CN111175269A - Micro-nano structure for realizing circular dichroism and chiral detection device - Google Patents
Micro-nano structure for realizing circular dichroism and chiral detection device Download PDFInfo
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- CN111175269A CN111175269A CN202010085132.4A CN202010085132A CN111175269A CN 111175269 A CN111175269 A CN 111175269A CN 202010085132 A CN202010085132 A CN 202010085132A CN 111175269 A CN111175269 A CN 111175269A
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- 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
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Abstract
The invention relates to a micro-nano structure for realizing circular dichroism and a chiral detection device, which comprise a substrate layer, wherein a plurality of chiral units which are periodically arranged are arranged on the substrate layer, and each chiral unit comprises a left-handed G-type structure and a right-handed G-type structure; according to the micro-nano structure for realizing circular dichroism and the chiral detection device, the absorbed circular dichroism signals can be generated due to the asymmetry of the left chiral structure and the right chiral structure. And moreover, the fluorescent molecular layer is laid on the chiral structure, and only one chiral junction can gather an electric field under the irradiation of one type of circularly polarized light, so that the luminescence of the fluorescent molecular layer on the chiral junction is enhanced, and the chiral signal is directly distinguished.
Description
Technical Field
The invention relates to the technical field of micro-nano optics, in particular to a micro-nano structure for realizing circular dichroism and a detection device thereof.
Background
Chirality is a phenomenon common in nature and widely exists in various fields of scientific research such as life chemistry. Chirality refers to the property that a structure cannot be completely coincident with its mirror image, as if the left and right hands were mirror symmetric but not coincident. Chirality plays a key role in biochemistry and life evolution. Many of the basic substances that make up life, such as proteins, amino acids, and ribonucleic acids, etc., are chiral. Similarly, more than half of the drugs used in clinical treatment have chirality, and different enantiomers of chiral drugs have certain differences in chemical properties such as potency and toxicity, and show different effects. Even when one enantiomer of a chiral drug is therapeutically effective, the other enantiomer appears to be deleterious. Therefore, the identification and quantification of chiral enantiomers is crucial.
Circular Dichroism (CD) spectroscopy is the primary method for detecting chiral features. The CD effect is utilized to research various biological molecules and drug molecules, and the CD effect has very important significance for scientific research and practical application. However, conventional CD spectroscopy requires high analyte concentrations due to weak interaction between light and molecules, which reduces the sensitivity and detection limit of the CD spectrum. How to effectively design artificial materials to realize strong CD effect becomes the focus of attention. In recent years, researches have found that artificial plasmonic metal chiral nanostructures generate very strong CD signals due to the interaction of the strong dipole moment of the LSPR thereof and an external optical field, and researchers have conducted extensive researches on the CD effect of plasmonic metal chiral nanostructures theoretically and experimentally.
But the design is usually such that one period includes one chiral structure, either a left-handed or a right-handed structure. The chiral detection device with such a structure usually requires a spectrum to determine the chiral characteristics of the molecule, making detection very difficult.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a micro-nano structure and a chiral detection apparatus for realizing circular dichroism, including a substrate layer, where the substrate layer is provided with a plurality of periodically arranged chiral units, and the chiral units include a left-handed G-type structure and a right-handed G-type structure.
Furthermore, the left-handed G-type structure and the right-handed G-type structure are two mirror-symmetric chiral structures.
Further, the thickness of the left-handed G-type structure and the thickness of the right-handed G-type structure are both smaller than 100 nm.
Further, the left-handed G-type structure and the right-handed G-type structure are both made of noble metals.
Further, the left-handed G-type structure and the right-handed G-type structure are made of gold or silver.
Furthermore, the number of the left-handed G-type structures is the same as that of the right-handed G-type structures.
Further, the left-handed G-type structure and the right-handed G-type structure have different heights.
Furthermore, the number of the left-handed G-type structures is different from that of the right-handed G-type structures.
Furthermore, a fluorescent molecular layer is arranged on the left-handed G-type structure and the right-handed G-type structure.
Further, the distance between the left-handed G-type structure and the right-handed G-type structure is less than 150 nm.
Compared with the prior art, the invention has the beneficial effects that:
(1) this application is through stagger the placement with left-handed and right-handed structure in a cycle, destroys the symmetry and produces the circular dichromatic signal of absorption. And moreover, the fluorescent molecular layer is laid on the chiral structure, an electric field can be gathered on only one chiral junction under the irradiation of one type of circularly polarized light, the light-emitting position of the fluorescent molecular layer on the chiral structure is enhanced, and a chiral signal is directly distinguished.
(2) The micro-nano structure for realizing circular dichroism is generated by the asymmetry of the left-handed and right-handed structures, and the circular dichroism signals can be increased by increasing the asymmetry of the left-handed and right-handed structures.
(3) The micro-nano structure for realizing circular dichroism and the chiral detection device can be formed by combining electron beam etching with dry etching, the structure is only limited to be a chiral structure, the requirement on the dimensional precision of the structure is not high, and the requirement on the preparation process is low.
(4) The micro-nano structure and the chiral detection device for realizing circular dichroism, provided by the invention, have a fluorescent molecular layer, and the concentration and the thickness of the fluorescent molecular layer are changed, so that the refractive index is changed, and the circular dichroism signal can be dynamically regulated and controlled.
Drawings
FIG. 1 is a schematic diagram of a micro-nano optical structure of an embodiment.
FIG. 2 shows the transmission spectrum and CD spectral lines of the micro-nano optical structure in example 2.
FIG. 3 shows the electric field distribution of the micro-nano optical structure of example 2 at a wavelength of 1000 nm.
FIG. 4 shows the electric field distribution of the micro-nano optical structure of example 2 at a wavelength of 1360 nm.
FIG. 5 shows the transmission spectrum and CD spectral lines of the micro-nano optical structure in example 3.
FIG. 6 shows the electric field distribution of the micro-nano optical structure of example 3 at a wavelength of 1000 nm.
FIG. 7 shows the electric field distribution of the micro-nano optical structure of example 3 at a wavelength of 1360 nm.
FIG. 8 is a schematic diagram of a micro-nano optical structure in example 4.
Wherein, in fig. 1: 1. a left-handed G-type structure; 2. a left-handed G-type structure; 3. a base layer.
Detailed Description
The method aims to solve the problem that the chiral detection device in the prior art generally needs a spectrum to judge the chiral characteristics of molecules, so that detection is very difficult. According to the micro-nano structure for realizing circular dichroism and the chiral detection device, the left chiral structure and the right chiral structure are arranged in a staggered mode in one period, and the symmetry is destroyed to generate an absorbed circular dichroism signal. And by paving the fluorescent molecular layer on the chiral structure, only one chiral junction can gather an electric field under the irradiation of one circularly polarized light, so that the light-emitting position of the fluorescent molecular layer on the chiral junction is enhanced, and the chiral signal is directly distinguished. The circular dichroism signal can be increased by increasing the asymmetry of the left-handed and right-handed structure placement. And a layer of fluorescent molecular layer is paved on the metal structure, so that the concentration and the thickness of the fluorescent molecular layer are changed, the refractive index is further changed, and the circular dichroism signal can be dynamically regulated and controlled.
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1:
the embodiment provides a micro-nano structure and a chiral detection device for realizing circular dichroism, which are shown in fig. 1, and the micro-nano structure and the chiral detection device comprise a substrate layer 3, wherein a plurality of chiral units which are arranged periodically are arranged on the substrate layer 3, and each chiral unit comprises a left-handed G-type structure 1 and a right-handed G-type structure 2.
This application is through staggering left chirality G type structure 1, right chirality G type structure 2 in a cycle and places, destroys the symmetry and produces absorptive circular dichroism signal. The asymmetry of placing through increase left hand nature G type structure 1 and right hand nature G type structure 2 can increase its circular dichroism signal, specifically as shown in fig. 1, left hand nature G type structure 1 is highly inequality with right hand nature G type structure 2, namely left hand nature G type structure 1 and right hand nature G type structure 2 are in different horizontal planes, and left hand nature G type structure 1 staggers each other with right hand nature G type structure 2, that is to say, in X axle or Y axle direction, left hand nature G type structure 1 is highly different with right hand nature G type structure 2, staggers each other. The left-handed G-type structure 1 and the right-handed G-type structure 2 are two chiral structures which are in mirror symmetry. The number of the left-handed G-type structures 1 is the same as that of the right-handed G-type structures 2.
Specifically, there is a space between the left-handed G-type structure 1 and the right-handed G-type structure 2. The distance between the left-handed G-type structure 1 and the right-handed G-type structure 2 is less than 150 nm. The thickness of the left-handed G-type structure 1 and the thickness of the right-handed G-type structure 2 are both smaller than 100 nm. The left-handed G-type structure 1 and the right-handed G-type structure 2 are both noble metals, such as gold and silver. The left-handed G-type structure 1 and the right-handed G-type structure 2 are both made of noble metal by combining electron beam etching and dry etching.
According to the embodiment of the application, the micro-nano structure for realizing circular dichroism and the chiral detection device are formed by combining electron beam etching with dry etching, the structure is only limited to be the chiral structure, the requirement on the size precision of the structure is not high, and the requirement on the preparation process is low.
Furthermore, a fluorescent molecular layer is arranged on the left-handed G-type structure 1 and the right-handed G-type structure 2.
This embodiment chirality detection device lays the fluorescence molecule layer on hand left chirality G type structure 1 and right chirality G type structure 2, and only one kind of chirality under the illumination of a circular polarized light will gather the electric field on the knot, strengthens the fluorescence molecule layer luminescence position on it, directly differentiates chiral signal. In addition, the micro-nano structure of the embodiment is provided with a fluorescent molecular layer, the concentration and the thickness of the fluorescent molecular layer are changed, the refractive index is further changed, and the circular dichroism signal can be dynamically regulated and controlled.
Example 2:
to further illustrate the circular dichroism characteristics of the planar micro-nano structure and the chiral detection device for realizing circular dichroism in example 1, as shown in fig. 2 to 6, this example discloses a transmission spectrum and a circular dichroism spectrum under left-handed and right-handed circular polarized light irradiation.
As shown in FIG. 1, the thickness t of the left-handed G-type structure 1 and the right-handed G-type structure 2 is set in the present embodiment1The lengths of the transverse rods in the left-handed G-type structure 1 and the right-handed G-type structure 2 are l respectively at 40nm1＝250nm,l2120nm, the lengths of the vertical bars in the G-type metal structure are respectively l3＝300nm,l4The line widths w of the left-handed G-type structure 1 and the right-handed G-type structure 2 are 100nm and 40 nm; the left-handed G-type structure 1 and the right-handed G-type structure 2 have a transverse distance G of 50nm and a longitudinal downward offset point distance d of 60 nm.
Referring to fig. 2, which is a transmission spectrum and a circular dichroism spectrum of the planar micro-nano structure implementing circular dichroism in the present embodiment, it can be seen from fig. 2 that three large CD signals are generated in the resonance modes of 580nm,1000nm and 1360nm, and the CD value thereof reaches 5%. As shown in fig. 3 and 4, the electric field distributions of 1000nm and 1360nm, we can see that under the irradiation of left-handed circularly polarized light and right-handed circularly polarized light, there is an electric field distribution only on the left-handed G-type structure 1 or the right-handed G-type structure 2. Specifically, at a wavelength of 1000nm, as shown in fig. 3(a), under the irradiation of the left-handed circularly polarized positive light, the electric field is distributed only on the left-handed G-type structure 1; as shown in fig. 3(b), under the irradiation of right-handed circularly polarized light, the electric field is distributed only on the right-handed G-type structure 2. At a wavelength of 1360nm, as shown in fig. 4(a), under irradiation of left-handed circularly polarized positive light, an electric field is distributed only on the right chiral G-type structure 2; as shown in fig. 4(b), under the irradiation of right-handed circularly polarized light, the electric field is mainly distributed on the left-handed G-type structure 1. It is also the difference in absorption caused by the different positions of the electric field distribution under the irradiation of the left and right optical rotations that produces the circular dichroism signal. Therefore, a fluorescent molecular layer is arranged on the left-handed G-type structure and the right-handed G-type structure, and the chirality of the fluorescent molecular layer can be directly judged according to the difference of luminescence enhancement of the fluorescent molecular layer through the difference of electric field distribution on the left-handed G-type structure and the right-handed G-type structure.
The planar micro-nano structure for realizing circular dichroism can generate circular dichroism signals in a planar structure, the structure belongs to a planar structure, the structure is only limited to a chiral structure, the requirement on the dimensional precision of the structure is not high, and the requirement on the preparation process is low.
Example 3:
the micro-nano structure and the chiral detection device for realizing circular dichroism in the embodiment are basically the same as those in the embodiment 2, and the difference is only that 60nm is staggered in the longitudinal direction.
Referring to fig. 5, which is a transmission spectrum and a circular dichroism spectrum of the micro/nano structure and chiral detection device for realizing circular dichroism in this embodiment, it can be seen from fig. 5 that three large CD signals are generated in the resonance modes of 580nm,1000nm and 1360nm, and the CD value thereof reaches 5%. As shown in fig. 6 and 7, the electric field distributions of 1000nm and 1360nm, we can see that under the irradiation of left-handed circularly polarized light and right-handed circularly polarized light, there is an electric field distribution only on the left-handed G-type structure 1 or the right-handed G-type structure 2. Specifically, at a wavelength of 1000nm, as shown in fig. 6(a), under irradiation of left-handed circularly polarized positive light, an electric field is distributed only on the right chiral G-type structure 2; as shown in fig. 6(b), under the irradiation of right-handed circularly polarized light, the electric field is distributed only on the left-handed G-type structure 1. At wavelength 1360nm, as shown in FIG. 7(a), under the irradiation of the levorotatory circularly polarized positive light, the electric field is distributed only on the left-handed G-type structure 1; as shown in fig. 7(b), under irradiation of right-handed circularly polarized light, the electric field is distributed mainly on the right-handed G-type structure 2. It is also the difference in absorption caused by the different positions of the electric field distribution under the irradiation of the left and right optical rotations that produces the circular dichroism signal. Therefore, a fluorescent molecular layer is arranged on the left-handed G-type structure and the right-handed G-type structure, and the chirality of the fluorescent molecular layer can be directly judged according to the difference of luminescence enhancement of the fluorescent molecular layer through the difference of electric field distribution on the left-handed G-type structure and the right-handed G-type structure.
Example 4:
the micro-nano structure and the chiral detection device for realizing circular dichroism in the embodiment are basically the same as those in embodiments 1 and 2, and are different only in the number of left-handed G-type structures 1 and right-handed G-type structures 2 in one period. As shown in fig. 8, since the G-type metal structures are not arranged in an aligned manner, under the irradiation of left-handed circularly polarized light and right-handed circularly polarized light, the absorption rates of the circularly polarized light are different due to the different electric field distribution positions, and circular dichroism is generated as in the mechanism of the CD generated in examples 1 to 3. And, by increasing the asymmetry of the left-handed and right-handed G-type structure 2 placement, its circular dichroism signal can be increased and modulated.
On the other hand, the different positions of the electric field enhancement cause different enhancement of the luminescence of fluorescent molecules above the micro-nano structure, so that the different luminescent areas are caused, and further the chiral signals can be judged directly through the different numbers of luminescent bright spots.
Example 5:
a micro-nano structure and a chiral detection device for realizing circular dichroism in this embodiment are basically the same as those in embodiments 1 and 2, and are different only in that a left-handed G-type structure 1 and a right-handed G-type structure 2 thereof may also be other chiral structures, such as an F-type structure, an L-type structure, cross-rod structures with different lengths, and the like. The chiral structures are not arranged in an aligned mode, and under the irradiation of left-handed circularly polarized light and right-handed circularly polarized light, the absorption rates of the circularly polarized light are different due to different electric field distribution positions, and circular dichroism can be generated. And, by increasing the asymmetry of the left-handed and right-handed G-type structure 2 placement, its circular dichroism signal can be increased and modulated.
The different positions of the electric field enhancement cause different enhancement of the luminescence of fluorescent molecules above the micro-nano structure, so that the different luminescent areas are caused, and the chiral signals can also be judged directly through the different numbers and positions of luminescent bright spots.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A micro-nano structure and chiral detection device for realizing circular dichroism is characterized in that: the chiral optical film comprises a substrate layer (3), wherein a plurality of chiral units which are periodically arranged are arranged on the substrate layer (3), and each chiral unit comprises a left-handed G-type structure (1) and a right-handed G-type structure (2).
2. The micro-nano structure and chiral detection device for realizing circular dichroism according to claim 1, wherein: the left-handed G-type structure (1) and the right-handed G-type structure (2) are two chiral structures which are in mirror symmetry.
3. The micro-nano structure and chiral detection device for realizing circular dichroism according to claim 1, wherein: the thickness of the left-handed G-type structure (1) and the thickness of the right-handed G-type structure (2) are both less than 100 nm.
4. The micro-nano structure and chiral detection device for realizing circular dichroism according to claim 1, wherein: the left-handed G-type structure (1) and the right-handed G-type structure (2) are both made of noble metals.
5. The micro-nano structure and chiral detection device for realizing circular dichroism according to claim 4, wherein: the left-handed G-type structure (1) and the right-handed G-type structure (2) are both made of gold or silver.
6. The micro-nano structure and chiral detection device for realizing circular dichroism according to claim 1, wherein: the number of the left-handed G-type structures (1) is the same as that of the right-handed G-type structures (2).
7. The micro-nano structure and chiral detection device for realizing circular dichroism according to claim 6, wherein: the left-handed G-type structure (1) and the right-handed G-type structure (2) are different in height.
8. The micro-nano structure and chiral detection device for realizing circular dichroism according to claim 1, wherein: the number of the left-handed G-type structures (1) is different from that of the right-handed G-type structures (2).
9. The micro-nano structure and chiral detection device for realizing circular dichroism according to claim 1, wherein: and a fluorescent molecular layer is arranged on the left-handed G-type structure (1) and the right-handed G-type structure (2).
10. The micro-nano structure and chiral detection device for realizing circular dichroism according to claim 1, wherein: the distance between the left-handed G-type structure (1) and the right-handed G-type structure (2) is less than 150 nm.
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Application publication date: 20200519 |