CN116678825A - High-sensitivity far infrared metamaterial device and concentration detection system for specific components in sample - Google Patents
High-sensitivity far infrared metamaterial device and concentration detection system for specific components in sample Download PDFInfo
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- 101710145634 Antigen 1 Proteins 0.000 claims abstract description 27
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- 238000000411 transmission spectrum Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 230000001276 controlling effect Effects 0.000 claims description 2
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- 239000000523 sample Substances 0.000 abstract description 35
- 206010027406 Mesothelioma Diseases 0.000 abstract description 23
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3581—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N2021/0106—General arrangement of respective parts
- G01N2021/0112—Apparatus in one mechanical, optical or electronic block
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention provides a high-sensitivity far-infrared metamaterial device and a concentration detection system of specific components in a sample. Through uniformly loading the biological sample containing the mesothelioma antigen-1 on the surface of the designed metamaterial rectangular ring periodic array, far infrared waves can be resonantly absorbed with the far infrared characteristic absorption frequency of the mesothelioma antigen-1 when passing through the biological sample containing the mesothelioma antigen-1 and the metamaterial, the far infrared characteristic absorption peak of the mesothelioma antigen-1 is amplified, and noise signals are restrained, so that the function of enhancing the far infrared detection signals of the mesothelioma antigen-1 is achieved, and the detection sensitivity and accuracy of specific components in the middle of the biological sample are improved.
Description
Technical Field
The invention relates to the technical field of far infrared detection equipment, in particular to a high-sensitivity far infrared metamaterial device and a concentration detection system for specific components in a sample.
Background
Far infrared wave means wavelength of 4-1000 μm and wave number of 400-10 cm -1 Electromagnetic waves in the range. The transition energy caused by the low-frequency molecular motion modes such as pure rotation, vibration-rotation, variable angle vibration, skeleton vibration and the like in the molecule is matched with the far infrared wave photon energy. Thus, when far infrared light is irradiated onto the molecules, the molecules absorb light wave energy of a specific frequency to generate the microscopic molecular motions. These absorption frequencies are closely related to the structural features of the molecule, forming a set of far infrared characteristic absorption peaks. Based on the far infrared characteristic absorption peaks, the object to be detected can be identified and detected from the molecular layer. Compared with other spectrum detection techniques, the far infrared spectrum detection technique is characterized in that: (1) Covering the vibration/rotation energy level of most biological molecules, and accurately reflecting the tiny structural change of the biological molecules; (2) The photon energy is low, so that the biological molecules are prevented from ionization damage. (3) Compared with the existing chemical detection method, the far infrared optical detection technology has the advantages of sensitivity, rapidness, economy and no damage. Therefore, the method has great application value in the field of biological molecule detection.
However, far infrared waves are absorbed by water molecules and greatly attenuated when penetrating through biological samples (tissues, blood, etc.), which leads to the fact that in the traditional far infrared spectrum detection, the water in the biological samples must be removed by heating, drying, freeze drying, etc.; uniformly mixing the dried sample with polyethylene powder with high transmittance in a far infrared band, and pressing the mixture into a tablet with smooth surface; then, obtaining far infrared absorption spectrum of the tablet by using a far infrared spectrometer; finally, performing characteristic frequency comparison with a far infrared standard spectrogram of the target molecule to qualitatively identify the target molecule in the biological sample; and obtaining the linear relation between the characteristic peak intensity and the concentration of the target molecules by measuring the far infrared characteristic peak intensity of the target molecules, and quantitatively detecting the target molecules in the biological sample. However, in the actual biological sample detection, the concentration of the target molecules is usually in the order of nmol/g-mu mol/g, and the far infrared characteristic peak tends to have lower intensity; the interference components are various, and the number of corresponding far infrared characteristic peaks is large; finally, far infrared characteristic signals of target molecules are often submerged in interference noise, and the identification accuracy and detection sensitivity of far infrared spectrum technology to the target molecules are limited. Therefore, how to solve this problem becomes a difficult problem for the application of far infrared spectroscopic technology in the field of biological detection.
Disclosure of Invention
The invention aims to provide a far infrared metamaterial device and a sample concentration detection system for effectively improving the detection precision and sensitivity of a far infrared spectrum technology to target molecules.
In order to achieve the above purpose, the present invention provides a high-sensitivity far infrared metamaterial device, which comprises a dielectric substrate and a plurality of split resonant rings;
the split resonant rings are arranged on the surface of the dielectric substrate at equal intervals in an array period;
the split resonant ring is of a double-split annular structure, the widths of the two split slits are the same and the positions of the two split slits are opposite, and the split resonant ring is of a sharp-angle structure at two sides of the split slits so as to form a double-sharp-angle split structure.
Further, the split resonant ring is of a rectangular annular structure;
the opening slit is positioned at the middle of the upper rectangular edge and the lower rectangular edge, and the distances from the opening slit to the left rectangular edge and the right rectangular edge are the same.
Further, the dielectric substrate surface is provided with a plurality of rows of metamaterial teams, and each row of metamaterial teams comprises a plurality of split resonant rings which are arranged in the same direction and at equal intervals.
Further, the angle of the sharp angle is more than 0 and less than 180 degrees; and regulating and controlling the half-peak width of the metamaterial resonance peak, the resonance frequency and the quality factor by changing the angle of the sharp angle.
Further, the split ring resonator is a metal material, a semiconductor material, and combinations thereof;
the material of the dielectric substrate is a material with high far infrared transmittance and a combination thereof.
The invention also provides a concentration detection system of the specific component in the sample, which comprises an infrared light source, a far infrared detector and a high-sensitivity far infrared metamaterial device; the infrared light source is arranged above the high-sensitivity far infrared metamaterial device, and the far infrared detector is arranged below the high-sensitivity far infrared metamaterial device; the infrared light source generates far infrared waves which vertically enter and penetrate through the high-sensitivity far infrared metamaterial device and then are received by the far infrared detector.
Further, the method is applied to high-precision detection of the concentration of the intermediate dermatome antigen-1 in the tissue sample.
Further, the detection method is as follows:
step 1: and (3) a clean and complete metamaterial device is taken and fixed on a spectrometer sample rack according to the polarization direction requirement, the transmission spectrum of the metamaterial device is measured by using the far infrared detector, and the transmission spectrum is recorded and recorded as a reference resonance peak signal.
Step 2: a tissue sample to be measured with a certain thickness is taken and attached to the surface of the metamaterial device, and free water molecules contained in the sample are removed through nitrogen purging;
step 3: and fixing the metamaterial device with the tissue sample loaded on the surface on a sample frame according to the polarization direction requirement, measuring the transmission spectrum of the metamaterial device by using the far infrared detector, and recording the transmission spectrum as a sample resonance peak signal.
Step 4: and comparing the two acquisitions to obtain a transmission spectrum, measuring and calculating the frequency offset and the amplitude variation between the sample resonance peak signal and the reference resonance peak signal, and calculating the concentration of the specific component in the sample.
Compared with the prior art, the invention has the advantages that:
1. the high-sensitivity far infrared metamaterial device is composed of a double-sharp-angle opening rectangular ring periodic array, and the sharp-angle opening design of the device can enhance the sensing sensitivity of the metamaterial; particularly in the detection of the mesothelioma antigen-1, the resonance frequency is matched with the far infrared characteristic absorption frequency of the mesothelioma antigen-1, the resonance absorption is generated with the far infrared characteristic absorption frequency of the mesothelioma antigen-1, the far infrared characteristic absorption peak of the mesothelioma antigen-1 is amplified, and the noise signal is restrained, so that the function of enhancing the far infrared detection signal of the mesothelioma antigen-1 is achieved, and the detection sensitivity and accuracy of the mesothelioma antigen-1 in a thyroid tumor biological sample are improved.
2. The high-sensitivity far-infrared metamaterial device provided by the invention can be used for adjusting the resonance frequency of the resonance peak, the half-peak width of the resonance peak and the quality factor of the resonance peak by adjusting the angle of the sharp corner, so that the characteristic absorption frequency of various antigens can be matched, and the high-precision detection of the various antigens can be further realized.
3. The high-sensitivity far-infrared metamaterial device is simple in structure, easy to produce in batches, and capable of detecting the concentration of a sample through simple steps and improving detection efficiency.
Drawings
Fig. 1 is a schematic structural diagram of a metamaterial unit in an embodiment of the present invention.
FIG. 2 is a schematic diagram of a metamaterial array according to an embodiment of the present invention.
Fig. 3 is a schematic diagram of a detection system based on metamaterial structure design in an embodiment of the present invention.
FIG. 4 is a graph showing the far infrared characteristic absorption spectrum of mesothelioma antigen-1 of the present invention.
Fig. 5 is a schematic structural diagram of a metamaterial according to an embodiment of the present invention.
Fig. 6 is a schematic structural view of a conventional double-opening rectangular ring.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be further described below.
As shown in FIG. 1, the invention provides a high-sensitivity far-infrared metamaterial device, wherein a metamaterial unit comprises a rectangular dielectric substrate 1-1 and an open resonant ring 1-2 attached to the surface of the dielectric substrate 1-1. The split resonant ring comprises two split slits 1-3 and 1-4 which are symmetrical in position and identical in width, and two ends of the two split slits are triangular sharp angles. The triangular sharp angle theta can realize the function of enhancing the metamaterial resonance signal, specifically, the theta is reduced from 180 degrees to 0 degrees, and the half-peak width of the resonance peak is firstly reduced and then increased; θ decreases from 180 ° to 0 °, and the resonance peak frequency shifts to high frequency; the triangular sharp angle theta is changed, the quality factor of the metamaterial resonance peak can be regulated and controlled, and when the triangular sharp angle of the two opening slits 1-3 and 1-4 is different, a quasi-continuous domain constraint state effect can be generated, so that the ultra-high quality factor is formed. The resonant ring array is uniformly distributed on the dielectric substrate; all the split resonant rings have the same split direction to form a row of metamaterial, and the metamaterial rows are aligned in the same direction to finally form a complete metamaterial structure which is formed by arranging metamaterial units in a transverse and vertical array mode, as shown in a schematic diagram of fig. 2.
To further discuss the enhancement effect of the high sensitivity far infrared metamaterial device of the present invention, the performance characteristics of the far infrared metamaterial device of the present invention as shown in FIG. 5 and the conventional double-opening rectangular ring as shown in FIG. 6 are compared as shown in the following table:
double sharp angle split resonant ring | Conventional double-opening rectangular ring | |
Resonant frequency (cm) -1 ) | 458 | 460 |
Half width of peak (cm) -1 ) | 9.7 | 20.1 |
Quality factor | 47 | 23 |
As shown in the table above, compared with a conventional rectangular slit double-opening rectangular ring absorber with the same structural parameters, the metamaterial resonant frequency is closer to the characteristic frequency of an object to be detected, the half-peak width is narrower, and the quality factor is stronger (2 times).
The detection system schematic diagram based on metamaterial structural design shown in fig. 3 comprises far infrared light sources 3-1, a transmission type single-frequency absorption metamaterial structure 1-2, a dielectric substrate 1-1 and a far infrared detector 3-3, wherein the far infrared light sources 3-1 are sequentially arranged on the same optical axis, and the transmission type single-frequency absorption metamaterial structure 1-2 is formed by a double-opening rectangular ring structural unit array; the emission spectrum range of the far infrared light source and the detection spectrum range of the far infrared detector should contain and be larger than the designed working frequency range of the metamaterial.
First, the metamaterial is fixed to the sample holder according to the polarization direction of the metamaterial. The far infrared wave is generated by a far infrared light source 3-1, sequentially vertically enters and penetrates through a double-opening resonant ring periodic array 1-2 of the metamaterial and a dielectric substrate 1-1, and finally is detected by a far infrared detector 3-3.
A distinct resonance peak appears on the display as a reference resonance peak signal. The biological sample, such as a tissue slice, blood, is then uniformly loaded on the surface of the array of dual-split resonant rings of the metamaterial. And then, the metamaterial stuck with the sample to be tested is fixed on the sample frame again according to the polarization direction requirement. The far infrared wave is generated by a far infrared light source 3-1, vertically enters and penetrates through a sample 3-2 to be detected, a double-opening resonant ring periodic array 1-2 of the metamaterial and a dielectric substrate 1-1 in sequence, and is finally detected by a far infrared detector 3-3, so that a sample resonant peak signal of a biological sample such as a tissue slice and blood loaded on the surface of the metamaterial is obtained. The double-split resonant ring periodic array in the metamaterial only absorbs far infrared waves with specific frequency to form a single-frequency resonant peak. When the surface of the metamaterial is covered by a biological sample, the electromagnetic field on the surface changes, so that the selective absorption frequency of the metamaterial for far infrared waves changes, and the change of the resonance peak position and the resonance peak-to-peak value is shown. Comparing the reference resonance peak signal with the sample resonance peak signal, measuring and calculating the frequency offset and the amplitude variation of the reference resonance peak signal and the sample resonance peak signal, and obtaining the concentration of the specific component in the sample to be measured through mathematical treatment.
Mesothelioma antigen-1 (HBME-1) is a highly sensitive (92.6%), highly accurate (89.1%) molecular marker of thyroid cancer. It is highly expressed in thyroid cancer and is not expressed in normal, inflammatory and proliferative thyroid. Thus, benign thyroid lesions and thyroid carcinomas can be identified by detecting the amount of mesothelioma antigen-1 in thyroid tissue. Currently, intermediate dermatologic antigen-1 in biological samples is detected mainly by immunohistochemical staining. Based on the antigen-antibody specific binding principle, the presence or absence of mesothelioma antigen-1 in the tissue is detected by the mesothelioma antigen-1 antibody labeled with a color developing agent. However, the method has the problems of complicated sample processing steps, long time consumption and easy interference.
Based on this, in order to verify the technical effects of the present invention, the mesothelioma antigen-1 concentration was detected by the detection system of the present invention.
By adjusting the structural parameters and materials of the resonant ring unit, the resonant frequency of the metamaterial is matched with the far infrared characteristic absorption frequency of the mesothelioma antigen-1 as shown in figure 4, and the far infrared characteristic signal of the mesothelioma antigen-1 can be further amplified through resonance.
Fig. 5 is a schematic structural diagram of a metamaterial according to a first embodiment of the present invention. In a first embodiment, the metamaterial is composed of a dielectric substrate and a metal resonant ring; the material of the dielectric substrate is polyimide, and the thickness is 20 mu m; the material of the resonant ring is gold, and the thickness is 50nm. The resonant ring unit is a square with a side length of 8 mu m, and the center is a square ring with a side length of 5 mu m and a width of 0.5 mu m; the resonance ring comprises two open slits which are symmetrical in position and have the width of 0.5 mu m, two ends of the two open slits are triangular sharp angles, and the angle of the sharp angles is 90 degrees. The geometric shape of the resonant ring is prepared by a photoetching process and an etching process, and the metamaterial sensor formed by the resonant ring array is square with the side length of 1 cm. The dielectric substrate may be replaced with other dielectric materials, the resonant ring may be replaced with other metallic and semiconductor materials, and the metamaterial unit density may be variable. All the parameters are designed and processed according to the far infrared absorption spectrum characteristics of mesothelioma antigen-1; in this embodiment, the resonance frequency band is 458cm for mesothelioma antigen-1 -1 Far red at the positionThe design of the external characteristic absorption peak and the implementation method of the enhancement of the far infrared characteristic peak signals of other mesothelioma antigen-1 are consistent with the implementation method.
The output frequency range of the far infrared light source 1 and the detection frequency range of the far infrared detector are 100 cm to 600cm -1 。
Firstly, taking a clean and complete metamaterial, fixing the metamaterial on a spectrometer sample rack according to the polarization direction requirement as shown in fig. 3, measuring the transmission spectrum of the metamaterial by using a far infrared detector 3-3, and recording; at this time, the resonance frequency of the metamaterial is 458cm -1 And is noted as a reference resonance peak signal.
Secondly, taking a tissue sample to be measured with the thickness of 10 mu m, attaching the tissue sample to the surface of the clean and complete metamaterial, and removing free water molecules contained in the sample through nitrogen purging;
thirdly, fixing the metamaterial with the tissue sample loaded on the surface on a sample frame according to the polarization direction requirement, measuring the transmission spectrum of the metamaterial by using a far infrared detector 3-3, and recording; at this time, the resonance frequency of the metamaterial is recorded as a sample resonance peak signal.
And step four, comparing the two acquired transmission spectra, measuring and calculating the frequency offset and the amplitude variation between the sample resonance peak signal and the reference resonance peak signal, and calculating the concentration of the intermediate dermatome antigen-1 of the sample. The invention can lead mesothelioma antigen-1 to be 458cm by only combining the tissue sample to be detected with the metamaterial -1 The far infrared characteristic absorption signal is obviously increased, and the operation is simple and convenient.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any person skilled in the art will make any equivalent substitution or modification to the technical solution and technical content disclosed in the invention without departing from the scope of the technical solution of the invention, and the technical solution of the invention is not departing from the scope of the invention.
Claims (8)
1. A high-sensitivity far infrared metamaterial device is characterized by comprising a dielectric substrate and a plurality of split resonant rings;
the split resonant rings are arranged on the surface of the dielectric substrate at equal intervals in an array period;
the split resonant ring is of a double-split annular structure, the widths of the two split slits are the same and the positions of the two split slits are opposite, and the split resonant ring is of a sharp-angle structure at two sides of the split slits so as to form a double-sharp-angle split structure.
2. The high-sensitivity far infrared metamaterial device according to claim 1, wherein the split resonant ring is of a rectangular annular structure;
the opening slit is positioned at the middle of the upper rectangular edge and the lower rectangular edge, and the distances from the opening slit to the left rectangular edge and the right rectangular edge are the same.
3. The high sensitivity far infrared metamaterial device according to claim 1, wherein a plurality of rows of metamaterial teams are arranged on the surface of the dielectric substrate, each row of metamaterial teams comprising a plurality of the split resonant rings arranged in the same direction and at equal intervals.
4. The high sensitivity far infrared metamaterial device according to claim 1, wherein the angle of the sharp corner is greater than 0 and less than 180 degrees; and regulating and controlling the half-peak width of the metamaterial resonance peak, the resonance frequency and the quality factor by changing the angle of the sharp angle.
5. The high sensitivity far infrared metamaterial device as set forth in claim 1, wherein the split ring resonator is a metallic material, a semiconductor material, and combinations thereof;
the material of the dielectric substrate is a material with high far infrared transmittance and a combination thereof.
6. A concentration detection system for a specific component in a sample using the high-sensitivity far-infrared metamaterial device as set forth in any one of claims 1 to 5;
the infrared detector is characterized by comprising an infrared light source and a far infrared detector; the infrared light source is arranged above the high-sensitivity far infrared metamaterial device, and the far infrared detector is arranged below the high-sensitivity far infrared metamaterial device; the infrared light source generates far infrared waves which vertically enter and penetrate through the high-sensitivity far infrared metamaterial device and then are received by the far infrared detector.
7. The system for detecting the concentration of a specific component in a sample according to claim 6, which is applied to high-precision detection of the concentration of the intermediate picotumor antigen-1 in a tissue sample.
8. The system for detecting the concentration of a specific component in a sample according to claim 6, wherein the detection method comprises the steps of:
step 1: and (3) a clean and complete metamaterial device is taken and fixed on a spectrometer sample rack according to the polarization direction requirement, the transmission spectrum of the metamaterial device is measured by using the far infrared detector, and the transmission spectrum is recorded and recorded as a reference resonance peak signal.
Step 2: a tissue sample to be measured with a certain thickness is taken and attached to the surface of the metamaterial device, and free water molecules contained in the sample are removed through nitrogen purging;
step 3: and fixing the metamaterial device with the tissue sample loaded on the surface on a sample frame according to the polarization direction requirement, measuring the transmission spectrum of the metamaterial device by using the far infrared detector, and recording the transmission spectrum as a sample resonance peak signal.
Step 4: and comparing the two acquisitions to obtain a transmission spectrum, measuring and calculating the frequency offset and the amplitude variation between the sample resonance peak signal and the reference resonance peak signal, and calculating the concentration of the specific component in the sample.
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CN117805327B (en) * | 2024-02-29 | 2024-05-14 | 中国计量大学 | Sensing chip and method for simultaneously detecting aureomycin and lactose hydrate in milk |
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