CN111982823A - Magnetic field bias chiral molecular sensing device - Google Patents
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- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 20
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000002983 circular dichroism Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002223 garnet Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- MTRJKZUDDJZTLA-UHFFFAOYSA-N iron yttrium Chemical compound [Fe].[Y] MTRJKZUDDJZTLA-UHFFFAOYSA-N 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical group [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 2
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 12
- 229940079593 drug Drugs 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 5
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 230000010354 integration Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229930002875 chlorophyll Natural products 0.000 description 4
- 235000019804 chlorophyll Nutrition 0.000 description 4
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 4
- 238000001142 circular dichroism spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229960000074 biopharmaceutical Drugs 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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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
- G01N21/19—Dichroism
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention relates to the crossing field of magneto-optical surface plasmon resonance nano optical devices and chiral molecule sensing, in particular to a magnetic field biased chiral molecule sensing device. According to the invention, the high magneto-optical effect and low-loss magnetic oxide material are combined with the surface plasmon resonance or cavity resonance design of the top layer noble metal plasmon resonance structure layer, so that the structural chirality of the top layer noble metal plasmon resonance structure layer is greater than or equal to the magnetic circular dichroism of the magnetic oxide layer, the structural chirality can be simply and effectively eliminated through the bias of an external magnetic field, the signal of a chiral molecule can be accurately obtained, the strong optical chirality near field enhancement is still maintained, and the problem of structural processing error is solved; and because the device is in a sub-wavelength structure, the device is beneficial to miniaturization and integration, and can be applied to detection of chiral drug molecules in the field of biological pharmacy.
Description
Technical Field
The invention relates to the crossing field of magneto-optical surface plasmon resonance nano optical devices and chiral molecule sensing, in particular to a magnetic field biased chiral molecule sensing device.
Background
Chiral molecules are ubiquitous in nature, such as amino acids, proteins, and carbohydrates that make up an organism. For human diseases, a specific single chiral drug is needed to cure the disease, and conversely, the chiral drug can harm human health. Therefore, chiral drug molecule detection is extremely important in the field of biopharmaceuticals.
At present, the commonly used method for detecting chiral drugs comprises the following steps: firstly, the optical circular dichroism of a chiral structure is utilized for detection; the other is to use a molecule of known chirality to interact with the molecule to be detected. The former test method is simple, fast, while the latter is time consuming and expensive. Therefore, the detection of chiral drug molecules by optical circular dichroism has become a hot point of research in this field in recent years. However, the optical chiral signal of chiral molecules is mainly in the ultraviolet band, and weak in visible light and near infrared chiral signals. We need a large amount of chiral molecule solution, and can obtain weak signals after long-time integration.
In recent years, researchers have increased the chiral signal of chiral molecules, such as swastika structure, by optical chiral near-field enhancement with chiral nano-optical structures[1]'hand sword' structure of gold[2,3]And the like. Although chiral nano-optical structures can achieve an order of magnitude improvement in chiral signals, the structural chiral signals of the chiral structures themselves mask the signals of the chiral molecules, and there is a risk of destroying the stereochemical information of the chiral molecules. In order to solve this problem, the existing solution is to use the chiral enantiomer structure and achieve the requirement of eliminating the chiral structure by the superposition of the two chiral signals. However, due to errors in preparation, the structural chirality is difficult to completely eliminate, and the risk of masking chiral signals still exists[4]And the signal-to-noise ratio is low.
[1]E.Hendry,T.Carpy,J.Johnston,et.al.Ultrasensitive detection and characterizationof biomolecules using superchiral fields,Nat.Nanotechnol.5,783(2010).
[2]R.Tullius,G.W.Platt,L.K.Khorashad,et.al.Superchiral plasmonic phase sensitivity for fingerprinting of protein interface structure,ACS Nano11,12040(2017).
[3]R.Tullius,A.S.Karimullah,M.Rodier,et.al.“Superchiral”spectroscopy:detection of protein higher order hierarchical structure with chiral plasmonic nanostructures.J.Am.Chem.Soc.137,8380-8383(2015).
[4]S.Yoo,Q-Han Park,Metamaterials and chiral sensing:a reviewof fundamentals and applications,Nanophotonics8,249-261(2019)
Disclosure of Invention
Aiming at the problems or the defects, the invention aims to provide a magnetic field biased chiral molecular sensing device in order to solve the problem that the structural chirality of a chiral nano optical platform cannot be eliminated.
The technical scheme adopted by the invention is as follows:
a magnetic field bias chiral molecular sensing device is composed of a top layer noble metal plasma resonance structure layer, a middle magnetic oxide layer, a bottom layer high temperature resistant conductive metal layer and a substrate which are sequentially stacked.
The top layer noble metal plasma resonance structure layer and the middle magnetic oxide layer realize plasma resonance or cavity resonance, the magnetic circular dichroism of the middle magnetic oxide layer is more than or equal to the structural chirality of the top layer noble metal plasma resonance structure layer, and magnetic field bias is realized through an external magnetic field and the magnetic circular dichroism of the middle magnetic oxide layer. The top layer noble metal plasma resonance structure layer is spin-coated on the structure surface through racemic chiral molecules, and the structural chirality at the resonance position is eliminated through magnetic field bias (wherein an external magnetic field can be realized by placing a small electromagnet below the device).
Further, the intermediate magnetic oxide layer is CeYIG/YIG film, rare earth doped yttrium iron garnet film or iron oxide film Fe3O4,γ-Fe2O3。
Further, the bottom high-temperature-resistant conductive metal layer is titanium nitride, titanium aluminum nitride or tantalum nitride.
Further, the top layer noble metal plasma resonance structure layer is a hexagonal hole structure of gold, silver, platinum or aluminum. The thickness of the top layer noble metal plasma resonance structure layer is 50 nm-100 nm, the hole radius is 50 nm-300 nm, the hole period is 500 nm-1 μm, the thickness of the magnetic oxide layer is 30 nm-150 nm, and the thickness of the high temperature resistant metal layer is 100 nm-200 nm.
When the device is used, under the magnitude of an external magnetic field, the left-handed chiral molecules and the right-handed chiral molecules are spin-coated on the top layer noble metal plasma resonance structure layer, signals of the chiral molecules are detected at resonance wavelengths, and the rotation states of the chiral molecules are distinguished through the symbols of circular dichroism CD.
According to the invention, the high magneto-optical effect and low-loss magnetic oxide material are combined with the surface plasmon resonance or cavity resonance design of the top layer noble metal plasmon resonance structure layer, so that the structural chirality of the top layer noble metal plasmon resonance structure layer is greater than or equal to the magnetic circular dichroism of the magnetic oxide layer, the structural chirality can be simply and effectively eliminated through the bias of an external magnetic field, the signal of a chiral molecule can be accurately obtained, the strong optical chirality near field enhancement is still maintained, and the problem of structural processing error is solved; and because the device is in a sub-wavelength structure, the device is beneficial to miniaturization and integration, and can be applied to detection of chiral drug molecules in the field of biological pharmacy.
Drawings
FIG. 1 is a schematic structural diagram of an embodiment;
FIG. 2 is a measured circular dichroism spectrum of an embodiment with and without applied positive and negative magnetic fields;
FIG. 3 is a circular dichroism spectrum measured in the examples under an applied magnetic field of-3.1 kOe to 3.1 kOe;
FIG. 4 is a circular dichroism spectrum of the sensing left and right chiral chlorophyll chiral molecules calculated in the example.
Detailed Description
As described in the background section, the method of using circular dichroism of light can analyze chiral structures of chiral molecules more conveniently and rapidly, and has an extremely important application in the field of biopharmaceuticals. In order to solve the problem that chiral molecular signals are weak in visible light and near infrared frequency bands, the problem can be effectively solved by utilizing the interaction of a chiral nano optical structure and chiral molecules. However, the influence of structural chirality on the chirality of molecules limits the applications of this device platform. Therefore, the structure chiral signal is eliminated by external bias, and the functional structure with strong near-field optical chirality has great significance. The invention uses magnetic field bias to solve the problem that the chiral molecule signal is covered by the structure chirality in the interaction system of the chiral nano optical structure and the chiral molecule. The elimination of the structural chirality by the magnetic field is realized by constructing a sub-wavelength resonance structure. Furthermore, the modulation of the magnetic field on the chiral signal can be realized, and the signal-to-noise ratio of the chiral signal is improved.
The invention is described in further detail below with reference to the figures and the detailed description. The invention mainly designs a chiral molecular sensing device based on magnetic field bias. In a preferred embodiment, the operating wavelength is 950nm, and the schematic structure is shown in FIG. 1.
The device comprises a gold top layer noble metal film hexagonal periodic hole structure, and a middle magnetic oxide layer is a cerium-doped yttrium iron garnet/silicon dioxide, titanium nitride and a quartz substrate.
The thickness of gold is 80nm, the hole radius is 185nm, the period is 540nm, the cerium-doped yttrium iron garnet is 55nm, the yttrium iron garnet is 45nm, and the silicon dioxide is 5 nm. Under the incident of circularly polarized light with an angle of 45 degrees, the circular dichroism can be changed from-0.6 degrees +/-0.2 degrees to +1.9 degrees +/-0.1 degrees by externally adding a magnetic field of +/-3.1 kOe. For chiral molecular sensing, a structural surface is covered with 80nm thick racemic chiral molecular chlorophyll, and a structural chiral signal at a resonance position is 0 by applying a magnetic field with a specific size. Then, under the magnetic field, the levorotatory or dextrorotatory chlorophyll molecules are externally added, so that the signals completely derived from chiral molecules are obtained. The refractive index of the chiral molecule is 1.343, and the chiral parameter is xi ═ 3 × 10-4。
The direction of the applied magnetic field is vertical to the surface of the device. At the cavity resonance wavelength, the change of the circular dichroism CD signal from-0.6 degrees +/-0.2 degrees to +1.9 degrees +/-0.1 degrees is realized by applying positive and negative magnetic fields, as shown in figure 2. Meanwhile, the continuous adjustment of the CD signal by the magnetic field can be realized by externally adding a continuously changing external magnetic field from-3.1 kOe to 3.1 kOe. And finally, the chiral sensing of chlorophyll chiral molecules is realized by utilizing the structural calculation.
The method mainly comprises the following steps: spin-coating racemic chiral molecules on the surface of a structure, and eliminating the structural chirality at a resonance position by applying a bias magnetic field; then, under the bias magnetic field, the chiral molecules in the left-handed state and the right-handed state are spin-coated, and the signals of the chiral molecules are detected at the resonance wavelength. The spin state of the chiral molecule is distinguished by the sign of the CD.
In conclusion, the magnetic oxide material with high magneto-optical effect is combined with the surface plasmon resonance or cavity resonance design of the top noble metal plasmon resonance structure layer, so that the magnetic circular dichroism of the magnetic oxide layer is greater than or equal to the structural chirality, the structural chirality can be eliminated through magnetic field bias, and the problem of structural processing errors is solved; and because the device is a sub-wavelength structure, the miniaturization and the integration of the device are facilitated.
Claims (7)
1. A magnetic field biased chiral molecular sensing device, characterized by:
the device comprises a top layer noble metal plasma resonance structure layer, a middle magnetic oxide layer, a bottom layer high-temperature-resistant conductive metal layer and a substrate which are stacked in sequence;
the top layer noble metal plasma resonance structure layer and the middle magnetic oxide layer realize plasma resonance or cavity resonance, the magnetic circular dichroism of the middle magnetic oxide layer is more than or equal to the structural chirality of the top layer noble metal plasma resonance structure layer, and magnetic field bias is realized through an external magnetic field and the magnetic circular dichroism of the middle magnetic oxide layer;
the top layer noble metal plasma resonance structure layer is spin-coated on the structure surface through racemic chiral molecules, and the structural chirality at the resonance position is eliminated through magnetic field bias.
2. The magnetic field-biased chiral molecular sensing device of claim 1, wherein: the applied magnetic field is perpendicular to the plane of the device.
3. The magnetic field-biased chiral molecular sensing device of claim 1, wherein: the top layer noble metal plasma resonance structure layer is a periodic hole structure of gold, silver, platinum or aluminum.
4. The magnetic field-biased chiral molecular sensing device of claim 1, wherein: the intermediate magnetic oxide layer is a CeYIG/YIG film, a rare earth doped yttrium iron garnet film or an iron oxide film Fe3O4,γ-Fe2O3。
5. The magnetic field-biased chiral molecular sensing device of claim 1, wherein: the bottom high-temperature-resistant conductive metal layer is titanium nitride, titanium aluminum nitride or tantalum nitride.
6. The magnetic field-biased chiral molecular sensing device of claim 2, wherein: the thickness of the top layer noble metal plasma resonance structure layer is 50 nm-100 nm, the hole radius is 50 nm-300 nm, the hole period is 500 nm-1 mu m, the thickness of the magnetic oxide layer is 30 nm-150 nm, and the thickness of the high-temperature resistant metal layer is 100 nm-200 nm.
7. The magnetic field-biased chiral molecular sensing device of claim 1, wherein: when the device is used, under the magnitude of an external magnetic field, the left-handed chiral molecules and the right-handed chiral molecules are spin-coated on the top layer noble metal plasma resonance structure layer, signals of the chiral molecules are detected at resonance wavelengths, and the rotation states of the chiral molecules are distinguished through the symbols of circular dichroism CD.
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| CN113237834A (en) * | 2021-07-08 | 2021-08-10 | 成都信息工程大学 | Chiral molecule chiral resolution device and method based on optical spin Hall effect |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113237834A (en) * | 2021-07-08 | 2021-08-10 | 成都信息工程大学 | Chiral molecule chiral resolution device and method based on optical spin Hall effect |
| CN113237834B (en) * | 2021-07-08 | 2021-09-14 | 成都信息工程大学 | Chiral molecule chiral resolution device and method based on optical spin Hall effect |
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