters.
And the data measured by the experiment is used as a unique coding data source of the strawberries, the data of each bit is measured respectively, the calculated data is compared with the given coding data respectively, and the authenticity of three strawberry samples can be verified by tracing the deviation between the numerical value of the strawberries and the reference numerical value within +/-3 percent.
Table 5 strawberry unique code data table
| Magnetic ball | Mixing ratio | Species of coupled targeting materials | Harmonic order | Base noise | Signal value (mV) | Signal value (mV) | Signal value (mV) | Average value (mV) | Signal ratio | Signal ratio | Signal ratio |
| A magnetic ball | 2 | 0.0075 | 0.0999 | 0.1 | 0.1001 | 0.0925 | 4/2 6/2 8/2 | 6/4 8/4 | 8/6 | ||
| A magnetic ball | 4 | 0.0028 | 0.0432 | 0.0432 | 0.0432 | 0.0404 | 43.78％ | 51.49％ | 71.63％ | ||
| A magnetic ball | 6 | 0.0016 | 0.0224 | 0.0224 | 0.0224 | 0.0208 | 22.49％ | 36.88％ | |||
| A magnetic ball | 8 | 0.0006 | 0.0156 | 0.0154 | 0.0155 | 0.0149 | 16.11％ | ||||
| A magnetic ball: b magnetic ball | 1：3 | 2 | 0.0075 | 0.0748 | 0.0748 | 0.0748 | 0.0663 | ||||
| A magnetic ball | 0.9% physiological saline | 2 | 0.0075 | 1.4152 | 1.4157 | 1.415 | 1.4078 |
Table 6 retrospective strawberry sample measurement data table
| Magnetic ball | Mixing ratio | Species of coupled targeting materials | Harmonic order | Base noise | Signal value (mV) | Signal value (mV) | Signal value (mV) | Average value (mV) | Signal ratio | Signal ratio | Signal ratio |
| A magnetic ball | 2 | 0.0075 | 0.0994 | 0.1008 | 0.1003 | 0.0926 | 4/2 6/2 8/2 | 6/4 8/4 | 8/6 | ||
| A magnetic ball | 4 | 0.0028 | 0.0436 | 0.0433 | 0.0430 | 0.0405 | 43.73％ | 50.56％ | 70.38％ | ||
| A magnetic ball | 6 | 0.0016 | 0.0222 | 0.0221 | 0.0224 | 0.0206 | 22.24％ | 35.8％ | |||
| A magnetic ball | 8 | 0.0006 | 0.0149 | 0.0152 | 0.0154 | 0.0145 | 15.65％ | ||||
| A magnetic ball: b magnetic ball | 1：3 | 2 | 0.0075 | 0.0756 | 0.0748 | 0.0761 | 0.068 | ||||
| A magnetic ball | 0.9% physiological saline | 2 | 0.0075 | 1.4136 | 1.4124 | 1.4089 | 1.4041 |
FIGS. 7-10 are graphs comparing strawberry encoded data with strawberry sample measured data, by comparing data, 3 strawberry sample measured data values with encoded data values, the deviation is within 3%; i.e. to verify the feasibility of the method.
Claims (3)
1. The product coding and quick anti-counterfeiting identification method based on the magnetic nano particles with different concentrations is characterized by comprising the following steps of:
firstly, respectively selecting two different kinds of magnetic nanoparticle solutions, mixing according to a certain proportion, wherein the mixed magnetic nanoparticle solutions are agglomerated to cause the difference of magnetic response signals of the two unmixed magnetic nanoparticle solutions and the mixed magnetic nanoparticle solution under the same concentration and the same dosage, encoding a product by utilizing the difference, sealing the mixed magnetic nanoparticle with different proportions in a bag by using an anti-counterfeiting sealing bag, adhering the sealing bag on the surface of the product, and further marking the product for the first time;
sealing the magnetic nano particles with the surface coating modified by functionalization in the anti-counterfeiting sealing bag, adhering the sealing bag on the surface of a product, and marking the product for the second time; the functional modification of the surface coating means that the surface of the magnetic core of the magnetic nanoparticle is coated by hydrophilic materials, so that the magnetic nanoparticle is hydrophilic while the magnetic aggregation of the magnetic core is prevented;
step three, placing the marked product in a detection hole of a product coding traceability detection device;
step four, respectively setting harmonic parameters as 2 times, 4 times, 6 times and 8 times of harmonic by adjusting harmonic components of the lock-in amplifier, detecting voltage amplitudes under the harmonic components, and recording the voltage amplitudes under the 2 times, 4 times, 6 times and 8 times of harmonic as first coding information;
step five, calculating the ratio of voltage amplitude values under every two harmonic components, and recording the ratio of the two corresponding harmonic components;
step six, adjusting the harmonic component into a 3 rd harmonic component by adjusting parameters of the lock-in amplifier, detecting second coded information of the product, and recording the second coded information; the second coded information refers to the voltage amplitude of the magnetic nano particles with the surface coating modified by functionalization under the 3 rd harmonic;
the step six, the encoding mode takes the magnitude of magnetic response signals of harmonic components of mixed solutions introduced with different magnetic nanoparticles as encoding data, takes 2, 4, 6 and 8 even harmonic signals of the magnetic nanoparticles as 4 encoding data bits of product encoding, and the magnetic response signals of all even harmonic components are different and have unique signal values; secondly, taking the even harmonic signal ratios of 8/2,6/2, 4/2, 6/4, 8/4 and 8/6 as the other 6 independent coded data bits;
step seven, setting 12 variables of the 2 nd harmonic signal value, the 4 th harmonic signal value, the 6 th harmonic signal value, the 8 th harmonic signal value, the 4/2 signal ratio, the 6/2 signal ratio, the 8/2 signal ratio, the 6/4 signal ratio, the 8/6 signal ratio, the magnetic response signal of the solution after mixing two or more different kinds of magnetic nanoparticles according to a certain proportion, and the magnetic response signal of the magnetic nanoparticles with the surface coating modified by functionalization as 12 coding variable parameters, wherein each variable parameter corresponds to a single coding bit, and each product can comprise one coding bit or several coding bits in parallel; each product is designed into independent coded data, the information is coded into independent data bits, the maximum of 12 coding bits are set, each bit represents one coded information, and the coded data of the product is imported into a coded database;
step eight, repeating the steps one to seven, and respectively importing the coded data of the product to be coded into a coded database to form a complete coded data set;
and step nine, carrying out data reduction test on the encoded product to be tested, and verifying the authenticity of the product.
2. The method for encoding and rapidly authenticating the product based on the magnetic nanoparticles with different concentrations according to claim 1, which is characterized in that: step eight, further comprising a verification process, namely: selecting the coded product, repeatedly repeating the third, fourth, fifth and sixth steps, and verifying whether the data are accurate and whether the error is within the allowable range when the coded information of the single product is detected; and after the coded product is placed for a week, whether the parameter value of each data bit in the product to be tested is consistent with the data in the coding database or the deviation is within the allowable range is measured, so that whether the product to be tested is a marked product can be determined, and the authenticity of the product can be verified.
3. The method for encoding and rapidly authenticating the product based on the magnetic nanoparticles with different concentrations according to claim 1, which is characterized in that: step nine, in the process of tracing the product, measuring the signal values of 2, 4, 6 and 8 harmonic waves of the tested product, calculating the ratio of the signal values of different harmonic waves, mixing two or more different types of magnetic nanoparticles according to a certain proportion, then mixing the magnetic response signals of the solution, and the magnetic response signal values of the magnetic nanoparticles with the surface coating functionally modified, comparing the measured data with the data of a database of the tested product, and determining whether the parameter values of each data bit and the database are consistent, if deviation exists, determining whether the deviation range is within an allowable range; thus, it can be verified whether the tested product is the product which has been encoded.
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