Sebum gas collection and infrared spectrum enhancement device

Abstract

To address the difficulties of collecting sebum gas from the human body and its low analysis accuracy, the present invention discloses a device for collecting sebum gas and enhancing its infrared spectrum. By combining a micro-electromechanical system (MEMS), functional two-dimensional materials, and metal surface plasmon resonance (MSPR) technology, the present invention produces a device similar in shape and size to a conventional Band-Aid. By applying the device to the human body for 3-5 minutes, trace amounts of sebum gas can be collected. Furthermore, the device can enhance the weak infrared spectrum of sebum gas, further improving the recognition of the sebum gas infrared spectrum, providing a simple, efficient, and accurate device for diagnosing diseases based on sebum gas.

Description

Technical Field

[0001] The present invention belongs to the technical field of early disease diagnosis instruments, and in particular relates to a sebum gas collection and infrared spectrum enhancement device. Background Art

[0002] Energy metabolism is a hallmark of living organisms. During human metabolism, sweat glands secrete cells that absorb water, inorganic salts, and urea from the blood and excrete them as sweat. Sebaceous glands, through the disintegration of glandular cells and the reaction with lipid droplets in the cytoplasm, excrete sebum. When sweat and sebum are excreted onto the body surface, gases are emitted, commonly known as body odor. When a person suffers from a disease, blood markers associated with the disease are produced in the blood. These markers are crucial for diagnosis. When specific disease-related substances are present in a patient's blood, they are excreted through metabolic products such as sweat and sebum, emitting specific gases. For example, in diabetic patients, fat is oxidized in the liver to produce ketone bodies, giving off a rotten apple odor. In patients with chronic nephritis or liver disease, the accumulation of urea nitrogen and creatinine in the blood produces an ammonia odor. In Parkinson's disease (PD), sebum contains organic gases such as perillaldehyde, resulting in a musk-like body odor. Alzheimer's disease also emits formaldehyde.

[0003] Many chronic diseases such as cancer, Parkinson's disease, and Alzheimer's disease are slow-growing diseases, and some may take 10 years or even longer to develop symptoms. Taking PD as an example, in 2015, the BBC reported that nurse Joy smelled a special odor from her husband's body 12 years before he developed related signs and symptoms of PD. In 2019, Dr. Tilo Kunath, a famous PD expert at the University of Edinburgh, also confirmed that hippuric acid (C9H9NO3) and perillaldehyde (C 10 H 14 O), eicosane (C 20 H 42 ) and octadecane (C 18 H 38 ) are closely related to PD. If these specific gases can be detected in patients in the early stages of the disease, it will provide a basis for diagnosis and treatment before the disease occurs, thus achieving early diagnosis and treatment of the disease, which is of great significance.

[0004] However, human body odor is difficult to detect. First, body odor is a mixture of gases released by human sweat, sebum, etc., which contains organic volatile components, which are very low in content and difficult to collect. The existing methods for collecting human sebum gas all use gauze to wipe the skin to collect sebum, and then precipitate the gas through thermal desorption. The collection process is cumbersome and complicated, and the equipment requirements are very high. In addition, the gas will be mixed with impurities that cannot be removed during the precipitation process, which seriously affects the detection accuracy; secondly, the analysis of sebum gas cannot avoid the expensive and complicated gas chromatograph, which greatly increases the threshold and difficulty of sebum gas analysis; thirdly, the composition of human sebum gas is complex and belongs to volatile organic compounds (VOC). The existing VOC detection method can only test the total concentration of VOC, but cannot determine its component content.

[0005] At present, the collection and analysis of human sebum gas at home and abroad is still limited by the sebum sampling method, detection instruments and analysis methods. It is complicated, costly and cannot achieve good results. Summary of the Invention

[0006] In response to the difficulties in collecting human sebum gas and its low analysis accuracy, the present invention discloses a sebum gas collection and infrared spectrum enhancement device. The device combines a micro-electro-mechanical system (MEMS), functional two-dimensional materials and metal surface plasmon resonance technology to prepare a sebum gas collection and infrared spectrum enhancement device that is similar in shape and size to a conventional Band-Aid. The device can be attached to the human body for 3-5 minutes to collect trace amounts of human sebum gas. At the same time, the device can enhance the weak infrared spectrum of sebum gas, further improving the recognition of the sebum gas infrared spectrum, providing a simple, efficient and accurate device for disease diagnosis based on human sebum gas.

[0007] In order to achieve the above-mentioned purpose, the present invention provides a sebum gas collection and infrared spectrum enhancement device, which includes a fixing belt and a fixing frame arranged on the fixing belt, wherein a nano gas sensitive core is arranged in the fixing frame.

[0008] The nano gas-sensitive core includes a substrate, the material of which is an optical window material with an infrared transmittance of more than 90%, preferably CaF2 crystal, to ensure that the nano gas-sensitive core can transmit infrared light and maintain an infrared transmittance of more than 85%; a two-dimensional material with gas sensitivity is attached to the upper surface of the substrate to adsorb sebum gas and allow infrared light to pass through; at the same time, a nano metal array is also provided on the upper surface of the substrate, which produces a surface plasmon enhancement effect under the irradiation of infrared light, thereby enhancing the infrared spectrum of the sebum gas adsorbed on the two-dimensional material.

[0009] The nanometal array is a tiny metal array formed by a single unit structure, or a tiny metal array formed by a combination of multiple different unit structures. The metal is preferably gold or silver. The unit structure is a bow-tie structure composed of a pair of isosceles triangles, an elongated rectangular structure, or other structures with plasma resonance peaks between 4.7 μm and 10.5 μm. The height of the unit structure is 80 nm to 120 nm. The above-mentioned different structures correspond to different plasma resonance peaks, and the plasma resonances of different resonance peaks enhance the infrared spectra of different sebum gases. The tiny metal array formed by a combination of multiple different unit structures has a wider range of plasma resonance peaks than the tiny metal array formed by a single unit structure, thereby enhancing multiple characteristic peaks of the infrared spectrum of sebum gases.

[0010] The fixed frame is also provided with a breathable protective layer, which is preferably a breathable protective gauze bonded to the outer edge of the fixed frame to prevent the skin from contacting the nano gas-sensitive core during human testing and to prevent the infiltration of impurities.

[0011] A single layer or multiple layers of two-dimensional material are attached to the upper surface of the nano gas-sensitive core substrate. The two-dimensional material is molybdenum disulfide, graphene, carbon nanotubes or other two-dimensional materials with gas sensitivity, so that the nano gas-sensitive core can adsorb sebum gas and increase the sensitivity and stability of gas adsorption.

[0012] The fixing tape is preferably a long strip of tape, so that the appearance and size of the sebum gas collection and infrared spectrum enhancement device are similar to a band-aid, which is convenient to use.

[0013] The present invention has the following beneficial effects:

[0014] 1) This invention combines MEMS, gas-sensitive two-dimensional materials, and metal surface plasmon resonance technology to fabricate gas-sensitive two-dimensional materials and micro-metal arrays on highly infrared-transmittant materials. This overcomes the limitations of metal surface plasmon resonance infrared spectroscopy, which is limited to liquid and solid applications, and extends its application to gas detection. This technology increases the sensitivity and stability of sebum gas adsorption while enhancing the infrared spectrum of gases.

[0015] 2) It provides a non-invasive diagnostic instrument and method for ultra-early diagnosis of diseases;

[0016] 3) The device is similar in shape and size to a Band-Aid, and the sebum gas collection process is as non-invasive, convenient, and efficient as operating a Band-Aid. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is an exploded view of the device for collecting sebum gas and enhancing its infrared spectrum;

[0018] Figure 2This is an assembly diagram of the sebum gas collection and infrared spectrum enhancement device of the present invention;

[0019] Figure 3 Schematic diagram of the three-dimensional structure of the nano gas-sensing core according to Example 1 of the present invention;

[0020] Figure 4 This is a Raman spectrum of molybdenum disulfide according to Example 1 of the present invention;

[0021] Figure 5 This is a schematic diagram of a nanometal array according to Example 1 of the present invention;

[0022] Figure 6 This is a SEM image of the surface of the nano gas-sensitive core of Example 1 of the present invention;

[0023] Figure 7 This is an enhanced infrared spectrum of the nano gas-sensitive core of Example 1 of the present invention to sebum gas in PD patients;

[0024] Figure 8 This is a unit structure diagram of the nanometal array according to Example 2 of the present invention;

[0025] Figure 9 The plasma-enhanced electric field and infrared spectrum obtained by simulating the unit structure of Example 2 of the present invention;

[0026] Figure 10 This is a unit structure diagram of the nanometal array according to Example 3 of the present invention;

[0027] Figure 11 The plasma-enhanced electric field and infrared spectrum obtained by simulating the unit structure of Example 3 of the present invention.

[0028] In the figure, 1-breathable protective layer, 2-fixed frame, 3-nano gas-sensitive core, 4-fixed belt, 5-nanometal array, 6-two-dimensional material, 7-substrate. DETAILED DESCRIPTION

[0029] The following describes the detailed technical solution of the present invention in conjunction with the accompanying drawings:

[0030] like Figure 1-2 As shown, the sebum gas collection and infrared spectrum enhancement device provided by the present invention includes a fixing belt 4 and a fixing frame 2 arranged on the fixing belt 4, and a nano gas sensitive core 3 is arranged in the fixing frame 2.

[0031] The nanometer gas-sensing core 3 includes a substrate 7 made of an optical window material with an infrared transmittance of over 90%. A single or multiple layers of two-dimensional material 6 are attached to the upper surface of the nanometer gas-sensing core substrate 7. The upper surface of the substrate 7 is also provided with a nano-metal array 5. The upper surface of the nanometer gas-sensing core 3 is bonded upwardly to the interior of the fixed frame 2, 1 mm to 2 mm from the lower surface of the fixed frame 2. The upper surface of the fixed frame 2 is also provided with a breathable protective layer 1, specifically a breathable protective gauze bonded to the outer edge of the fixed frame.

[0032] like Figure 3 As shown, the nanometal array 7 is a tiny metal array formed by a unit structure, or a tiny metal array formed by a combination of multiple different unit structures. The metal is preferably gold or silver. The unit structure is a bow-tie structure composed of a pair of isosceles triangles, an elongated rectangular structure or other structures with a plasma resonance peak of 4.7μm-10.5μm, and the height of the unit structure is 80nm-120nm.

[0033] The two-dimensional material is molybdenum disulfide, graphene, carbon nanotubes or other two-dimensional materials with gas sensitivity.

[0034] Example 1

[0035] This embodiment takes the sebum gas collection and infrared spectrum enhancement device for diagnosing PD as an example. First, based on the infrared spectra of four organic gases closely related to PD (hippuric acid, perillaldehyde, eicosane, and octadecane) reported by Dr. Tilo Kunath, it is determined that the main peak of the infrared spectrum of the mixed gas formed by the mixture of hippuric acid, perillaldehyde, eicosane, and octadecane appears between 5.85μm and 6.18μm.

[0036] Then, a device for collecting sebum gas and enhancing its infrared spectrum is designed accordingly, such as Figure 1-2 As shown, the device includes a fixing belt 4 and a fixing frame 2 mounted on the fixing belt 4, wherein a nano gas-sensing core 3 is mounted in the fixing frame 2. The fixing frame 2 is a square hollow structure with a height of 6 mm and a wall thickness of 2 mm, and an internal dimension of 5.5 mm x 5.5 mm.

[0037] The nano gas-sensing core 3 includes a substrate 7. In this embodiment, the substrate 7 is a double-sided polished square CaF2 crystal with a length, width, and height of 5 mm, 5 mm, and 0.5 mm, respectively. A single layer of molybdenum disulfide is attached to the upper surface of the CaF2 crystal. The Raman spectrum of the single layer of molybdenum disulfide is as follows: Figure 4 As shown, the two absorption peaks of the Raman spectrum appear at 384.13 and 408.50, respectively.

[0038] like Figure 3As shown, a nanometal array 5 is fabricated on a CaF2 substrate with a monolayer of molybdenum disulfide attached by electron beam lithography. The nanometal array 5 is bonded and fixed, with its upper surface facing upward, within a fixed frame 2, 1.5 mm from the lower surface. The nanometal array 5 is composed of four bow-tie-shaped unit structures of varying sizes and spacing. Each bow-tie unit structure consists of two equal-sized isosceles triangles, with their vertices corresponding to their vertex angles facing each other, a spacing b between them, and symmetry about a line parallel to the base of the triangle. The metal used is gold, with a thickness of 80 nm. Figure 5 The structure of the nanometal array 5 is schematically shown. The base lengths L of the triangles in the four bow-tie unit structures are 80 nm, 90 nm, 100 nm, and 116 nm, respectively. The heights H are 100 nm, 120 nm, 135 nm, and 150 nm, respectively. The distances b between the two triangle vertices are 46 nm, 75 nm, 95 nm, and 120 nm, respectively. The lateral spacings T within the four bow-tie arrays are 60 nm, 100 nm, 300 nm, and 500 nm, respectively. The longitudinal spacings S within the four bow-tie arrays are 1 μm, respectively. The lateral spacings T between the four bow-tie arrays are 1 μm, respectively. h The longitudinal spacing between the four bow-tie arrays is 600 nm. L 2μm; Figure 6 This is a scanning electron microscope (SEM) image of the prepared nanometal array 5.

[0039] like Figure 1-2 As shown, a breathable protective layer 1 is provided on the fixed frame 2. In this embodiment, the breathable protective layer 1 is a 9.5mm×9.5mm square sterile breathable gauze, the edge of which is aligned with the outer edge of the fixed frame 2 and bonded to the upper surface of the fixed frame 2; the fixing belt 4 is a long strip of tape with glue at both ends of the upper surface and no glue in the middle and lower surfaces of the upper surface. The part without glue in the middle of the upper surface is a 10mm×10mm square, and the lower surface of the fixed frame 2 is bonded to the middle part of the upper surface of the fixing belt without glue.

[0040] During use, taking the diagnosis of Parkinson's disease patients as an example, the sterile breathable gauze of the sebum gas collection and infrared spectrum enhancement device of this embodiment is brought into contact with the back of the person being tested, and fixed by a fixing belt for 5 minutes. Then, the sterile breathable gauze and the fixing belt are removed, the upper surface of the nano gas-sensitive core is facing upward, and a microscopic infrared spectrometer is used to scan the transmission infrared spectrum of the nano gas-sensitive core that has adsorbed the sebum gas of the person being tested. In addition, this embodiment also uses a microscopic infrared spectrometer to scan the transmission infrared spectra of the following three comparison samples: 1) a clean, simple monolayer molybdenum disulfide film, 2) a monolayer molybdenum disulfide film that has adsorbed the sebum gas of PD patients, and 3) a nano gas-sensitive core that has adsorbed the sebum gas of healthy young men who do not suffer from PD. The results are as follows: Figure 7 As shown in the figure, by comparing the transmitted infrared spectrum of a simple single-layer MoS2 film without metal plasma enhancement, it can be seen that the nano gas-sensitive core provided in this embodiment has a significant enhancement effect on the infrared spectrum of the adsorbed sebum gas; although, after adsorbing sebum gas, the infrared spectrum of the MoS2 film is cleaner, the infrared spectrum of the MoS2 film has absorption changes at 5.86μm, 5.93μm, and 6.02μm-6.06μm, but the absorbance change is very small, indicating that the single-layer MoS2 film has the ability to adsorb sebum gas, but the recognition of its infrared spectrum is poor.

[0041] Furthermore, unlike the narrow-peak spectrum enhanced by metal plasma of conventional single-unit structure, the nanometal array used in this embodiment obtained a wide-peak metal plasma-enhanced infrared spectrum of 5.88μm-6.09μm (when clean and without adsorption of the analyte). After adsorbing the gas of PD patients' sebum, spectral enhancement occurred between 5.95μm-6.08μm (after adsorbing the sebum gas of PD patients). At the same time, a slight secondary peak enhancement also occurred between 5.85μm-5.88μm; after adsorbing the sebum gas of healthy young people who do not suffer from PD, only a slight spectral enhancement occurred between 5.86μm-5.89μm (after adsorbing the sebum gas of healthy young people who do not suffer from PD), and no spectral enhancement occurred between 5.95μm-6.08μm. Therefore, the enhanced spectral range of 5.95μm-6.08μm is a unique infrared spectral range that distinguishes PD patients from people without PD. By collecting a sufficient amount of infrared spectral data and establishing a classification model, it is possible to diagnose whether the person being diagnosed has PD.

[0042] Example 2

[0043] The unit structure of the nanometal array of Example 1 was adjusted, and the thickness of gold was adjusted to 90 nm; Figure 8As shown, the unit structure includes a pair of A structures with opposite sharp corners, and the A structure includes a semicircle, a trapezoid, a rectangle and an isosceles triangle, wherein the diameter of the semicircle is the same as and coincides with the upper base of the trapezoid, the short side of the rectangle is the same as the base of the isosceles triangle, one short side of the rectangle coincides with the lower base of the trapezoid and is located in the middle of the lower base of the trapezoid, and the other short side of the rectangle coincides with the base of the triangle; the diameter of the semicircle is 0.5μm, the upper base, lower base and height of the trapezoid are 0.5μm, 1.2μm and 1.65μm respectively, the long side and short side of the rectangle are 0.5μm and 0.2μm respectively, the base and height of the isosceles triangle are 0.2μm and 0.5μm respectively, and the spacing between the two A structures is 0.1μm. Simulation results show that the peak of the metal plasma enhanced infrared spectrum of the gold array in this embodiment red-shifts to 7.33μm, and the electric field strength increases to 3.09, as shown in FIG. Figure 9 shown.

[0044] The sebum gas collection and infrared spectrum enhancement device of this embodiment can be used to diagnose diseases related to the specific sebum gas infrared spectrum with a peak value of 7.33 μm.

[0045] Example 3

[0046] The unit structure of the nanometal array of Example 1 was further adjusted, and the thickness of gold was adjusted to 90 nm; Figure 10 As shown, the unit structure includes a pair of B structures with opposite sharp corners, and the B structure includes a semicircle, a trapezoid, a rectangle and an isosceles triangle, wherein the diameter of the semicircle is the same as and coincides with the lower base of the trapezoid, the short side of the rectangle is the same as the base of the isosceles triangle, one short side of the rectangle coincides with the upper base of the trapezoid and is located in the middle of the upper base of the trapezoid, and the other short side of the rectangle coincides with the base of the triangle; the diameter of the semicircle is 0.5μm, the upper base, lower base and height of the trapezoid are 0.4μm, 0.5μm and 1.65μm respectively, the long side and short side of the rectangle are 0.5μm and 0.2μm respectively, the base and height of the isosceles triangle are 0.2μm and 0.8μm respectively, and the spacing between the two B structures is 0.1μm. Simulation results show that the peak of the metal plasma enhanced infrared spectrum of the gold array in this embodiment red-shifts to 8.73μm, and the electric field strength increases to 3.42, as shown in FIG. Figure 11 shown.

[0047] The sebum gas collection and infrared spectrum enhancement device of this embodiment can be used to diagnose diseases related to the specific sebum gas infrared spectrum with a peak value of 8.73 μm.

Claims

1. Sebum gas collection and infrared spectrum enhancement device, characterized in that: It includes a fixing belt and a fixing frame arranged on the fixing belt, and a nano gas-sensitive core is arranged in the fixing frame; the nano gas-sensitive core includes a substrate, the material of the substrate is an optical window material with an infrared transmittance of more than 90%, and a single layer or multiple layers of gas-sensitive two-dimensional material are attached to the upper surface of the substrate. At the same time, a nano metal array is also arranged on the upper surface of the substrate, which produces a surface plasma enhancement effect under the irradiation of infrared light, thereby enhancing the infrared spectrum of sebum gas adsorbed on the two-dimensional material.

2. The device for collecting sebum gas and enhancing its infrared spectrum according to claim 1, characterized in that: The material of the substrate is CaF2 crystal.

3. The device for collecting sebum gas and enhancing its infrared spectrum according to claim 1, characterized in that: The nanometal array is a tiny metal array formed by a unit structure, or a tiny metal array formed by a combination of multiple different unit structures. The unit structure is a bow-tie structure composed of a pair of isosceles triangles, an elongated rectangular structure, or other structures with a plasma resonance peak of 4.7 μm-10.5 μm, and the height of the unit structure is 80 nm-120 nm.

4. The device for collecting sebum gas and enhancing its infrared spectrum according to claim 1, characterized in that: The metal of the nanometal array is gold or silver.

5. The device for collecting sebum gas and enhancing its infrared spectrum according to claim 1, characterized in that: A breathable protective layer is also provided on the fixing frame.

6. The device for collecting sebum gas and enhancing its infrared spectrum according to claim 5, characterized in that: The breathable protective layer is a breathable protective gauze bonded to the outer edge of the upper surface of the fixed frame.

7. The device for collecting sebum gas and enhancing its infrared spectrum according to claim 1, characterized in that: The two-dimensional material attached to the upper surface of the nano gas-sensitive core substrate is molybdenum disulfide, graphene, carbon nanotubes or other two-dimensional materials with gas sensitivity.

8. The device for collecting sebum gas and enhancing its infrared spectrum according to claim 1, characterized in that: The fixing tape is a long strip of adhesive tape.

9. The device for collecting sebum gas and enhancing its infrared spectrum according to claim 3, characterized in that: The nanometal array is composed of four bow-tie-shaped unit structures with different sizes and spacings. The bow-tie-shaped unit structure includes two isosceles triangles of equal size. The vertices corresponding to the vertex angles of the two isosceles triangles are opposite, the spacing is b, and they are symmetrical with a straight line parallel to the base of the triangle. The metal is gold, and the thickness of gold is 80 nm. The base lengths L of the triangles in the four bow-tie-shaped unit structures are 80 nm, 90 nm, 100 nm and 116 nm, respectively. The heights H are 100 nm, 120 nm, 135 nm and 150 nm, respectively. The spacing b between the two triangle vertices is 46 nm, 75 nm, 95 nm and 120 nm, respectively. The lateral spacing T within the four bow-tie arrays is 60 nm, 100 nm, 300 nm and 500 nm, respectively. The longitudinal spacing S within the four bow-tie arrays is 1 μm, and the lateral spacing T between the four bow-tie arrays is 1 μm. h is 600 nm, and the longitudinal spacing S between the four bow-tie arrays is L 2 μm.

Images